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GRB OP Tandon Organic Chemistry
GRB OP Tandon Organic Chemistry
CONTENTS
~. ~ ~ • - - ~ .-..>- > .,,~
. " - ,- .~,
,
Chapters Pages
Molecular
;... .
.,,"
Analysis of Organic Compounds
~
39-65
2.1 General (39); 2.2 Detection of Elements (Qualitative Analysis) (39); 2.3 Estimation of Elements (Quantitative
Analysis) (42); 2.4 Determination of Molecular Mass (47); 2.5 Empirical Formula and Molecular Formula (51); 2.6
Molecular Formula of G!1seous Hydrocarbons (52); 2.7 Modem Methods of Structure Elucidation (54); Summary
(55); Questions (56); Answers (57); Numerical Problems for Practice (58); Objective Questi9ns (59); Assertion-
Reason Type Questions (62); Answers Objective Questions (63); Brain Storming Problems (64); Linked
Comprehension Type Questions (65). Q
Isomerism 117-180
4.1 Introduction (117); 4.2 Chain or Nuclear Isomerism (118); 4.3 Position Isomerism (119); 4.4 Ring-Chain
Isomerism (119); 4.5 Functional Isomerism (120); 4.6 Metamerism (120); 4.7 Tautomerism (121); 4.8 Geometrical
Isomerism (125); 4.9 Optical Activity (131); 4.10 Optical Isomerism of Lactic Acid (134); 4.11 Optical Isomerism in
Tartanc Acid (134); 4.12 Number of Possible Stereoisomers in Compounds Containing Different Number of
Asymmetric Atoms (135); 4.13 Resolution of Racemic Mixtures (137); 4.14 Diastereomers (139); 4.15 Fischer
Projec'tion Formulae (139); 4.16 Specification of Configuration (140); 4.17 Conformational Isomerism (147);
Summary, (150); Questions (152); Answers (156); Objective Q!lestions (160); Assertion-Reason Type Questions
(168); Answers Objective Questions (169); Brain Storming Problems (170); Linked Comprehension Type Questions
(178).
Reagents (199); 5.6 Types of Organic Reactions (200); 5.7 Types of Mechanism (202); 5.8 Mechanism of Substitution
Reactions (203); Free Radical Substitution Reactions (203); Nucleophilic Substitution (206); Electrophilic
Substitution (210); 5.9 Mechanism of Addition Reactions (210); Electrophilic Addition Reactions (210); Addition
Reactions in Alkadienes (213); Nucleophilic Addition Reactions (215); Free Radical Addition Reactions (216); 5.10
Mechanism of Elimination Reactions (216); Summary (224); Questions (230); Answers (233); Objectb:.e Questions
(236); Asseltion-Reason Type Questions (248);Answers Objective Questions (249); Brain Storming Problems (250);
Linked Comprehension Type Questions (255).
6.1 Hydrocarbons (259); 6.2 Saturated Hydrocarbons (259); 6.3 Structural Isomerism in Alkanes (260); 6.4 Natural
Sources (occurrence) of Alkanes (260); 6.5 General Methods of Preparation (260); 6.6 General Characteristics of
Alkanes (265); 6.7 Petroleum (272); LPG and CNG (Petroleum Gases) (274); 6.8 Artificial Methods for Manufacture
of Petrol or Gasoline (274); 6.9 Knocking and Octane Number (275); 6.10 CetaneNumber (276); 6.11 Flash Point
(277); 6.12 Petrochemicals (277); Summary (277); Questions (280); Answers (282); Problems Based on Properties
and Structure (284); Objective Questions (287); Assertion~Reason Type Questions (293); Answers Objective
Questions (293); Brain Stonning Pr.oblems (294); Linked Comprehension Type Questions (296).
7.1 Introduction (298); 7.2 Nomenclature of Alkenes (298); 7j Isomerism inAlkenes (299); 7.4 Stability' of Alkenes
(299); 7.5 General Methods of Preparat~on of Alkenes (300); 7.6 General Characteristics of Alkenes(306); 7.7
Alkynes (323); 7.8 Isomerism inAlkynes (324); 7:9 General Methods of Preparation ofAlkynes (324); 7. 10 General
Characteristics ofAlkynes (325); 7.11 Tests of Un saturation (333); Degree of Unsaturation (334); 7.12 Inter-
, conversions (335); 7.13 Separation of Alkane, Alkene and Alkyne (336); 7.14 Distinction Between Alkanes, Alkenes
.~ --
and Alk:ynes(337); 7.15 Cycloalkanes (342); 7.16 Baeyer's Strain Theory (343); 7.17 Cycloalkenes(344)~7.18
Dienes (34,4); Summary (350); Questions (356);Answers (361); Problems Based on Structure and Properties (363);
Objective Questions (365); Assertion-Reason Type Questions (375); Answers Objective Questions (376); Brain
Storming Problems (377); Linked Comprehension Type Questions (386).
8.1 Halogen Derivatives ofAlkanes (388); 8.2 Isomerism in Monohalogen Derivatives.(390); 8.3 General Methods of.
Preparation of Monohalogen Derivatives (392); 8.4 Properties of Alkyl Halides (395); 8.5 Di-halogen Derivatives
(401); 8.6 Tri-halogen Derivatives, Chloroform (402);8.7 Iodoform (405); 8.8 Carbon Tetrachloride (406); 8.9
Unsaturated Halides (407); 8.10 Some More Important Halogen Derivatives (408); 8.11 Organometallic Compounds
(411); Summary (413); Questions (418); Answers (423); Problems Based on Structure and Properties (425);
Objective Questions (428); Assertion-Reason Type Questions (438); Answers Objective Questions (439); Brain
Storming Problems (440); Linked Comprehension Type Questions (445). '
4484682;",
9.1 Introduction (449); 9.2 Monohydric Alcohols (449); 9.3 Nomenclature (450); 9.4 Isomerism (451); 9.5 General
Methods of Preparation of Monohydric Alcohols (453); 9.6 General Characteristics of Alcohols (460);9.7 Methods
of Distinguishing Between Primary, Secondary and Tertiary Alcohols (469); 9.8 Analytical Tests for Alcohols (470);
9.9 Some Commercially Important Alcohols, Methyl Alcohol (470); Ethyl Alcohol (471); 9.10 Alcoholic Beverages
andAlcoholometry,(473); 9.11 Interconversions (474); Conversion of Ethyl Alcohol into Various Compounds (476);
9.12 Ethylene Glycol (477); 9.13 Glycerol (479); 9.14 Estimation of the number of Hydroxyl Groups in a Polyhydric
Alcohoh(4-84);9.15 Unsaturated Alcohols (484); Summary (491); Questions (495); Answers (502); Problems Based
.on Structure and Properties (505); Objective Questions (506); Assertion-Reason Type Questions (517); Answers
Objective.Questions (518); Brain Stonning Problems (519); Linked Comprehension Type Questions (530) ..
(xi)
·.'·353~565
10.1 Introduction (533); 10.2 Nomenclature (533); 10.3 Isomerism (534); lOA General Methods oL.Preparation
(534); 10.5 General Characteristics of Ethers (537); 10.6 Diethyl Ether or Ethoxy Ethane (541); 10.7 Epoxides
(Oxiranes)(544);10.8 Crown Ethers (545); Summary (546); Questions (548); Answers (553); Objective Questions
(554); Assertion-Reason Type Questions (558); Answers Objective Questions (559); Brain Storming Problems (560);
Linked Comprehension Type Questions (564).
'H56~55
ILl Introduction (566); 11.2 NomenclatUre (567); 11.3 Isomerism (568); llA General Methods of Preparation of
AldehYQes and Ketones (569); 11.5 General Characteristics (578); 11.6 Tests ofAldehydes and Ketones (Distinction)
(601); 11.7 Some Commercially Important' Carbonyl Compounds; Formaldehyde (601); Acetaldehyde (604);
Acetone (606); 11.8 POlymerisation and Condensation (608); 11.9 Acrolein (612); Summary (613); Questions (618);
Answers (627); Problems. Based on Structure and Properties (630); Objective Questions (632); Assertion-Reason
Type Questions (643); Answers Objective Questions (644); Brain Storming Problems (645); Linked Comprehension
Type Questions (652); .
.(;66&;-712
12.1 Introduction (656); 12.2 Nomenclature (657); 12.3 Isomerism (657); 12.4 General Methods of Preparation
(658); 12.5 General Physical Properties (662); 12.6 Acidity of Carboxylic Acids (663); 12.7 General Chemical
Characteristics of Fatty Acids (664); 12.8 General Tests for Carboxylic Group (669); 12.9 Formic Acid (669); 12.10
Acetic Acid (670); 12.11 Interconversions (673); 12.12 Dicarboxylic Acids (677); 12.13 Higher Fatty Acids (677);
. 12.14 Substituted Carboxylie Acids (679); Summary (681); Questions (683); Answers (687); Problems Based on
Structure and Properties (689); Objective Questions (693); Assertion-Reason Type Questions (701); An§wers
Objective Questions (701); Brain Storming Problems (702)~ Linked Comprehension Type Questions (711).
13.1 Derivatives of Carboxylic Acids (713); 13.2 Nomenclature (714); 13.3 Acetyl Chloride (715); 13A Acetie
Anhydride (718); 13.5 Acetamide (719);.13:6 Ethyl Acetate (722)i 13.7 Urea or Carbamide (727); 13.x FatR, Oils and
Waxes (732); 13.9 Soap (735); 13.10 Non-soapy Detergents (736); 13.1 1 Waxes (738); Summary (739); Questions
(743); Answers (747); Problems Baseq on Structure and Properties (750); Objective Questions ('754); Assertion-
Reason Type Questions (760); Answers Objective Questions (760); Brain Storming Problems (761); Linked
Comprehension Type Questions (768).
14.1 Introduction of AliphatiC Amines (770); 14.2 Nomenclature (771); 14.3 Isomerism (772); 14A Basic 'nature of
Amines (772); 14.5 General Methods of Preparation (774); 14.6 Distinction Between Primary, Secondary and
Tertiary Amines (784); 14.7 Conversions (785); 14.8 Introduction of Cyanides and Isocyanides (786); 14.9 Alkyl
Cyanides (786); 14.10 Alkyl Isocyanides (788); 14.11 Alkyl Nitrites and Nitro-Alkanes (790); Ethyl Nitrite (790);
Nitro Compounds (790); Distinction Between Ethyl Nitrite and Nitroethane (792); Summary (794); Questions (796);
Answers (798); Objective Questions (802); Assertion-Reason Type Questions (808); Answers Objective QU,estions
(809); Brain Storming Problems (810); Linked Comprehension TypeQuestions (815~.
15.1 Introduction (817); 15.2 Carbohydrates (817); 15.3 Monosaccharides (819); Configuration of Monosaccharides
(820); Glucose (821); Fructose (826); Comparison of Glucose and Fruetose (827); 15.4 Interconversions of
Monosaccharides (827); 15.5 Disaccharides (829); 15.6 Polysaccharides (Starch and Cellulose) (831); 15.7 Proteins
and Amino Acids (832); 15.8 Nucleic Acids (839); 15.9 Funetions of Nucleic acids (842); 15.10 Lipids (843); 15.11
(xii)
Our Food (844); 15.12 Balanced Diet (846); Table of Vitamins (847); Summary (848); Questions (850); Answers
(853); Objective Questions (855); Assertion-Reason Type Questions (867); Answers Objective Questions (868);
Brain Storming Problems (869); Linked Comprehension Type Questions (872).
·Scheele, in the years 1769-85, isolated taf!aric acid from grapes, citric acid from lemons, malic acid from apples, lactic acid from milk and uric acid
from urine, Roulle, in 1773, isolated urea from human urine. Liebig, in 1829, isolated hippuric acid from horse urine and Serturner, in 1805 isolated
morphine from opium.
2 G.R.B. Organic Chemistry for Competitions
Catenation property (long chains of identical atoms) Now-a-days, many of the natural products such as dyes, fibres,
depends upon the value of bond energy which is maximum in rubber, drugs, vitamins, etc., are prepared by synthetic re3btions.
the case of carbon. SOURCES OF ORGANIC COMPOUNDS· .
Bond C":""C Si-Si S...,-SP-P N-N 0-0 I .
. distillation. Hundreds of useful organic compounds are or one carbon atom can share its four electrons with two atoms
prepared from the wide range of hydrocarbons which serve as of a bivalent element (0), i. e., forming two double covalent
starting materials for the synthetic reactions. . . bonds,
•. xx xx xx
(~») SlIDihetk; Sources; .C.+20~ ~ O~:C:~o~ or O=C=O
• xx xx
More than 90"10 of the known organic compounds are
or one carbon atom can share its four electrons with one atOm
synthetic, i.e., prepared by artificial methods. Simple organic
of a bivalent element along with two atoms of an univalent
·compounds derived from petroleum and coal have been
element, i. e., fonning one double bond and two single bonds,
converted into useful products by synthetic methods.
Introduction to Organic Chemistry .;3
-- ;:
Iil ethane, there are six C-H sigma bonds and one C--.:..c
sigma bond. Each C-H bond is formed by th~ overlap of an
. spJ -hybrid orbital of carbon and la-orbital of hydrogen. The
. C--.:..c bond results from the. oveilap of two sp3 -hybrid
Orbitals, one from .eachcarbon atom: This has been shown in
fig. 1.3. The bond angle is ;again 109~8~ as two tetrahedrons-
o have linked together. . .
Fig. 1.5 Bonding In ~lene
. Introduction to Organic Chemistry 5
unhybridized 2p=-orbii~1sof the two carbon atoms overlap The three types of ~ybridization of carbon can, thus, be
...
laterally to form a n-bond. For the proper sidewise overlap of summarised in the following manner:
these 2p-orbitals, tHe formation of 1t-bond restricts the
ethylene molecule into a planar: shape. Therefore, ethylene is a ~G#.
..~
flat or trigonal planar molecule. The double bond between ~, ....".. ~.
T~ .~.
two carbon atoms (C=C), thus, consists of one sigma and one
1t-bond. .
~
~'.
~~
(iii) sp-bybridization: sp-hybridization occurs when il Tetrahedral 109°28" 0 25~0 75.0
.one s-orbital and one p-orbital' mix together to form two (109.5°)
equivalent hybrid orbitals. The other two 2 p-orbitals are left si 'Trigonal 120° 1 33.3 66.6
planar
unhybridized. Each sp-orbital and unhybridized p-orbital
sp Linear 180° 2 50.0 50.0
contain an unpaired electron. Each hybrid orbital p~ssesses
same energy and shape. Two sp-hybrid orbitals lie in a straight Relative slze$ of sp, sp 1. and sp 3 .-orbitals t s-orbital
line, i.e., the angle between. them is 180°. The unhybridized
,character, in the three hybrid orbitals varies in the following
Qrbitals are at right. at;lgles. to tile line of sp-hybrid orbitalS-. manner: .
Whenever a carbon atom is bonded to two other atoms Sp>Sp2 >sp3
or groups, it always uses sp-hybrid orbitals and two
Since, &-orbitals are closer to the nucleus than p-orbitals,
2p-unhybridized orbitals to form its. bonds. The best
it is, thus, expected that greater the s-ebaracter of tbe
example is the acetylene molecule. One sp-hybrid orbital of a bybrid orbitaltbe smaller is its size. Therefore, the order of
Py the size of the three hybrid orbitals is:
sp3 >sp2 >sp
Carbon in excited state On the basis of the sizes, sp-orbital forms shortest and
2s 2p sp3 -orbital longest bonds with other atoms.
OJ I i i. i
~
i 1---+ ~pl~ .t.., Indicate the number of0'- and 1t-bonds in
sp-hybridization the following· molecules:
(i) CH 3-CH==CH 2 (ii) CH 3-CH 2--CH 2--CH 3
Carbon-3 is linked with two atoms =sp-hybridization bond length, greater is the bond energy, i. e., greater is the
Carbon-4 is linked with four ator;ns == sp 3 -hybridization strength of the bond. The carbon-carbon bonds, single, double
•• 1 2, 3 , 2 2 and triple, are not of equal strength, i.e., with the shortening of
(u) H 2 C=C=CH 2 C.sP, C 2 == sp and C 3 == sp
1 2 3 4
bond length, bond strength increases. It is in the following
(iii) CH 3 -CH=CH-CH 3 order:
C1 =Sp3, C 2 == sp2, C 3 =.sp2 and C 4 Sp3 Triple bond> Double bond> Single bond
.23 The value of a bond energy of a. 'particular bond may
(iv) CH 3-CH 2 -CH 3 sp 3 , C 2 == sp 3 , C'3 == sp 3 slightly change in different molecules depending on structural
enviromnent of the bond. Bond energies are determined
Bond Length
experimentally as heats of chemical reactions (calorimetry)
The average distance between the centres of the nuclei of and by spectroscopic methods. The unit of bond energy is
the two bonded atoms in a molecule i~called the bond length. kcallmol. Bond energies of some common bonds are listed
The length of a ¢ovalent bond between two given atoms below:
depends on whether it is a sigma bond or combination of a
sigma and n-bond or n-bonds, i.e., it is a single, double or aoj,dffteJ'ay
triple bond. It also depends Ot:! the type of hybridization and (kcarIDOI":l)
the resonance. The bond length i~ :
c-C 83 C~l 81
Single bond > Double bond > Triple bond
C=C 146 C-Br 68
The bond length of the sigma bond in, different types of
C_C 192 e-:-I 51
hybridization follows the following order:
,a-bond (sp 3) > a-bond (sp2) > a-bond (sp) C-H(si-s) 97 H-H 103
Bond length between two given atoms is approximately C-H(sp2~s) 104 O-H III
constant in different molecules depending upon the ,above ' N-H
e-:-H (sp"'s) 120 93
conditions unless it is not affected by inductive effect and
C-O 86 C-F [07
mesomerism. The bond length is expressed in angstrom units
(A) or picometre (pm), (lA 10- 10 m, 1 pm 10-12 m). The C=O 179 H-F - 136
bond lengths are measured by X-ray crystallography and by C==O 256 ' ~. ~ c:
H~l
, . ' '
103
:"< ',;
-'I" I:'" . '1, " '.~ ''':,".:
microwave llpectroscopy. For most of the bonds the values are 0-0 35" ~£ ", H';7""Bf "., 88
1 to 2 A. It may be noted that the values of bond lengths are 0=;0 119 H-I 7f
subject 'to small changes, depending on the 'structural
N-N 39 F-F 38
enviromnent of the bond and the experimental method used to
measure it. N N 98 Cl~l 58
"The bond lengths of some common covalent bonds are N N 226 Br-Br 46
....
listed below:
C--,-C
.... __ <A)
1.54
....
C-N' 1.47
C-N 73
lYe
Introduction to Organic Chemistry 7
Ethane
.
Structural fonnula
condensed structural fonnula double and triple bonds are
shown by double line (=) and triple line (==) respectively.
H H Some examples are given in the following table:
I I
H-C-C-O--H
C 2 H sOH
I I
H H
Molecular fonnula
. Structural fonnula
..
Ethyl alcohol
0...••• ... i• • •~
..... ! , .'"".,.'
@~
(o~
01.1...... .......
IJlWM.II •. .~
H H
..
H H I I
Isopropyl alcohol C3HsO H-C-C-O-H
II
Ethane' ·H-C-C-=-H
II kI
H-C-H
H H
I
H
H H
Ethyl chl()ride
I I
H-C-C-Cl
y W··.
H-C-C-O-H
. I I '1
H"H H
H H
I I, H-I_~_N<H
Ethylene' R-C=C-H I H
H
o
H H
I I
,.~!
H-C--':""C=O
;.,' . ,I CH 3 f=O Cyclohexane
H H
';..·v.,"\.:~.r~~_~ ~!-:!i7:~~.\ . .·~o.,·~~ '~~" ~,r .;·;:"~N: ~;. ;::_",~ .-
o
H H 0 H
I . I III
Ethyl methyl H-C-C-C-C~H Benzene
. ketone I II
H H H
1.7 'POLAR AND NON';POlARBONDS When two identical atoms are joined by a sigma bond,
both· attract the cr-electrons equally. For example in C---C,
The nature of the covalent bond can be predicted on the basis
H-H and F-F, the electrons involved in the sigma bond are
of the values of electronegativities of the two atoms forming
the bond. Electronegativity of an atom is a measure of its shared equally, i. e., electron density in the molecular orbital
power to attract electrons that it is sharing ina covalent binding the two atoms together is same around each atom.
bond. The decreasing order of electronegativity of some There is no development of charge on any of the two atoms.
commOn atoms which are generally encountered in organic Such a bond is known as nonpolar bond.
chemistry is: When two atoms of different electronegativities are .
bonded by a sigma bond, the electrons involved are not shared
F >0> CI= N > Br > C> H
n
.. -
. nsf
8 G.R.B. Organic Chemistry for Competitions
. .
electrons more closely than the less electronegative atom, i. e., measure the total moment of the molecule which is a vectorial
the electron density in. the molecular' orbital will be more sum of the individual bond moments. Dipole moment of a .
around the atoin with higher electronegativity. As a result ~e molecule does not depend only on the polarity ofthe bond but
more electronegative atom will acquire a small negative also depends on the directions of the bond, i.e., the shape'of
charge, syrubolised by£)- and less electronegative atom a the molecule.
small positive charge, symbolised by £) +. Such a bond which (i) Dipole moment of symmetrical compound is always
appears to have a positive and a negative end, is said to be a' zero (J.1 = 0). ,
polar bond. The bonds such asC-Cl, C-Br, C-N, C-O, For example H 2, 02' N 2' C1 2, Br2' CH 4 , CCI 4 , BH 3 , BF3 ,
etc., are polar in nature. . CO 2, CS 2, H 2C=CH 2 and HC=:i=CH, etc.
The· polarity of bonds can lead to polarity of molecules (ii) Dipole moment. of . unsymmetrical compound is
always greater than zero.
and affect melting point, boiling point and solubility. A
. molecule is said to be polar if it contains one or more polar
.. ..
bonds and the polar bonds are so directed that there are .. ..
For example H2 0; H2 S ,HCI, CHCI 3 , CH 3 CI, NH3 and ,
II
H3C~C/H
I
C .
'~C~CH3
. I
. /,C;::-....
and negative charge H / ~CI CI"?"- H H/Sf"~CH3 H Sf" '-:;;: CH
.~ sp3 3
The molecules such as H-F, H 20, NH 3 , CH 3CI, CHCI 3 , (cis) (trans) (trans) .(cis)
1l=1.85D \.1=0 1l=0 \.1=0.33 D
etc., are polar molecules. Polar molecules behave as small
dipoles and possess a dipole moment. The dipole moment (J.t) ~C~CH3 ~~CH3 H"&,COOH EtOOC~C/H
of a bond X -.:.. Y is the product of the magnitude of the
.charges and the distance between the charges. It is roughly I I I . I
equal to the difference in the electronegativities of X and Y in
debye.
H/C~CI CI"?"- H HOOc:?'"C""- H EtOOC-?""-H
(cis) (trans) (trans) (cis)
Jl exd \.I = 0.27 D Il = 0.93 D =
\.I 2.38 D Il =2.54 D
.. H CI
Some exceptions are:
OH ·COOR
11 I 11
~. ~
N ·~C~ ~
:7\~F.
/< C
CIY\~CI C(/\\~CI
F CI CI
Nitrogen trifluorjde Chloroform Carbon tetrachlOride
OH COOR
Il = 0:?4 0 J.l = 1.02 D J.l=0.0
(Il *0, but Il 0.83 D) (Il '* 0, but J.L = 0.27 D)
Fig. 1.8
fmd
Introduction to Organic Chemistry . 9
(b) Wh~n one group is electron withdrawing and the other in them. Examples of H-bonding in between the .two
group is electron donating then molecules of same compounds are:
~ =~r~-t=-+-~-~---2j.t-I~-2-C-O-s-6 H-F---H-F; H-O,---H-O, ;
Hydrogen fluoride
Hence, dipole moment is as follows: (associated) H H
p-disubstituted > m-disubstituied > o-disubstituted Water
(associated)
For example, chlorotoluenes: p- > m- > 0-
. So~ the linkage between hydrogen and the other fluorine is Types 01 Hydrogen Bonding
simply due to electrostatic forces of attraction, which results a Generally speaking, the hydrogen bonds can be classified
weak: bond, commonly known as Hydrogen bond and. . into two categories:
represented by dotted lines (- - -). 1. Intermolecular hydrogen bonding: This type of
Thus, hydrogen bond is defined as "an electrostatic bonding is between two or more same or different molecules
attractive force between the. covalent bonded hydrogen when combine together to form a dimer or polymer respec-
atom of one molecule and an electronegative atom (such as tively and leads to a phenomenon called association.
F, 0, N) of the 'other molecule'" The resultant bond . Examples are:
(hydrogen bond) is weaker (strength about 2-10 kcallmol or
8.4-42 kJ/mol) as compare to a covalent bond (strength about t.55A/F l.o9A , >F H H H
50-100 kcallmol or 209-418.4 kJ/mol). Liquids in which
, H' "H It I. I I
"F/ -"F/ ---N---II---N~II--~N---II---
molecules are held together by hydrogen bonds are said to be I I I
Hydrofluoric acid
associated. Such liquids have high boiling points due to the H H H
greater energy required to break: the hydrogen bonds present Ammonia molecule
10 . G.R.B.~ Or:ganic Chemistz.for Commtitions
"0',· . "
..... COOR
«'''~'t··O·'
"'' 1 '\?'.«,}"',
. , COOl! . .. COOH
<
• '9;; <.:; ·AI:J'I1i:'-p,'.
.j '!on.)."''' .•'';';
O-H---O> .
H-C,- C-H, ~., ..... ~ . .
O---H-O OH
o Fonnic acid (Dimer) Benzoic acid Salicylic acid p-hydroxy benzoic acid
6.2 x 10-5 105 X 10-5 t9 x IO-s ..
~ The large acidity is due to the intramolecular hydrogen
---CI~O-H---CI~O-H--- bonding which is capable of stabilizing the salicylate ion.
m-Chlorophenol
Thus, intramolecular H-bonding is weaker than
intennolecular H-bonding.
6-~
so the boiling and melting points generally increase with
increase in number of carbon atoms in most of the
homologues series. Examples are:
(i) Water: The boiling point of covalent compounds
o-Fluorophenol. 0- Nitrophenol 2,6-Dihydroxy increases with increase in molecular weight and thus H 20
t':);;" :hbenzeie: acid
(mol. wt. =18) should have low boiling point than H2S(mol.
This type of hydrogen bonding decreases the boiling wt. = 34). But H 20 is liquid (high boiling point) and H 2S is
point of the compound and also its solubility In water. The gas. Beclil-use in water molecule, qydrogen bonding is presept
chelation between the orrho substituted groups restricts the and so become more compact and requires more energy to get
possibility of intermolecular hydrogen bonding and thus them separated during evaporation, while sulphur is less
prevents association of the molecules which would have electronegative nature than oxygen and give S-H bond, a
. raised the melting point or boiling point. In m- and p-isomers smaller ionic character than the O-H bond and thus H 2 S
chelation does not take'place because the two groups (atoms) fonns very weak hydrogen bond. Hence, it is the H-bonding
are far away from each other and hence in such cases which leads for the facts that: ..
intennolecular hydrogen bonding occurs. Thus, we can (ii) Boiling point of HF (liquid) is greater than boiling
explain the low melting and boiling points of the ortho . point of HCI (gas) .
Introduction to Organic Chemistry 11
(iii) NH3 has high boiling point than PH 3 . (b) Solubility in water: A hydrogen-bonded organic
(iv) Alcohols: (R-OH) have high boiling point than compound is usually soluble in another hydrogen-bonded
those of corresponding thioalcohols (R-SH, mercaptans) and substance. So, compounds whose molecule can form H-bonds
ethers (R-O-R). But the b.pt. of water (100°C) is higher with water molecule are soluble in water. Because of this
than ethyl alcohol (78°C) because greater number of water reason lower members of alcohols, acids, primary and
molecules are associated (through H-bonding) than the ethyl secondary amines, phenols and carbonyl compounds ate more
alcohol. soluble in water, whereas alkanes, ethers and thiols are
(v) Polyhydric alcohols have higher boiling points than insoluble in water.
their ethers, inspite of increase in the molecular masses of R HR··
ethers. For example: I I I-
CH 2OCH 3 - - - 0 -H- - -0-H- - -0-H- - -
CH 20H CH 2OCH 3
I I I
CH 2OCH 3
However, as the hydrocarbon chain (R-) in organic
CH 20H CH 20H compounds increases, the hydrophobic character of alkyl
. 85°C
chain predominates over H-bonding with' the result the
b.pt. 197°C 125°C
solubility of alcohols in water decreases. with .increase in
CHzOH CH ZOC 2 H s CH ZOC 2 H s CH 2OC 2 H s molecular mass and alcohols become almost insoluble when
I I I I alkyl groups of more than seven carbon atoms are present,
CHOH CHOH CHOH CHOCzH s while methyl, ethyl and propyl alcohols are very much soluble
I I I I in water. .. .... .
CHzOH CHzOH CHzOCzH s CH 2OC 2 H s When the compound has a large ratio of ~H groups to
b.pt. 290°C 230°C 191°C 185°C hydrocarbon groups, the compound wiH have a significant
solubility in water. For example. spgars~ ce$in ,starches and
Glycerol (CH 20H CHOH CH 20H) having three polyvinyl alcohols are fairly soluble ill water. .
-OH groups per molecwe (b.pt. 290°C) can· form more
It is important to note that while the intermolecular
hydrogen bonds per molecule than that of water. So, glycerol is
hydrogen bonding increases solubility of the compound in
more viscous than alcohol because of more binding sites available
for H~bonding. water, th,e intramolecular hydrogen bonding decreases and
(vi) Boiling points of aldehydes and ketones are lower therefore the solubility of o-nitrophenol is lower (because of
than alcohols. chelation) than m- and p-nitrophenois.
(vii) Andnes:' The boiling points of primary (R-NH2) (c) Stereo isomerism: Intramolecular H-60nding have
a strong influence on the spatial configuration of a molecule
and secondary amines (~NH) are higher than the isomeric and inhibits isomerisation of one form to another. For
tertiary ~nes (R3N) because like water and alcohols, the example, the trans-isomer of indigo is so stabilised by
primary and secondary amines are capable of forming H-bonding that it resists photochemical isomerisation to the
intermolecular hydrogen bonding but tertiary amine does not. cis-isomer,
Hence, in general the boiling point is increased due to
(d) Adsorption: Intermolecular H-bonding plays a
intermolecular hydrogen bonding but there are certain
very important role in the process of dyeing of textiles.
cases where the boiling point is decreased _due to
(e) Miscellaneous effects: Besides 'these' many other
intramolecular hydrogen bonding. For example, the ortho
properties such as colour, dipole moments, heat of mixing,
isomers of hydroxy -nitro, -carbonyl, -carboxylic or -chloro
heat of vaporisation, viscosity and refractive index, etc., are
compounds have lower melting and boiling points than the
also affected by H-bonding.
respective meta or para isomers. Example (given inibe table):
In fact, H-bonding is likely to affect most of the physical
Compound ortho-isomer pa",~somer properties.
m.pt. m.pt. (t) Effect of hydrogen bonding on chemical
Nitrophenol 44°C 114°C properties: The presence of H-bonding also affects the
Nitrobenzaldehyde 44°C 106°C chemical property of certain- compouuds. For example, the
Nitrobenzoic acid 144°C 241°C dibenzoyl methane does not give the nonnal reactions of
carbonyl group, i.e., it does not add HCN or NaHS0 3 , etc.
So, intermolecular H-bonding is more stronger than intra-
This is due to the formation of H-bonding which ties up the
molecular H-bonding. That is why m- or p-nitrophenol has
carbonyl group (enolic form).
high boiling point than o-nitrophenol (which is steam volatile) /H-,_
and 0- substituted compound leads to chelation which decreases o 0
boiling point. Chelation also explains the low boiling poiDt of I ~ .
enolic form of acetoacetic ester than the ketonic form of the
same.
O-H---O
V
~C
~CH'
/C~
V
(Enol fonn) I
I I
CH 3 -C=CH-C-OC zH s Dibenzoyl methane
(enol form) chelation
12 G.R.B. Organic Chemistry (or Competitions
Moreover the -OH group formed is also not free and is The actual structure of benzene, which can explain all the
neither acetylated by acetic anhydride nor does it give observed properties, lies somewhere in between these two
methane with methyl magnesium iodide. Similarly 0- hydroxy structures.
azo-compounds unlike p-isomers, do not give the normal
reactions of hydroxyl group.
(g) Hydrogen bonding In biologiea. systems:
H-bonding iri biological systems also plays an important role
and stabilizes usual structure of proteins and nucleic acids.
O· · 0
(i) (ii)
0
1.10 RESONANCE are fixed and these are the pr-operties of the actual hybrid
structure. Thus, resonance is hybridization of resonating
An organic molecule is generally represented by an structures and takes place in conjugated. compounds
electronic structure and it is expected that this .1. ~ (containing alternate single bond·and multiple bond).
structure satisfactorily explains all the observed //
Conditions of Resonance
properties of the compound. But very often single
.electronic structure cannot explain all the observed properties. (i) Structures contributing towards the hybrid must
For' example, bepzene is ordinarily represented as inside conform to real Lewis structures.
figure. ' (ii) The arrangement of atoms must be identical or almost
the same in every contributing structure, i. e., canonical form.
This structure has two types of carbon-carbon bonds.
(iii) Resonance involves delocalization of only 1t-electrons.
Three carbon-carbon bonds are single bonds and three
(iv) All canonical forms must have same number of
carbon~ca:rbcin bonds are double bonds. However, it has been
unpaired electrons.
observed experimentally that all carbon-carbon bonds are (v) The energy contents of all the canonical forms must'
identical and have the same bond length (1.39 A). The normal be nearly the same.
carbon-carbon single bond length is 1.54 A and .normal (vi) All resonance structures (canonical forms) do not
carbon-carbon double bond length is 1.34 A. Actually contribute equally to the hybrid. Structures with more
benzene can be represented by the given two alternative covalent bonds are more stable than those with lesser number
structures but none is able to explain fully all the observed of covalent bonds. The non-polar form of butadiene (I) is most
properties of benzene. These two structures differ only in the stable of all its canonical forms (II and III).
position of electrons.
it
Introduction to Organic Chemistry 13
e
(III)
. . "'0-
(Iv) Sulphur trioxide, S03
/0
O=C< f-'-'7
. 0-
/0
"0
/0
(ix) Structures with negative. formal charge on the most O=S~ ~O~S~ ~O~S,
electronegative atom. and positive charge on the least o 0 0
electronegative atom have significant contribution. Structures
(v) Diazo methane,CH 2 N 2
with negative formal charge on the electropositive atom and
positive ch~ge on the electronegative atom have least' +.. .. +
contribution to the resonance hybrid. The structure (II) is more H 2C=N=N: ~ H 2 C-N::sN:
contributing than structure (III) to the resonance hybrid of (vi) Vinyl chloride, H2C == CHCI
acrolein [acrylic aldehyde, an Il, ~unsaturated aldehyde (I)].
•• •• +
o Oe H 2C=CH-CI: ~ H 2C-CH=CI: ~
~ a II ED I •• ••
CH2=CH-C-H ~ CH 2-CH=C-H (a) (b)
ex, ~-unsaturated (II) + ••
aldehyde (1) H 2C-CH=CI- :
••
+ (c)
:0 (The order of stability (a) > (b) > (c), i.e., structure (a) is
e I more stable because it has no formal charge and (c) is least
~ CH 2-CH=C-H
(III) stable having an electron deficient carbon.)
(x) Structures with electron deficient atom (i.e., (vii) Carboxylic acld, R--COOH
••
possessing less than eight electrons in its outermost shell)
have high energy, i.e., low stability, hence they contribute less
than those structures in which octet rule is not violated. Thus,
R-C~~.
0
2
"'-O.:.........H
~ R-C,+
/
0:
••
o
resonance energy of benzene from the following data:
+ H,
Cyclohexene
GaIaIy~ • 0 +28.6
Cyclohexane
~cM!niol
5. The electronegativity follows the order :
(a) F>CI> Br>O
(c) 0> F>CI> Br
[Ans. (b)]
(b) F>O>CI> Br
(d) CI> F>O> Br
0
~ .
1
Catalyst
+ 3H2 --"-+~ 0 ,'" +3 x'28.6='85.8'kcaVmol
in order of decreasing electronegativity.]
6. In which of the following compounds, delocalized
bonding is not possible?
(a) 1,3-Butadiene . (b) 1,4-Pentadiene
Cyclohexatriene Cyclohexane (c) 1,3,S-Hexatriene (d) Benzene
(hypothetical) [Ans. (b)]
But, however, the experimentalvalue of heat of hydrogenation [Hlot; (b) is not a conjugated system.]
of benzene is·49.8 kcaVmol. 7. The carbonyl group has following resonating structures,
Therefore, benzene is having 36 kcaVmol (8S.g..... 49.8) (i) )C=O (ii) )C-O (iii) )C+-O-
less energy than, expected for a typical compound which is
The correct order of stability of these structures is:
having three double bonds. Hence, resonance energy of
(a) (i»(ii»(iii) (b) (iii»(i»(ii)
benzene molecule is 36 kcaVmol by which the benzene
(c) (i) > (iii) > (ii) (d) (iii) > (ii) > (i)
molecule gets stabilized. The greater the resonance energy, the
[Ans. (c)]
Introduction
__ ..... ' ... z .. __ to
.. _. Organic
t
Chemistrv
_ ,... " .. _, __ .', ,- .,~Z
15
!.Hlat: The reS()nat;ng sp,-ucng:e with minimum or no charge is when the less soluble component crystallises out earlier than
more stable. Thus; the stahility of structure (i) is maximum. As the the more soluble component. The various fractions are
, negative charge is present on more electronegative oxygen atom
. {as in structure (iii)}. (iii) i~ more stable than structure (ii).] separated from time to time. These fractions are now sepa-
8.. The ratio of 0' and rc-bonds in mesitylene is: rately" ,put" to:, ,~rystallisation. ,cA., series~; ';ot ii rep,eated
(a) 3 (b) 5 crystallisations separate the two compounds in pure;fQrrn,
(c) 6 (d) 7 (il) SubUmation: Certain organic substances pass
[Ans. (d)] directly from so1id to vapour state on heating and vice-versa '.
tHlat: The structure of mesitylene is on cooling. This is called sublimation and the process is very
H
useful for separation of substances which sublime on heating
I from non-volatile impurities. The organic compounds such as
H-C-H benzoic acid, naphthalene, anthracene,· camphor, indigo.
CI ' , anthraquinone, etc., are purified by this process.
H HC-P 'CH H Heat
I I II I Solid .-----'" Vapours
H-C--C~ .......C--C-H Cool
I CH I,
a H, . The process of sublimation requires no solvent and is
Total number of a-bonds = 21 completed in a short time but it can be applied to only a
Total number of tt-bonds 3 = limited number of organic subs~c~~ .which possess high
So, ratio .of 0' and 1t~"9Pds
. .. .' '" ::: .isj:,l]
- -. . "", ' , ~ ~
vapour pressure at normal atmospheric'pressure~ . , , ?
mixture of methanol (b.pt. 65°C) and propanone (b.pt. 57°C) Mobile pbase
or a mixture of benzene and toluene may be separated by I
fractional distillation. I
. (e) DlstlUation under reduetd pressure (VacuulD
I
Liquid Gas
dlstiUatiod): The compounds, which decompose at a
temperature below their normal boiling points, cannot be
I I
Liquid-solid Gas-solid
purified by distillation under ordinary atmospheric pressure. chromatography chromatography
Glycerine is one such compound which decomposes at its (LSC) (GSC)
,boiling point. I
The pressure is reduced by suction, pump and the
distillation is carried out at lower temperature as glycerine can
I
Adsorption column Adsorption
be distilled at 180°C (normal b.pt. 290°C) under a pressure of chromatography thin-layer
10-12 mm. Cane juice can also be concentrated by this (ACC) chromatography
method. This technique can be used to separate glycerol from (TLC)
spent lye in soap industry. (b) When stationary phase is liquid, the chromatography
Distillation under reduced pressure is not only useful in isknown as partition chromatography. Depending upon the
avoiding decomposition but also serves to economise fuel for natUre of mobile phase, partition chromatography is further
industrial concerns. classified as follows: .
(d) StealD dlstUlatlon: This type of distillation is
essentially a co-distillation With water and is carried out when Mobile phase
a solid or liquid, practically insoluble in water, is volatile with I
steam, possesses a vapour pressure of about 10-15 'mm of I I
mercury but the impurities are non-volatile. Liquid Gas
This process is used in the purification of compounds I I
such ,as chlorotoluenes, aniline and nitrobenzene. It is also Liquid-liquid Gas-liquid
empioyed in the isolation of essential oils from flowers. chromatography chromatography
(LLC) (GLC)
(il) Solvent extraetion: The process of separation of
an organic compound from its aqueous solution by Shaking
I
with a suitable organic solvent is termed solvent extraction. Partition Partition Paper Reverse phase
The solvent should be immiscible with water and the organic thin-layer column chromatography partition
compound to be separated (by using separating funnel) should chromatography chromatography (PC) chromatography
• (TLC) (PCC) (RPPC)
be highly soluble in it. .
(Hi) Cbr.omatograpby: It is a recent and most The most common ones are:
effIcient technique which was first used by Tswett, a botanist, (i) Column chromatography or adsorption chromato-
in 1906 for the separation of coloured substances into graphy,
(ii) Thin layer chromatography (TLC),
individual components. The name chromatography (Greek (iii) Paper chromatography,
word, chroma colour and graphy =writing) means colour (iv) Gas chromatography,
writing. The name is no longer accurate as the technique has (v) Ion-exchange chromatography.
undergone tremendous modifications and is now used to The first three techniques have been described as:
separate almost any given 'mixture, whether coloured or Column (Adsorption) ~hromatograpiay: This is
colourless, into its .constituents and to test the purity of these based on adsorption (or surface) phenomenon: The extent of
constituents. This technique is even applicable to micro adsorption of various constituents present in a mixture lIquid
quantities (even less than 50 mg or 1 mL). (mobile phase) varies with a given adsorbent (stationary
Chromatography. is based on selective distribution of the phase). The common adsorbents used are magnesium oxide,
vari,ous, constituents of a mixture between two phases, a alumina, cellulose powder, silica gel, active animal charcoal,
stationary phase ,and a moving (mobile) phase. ,Different etc.
constituents migrate, at different rates, through the stationary Column chromatography involves the
phase. The stationary phase can be a solid or a liquid, while the (i) preparation of adsorbent column,
mobile (moving) phase is a liquid or a gas. Based on the nature of (ii) adsorption and
the stationary phase and the mobile phase, different types of (iii) elution of components and recovery.
chromatographic techniques have been developed, ' Thin layer chromatography (TLC): It is a special
(a) When stationary phase is solid, the chromatography is technique of adsorption chromatography in which thin layers
,known as adsorption or column chromatography. of adsorbents such as silica gel are spread on glass plates. A
Depending upon the nature of mobile phase, adsorption slurry of the adsorbent in an organic solvent is prepared. The
chromatography i~ further classified as follows: ~lurrY is then, coated on the glass plate with the help of a
device called applicator. A spot of the selution of the mixture
Introduction to Organic Chemistry 17
. ..
to be separated is kept at a distance of 2 em frOIn'one; side of . mixture is.detennmed. Ifthe meltiQg point of the mixture is sharp
the· glass plate with th~.help 9f capillary. The siz~ of the spot . and comes out to be the same as that of pure compound, it is sure
should be as small as possible. The plate is then dried. The that the compound under test is pure. On the other hand, if the
glass plate is now placed vertically in a developing chamber melting point of the mixture is less than the melting point of the
(close jar) containing a suitable solvent or solvent mixture at pure compound, the compound in question is not pure.
the bottom (about 1 cm deep). The end which has the sample
Bolling point*: The boiling point of a liquid is defined
spot is dipped in the solvent. The chamber is closed and the
solvent is allowed to ascend. The solvent consequently as the temperature at which the vapour pressure of a liquid is
resolves the original spot of mixture into a series of spots, each equal to external pressure. Boiling points .are also normally
corresponding to a single component. The relative adsorption quoted for standard atmospheric pressure. A pure organic
of each component of the mixture is expressed in terms of its liquid boils at a fixed temperature which is characteristic' of
retardation factor, i.e., RJ value. that substance.
If enough liquid is available, it can be distilled in a
R = Distance moved by the substance from base line
distillation apparatus and the constant temperature recorded
f Distance moved by the solvent from base
by the thermometer is the bQiling point.
The plate is taken off and dried. Each spot is now eluted When the amount of the liquid is small, Siwololf's
separately. method (capillary tube method) is used. .
Paper chromatography: It is a type of partition
chromatography•. The process is similar to thin layer ILLUSTRATIONS OF OBJECTIVE QUESTIONS
chromatography, exc~t that a strip of paper acts as the
adsorbent. Paper chromatography is based on a mechanism 9•. Suggest a method to purity benzene containing non-volatile
which is partly partition and partly adsorption. The paper impurities:
consists of cellulose fibres having molecules of water strongly (a) steam distillation
adsorbed on them. This serves as the stationary pbase while a (b) distillation under reduced pressure
suitable organic solvent is used as a mobile phase. A drop of (c) simple distillation
the solution of a mixture to be separated is placed on a strip of (d) sublimation
chromatographic paper and the solvent is allowed to travel [Ans. (c)]
along the strip. When the eluting solvent moves upwards, it is 10. A substance has boiling point 563 K, but it starts
termed ascending paper chromatography and when the decomposing near this temperature. Which type of
eluting solvent moves downwards, it is termed f,lescending distillation process is suitable for its purification?
paper chromatograpby. (a) Distillation
Finally, the paper strip is taken out and dried in air. The (b) Fractional distillation
position of various components, on the paper, is determined (c) Steam distillation
by spraying some suitable reagent which makes the spots
(d) Distillation under reduced pressure
(components) visible. In the separation and identification of
[Ans. (d)]
amino acids, ninhydrin is used for developing the coloured
11. Petroleum refining involves:
spots.
·(a) vacuum distillation
1.12 CRITERIA OF PURITY OF ORGANIC (b) fractional distillation
COMPOUNDS ( c) steam distillation
(d) passing over activated charcoal
Melting point: A pure organic solid has a definite and [Ans. (b)]
sharp (sudden, rapid and complete) melting point, while an [HInt; Crude petroleum is subjected for fractional (iistillation to
impure substance has a lower and indefinite melting point. get different products.]
The melting point of a solid may be defined as the temperature U. In steam distillation of toluene, the pressure of toluene
at which the solid and liquid states of the compound are in vapour is:
equilibrium with each other at an external pressure of I (a) equal to the pressure of barometer
atmosphere. (b) less than the pressure of barometer
Mixed melting point: The melting point of two (c) equal to vapour pressure of toluene in simple
~oroughly mixed substances is called mixed melting point. distillation
This can also be used for ascertaining. the purity of a (d) more than the vapour pressure of toluene in
compound. simple distillation
[Ans. (b)]
The substance, whose purity is to be tested, is mixed with a
pure sample of the same compound. The melting point of the
"'Boiling point is not as reliable a test of purity as is the melting point for the solids. There are many liquids which are miscible with other liquids and
mixtures have fixed boiling points (azeotrQPe). Thus, other physical properties are being used fur deciding the purity.
11 G.R.B. Organic Chemistry tor Competitions
:~c~o~~~~::~:~~ti!~ff:P~~~~~:~
30-50 K.
:::! ~x:':a~ a. ~=fl:::~ri~~~' t~~~:t~~o~di~!01;f
available in very small amount.
[J Fractional distillation is applied for separating two' or [J'Adsorption (column) chromatography is based on the
more volatile liquids from a liquid mixture in which the differences in rates at which the components of a mixture
components differ in boiling points close to each other by ,liquid (moving phase) are adsorbed on an adsorbent
10 to 20 K. (stationary phase).
[J Vacuum distillation' is applied for liquids, which a Partition chromatography involves. continuous
decompose at a temperature below their normal boiling partitioning of the components of a mixture between
points.' stationary and mobile phases. Paper chromatography is a
[J Steam distillation is 'applied for separation and "type of partition chromatography.
purification of liquids which is appreciably volatile in a Criteria of purity, of an organic compound is best
steam, practically immiscible with water but the impurities determined by mixed melting point.
are non-volatile. '
(i) Resonance decreases the stability of the molecule and 6. Classify the following in~o polar and non-polar molecules:
,
increases its reactivity. (i) CO 2 , (ii) CHCI 3, (iii) CCI 4 , (iv) CH3 0CH 3 ,
G) With the shortening of bond le.n~, bond strength (v) C 2H s OH, (vi) C 2H 6 , (vii) CHzCl z, (viii). NH 3 ,
. ,~ ;.", '
increases. ~, (ix) HzO, (x) CH3 CL
(k) A symmetrical molecule is non-polar even though it 7. Indicate the type of hybridization of each carbon atom in the
contains polar bonds. following molecules:
t (I) CCI 4 has high value of dipole moment.
(m) Resonance involves movement of cr- and 1t-electrons.
I z 34
(i) CH3-CH=CH--'CH3 (ii) H-C==C-C==C-H
1234
[
I Z 3 4 1 Z 3
(n) The greater the resonance energy, the lower is the (iii) CH3 -C==C-CH 3 (iv) CH r -CHz-CH3
stability of the molecule.
(0) More is the number of canonical forms for a molecule,
more is the resonance energy of molecule.
I
(v) CH 3 -C==N
2 III°
(vi) H-C-NH2
(p) A carbon--carbon double bond is stronger than a I 2 3 4
carbon--carbon single bond. (vii) CH3 --CH CH-C==N
(q) A polar bond results when the atoms have same
electronegativity.
(r) Acetylene is a linear molecule.
I
(viii) CH3 -C-CH3
°
211 3
(ii) General characteristics of organic compounds. (vii)C 1 =sp3, C 2 =Sp2, C 3 =Sp2, C4 =sp
(iii) Hybridization. (viii) C 1 = sp3, C 2 = Sp2, C 3 = sp3
(iv) Polar and non-polar bonds. (ix) Sp2, sp (x) sp3, Sp2
(v) Hydrogen bonding. (xi) sp3, sp3 (xii) sp3, sp3
(vi) Resonance. 8. (i) a-bonds = 6, x-bonds = 2
(vii) Fractional crystallisation. (ii) a-bonds = 8, x-bond = I
(viii) Vacuum distillation. (iii) a-bonds = 6, x-bonds = 2
(ix) Mixed melting point. (iv) a-bonds = 10
(x) Purity of an organic compound. (v) a-bonds = 9, x-bonds = 2
(vi) a-bonds = 10, x-bonds = 3
(vii) a-bonds = 6, x-bonds = 3
(viii) a-bonds = 5, x-bonds = Nil
1. (a) hydrocarbons; (b) catenation; (c) Berzelius; (d) ammonium
(ix) a-bonds = 5, x-bonds = 2
cyanate; (e) acetic acid; (t) covalent, molecular, slow; (g) carbon
(x) a-bonds = 6, x-bond = I
dioxide; (h) synthetic; (i) three; G) sp3; (Ie) Sp2; (I) sp3; (m) sigma,
(xi) a-bonds = 4
two pi; (n) sp3, 109°28'; (0) smallest, longest; (P) 146; (q) higher; (xii) a-bonds = 17, x-bond = I
(r) 1.20 A; (s) sp; (t) Sp2; (u) hydrogen; (v) lower, less; (w) more; 9. (a) Bond length order C-C > C=C > C=C
(x) three; (y) non-polar; (z) CH 3-C=CH-C-CH 3. Bond strength order C=C > C=C > C-C
I I (b) (i) sp-s < Sp2 -s <·sp3 -s (ii) sp3 < Sp2 < sp
0, /0 (iii) sl < Sp2 < sp (iv) sp < Sp2 < sp3
'H'
2. (i) vacuum distillation; (ii) fractional distillation; (iii) sublimation; (v) sl < Sp2 < sp
(iv) steam volatile, sparingly soluble; (v) alumina or silica gel; 10.• Form A in (i), (ii), (iii) and form C in (iv) is the major contributor
(vi) rapidly; (vii) crystallisation· from solution in ethanol; because in these structures each atom has octet and no formal
(viii) melting point; (ix) boiling point; (x) less; (xi) steam charge is present.
distillation; (xii) elution; (xiii) sublimation; (xiv) steam distillation; 11. (i) sl; (ii) Sp2; (iii) sp; (iv) resonance in benzene molecule;
(xv) vacuum distillation; (xvi) fulctional distillation; (xvii) steam (v) hydrogen bonding is present in alcohols; (vi) oxygen is more
distillation; (xviii) fractional distillation; (xix) separating funnel; (xx) electronegative than sulphur. Thus, hydrogen bonding is present in
vacuum distillation. CH 30H; (vii) o-chlorophenol involves intramolecular hydrogen
J. (a) True; (b) False-organic compounds have low melting and bonding while p-chlorophenol involves intermolecular hydrogen
boiling points. These are bad conductors and insoluble in water; bonding; (viii) due to resonance; (ix) no resonance is present in
(c) True; (d) True; (e) False-More than 90% of organic formic acid molecule but in formate ion resonance exists;
compounds have been prepared by synthetic methods; (t) False- (x) chromatography; (xi) melting point; (xii) C-C ... 1.54 A,
s-character 33%, p-character 66%; (g) True; (h) True; (i) False- C=C ... 1.34 A. C=C ... 1.20 A:, (xiii) sp3 ... 109°28', Sp2 ... 120°,
Resonance increases the stability of a molecule and decreases its sp ... 1800; (xiv) Chloral hydrate is stable due to intramolecular
reactivity; G) True; (k) True; (I) False-CCl4 being symmetrical hydrogen bonding between hydrogen and chlorine atom; (xv) With
has zero dipole moment; (m) False-resonance involves only increase in s-character, the size of hybridized orbital decreases
x-electrons; (n) False-The greater the resonance energy, the which leads to more overlapping and shortening of bond length in
greater is the stability of the molecule; (0) True; (P) True; C=C; (xvi) o-hydroxy benzaldehyde has intramolecular
(q) False-Polar bond results when atoms have different H-bonding (so low melting point and is a liquid at room
electronegativity; (r) True; (s) False-criterion of purity ofa solid temperature), while p-hydroxy benzaldehyde have interinolecular
organic compound is its melting point; (t) True; (u) False-With
H-bonding (so high melting point).
the help of water; (v) True; (w) True; (x) False-Carbon
12. (a) HI < HBr < HCI < HF
undergoes sl-s/- or sp-hybridization; (y) False-All bond lengths
(b) CH3I < CH3Br < CH 3CI < CH3F
are same except between carbon and carbon atoms; (z) True. (c) CHI 3 < CHBr3 < CHCI 3 < CHF3
4. (a) (A-viii); (B-vii); (C-x); (D--ix); (E-i); (F-iii); (G-ii); (d) CH 4 < CH 3CI < CH 2CI 2 < CHCl 3
(H-v); (I-iv); (J-vi). (e) SbH 3 < AsH3 < PH 3 < NH3
(b) (A-iii); (B-ii); (C-iv); (D--i). (t) CI 20 7 < S03 < P20 S < Si0 2
5. A. (ii); B. (i); C. (i); D. (ii); E. (i). (g) o-chlorotoluene < m-chlorotoluene < p-chlorotoluene
6. CO 2 , CCI 4, C2I-4 are non-polar molecules while rest are polar (h) p-nitrophenol < m-nitrophenol < o-nitrophenol
molecules. (i) p-dichlorobenzene < m-dichlorobenzene < o-dichlorobenzene
7. (i)C 1 =sp3, C 2 =Sp2, C 3 =Sp2, c 4 =sl . 13. (i) In ethylene each carbon atom undergoes sp2-hybridization
(ii) C 1 = sp, C 2 = sp, C 3 = sp, C 4 = sp while in acetylene each carbon undergoes sp-hybridization; (ii) As
(iii) C 1 =sp3, C 2 =sp, C 3 =sp, C 4 =sp3 the s-character increases in the hybridized orbitals, greater
overlapping occurs with the shortening of bond length; (iii)
(iv) All carbon atoms are sp3-hybridized.
CH 30H has higher boiling point than CH 3SH due to hydrogen
(v) C 1 = sp3, C 2 = sp bonding. Diethyl sulphide has higher boiling point than diethyl
(vi) C 1 = Sp2 ether due to larger molecular mass; (iv) Oxygen being mere
electronegative than nitrogen forms stronger hydrogen bond than
24 G.R.B. Organic Chemistry for Competitions
I Z 3
the latter; (v) Resonance decreases the dipole moment of vinyl
15. (iv) Allene are cummuJative dienes, CHz=C=CHz (Propa-I,2-
chloride as the positive charge on chlorine and a negative charge on
diene). In allene C 1 and C3 are sl-hybridized and C2 is
carbon oppose each other; (vi) 1,3-butadiene has si
_Sp2 C-C
sp-hybridized. The two 7r-bonds are present in the central carbon,
bond length, while n-butane has si
_Sp3 C-C bond length. More is
one each from Py- and pz-orbitals thus, overlapping planes in C 1 and
's' character in hybridization, lesser is bond length; (vii) (a) C3 are also different.
catenation, (b) carbon can link with other carbon atom with single,
double and triple bonds. It can form bonds with other atoms also,
(c) isomerism; (viii) The dipole moment ofCCI 4 is zero inspite of
four similar polar (C-CI) bonds on account of symmetrical
structure; (ix) The polarity of bond depends upon electronegativity
• difference of two atoms involved in covalence; (x) The size of CI
atom is large as compared to nitrogen and so it pulls the shared pair
of electron from hydrogen atom less effectively and thus it does not
possess appreciable partial charge to show hydrogen bonding.
14. (i) By fractional distillation; (ii) By sublimation; (iii) By
chromatography; (iv) By simple distillation; (v) By distilling of
water.
.......
.+
GfHaH
..
();;:::
CI.......
~ +
Cl
r!::l<H
0 CI
Base
---""
~
. :~:
(D) CHz=CH-C-H ~ +CHz-CH=C-H ~ :CHz-CH=C-H
:?: ~ :r +
I IT m
Stability I > II > III
Structure I: More stable, because it has more number of covalent bonds and have no formal charge. Each carbon and oxygen atom has an
Octet.
Structure II: Less stable, because it has negative charge on more electronegative atom and positive charge on more electropositive atom.
Structure III: Least stable, beca~se it does not contribute as oxygen has positive charge and carbon has negative charge .
Introduction to Organic Chemistry 25
OIJtCllvt IS
SET I: This set contains questions with single correct answer.
1.' The propertY of catenation is strongest in carbon because: TH 3
(a) its ionisation potential is low 0 12. In the compound HC=:::C--C-CH2, the hybridization of
(b) its electronegativity is low 0 C 2 and C 3 carbons are respectively: [JEE (WB) 2009)
(c) the C-Cbond energy is high 0 (a) Sp3 and sp2. 0 (b) sp2 and sp3 0
(d) its atomic radius is small 0 (c) sp3 and sp 0 (d) sp2 and sp 0
1.. The main source of organic compounds is: 13. The CI-C-CI angle in 1,1,2,2-tetrachloroethene and
(a) vegetable kingdom 0 (b) synthetic reactions 0 tetrachloromethane will be about:
(c) animal kingdom 0 (d) petroleum 0 (a) 9()0 and 109S' 0 (b) 109.50 and 900 0
3. The ftrst organic compound prepared from inorganic 0
(c) 109.5 and 120 0
o
compounds was:
14. Which of the following molecules does not have net dipole
(a) acetic acid 0 (b) methane 0 moment? IAMU (Engg. 2010»)
(c) urea 0 (d) ethyl alcohol 0 (a) CH 3 -Br 0 (b) CH2Cl 2 0
4. The flfSt organic compound synthesised in the laboratory
from its elements: t (c) H)e=c<H 0 (d) HCOOH o
(a) urea 0 (b) methane o H H
(c) ethylene 0 (d) acetic acid X
5. The bond between carbon atom (I) and carbon atom (2) in
I 2
compound N=G-CH=CH 2 , involves hybridization:
(a) sp 2 and sp2 0 (b) sp3 and sp o
15. Dipole moment Of© is 1.5 D. The dipole mo..... of
o
[UGET (Med.) 1006)
(b) C2 H4
o (d) C2H2Br2
0
0
X*x'S: X
[JEE (WB) 1010)
, (a) identical arrangement of atoms 0 33. Maximum hydrogen bonding would be observed in the
(b) nearly the same energy content 0 compound:
(c) the same number of paired electrons 0 (a) methanol 0 (b) glycol 0
(d) identical bonding 0 (c) diethylamine 0 (d) diethyl ether 0
24. Which of the following statements is false about resonance? 34. . ..... bond is the most polar.
(a) It increases stability of the molecule (a) C-O 0 (b) C-Br 0
(b) It leads to similar type of bonding 0 (c) C-S 0 (d) C-F 0
(c) It increases reactivity of the molecule D 35. Examine the following two structures for the anilinium ion
, (d) It decreases reactivity of the molecule 0 and choose the correct statement from the ones given below.
, +
o ~·6
25. How many sigma and pi-bonds are there in the molecule of
dicyanoethene (CN-CH CH-CN)?
(a) 3 sigma and 3 pi 0 (b) 5 sigma and 2 pi Of
(c) 7 sigma and 5 pi 0 (d) 2 sigma and 3 pi 0
26-. Which of the following compounds shows evidence of the I II
strongest hydrogen bonding? (SEE (WB) ZO.O) (a) II is not an acceptable canonical structure because
(a) Propane-I,2,3-triol 0 (b) Propane-l,2-diol 0 carbonium ions are less stable than ammonium ions 0
(c) Propan-I-ol 0 (d) Propan-2-01 0 (b) II is not an acceptable canonical structure because it is
27. The hydrogen bond is strongest in which one of the non-aromatic 0
following? IDPMT ZOO6; AilEE %007] (c) II is not an acceptable canonical structure because
(a) F~H-:'-F 0 (b) O-H---O 0 nitrogen has 10 valence electrons 0
(c) S-H - - - F 0 (d) F-H - - - 0 0 (d) II is acceptable canonical structure 0
28. C-C bond length would be minimum in: 36. s-character of sp-sp2 -and sp3 -hybrid orbitals follows the
I I I
(a) ==c-y- 0 (b) =C-
y- o decreasing order:
(a) sp3 > Sp2 > sp o
(b) sp> sp2 > sp3 o
(c) =y-y= 0 (d) ==C-C== o (c) sp2 > sp3 > sp o (d) sp2 > sp> Sp3
, _______________________________________________ ~~t_.~~!=1Z.r~
.
Introduction to .Organic Chemistry 27
41. In a resonance hybrid, the bond length: (b) C-I> C-Cl > C-Br t)'
(a) is smaller than in canonical structure 0 (c) C-Br> C-CI > C-I 0
(b) is greater than in canonical structure 0 (d) C-I > C-Br > C-CI 0
(c) is the same as in canonical structure 0 54. Arrange the following compounds in order of increasing
(d) none of the above 0 dipole moment:
42. Resonance energy of benzene is about so much kcallmol: (i) toluene (ii) m-dichloro benzene
(a) 35 0 (b) 58 0 (iii) o-dichloro benzene (iv) p-dichloro benzene
00100 0 OOI~ 0 (a) (i) < (iv) < (ii) < (iii) o
43. Resonance in a molecule results in: (b) (iv) < (i) < (ii) < (iii) o
(a) destabilisation 0 (c) (iv) < (i) < (iii) < (ii) o
(b) stabilisation 0 (d) (iv) < (ii) < (1) < (iii) o
(c) increase in bond length 0 55. Sublimation is a process in which a solid:
(d) none of the above 0 (a) changes into another allotropic fonn o
44. In which of the compounds below is there more than one (b) changes into liquid form o
kind of hybridization (sp, sp 2 , sp 3 ) for carbon? (c) changes into vapour form o
(i) CH3 CH2 CH2 CH3 (ii) CH 3-CH=CH-CH3 (d) none of the above o
(iii) H 2 C=CH-CH=CH2 (iv) H-O=G-H 56. Naphthalene is a volatile solid. It is best purified by:
(a) (i) and (iv) 0 (b) (ii) and (iii) 0 (a) crystallisation 0 (b) distillation o
(c) (ii) 0 (d) (iii) and (iv) 0 (c) steam distillation 0 (d) sublimation o
45. Which of the following has a bond fonned by overlap of 57. Methanol and acetone can be separated by:
Sp3 -sp-hybrid orbitals? (a) fractional distillation 0 (b) distillation 0
(a) CH3-C=C-CH 3 [J (c) steam distillation 0 (d) vacuum distillation O.
(b) CH 3 -CH=CH-CH 3 0 58. Separation of two substances by fractional crystallisation
depends upon their differences in:
(c) CH2 =CH-CH=CH 2 0
J . (d) HC=CH 0
(a) densities 0 (b) volatility o
I
(c) solubility 0 (d) crystalline shape o
46•. Maximum amount of hydrogen bonding occurs in case of: 5'. Aniline is separated from a mixture by:
(a) HOH 0 (b) HF 0: . (a):tra.ctiQnal crystallisation . tJ
~ (c) C2 H 5 0H 0 (d) NH3 0 (b) fractional distillation 0
47. Intramolecular hydrogen bonding is exhibited by: (c) vacuum distillation 0
(a) o-nitrophenol 0 (b) catechol 0 (d) steam distillation 0
(c) salicylic acid 0 (d) all of these 0' 60. Glycerol is purified by: IPMT (Kefala) 10101
48. The maximum possible number of hydrogen bonds, a water (a) steam distillation 0 (b) vacuum distillation 0
molecule can form is: tCET (Karnataka) 1088] (c) sublimation 0 (d) simple distillation 0
(a) 4 .0 (b) 3 0 61. Two inuniscible liquids are separated by:
(c) 2 0 (d) 1 0 (a) separating funnel 0 (b) fractional distillation 0
49. Which of the following explanations accounts for o-nitro- (c) chromatography 0 (d) sublimation 0
phenol to be more volatile than p-nitrophenol? 62. Latest technique for purification, isolation and separation of
(a) Intermolecular hydrogen bonding· 0 organic compounds is: rPMT (Kerala) 2007;
Punjab CET (En. .) 20081
(b) Resonance 0
(a) chromatography 0 (b) steam distillation 0
(c) Intramolecular hydrogen bonding 0 (c) crystallisation 0 (d) vacuum distillation 0
(d) Inductive effect 0 63. Steam distillation is applied to those organic compounds
so. Bond energy is maximum in: which are steam volatile and:
(a) 0-{) 0 (b) O=C 0 (a) soluble in water 0
(c) C~N 0 (d) N N 0 (b) insoluble in water 0
51. The bond energy: of C-C bond in kcallmol is: (c) sparingly soluble in water 0
(a) 58 0 (b) 83 0 . (d); insoluble in all solvents 0
(c) 145 0 (d) 192 0 64. There are several criteria for purity of organic compounds.
51. The maximum bond energy is present in: Out of these which one is considered best?
(a) C-H o (b) C-C (a) Melting point o
[]
(c) C-N 0 (d) G-O 0 (b) Microscopic examination
(c) Mixed melting point []
53. Among the C-X bonds, the correct bond energy order is:
(a) C-CI > C-Br> C-I 0 (d) Colour []
65. Two volatile and miscible liquids can be separated by 75. Anthracene is purified by:
fractiorial distillation into pure components under the (a) filtration 0 (b) distillation
conditions when: (c) crystallisation 0 (d) sublimation 0
(a) they have low boiling points 0 76. Which of the following is useful for making pure water
(b) the differcmce in their boiling points is large 0 from a solution of salt in water?
(c) the boiling points of the liquids are close to each other (a) Filtration 0 (b) Simple distillation 0
o (c) Steam distillation 0 (d) Chromatography 0
(d) they do not form azeotropic mixture 0 77. Water and alcohol can be separated from a mixture by:
66. The boiling points of two miscible liquids, which do not (a) fractional distillation 0 (b) sublimation 0
form azeotropic mixture, are close to each other. Their (c) decantation 0 (d) evaporation 0
separation is best carried out by: 78. A mixture of water and NaCI can be separated by:
(a) vacuum distillation 0 (b) fractional distillation 0 (a) sublimation 0 (b) evaporation 0
(c) steam distillation 0 (d) redistillation 0 (c) decantation 0 (d) filtration 0
67. In paper chromatography: 79. In laboratory, solvent can be separated from solute by the
(a) the moving phase is a liquid and stationary phase is a process:
solid 0 (a) decantation 0 (b) sedimentation 0
(b) the moving phase is a solid and stationary phase is a (c) distillation 0 (d) filtration 0
liquid 0 80. In simple distillation of liquids, it involves simultaneously:
(c) both the phases are liquids 0 (a) vaporisation and condensation 0
(d) both the phases are solids 0 (b) heating and sublimation 0
68. Oils are purified by: (c) vaporisation and sublimation 0
(a) fractional distillation 0 (b) steam distillation 0 (d) boiling and filtration 0
(c) vacuum distillation 0 (d) simple distillation 0 81. Distillation under reduced pressure is used to purity liquids
69. Chromatography technique is used for the separation of: which:
(a) small samples of mixtures 0 (a) are highly volatile 0
(b) plant pigments 0 (b) have high boiling points 0
(c) dye stuffs 0 (c) are explosives 0
(d) all of the above 0 (d) decomposes below their boiling points - 0
70. A mixture of naphthalene and benzoic acid can be separated 12. which one of the following reagents is useful for separating
by: [JIPMER 2007) aniline from nitrobenzene?
(a) chromatography· 0 (a) Aq. NaHC0 3 p (b) Aq. NaHS0 3 0
(b) sublimation 0 (c) Aq. HCI 0 (d) Dilute H2 S04 0
(c) fractional crystallisation 0 83. A mixture of phenol and benzoic acid will completely
(d) distillation 0 dissolve in an aqueous solution of:
71. In column chromatography, the moving phase is: (a) HCI 0 (b) NaCI 0
(a) the substances which are to be separated 0 (c) NaHC0 3 0 (d) NaOH 0
(b) eluent 0
84. Silica gel is used for keeping away the moisture because it:
~~~~ 0 (a) adsorbs water molecule 0
(d) mixture of eluent and substances to be separated 0 . (b) absorbs water molecule 0
72. Azeotropic mixtures: (c) reacts with water 0
(a) boil at different temperatures 0 (d) none of the above 0
(b) are mixtures of solids 0 85. Anhydrous CaCl 2 is used as drying agent, because it:
(c) are constant boiling mixtures 0
(d) none of the above 0 (a) adsorbs water molecule 0
73. Which is useful for the separating benzoic acid from methyl (b) absorbs water molecule 0
benzoate? (c) both adsorbs and absorbs water molecule 0
(a) Aq. NaHC0 3 0 (b) Oil. HCI 0 (d) none of the above 0
86. The function of fractionating column is:
(c) Aq. NaHS0 3 0 (d) Oil. H 2 S04 0 (a) to separate the two components 0
74. A mixture of camphor and benzoic acid can be easily (b) to provide greater.cooling surface to the vapours 0
separated by: [BBU 2005) (c) to kept the vapour pressure constant . 0
(a) sublimation 0 (d) to avoid mixing of the vapours of two components 0
(b) fractional distillation 0 87. One having high vapour pressure at temperature below its
(c) chemical method 0 melting point is:
(d) extraction with solvents 0 (a) benzoic acid 0 (b) salicylic acid 0
(c) citric acid 0 (d) all of these 0
Introduction to Organic Chemistry 29
II. Osazone formation is used to separate and identifY: (c) 8 sigma, 3 pi and 4 non-bonded electrons 0
(a) alcohols 0 (b) carboxylic acids 0 (d) <} sigma, 3 pi and 2 non-bonded electrons 0
(c) carbohydrates 0 (d) starch 0 100. In th~ compound CH 2 =CH-CH 2 -CH z-C==CH, the
89. Fractional distillation is used to separate liquids which C 2-C 3 bond is of the type:
differ in their boiling points by: (a) sp_sp2 0 (b) sp3_sp 3 o
(a) 0-100 C 0 (b) 10- 20° C 0 (c) sp_sp3 0 (d) sp2_sp 3 .0
(c) 20~ 40" C 0 (d) 40- 800 C 0
101. p-nitrophenol and o-nitrophenol are separated by:
90. Which of the substance is purified by subliinaflion?oo
[D<!E (Engg.) 2007) IDPMT 2003; PMET (Punjab) 2008]
(a) Naphthalene 0 (b) Benzoic acid 0 (a) crystallisation 0 (b) fractional distillation 0
. (c) Catl!phor 0 (d) All of these 0 (c) distillation 0 (d) steam distillation 0
91. A mixture of oil and water is separated by: 102. Intermolecular hydrogen bonding is strongest in:
(a) filtration 0 [ADMS 2003]
(b) using separating funnel 0 (a) methylamine o (b) phenol o
(c) sublimation 0 (c) formaldehyde o (d) methanol o
l 2 3 4
(d) fractional distillation 0 103. In the compound H2 C=C=CH-CH3 ,the hybridization of
92. Styrene can be purified by: iJIPMER 2008]
1st and 2nd carbon atom is: IBHU 2003)
(a) simple distillation 0 (b) fractional distillation 0 (a) sp3_sp 0 (b) sp2_sp3 0
(c) vacuum distillation 0 (d) steam distillation 0
'3~(A) is a higller phenol and (B) is an aromatic carboxylic
(c) sp2_sp 0 (d) SpZ_sp2 0
.. acid~ Separation of a mixture of (A) and (B) can be carried 104. Camphor is often used in molecular mass determination
out easily by using a solution of: because: feBSE (Med.) 2004)
(a) NaOH 0 (b) lime 0 (a) it is readily available 0
(c) NaHC0 3 0 (d) Na zC0 3 . .0 (b) it has very high cryoscopic constant 0 .
94~ Which IS correct statement about azeotropic mixture? (c) it is volatile 0
(a) It boils at constant temperature (d) it is a solvent for organic substances 0
(b) It does not obey Raoult's law 0 lOS. How will you separate a solution (miscible) of benzene +
(c) It cannot be separated by fractional distillation 0 . CHCI 3 ? -IAFMe 2005)
(d) All of the above 0 (a) Distillation 0 (b) Sublimation 0
95. Separation of organic compounds by column (c) Filtration 0 (d) Crystallisation 0
chromatography is due to: 106. Allyl cyanide contains 0' and n-bonds: [PMT (MP) 2004)
(a) selective absorption. 0 (a) 50',7n 0 (b) 90',3n 0
(b) selective adsorption 0
(c) both absorption and adsorption 0 (c) 30',411: 0 (d) 90',911: 0
(d) solubilities 0 .107. Which of the following gives correct arrangement of
96. The technique of gas liquid chromatography is suitable for compounds involved based on their bond strength?
compounds which are: . IBHU 2005)
(8) soluble in water 0 (a) HF>HCl>HBr>HI 0 (b) HI > HBr >HCI >HF 0
(b) highly volatile 0 (c) HF>HBr>HCI>HI 0 (d) HCI>HF>HBr>HI 0
(c) vaporise without decomposition 0
(d) liquids
97. Two substances when separated out on the basis of their
0 .11. How many bonds are there in~ ?
extent of adsorption, by one material, the phenomenon is . . . IDeE 2005)
called: (a) 140',811: 0 (b) ·180',811: 0
(a) chiomatography 0 (b) paper chromatography 0 , (c) 190',411: 0 (d) 140',2n 0
(c) steam distillation 0 (d) sublimation 0 109. The correct order regarding the eleetronegativity of hybrid
98. When a hybridization state of carbon atom changes from orbitals of carbon is: leBSE (Med.) 2006)
sp3 to spz and finally to sp, the angle between the (a) sp< sp2 > sp3 0 (b) sp< spz < sp3 0
hybridized orbitals:
(c) sp>spZ<sp3 0 (d) Sp>Sp2>sp3 0
(a) is not affected 0
(b) increases progressively 0 110. Among the following mixtures, dipole-dipole as the major
(c) decreases gradually 0 interaction is present in: rAIEEE 2006)
<I'
(d) decreases considerably 0 (a) benzene and ethanol 0
99. Allyl isocyanide has: (b) acetonitrile and acetone
(a) 9 sigma and 4 pi bonds 0 (c) KCI and water o
(b) 8 sigma and 5 pi bonds 0 (d) .benzene and carbon tetrachloride o
30 G.R.B. Organic Chemistry for Competitions
Ill. Consider the following compounds: (b) F2 > Cl z > Br2> 12 : Electronegativity ,0
(A) chloroethene (B) benzene (c) F2 > Cl 2 > Br2> 12 : Oxidising power o
(C) buta-l,3-diene (D) 1,3,5-hexatriene (d) F2 > Cl 2 > Br2> 12 : Electron gain enthalpy o
All the carbon atoms are Sp2 -hybridized in: U9. In the hydrocarbon,
(PET (Kera.l) 1006] H3 C-CH=CH-CH2 -C==CH
6 5 4 3 2 I
(a) A, C, D only 0 (b) A, B only 0 'The state of hybridization of carbons 1,3,5 are in the
(c) B, C, D only 0 (d) C, D only 0 following sequence: ICPMT (Med.) 1008]
(e) A, B, C, D 0 (a) sp,Sp2,sp3 . 0 (b) sp3,Sp2,SpO
112., The d~creasing order· of bond. dissociation energies of
(c). spz ,sp,sp3 0 (d) sp,sp3,sp2 0
C----C, C-H and H-H bonds is:
(EAMCET (EnS8-) 10071 120. The enolic form of butanone contains: '
(a) H-H > ----C-H > ----C----C- ,0 tPMT (Kerala) 1008)
. (b) .----C----C- > ----C-H > H-H 0 (a) 121.1 bonds, Ix bond and 2 lone pairs of electrons I. '0
(c) ----C-H > ----C----C- > H-H 0 (b) 111.1 bonds, Ix bond and 2 lone pairs of electrons 0
(d) ----C----C- > H-H > ----C-H 0 (c) 121.1 bonds, Ix bond and I lone pair of electrons []
113. Number ofl.1 and x-bonds in C6 H sCOOH is: . (d) I (b bonds, 2x bonds and 2 lone pairs of electrons 0
©
(e) 131.1 bonds, Ix bond and 2 lone pairs of electrons 0
(DPMT 10071
'(a) 131.1,4x 0 (b) 14G,4x 0
121. Hybridization of nitrogen atom in pyridine [ liS:
(c) 151.1,4x 0 (d) 16o',4x 0
114. Compare List I and List II and choose the correct matching
codes from the choices given: . '" (BOU (Main.) 1001]
List I List D (a) sp3 0 (b) spz 0
(A) Glycerol (i) Sublimation. (c) sp 0 (d) sp 3d 0
(B) o-nitrophenol (ii) Beilstein's test 122. The number of x-bonds in the following compound
(C) Anthracene (iii) Victor-Meyer's method OzN---C==C-NO z is: (DPMT 2008]
(D) Halogens (iv) Steam distillation (a) 2 0 (b) 3 0
(E) Molecular weight (v) Vacuum distillation (c) 4 0 (d) I 0
(vi) Eudiometry , Ill. The compound in which underlined carbon uses only its
Copes: [PET (Kerala) 20071
sp3 -hybrid orbitals for bond formation is:
(a) (A-v), (B-iv), (C-i), (D-ii), (E-iii) 0
(b) (A-iv), (B-v), (C-i), (D-vi), (E-ii) 0 (BelCE (Med.) 200S]
(c) (A-vi), (B-iv), (C-i), (D-iii), (E-ii) 0 (a) CH3 gOOH o (b) CH3 gONH2 0
, (d) :(A-'-v), (B-iv), (C-vi), (D-ii), (E-Ui) 0 ' (c) CH3 CHzOH o (d) CH3 CH=CH2 0
(e) (A-iv), (B-vi), (C-ii), (D-iii), (E-v) 0 124. Match the following:
11S. Which one of the following can be purified by sublimation? (A) Simple distillation (i) to separate the liquids
(MOCET (Med.) 10M! which are steam volatile,
(a) F2 0 (b) Cl z 0 insoluble in water arid
(c) Br2 0 (d) 12 0 contains non-volatile
116. What is the percentage of p-character of hybrid orbits of impurities
carbon in methane, ethene and ethyne respectively?
(B) Fractional distillation (ii) to separate liquids which
(SCRA (Med.) 10071 decomposes at a tempera-
(a) 75,66,50 0 (b) 50,66,75 ,0
ture below their normal
(c) 25, 33, 50 0 (d) 50, 33,25 'D boiling points
. 1t7. In the following the least stable resonance structure is:
, . (UT 1007] (C) Vacuum distillation (iii) to separate two or more
liquids which have boiling
~ @ -?,O ~.®-?,O
(a) e N (b) ® N points close to each other.
I I "',;1
(D) Steam distillation (iv) to separate liquid fr,Qm
o 0
e non-volatile impuritieS
e ABC D
(c) ~~-?,O (d) ~~/O (a) (i) (ii) (iii) (iv)
I @ I • ?i (b) (iv) '(iii) (ii) (i)
oe 0
e (c) (iii) (i) (iv) (ii)
(d) (ii) (iv) (i) (iii)
US. Which one of the following arrangements does not give the •
US. Match the following:
correct picture of the trends indicated against is?
(A) Sublimation (i) Ether + toluene
(CPMT (Med.) 2oo8J
(a) F2 > Cl 2 > Brz > 12 : Bond dissociation energy 0 (B) Distillation (ii) o-Nitrophenol + p-nitrophenol
Introduction to Organic Chemistry 31
(C) Vacuum distillation (iii) Benzoic acid + benzaldehyde IlS. Mixed melting point is determined to check:
(D) Steam distillation (iv) Glycerol from spent lye (a) the purity of organic compound o
ABC D (b) whether the two compounds are same o
(a) (iv) (iii) (ii) (i) (c) whether the two compounds are different o
(b) (i) (ii) (iii). (iv) (d) whether the two compounds can be separated by
(c) (iii) (i) (iv) (ii) fractional crystallisation method 0
(d) (ii) (iv) (i) (iii) 129. Which of the following compounds can be purified by
SET II: This set contains the questions having one or more, correct vacuum distillation?
answers. ',~ { "" (a) Glycerine 0 (b) Glycerol 0
(c) Propane-l,2,3-triol 0 (d) Ethanol 0
126. Which resonance form in each of the fdtlowing sets is the 130. Which of the following compounds can be purified by
major contributor to the real structure? . 'I" steam distillation? ',
•• •• +
(i) H2C=CH-CI: ~ H2 C-CH=CI: (a) Salicylaldehyde o
•• •• (b) Bromobenzene :0
(a) (b)
+ • •• - (c) p-Hydroxy benzaldehyde o
~ H 2 C-CH. CI:
,- +
00 (d) Nitrobenzene o
(ii) H2 C-CH=NH2 ~ H 2 C=CH-NH 2 (e) 131. Mixture of benzene and aniline can be separated by:
(a) (b)
(a) distillation 0 (b) steam distillation o
(c) dil. HCI 0 (d) dil. NaOH
132. Absolute alcohol can be prepared from rectified spirit by:
(a) azeotropic distillation with benzene 0
(b) fractional distillation 0
(c) keeping over fresh CaO for few hours and then
O l-O~ -(1)-~
(iv) distilling o
~ '. # llJ)J V, " _ (d) distillation under reduced pressure o
(a) (b) (e) (d)
, 113. Select the wrong statements about chromatography.
(a) Moving phase is liquid and stationary phase is solid 0
+ (b) Moving phase is liquid and stationary phase is liquid 0
0- :0
+ '. 1 _I (c) Moving phase is solid and stationary phase is solid 0
(v) H 2 C-CH=C-H ~ H 2 C-CH C-H (d) Moving phase is solid and stationary phase is liquid'
'W' 00 -0
134. A substance which decomposes at or below its boiling point
6 -6:
}, Ell Ell_
H cannot be purified by:
'(a) steam dit>tillation '0
(b) simple distillation []
(Vi1 o
(c) fractionaJ distillation . '
e
(a) (b)
(d) distillation under reduced pressure o
135. Refining of petroleum does,not involve:
·127. Chromatography technique is used in the sepafl:!,tion of: (a) simple distillation o
(a) volatile liquids 0'(1» amino acids (b) steam distillation o
(q) plant pigments o (d) sugars o '(c) fractional distillation ' ,0
," .'
,
(d) distillation
,
under reduced pressure o
ASSERrI9N·RE~ON TYp(~~:i~9~~s~I~~"j~;;:;~;= i.'~ ~~,~-:::::I,:i:::f::::::::::=:~::I: I
.: ' . "
i Instiructiom: Each question contains statement-l (Assertion,
•A) and statement-2 (Reason, R). Of these statement,. 'Irk ;(c) Statement~ r (A) is true; ~tatement-i (R) is false. ' {
: Co !Teet choice i f : ; ,' ,(d) StatemeI):t.l (A) is false,! statement-2 (R) is true.... ,. -
(a) Statement-l (A) and statement-2 (R) are true and I. (A) Oils are purified by steam distillation.
statement-2 (R) is the correct explanation for (R) The compounds which decompose at their boiling
statement-l (A). . points can be purified by steam distillation. .
(b) Statement-I, (A) and statement-2 (R) are true and - . IAIIMB--.
; ....... statement-2 (R)is not the correct explanation for 2. (A) Mixture of glucose andm-dinitrobenzene can-be
statement-l (A). separated by shaking it with ether,
32 G.R.B. Organic Chemistry {Or Competitions
(R) Glucose is soluble in water. (R) Fractional distillation helps in -separating two liquids
3. (A) Thiophene present in benzene as impurity can be from their mixture when their boiling points differ by
removed by shaking the mixture with cold cone. lOoC.
H 2 S04 , 7. (A) Aniline has odd molecular mass, i.e., 93.
(R) Thiophene is a heterocyclic aromatic compound. (R) All nitrogenous compounds containing odd no. of
4. (A) A mixture of camphor and benzoic acid cannot be nitrogen has odd molecular mass.
separated by sublimation. 8. (A) Molecular nitrogen is less reactive than molecular
(R) Camphor on heating sublimes but benzoic acid does oxygen.
not. (R) The bond length ofN2 is shorter than that of oxygen.
5. (A) A mixture of o-nitrophenol and p-nitrophenol can be 9. (A) p-hydroxy benzoic acid has a lower boiling point than
. separated by steam distillation. o-hydroxy benzoic acid.
(R) o-nitrophenol is steam volatile but p-nitrophenol is not (R) o-hydroxy benzoic acid has intramolecular hydrogen
though both are water soluble. bonding. (lIT 1007)
6. (A) Acetone (b.pt. 329K) and methyl alcohol (b.pt. 338 K) 10. (A) Chlorine has higher electron affinity than fluorine.
are separated by fractional distillation. (R) Chlorine is a poor oxidising agent than fluorine.
(AIIMS 1007)
ANSWERS
OBJECTIVE QUESTIONS
1. (c) 2. (b) 3. (c) 4. (d) 5, (c) 6. (c) 7. (a) 8. (b) 9. (a) 10. (d)
11. (d) 12. (d) 13. (d) 14. (c) 15. (b) 16. (a) 17. (b) 18. (b) 19. (c) 20. (b)
21. (d) 22. (b) 23. (d) 24. (c) 25. (c) 26. (a) 27. (a) 28. (d) 29. (d) 30. (d)
31. (a) 32. (b) 33. (a) 34. (d) 35. (c) 36. (b) 37. (b) 38. (c) 39. (c) 40. (c)
41. (a) 42. (a) 43. (b) 44. (c) 45. (a) 46. (b) 47. (d) 48. (a) 49. (c) 50. (d)
51. (b) 52. (a) 53. (a) 54. (b) 55. (c) 56. (d) 57. (a) 58. (c) 59. (d) 60. (b)
61" (a). 62. (a) 63. (b) 64. (c) 65. (d) 66. (b) 67. (c) 68. (b) 69. (d) 70. (a)
71. (d) 72. (c) 73. (a) 74. (c) 75. (d) 76. (b) 77. (a) 78. (b) 79. (c) SO. (a)
81. (d) 82. (c) 83. (d) 84. (a) 85. (b) 86. (b) 87. (a) 88. (c) 89. (a) 90. (d)
91. (b) 92. (d) 93. (c) 94. (d) 95. (b) 96. (c) 97. (a:) 98. (b) 99. (d) 100. (d)
101. (d) 102. (d) 103. (c) 104. (c) lOS; (ay , ; l06.)(b) , . lQ7. (a) -',:iOS: (c),' 109.-(dj 110. (b)
11:t (e) 112. (a) 113. (c) 114. (a) '115. (d) 116. (a) 117. (a) 118. (a) 119. (d) 120. (a)
121. (b) , 122. (c) 123. (c) 124. (b) 125. (c) 126. (i) (a) (ii) (b) (iii) (c) (iv) (a,b) (v) (a) (vi) (b)
127. (b,c,d) J128. (a,b,c) 129. (a,b,c) 130. (a,b,d) 131. (a,c) 131. (a,c) 13J. (a,c,d) 134. (a,b,c) 135. (a,c,d)
~CI
¢
CI
(a) 2,2,3-trirnethyl pentane 0
(b) 2,3,4-trirnethyl pentane 0
(c) both (a) and (b)
(d) none of the above
3. Two molecules indicated below are capable to intra-
0
0
(iii)
U (iVl
CI
moiecular H-bonding. Which is likely to form more stable
hydrogen bonds? (a) (i) < (iv) < (ii) < (iii) 0 (b) (iv) < (i) < (ii) «iii)
0
H (c) (iv)«i)«iii)«ii) 0 (d) (iv) < (ii) «i) «iii) 0
I
10. H-C ~
yO H-C
.>-0
~ , c-o bond lengths.
CH3'-...C"""C'::::::::'C,..,.,CH3
p a-.:-H I) o·
~ 6
H ....--
designated by u, Il, y and 0 are in order:
(a) u=y<ll=o 0 (b) u<ll<y=o 0
(I)
(c) u< y =0< Il 0 (d) all are equal 0
WI 0 [HInt: Length of 'Y and /) will be same due to the resonance.
(b) II 0 o o· r 01
( c) Both are equally capable
(d) Cannot be predicted
0
0
H-c(O. ~ H-C(O = lH-:X~OJ}
4. Which one of the underlined carbons is sp 3 -hybridized?
11. Which one ofthe following compounds is an allylic halide?
(a) CH39i=CHz 0 (b) CH 3 9iZNHZ 0 Br
(c) CH 3 §ONHZ 0 (d) CH 3 CH2QN 0
(a) CH3-@--cH=t-CH3 0
s. The hybridization of iodine in iodosobenzene is :
(a) sp 0 (b) sp2 0
(c) sp3 0 (d) sp 3d . 0 (b) BrCH2--@-cH=CHCH3 0
6•. Carboxylic acids do not give the characteristic reactions of
> C= 0 group because of:
(a) p()lar nature 0 (b) resonance 0 (c) CH3-@--cH=CHCHzBr . o
(c) symmetrical structure 0 (d) attached alkyl group 0
(d)CH~~HCH' .
7. Which among the following has highest boiling point?
(a)CH3 CH 2CH zCH2CI D. o
(b) (CH3)2CHCH2CI 0
(c) (CH3 h C-CI 0 [Hint: (a) is vinylic (b) is benzylic
(d) None of the above 0 (c) is allylic (d) is arylic]
8. Which among the following has highest melting point? ll. The compound in which all carbon atoms use only sp3 -
(a) (CH3CO)20 0 (b) CH3CN 0 hybrid orbitals for bond formation is:
(c) CH3CONHZ 0 (d) CH3 COCI 0 (a) CH3 CHO 0 (b) CH 3 COCH 3 0
[Hint: (c) Amide has highest melting point due to fonnation of . (c) (CH3)3COH 0 (d) HCOOH· O.
intennolecular hydrogen bonding.) 13. Which of the following is unacceptable resonating structure
9. Order of arrangement of the following compounds with of buta-l ,2,3-triene?
increasing dipole moment is : ~
(a) CHz-C==C-CHz 0
~
(b) CH z =C-:-C=CH2
0
34 G.R.B. Organic Chemistry for Competitions
14. The resonating structures of cyanate ion are, the hybridization state of marked carbon atom changes
O=C==N- ~ -O-C55N ~ +Q==C-N 2-" from:
(i) (il) (iii) (a) Sp2 to sp (b) Sp3 to spo. o
The correct set of oxidation states of 0, C, and N (c) Sp3 to sp2 o (d) Sp2 to sp3 o
respectively with the most stable structure out of the above 19. Which of the following structures have resonance stability?
is: .
(a) (i) -3, +4,-2 o
(b) (ii)-2,+4,-3 o CH3-C "'" ~ CH 3-C
/0 <'H
+ ~
(c) (iii) -1,+4,-3 o
(d) (i) 0,+4,-5 o OH OH
(a) (b)
IS. Arrange the following molecules in increasing order ofcs to
o
(1)0
1t bond ratio: 0-
(2) 'CO~
. ". I
CH - C.<0(-) ~ CH -C( 0
3 3 + H+
~ ~ (e) (d) .
20. Arrange the following resonating structures of formic acid
in order of decreasing stability :
(3) 000(4)00
~ ~ ~ ~ ~ H-C-OH
o
~
~
6
I +
H-C=OH ~ H-C-OH
0-
I
(a) 2<3<4<1 0 (b) 2<4<3<1 0 (I) (II) (~II)
(c) 3<2<1<4 0 (d) 2<3<1<4 0 0+
I
[HiDt:O
120,31t
CO
~ ~
190,51t , (a) II>I>III>IV o (b) I>III>I1>IV
~ H---,C-OH
(IV)
0
o 4 o 19
i' .. 1'=4 i' .. '5=3.8 (c) I1I>II>IV>1 0 (d) IV>III>!>11 0
21. Arrange the following resonating structures of vinyl
000
~
0
~.-9
260',71t .
2;=3.71
co
.~
0'
250,61t
25
#
CH 2 =CH-Cl
(I)
(a) I > II > III
(c) II> I > III
~
-
CH 2 -CH=O
o
(II)
(b) III> II > I
o
(d) I> 11= III
+
.
~
+
CH 2-CH=Cl
(III)
-
o
o
i' 22. Among the following four structures, one is not a
16. Whicb one of the following ions is the most resonance permissible resonance form. Identify the wrong structure.
stabilized? [PMT (Kerala) 2010] + •••• + ••
(a) Ethoxide' 0 (b) iso-Propoxide 0 (a) CH 2 -N-0: o (b)CH2 N---,O:
I •• o
.1 ••
, (c) n-Butoxide 0 (d) tert. Butoxide 0 .CH3 'CH3
(e) Phenoxide 0
17. Arrange the following C- H bonds (a, p, y) in decreasing (c) CH
2
N=O:
I •• ' o (d): CH2 -:N=0: o
order of bond energy :
I -
CH3 CH3
H-~-H
f H-C55C-H
(r) 23. Which of the following compounds has (have) sp-
hybridized carbon atom?
1(<<)
(a) CH2=C=0 0 (b) CH2=CH-CN 0
H
(a) a>p>y (b) y>p>a o (c) CH3 -CH=CH2 0 (d) H 2C=0 0
(c) p>a>y . o (d) y> Cl > p o ,24. Identify the weakestC-Hbond among the following:
18. In the reaction, H R R
o I I I
H-C-H R-CH2-H R-CH-H ' R-C-H
I Ia ' ll' I Y' I I)
CH3-C~NH2
• H R
Introduction to Organic che;"i~try-'-'--' 35
(a) a (b) ~
0 0 (c) Four carbons are in sp2 and two in Sp3 -hybrid state 0
(c) y 0 (d) 0 0 (d) Four carbons are in Sp3 and two in sp2-hybrid state 0
lS. Which of the following is the correct sequence of the bond 31. The pair of structures that are resonance hybrid is :
.length? •• + +
(a) S-H>C-H>N-H>O-H 0
(a) HO-CHCH3 and HO=CHCH3
•• ••
o
(b)C-H>~H>O-H>N-H 0
(e) O-H>N-H>C-H>~H 0 o
(d) ~H>O-a>N-H>C-H 0
16. Arrange the following bonds in decreasing order of bond
length: :-0: O-H
••
CI H H II I
a4LOJ IHf;al
CI CI
CH:?, 01
H
H-+.OI
H
(c) CH3-C-H and CH2=C-H
+
(d) CH 3 CH 2 and CHzCH3
+
o
'31. The correct decreasing order of stability of I, II and III
(a) } > 2 > 3 > 4 0 (b) 4 > 3 > 2 > I 0 carbocations is:
(c) 2 > 3 >.1 > 4 [J (d) 4 > I > 2 > 3 0 (I) CH 3 - r n -CH3 (II) CH3-rn-COCH3
17. Which of the following compounds has weakest C-X +
(III) CH3 -CH-OCH 3
. bond?
(a) CH3F 0 (b) CH 3 C} 0 (a) I> II > III ' 0 (b) II >. III > I 0
(c) III> I > II 0 (d) II> I > III 0
(c) CH3 Br 0 (d) CH31 0 B A
18. How many electrons are present in the p-orbitals of a methyl 33. The hybrid states of carbon atoins in (CN)4 C 2 are A and B
cation? and number of x bonds in compound is C. Then: '
(a) 2 0 (b) 3 .D (a)A=sp,B=sp2 andC=9 0
(c) 4 D. (d) None of these 0 (b) A =sp2 ,B =sp, and C = 9 CI
19. In which of the following, delocalisation of x-electrons (c) A =sp3 ,B=sp and C= 9 0
is/are possible?
(d) A =sp2 ,B =sp2 and C =9 D
(a) CH 2 =CH2 0
+ • .. -
(b) CH3-CH2-CH=CH2 0 34. -C- C - C -C- Select the correct state of
(c) CH 2=CH-CH=CH2 0
XI I X2 X3 I X4 '
(d) CHi =CH-:-CH 2-CH=CH2 0 hybridization at X I , X Z ,X 3 and X 4'
XI Xi X3 X4
H
(a) sp2 sp sp2 sp3 0
, H,e-b-C/H
(b)sp3 sp2 sp sp CJ
30. II I II
C (c) sp2 sp2, " :sJr .• sp3 0
H/ 4-C'H
(d) Sp3 Sp2 Sp2 sp·
H
In the given Dewar structure of benzene, which of the 3S. Resonating structures of a molecule have :
following statement(s) is/are correct? (a) identical bondmg 0
(a) All the carbOns are in sp2-hybridstate 0, (b) different bonding CJ
(c) identical arrangement of atoms and nearly same
(b) All the carbons are in Sp3 -hybrid state Cl energies CJ
(d) the same number of paired and unpaired electrons
2) ¢
Passage 1
A polar covalent bond is fonned between the two elements of
different electronegativities. The polarity of a bond depends on
the electronegativity ditlcrence, the bonding atoms and also on
the shape of the molecule.
>
QCF3
>
CF3
A-B , True (a) False (b)
Let X:,4 and.xa are the eiectronegativities of bonding atoms A
and B then, percentage ionic character of the bond can be Passage 2
calculated as,
. Geometry of organic compound is often described in tenns
% ionic character =211 x A - Xo I +3.51 x A - xal 2 of the valence shell electron pair repUlsion theory. The VSEPR
Dipole moment of the bond ( J1) depends on the bond length model rests on the premise that an electron pair, either bonded
and the polarity of the bond. pair or an unshared pair, assOCiated with a particular atom will be
as far away from the atom's other electron pairs as possible.
}l=qxd The tricoordinate carbon atoms of an alkene or carbonyl
Here, q =charge of the dipoles group also fonn bonds with angles near 1200 • In these
d = bond length compounds, unsaturated double bonds have two electron
pairs-those of the sigma and pi bonds. RePulsion by these two
It is observed that the dipole moment increases with increase
pairs are some what greater than those between single bonds, so
in the inductive effect.
that deviation from exact '1200 trigonal geometry is observed.
Answer the following questions as indicated:
Another factor which has important influence on shapes is
Select code (a)ifthe statement is true and code (b) if the non bonded repulsion between the atoms within the molecule.
statement is false. Such repulsion is also referred to as sterle effects.
1. The dipole moment of CH 3 -X bond lies in the Answer the following questions:
following sequence: l,~ ~
CH3 -1 < CH3-Br < CH3-CI • HuH H ~ 'CH3
True (a) False (b)
2. Dipole moment of methanol is less than ethanol: CH3~
y CH 3 (CH3)3C ~
li qCH3)3
True (a) False (b) Select the correct sequence of bond angles indicated in the
3. pipole moment of C-Cl bond is greater than C-Fpond : above molecules.
True (a) False (b) (a) a<13<'Y<6 (b) a:~ 'Y 0
, . /0"", (c) a>~>'Y>o (d) a<~dk'Y
4. Dipole moment of methyl alcohol (CH3 H) is less
F~ Cl~ H~
than that of water : 2. F/C-O Cl/C-O H/ C - O
True (a) False (b)
5. Dipole moment of trans-2-butenai is greater than butanal : Select the correct sequence of indicated bond angles.
o (a) a<~<'Y (b) a>~>'Y
(c) a ~='Y (d) a<~>'Y
I
/CH~ /C",
CH 3 CH 2 H
butanal
o Select the correct sequence of indicated bond angles.
(a) a>~>'Y (b) a=~='Y
H II, ' (c) a<~<'Y (d) a>~<'Y
tH/
""'C = ~I / "'H ~H
4. Cl---l.(,;(,tU
3 H • "q'H
trans-2-butenal H
True (a) False (b) Which amo~g the following is correet about the indicated
..6. Dipole moment of para-nitlUphenol is greater than phenol: bOnd angles?
" True (a) '. False (b) (a)a= ~ (b) a> ~
7. ,pipole moment of anilin,e, trifluoromethyl benzene and (c) a<~ (d) , Can not be predicted
p-trifluoromethyl aniline lies in the following sequence:
~-"--j
,P('>' .. 'ief
Introduction to Organic Chemistry 37
S. Which compound has bond angles nearest to 120°?
(a) O=C=S (b) CHI 3
(c) H 2 C=0 (d) H-C=C-H
(e) CH4
Passage 3 CH3
Double bond equivalents help in search for structure of a
compound. It involves following .steps:
• Calculate the expected number of hydroge!1 atoms in the
[Hint: Tertiary arnines (CH 3-,I N) are· not involved in
CH 3
saturated structure. intennolecular hydrogen bondhig, hence their boiling
(a) For C n there would be : (2n + 2) hydrogens if point is lowest as compared to corresponding primary
compound contains C, H, 0 only. . and secondary arnines.]
(b) For CnN m, there would be (2n + 2+ m)hydrogens. 2. Which of the following molecules is dimerised' when
• Subtract the actual number of hydrogen and divide by 2. dissolved in nonpolar or organic solvent?
This gives the double bond equivalents.
• rung is considered to possess single DBE. COOH
Answer the following questions on DBE: (a) R-COOH (b) I
1. Double bond equivalent of compound C 7 H 12 0 is: COOH
(a) 2
(c) 4
(a) 2
(c) 4
(b) 3
(d) 1
2. Double bond equivalent of benzene will be:
(b) 3
(d) 1
(c) R-OH (d) 0
3. Which of the following compounds is (are) stablised by
3. Which of the following is not correct? intramolecular hydrogen bonding? .
Compound DBE
(a) C7 HlO O 2 CI OH
(b) C 7 H g O 4 .. - 1 I
(c) C 7 H17 N
(d) C7H'3NO
3
2
(a) Cl-f-f-H
4. Double bond equivalent ofC7H 16 0wouid be ...
CI OH
(a) 0
(c) 2
(b) 1
(d) 3
fH
(c) CH3-C==CH-C-OC2Hs
V
Passage 4 CH 20H
The hydrogen bond is an electrostatic attractive force
(d) I
CH2 0H
between covalently bonded hydrogen atom of one molecule and
an electronegative atom like (F, 0, N) of other molecule. 4. Select the compound which involves intramolecular
Hydrogen bond is nearly an electrostatic attractive force and not a hydrogen bonding.
normal chemical bond. It is very weak (2-lOkcaJ/mol) as (a) HCOOH (b) CH3COOH
compared to a covalent bond (strength 50-100kcal/mol). (c) C6 Hs COOH (d) CH3 COOOH
In intramolecular hydrogen bonding, the two or more than [Hint: Per acids fonn intramolecular hydrogen bond.
two molecules of the same or different substances are linked to r-
form polymeric aggregate. Intermolecular hydrogen bonding
increases the boiling point ofthe compound and also its solubility
in water. Intramolecular hydrogen bonding occurs within two
Cfl3-C("',f,+ ]
0-0
atoms of the same molecule. Intramolecular hydrogen bonding is
also calied chelation, since it. involves· . ring ~ormation. 9. . 9. . OH P.
Intramolecular hydrogen bonding decreases the boiling point of II ' II . I .II
the compound and also its solubility in water. S. CH3 -C-CH 2-C-CH 3..----'" CH3-C=CH-C-CH3
Answer the ·following questions: 2,4-pentadione 4-hydroxypent-3-en-2-one
. (.4) . (B)
1. Which among the following has lowest boiling point?
Select the correct statement about above tautomers.
(a) Form (A) is· more stable due' to formation of
6
. NH2
intramolecular hydrogen bond
(b) Form (B) is more stable due to formation of
(a) intermolecular hydrogen bond
· 38·· G.R.B. Organic Chemistry (or Competitions
(c) Form (B) is more stable due to the formation of (d) Form (A) is more stable due to the formation of
intramolecular hydrogen bond intermolecular hydrogen bond
'~ .. "
2.1 GENERAL delivery tube is immersed in lime water. The bulb of the
delivery tube contains anhydrous copper sulphate
In order to establish the correct structure of an organic (colourless). The mixture is heated very strongly. Carbon and
compound, it is necessary to know precisely its molecular hydrogen present in the organic compound are oxidised by
formula. The following steps are .involved jn the cupric oxide to carbon dioxide and water; relpectively
determination of the molecular formula of a compound. (Copper Oxide Test).
(i) Detection of elements (Qualitative analysis).
(ii) Estimation of elements (Quantitative analysis). C+2CUO ~ 2Cu+C0 2
(iii) The determination of molecular mass.
(iv) Calculation of empirical and molecular formula. H2 +CuO ~ Cu+H 20
2.2 DETECTION OF ELEMENTS Carbon dioxide turns' the lime water milky and water
(QUALITATIVE ANALYSIS) vapours turn anhydrous copper ,sulphate. blue .. Water vapours
condense on the cooler part of the tube.
Most of the organic compounds contain 2 to 5 different elements. Ca(OHh +C02 .---,---+ CaC0 3 + H 20
The principal elements present are: carbon, hydrogen and Milky
oxygen. Less commonly present elements are: nitrogen,
sulphur and halogens. In few organic compounds, phosphorus CuS04 + 5H 20. ---'---+ CuS04 ·5H 20
and metals may also be present. The order of abundance of (Colourless) (Blue)
Anhydrous Hydrated
these elements in organic compounds is given below:
Carbon -Always present If the substance under investigation is a volatile liquid or
Hydrogen -Nearly always present gas, the vapours are passed over heated copper oxide kept in
Oxygen -Generally present combustion tube and the gaseous products are tested as above.
Nitrogen, halogens, sulphur -Less commonly present If the substance under examination contains sulphur also,
Phosphorus and metals -Rarely present the.gases evolved are fust passed through an acidified-solution
of potassium dichromate which absorbs all the. sulphur
Detection of Carbon and Hydrogen dioxide and then through lime water which turns milky.
Carbon is always present in an organic compound and S +2CuO ---'---+ 2Cu +S02
hydrogen, too, is rarely absent However, the presence of these
K 2 Cr20 7 + H2 S04 + 3S02 ~ KZS04+Cr2(S04)3 + H 2 0 >
two elements is confIrmed by the given common test.
A small amount of dry organic compound mixed with [S02 like CO 2 turns lime water milky due to formation of
about eight times dry cupric oxide· is taken in a hard glass caS° 3 • .
tube. The glass tube is clamped and fItted with a delIvery tube Ca(0H)2 + S02 .---'---+ Caso l + H 20] ..
carrying a bulb in the horizontal length. The end of the
*Cupric oxide, CnO, is hygroscopic. It is always ignited before use as to ma1ce it completely dry.
"
40 G.R.B. Organic Chemistry for Competitions.
Organic compounds (suppose to contain phosphorus) are Chemistry of the test: Lassaigne's filtrate consists of
heated with oxidising agents (like sodium peroxide, Na202)' sodium cyanide and sodium hydroxide.
The phosphorus present in the organic compound is oxidised
Na + C + N NaCN
to phosphate. '-----v----' Sodium cyanide
From organic
Detection of Nitrogen, Sulphur and Halogens compound
. These elelilentsare test~d,in ~-organic compound by 2Na + 2If20 ---7 2NaOH + H2
Lassaigne's t~st.TIie organic compoimd (N, S or halogens) is Sodium hydroxide
fused with sodium metal as to convert these elements into When the filtrate is boiled with ferrous sulphate solution,
ionisabl~in()rgani<tsubS1{mces, i.e., 'nitrogen into sodium,. the following .reactions take place.
: -
cyanide: sulphtirintosodhun sulphide andhalogensirito ' FeSO" +2NaOH ---7 Fe(OHh + Na 2S0 4
sodium halides. .. . Ferrous hydroxide
(Green)
Na+C+N ~ NacN
Fe(OHh +6NaCN ---7 Na 4[Fe(CN)'6] +2NaOH
2Na+S ~ Na2S Sodium ferrocyanide
[Sodium
2Na + X 2 ~ 2NaX' (X may be Cl, Br or I) . hexacyanoferrate' (II)]
Note: .Sodium metal should be' in slight excess otherwise in At the same time some ferrous sulphate is converted to
compounds containing N and S together, sodium thiocyanate is ferric sulphate. This reacts with sodium ferrocyanide to form
. formed. With excess of sodiUm, the thiocyanate formed ferric ferrocyanide or iron (III) hexacyanoferrate (II) which
decomposes into cyanide a:ndsulphide.
gives prussian blue colour or precipitate.
Na + C + N + S ~ NaCNS
Sodium thiocyanate 3Na4[Fe(CN)6] + 2Fe2(S04)3 ~ Fe4[Fe(CN)6h + 6Na2S04
NaCNS + 2Na ~ NaCN + Na2S . Ferric ferrocyanide
(Prussian blue)
The cyanide, sulphide' or halide ions can be confirmed in In case ferric chloride (FeCI 3 ) is added, the following reac-
the aqueous solution by usual tests. The aqueous solution is tion occurs.
called Lassaigne's filtrate. .
4FecI3+3Na4[Fe(CN)6] ~ Fe4[Fe(CN)6h +12NaCI
Instead of sodium metal, mixture of sodium carbonate and
zinc can be used. It is called Middleton's fusion method. Note: (i) Sometimes when the amount of nitrogen present is small, the
Preparation or Lassalgne's filtrate: A small piece of . prussian blue is present in colloidal form and the solution
sodium of pea size is freshly cut and dried between the folds of looks I!reen.
(ii) When the alkaline solution is acidified with HCI, the yellow
filter paper. It is taken in a fusion tube (ignition tube) and
colourofferric chloride produced by the acid with ferric ions
heated gently. When it melts to a shining globule, the tube is '.
makes the blue colour to appear as green.
removed. from the flame and a small amount of organic
(iii) When the organic substance contains both N and S, sodium
compound (0.05 g of solid or 3-4 drops of liquid) is added to
thiocyanate is formed which gives a blood red colouration of
. the sodium. The tube is first gently heated till the reaction ferric sulphocyapide (or ferric thiocyanate) with ferric ions. .
ceases and then strongly till it is red hot. It is now plunged
directly into 10 to 15 mL of distilled water taken in a porcelain 3NaCNS + FeCI 3 ~ Fe(CNS)3 + 3NaCI
Ferric sulphocyanide
basin and crushed by the tip of the tongs. The contents are (Blood red in colour)
heated for five minutes and then filtered. The filtrate is known . (iv) This test fails in case of diazo compounds.
as Lassaigne's filtrate or sodium extract.
Organic compounds being covalentsnormally do not Detection of Sulphur
have ionisable groups, hence direct test is not possible. 1. Lassaigne's test: Sulphur is present in the sodium
Detection of Nitrogen extract in the· form of sodium sulphide.
2 mL ofLassaigne's filtrate (sodium extract) is taken in a S+2Na ~ Na2S
test tube and two or three drops of freshly prepared ferrous
sulphate solution are added. As the solution is alkaline (excess (When sulphur and nitrogen both are present, sodium
of sodium reacts with water to form sodium hydroxide), a thiocyanate is formed. Both are tested simultaneously with
green precipitate of ferrous hydroxide appears. The mixture is ferric chloride solution, when a blood red colouration
boiled for two minutes, cooled and acidified with, dilute appears).
sulphuric acid (H2S0 4 dissolves ferrous hydroxide). Sulphur is tested in the sodium extract in the following
Appearance of a green or prussian blue colour confirms the manner:
presence of nitrogen. Alternatively FeCl 3 and dilute HCI may (i) To a little of sodium extract, freshly prepared solution
be added. . of sodium nitroprusside is added; a deep violet colour
indicates the presence of sulphur.
Molecular Analysis of Organic Compounds 41
,.
42 G.R.B. Organic Chemistry (or Competitions
•
Molecular Analysis of Organic Compounds 43
Observations: N
Unused acid required = 40 mL 10 NaOH
(i) Mass of the organic compound taken = W g
(ii) Normality of the standard acid = Nt N N
40 mL - NaOH == 40 mL - H 2S0 4
(iii) Volume of the acid taken = VI mL 10 10
(iv) Volume of the acid left after NH3 absorption =V2 mL N
==20 mL 5 H 2S0 4
(Determined by titrating with standard alkali solution)
(v) Volume of NI acid used, i.e., neutralised by ammonia Acid used for absorption of ammonia
=(VI -V2 ) mL V mL N.
Calculations: Since, V mL Nl acid = V mL Nl NH3 ::: (60 20) mL 5 H 2S04
PI VI T2 = 32 x 500 mL N NaOH
Volume of nitrogen at STP, V2 = ~. P 20 10
2
==80mL NNaOH
=
756x 48.6 273
x- 80 mL N NaOH = 80 mL N H 2 S0 4
300 760 Acid used for the neutralisation of NH 3
=43.99mL =(100-80) mL N H 2S0 4 '
From the mass of silver halide formed, the percentage of the Problem 7. 0.1170g of an organic compound on
halogen can be calculated. heating with conc. RN0 3 and silver nitrate in Cariusfurnace
Calculations: Mass of the organic substance = W g gave 0.42 g of AgCl. Find the percentage of chlorine in the
compound.
Mass of the silver halide = WI g
Solution: Mass of organic compound, W = 0.1170 g
(a) Chlorine: AgCl = CI Mass of AgCl, W; = 0.42 g
,143.5 g 35.5 g
143.5 g of AgCl contains chlorine = 35.5 g AgCl = CI
143.5 g 35.5 g
W; g AgCl contains chlorine = 35.5 x W; g . 35.5 W;
143.5 Percentage of chl onne = - - x - xl 00
143.5 W '
Percentage of chlorine = 35.5 x WI x 100
143.5 W = 35.5 x 0.42 x 100=88.80%
143.5 0.1170
(b) Bromine: AgBr = Br Hmogens can also be estimated by Schiff's and Piria
188 g 80 g
method.
188 g of AgBr contains bromine = 80 g In this method the accurately weighed organic compound
is taken in a small plat~um crucible with a mixture of lime
W; g of AgBr contains bromine = ~ x W; g
188 and sodium carbonate, (CaO + Na 2C0 3). It is now heated
. 80 WI strongly and then cooled and dissolved in dilute nitric acid in a
Percentage of b romme = - x - x 100 beaker. The solution is then filtered and the halide is
188 W
precipitated with silver nitrate solution. Halogen is now
(c) Iodine: AgI = I calculated as in Carius method.
235 g 127 g
235 g of AgI contains iodine = 127 g Estimation of Sulphur
. . d· 127 Sulphur in organic compounds may be estimated by any
W; gAgI contams 10 me = - x W; g
235 one of the following method:
(a) Carius method
Percentage 0 f · 127 x -WI x 100
• = -'-
lodme (b) Messengers method
. 235 W
(c) Fusion method
Problem: 5. 0.5264 g silver bromide is ,obtained from The most common method for the estimation of sulphur is
0.5124 g ofan organic compound. Calculate the percentage of Carius method.
bromine in the compound. Principle: When anorganic compound containing
sulphur is heated with fuming nitric acid, sulphur is
Solution: Mass of organic compound, W = 0.5124 g
quantitatively oxidised to sulphuric acid. This is precipitated
Mass of silver bromide, W; = 0.5264 g as barium sulphate by adding barium chloride solution. From
AgBr = Br the amount of barium sulphate, percentage of sulphur can be
188g 80g calculated.
. 80 W; S + RN0 3 (fuming) Heat) H 2 S0 4
Percentage of bromme = - x - x 100
188 W H 2 S0 4 + BaCI 2 ) BaS0 4 +2HCI
=~ x 0.5264 xl00 = 43.71% Calculations: Mass of organic compound = W g
188 0.5124
Mass of barium sulphate = WI g
Problem 6. 0.156 g ofan organic compound on heating
with fuming RN0 3 and AgN03 gives 0.235g of Agl. BaS0 4 == S
233 g 32 g
Calculate the percentage of iodine in the compound.
233 g of barium sulphate contains sulphur = 32 g
Solution: Mass of organic compound, W =:= 0.156 g
contain~ sulphur =
~ :. ".
Mass of AgI, W; =0.23Sg W; g of barium sulphate 32 x W; g
233
AgI = I 32 W'
235 g 127 g Percentage of sulphur = - x _1 X 100
233 W
.. 127 W.
Percentage of Iodme = -, x _ I xl 00 Problem 8. On heating 0.32 g of an organic compound
235 W
with concentrated nitric acid and barium chloride, 0.932 g
= 127 x 0.235 x 100=81.41 % barium sulphate was obtained. Calculate the percentage of
235 0.156 sulphur in the given compound.,
'-.':.
L,~-
46 G.R.B. Organic Chemistry for Competitions
Seludon: Mass of organic compound, W =0.32 g passed over heated carbon at 1100°C. The oxygen combines
with carbon forming carbon monoxide.
Mass of barium sulphate, Wt =0.932g
. Pyrolysis
BaS04 === S Compound ) Oxygen + Gaseous products
233 g 32 g
Percentage of sulphur = -
32 Wt
x - x 100
°z + 2C(~aphite) 11 OO°C) 2CO
233 W The gas is then passed through a tube containing iodine
pentoxide at 175°C to liberate iodine.
= 32 x 0.932 xIOO=40%
233 0.32 5CO+IzOs ---+ I z +5CO z
By determining the amount ofCO z or I z produced, the
Esdmadon of Phosphorus percentage of oxygen in the organic compound can be
It is also estimated by Carius method. The organic calculated.
compound containing phosphorus is heated' with fuming
•
The resulting gaseous mixture (CO z and I z ) is passed
nitric acid. Phosphorus is oxidised to phosphoric acid. through potassium iodide which absorbs iodine and the COz
It is precipitated as ammonium phosphomolybdate, left is then absorbed in KOH. Knowing the increase of weight
(NH4) 3 PO 4·12Mo03 by heating it with conc. HN0 3 and then
ofKOH, i.e., the weight ofCO z , the percentage of oxygen can
adding ammonium molybdate. The yellow precipitate is
filtered, washed, dried and weighed .. be calculated.
Alternatively phosphoric acid is precipitated as magne-
sium ammonium phosphate, MgNH4P04, by the addition of
°
16g
=CO===CO z
44 g
magnesia mixture (MgS0 4 + NH 40H + NH 4CI). The
16 Olass of CO 2
magnesium ammonium phosphate -is washed, dried and Percentage of oxygen =-x x 100
ignited when it is converted to magnesium pyrophosphate 44 mass of org. oompd.
(Mg ZPZ0 7 )· NowadaYs, the estimation of elements (C, H and N) in an
organic compound is done by taking only very small (micro)
quantities (about 1-3 mg) of the substance with the help of
instrumental automatic experiment techniques (CRN
Magnesia mixture
H 3P0 4 ) MgNH4P04 elemental analyzer) and the results are obtained on a screen
Phosphoric acid (Mg2+ + NH40H) Magnesium ammonium (LED) within a short time.
phosphate
Heat ILLUSTRAnONS OF OBJEcnVE QUESTIONS
2MgNH4 P04 -~ Mg ZPZ0 7 +2NH3 +HzO
From the mass of magnesium pyrophosphate, the I. Lassaigne's test for the detection of nitrogen will fail in the
percentage of phosphorus in the compound can be calculated. case of:
(a) NH2 CONHZ (b) NHZCONHNH2 ·HCI
Caleulatlons: Mass of organic compound = W g
(c) NH2NH2 ·HCI (d) C6HsNHNH2 ·2HCI
Mass of magnesium pyrophosphate =Wt g [Ans. (c)]
Mg ZPZ 0 7 === 2P [HInt: For Lassaigne's test of nitrogen, compound must
222 g 62g contain N in addition to carbon to form NaCN in sodium
62 W . extract.]
Percentage of phosphorus = - x _1 X 100
222 W Z. The function of boiling the sodium extract with conc. HNO]
EsdOladon of Oxygen before testing for halogen is:
(a) to make the solution acidic
The usual method of determining the percentage of (b) to make the solution clear
oxygen in an· organic compound is by the method of (c) to convert Fe 2+ to Fe 3+
difference. All the elements except oxygen present in the (d) to destroy CN- and Sz- ions
organic compound are estimated and ·the total of their [Ans. (d)]
percentages is subtracted from 100 to get the percentage of [HInt : If N and S are already present, they will hinder in
oxygen. test of halogens as NaCN and Na 2 S will giv" white or black
Percentage of oxygen =100 - (Sum of the percentages precipitate with AgN03' Boiling conc. HN0 3 is thus used .
of all other elements) to remove ~and S2-. ions in the form of volatile HCN
However, a direct method for the estimation of oxygen andH 2 S.]
was discovered in 1947. This is known as Aluise's method. A 3. Sodium nitroprusside when added to an alkaline solution of
known amount of organic compound is subjected to pyrolysis sulphide ions produces a colouration : 1A.J.i'M.C lOM1
(decomposition by heat) in a stream of nitrogen. The oxygen (a) red (b) blue
and other gaseous products formed during pyrolysis are (c) brown (d) purple
.3
Molecular Analysis of Organic Compounds 47
[Ans. (d)] 2. Chemieal methods:
[HInt: Purple (deep violet) colour is due to the fonnation (i) Silver salt method for acids
of sodium thionitroprusside, Na 4 [Fe(CN)s NOS].] (ii) Platinichloride method for bases
4. In Kjeldahl's method, nitrogen present is estimated as: (iii) Volumetric method for both acids and bases
(a) N2 (b) NH3
(c) N0 2 (d) none of these 1. (i) Physical MethiHIs for Volatile Compounds
[Ans. (b)]
[HInt: In this method the nitrogen present is (a) Vidor Meyer's method: Molecular mass of
quantitatively. converted into (NH4 )2 SO 4 on. heating with volatile liquids and solids can be easily determined from the
conc. H2 SO4' The (NH4 )2 SO4 is then treated with standard application of Avogadro hypothesis according to which the
alkali solution to liberate NH3 ' which is absorbed in H2 SO4 mass of 22.4 litres or 22400 mL of the vapour of any volatile
to obtain percentage of nitrogen.] substance at NTP is equal to the molecular mass of the
5. In Kjeldahl's method, nitrogen present' is quantitatively substance.
converted to : In Victor Meyer's method, a known mass of the volatile
(a) N2 (b) (NH4}z SO4 substance is vaporised in a Victor Meyer's tube, The vapours
(c) N0 2 (d) none of these fonned displace an equal volume of air into a graduated tube.
[Ans. (b)] The volume of air collected in graduated tube is measured
6. In Kjeldahl's method of estimation of nitrogen, K2 SO4 acts under experimental conditions. This volume is converted to
as: NTP conditions.
(a) an oxidising agent (b) catalytic agent Calculations: Mass of the organic substance =W g
(c) hydrolysing agent (d) boiling point elevator
[Ans. (d)] Let the volume of the air displaced be VI mL
[Hint: Addition ofK 2S04 increases the boiling point of Temperature =TI K
H 2 S04 ,] Pressure (after deducting aqueous tension) PI mm
7. Positive Beilstein test shows that: Let the volume at NTP be =V2 mL
(a) halogens are surely present
(b) halogens are absent Applying gas equation,
(c) halogens may be present PI XVI 273
Vz x-
(d) none of the above 11 760
[Ans. (c)]
[Hint: Beilstein test is also given by some other 22400 mL of vapours weigh at .NTP = M (mol. mass)
_ compounds such as urea, pyridine thiourea and organic V2 mL of vapours weigh at NTP =W g
acids, etc., which imparts colour to the flame.] W .
8. In an organic compound, the phosphorus is estimated as:
22400 mL of vapours weigh at NTP - x 22400:: M
V2
(AFMC 2010)
(a) Mg 2 Pz 0 7 (b) Mg 3 (P0 4 h or Vapour density of substance
(c) H 3 P04 (d) P2 0 S Mass of I mL of vapours at NTP
[Ans. (a)]
Mass of 1 mL of hydrogen at NTP
2.4 DETERMINATION OF MOLECULAR MASS . W/V
or V.D.= 2
0.00009
The molecular mass of the organic compounds can be
determined by various methods. The methods may be divided W
or V.D.=-~·--
into two groups: V2 xO.000Q9
1. Physical methods: These are of two types: 2W
Mol.mas<;. M=2xV.D.=----
(I) For volatile compounds V2 xO.00009
(a) Victor Meyer's method Note: Alternately volume of the vapours is changed to STP values.
(b) Duma's method (l mol of every gaseous substance has volume 22.4 L at STP)
(c) Hofinann's method s
Problem 9. In a Victor Meyer determination, the
(Ii) For non-volatile compounds following observations have been made:
(a) Ebullioscopic method or elevation in boiling Mass of compound =0.17 g
point method
Volume of air collected =34.2 mL
(b) Cryoscopic method or depression in freezing
P9int method Temperature =15° C
Atmospheric pressure =750 mm
48 G.R.B. Organic Chemistry for Competitzons
. compound.
Problem 10. A Duma s bulb full of air weighs 22.567 g
Solution: Given
at 20°C and 755 mm pressure. Full of vapours of a substance
VI =34.2mL V2 =1 at l20°C and the same pressure, it weighs 22.8617 g. The
NTP
PI = (750 -13) = 737 nnn P2 =760nnn capacity of the bulb is 200 mL. Find out the mo{ecular mass of
) conditions
TI = (l5 +273) =288 K T2 =237K the substance. [Density of air =0.00129 g/mL]
By gas equation, Solution: Given
V = 737x 34.2 x 273 =31.4376 mL VI = volume of bulb = 200 mL V2 = ?
288 760 NTP
2 TI =(20+273)=293K T2 =273K
) conditions
W 0.17 PI = 755 nnn P 2 = 760 nnn
Vapour density = =------ 60.08
V2 x 0.00009 31.4376 x 0.00009 So V2 = Volume of bulb at NTP
Mol. mass = 2 x Vapour density = 2 x 60.08 = 120.16 200x 755 273 18
- - - x - = 5.122mL
(b) Duma's method: The apparatus consists ofa glass 293 760
bulb of about 250 mL capacity with a narrow outlet tube. It is Mass of air = V2 x 0.00129= 185.122x 0.00129
cleaned, dried and weighed at the room temperature. A few
=0.2388g
mL of the organic substance (liquid) is placed in the bulb. The
bulb is now placed in a bath and clamped. The bath consists of Mass of empty bulb = (22.567 - 0.2388)
a liquid having 30-40 0 e higher boiling point than that of the = 22.3282 g
substance whose molecular mass is to be determined. The bath
Mass of vapours = (22.8617 - 22.3282)
is now heated to about 20 0 e higher than the boiling point of
the substance kept inside the bulb. When whole of the = 0.5335 g
substance inside the bulb has vaporised and no more vapours Let the volume of vapours at NTP be V.
come out, the mouth of the bulb is sealed with a blow pipe
flame. The bulb is now taken out of the bath, cleaned and V = 200 x 755 x 273 =138 mL
dried from outside. It is now weighed. The volume of the bulb 393 760
is determined by breaking the enq of the sealed mouth under mass of vapours
Mol. mass of the substance = x 22400
water and weighing the bulb full of water along with broken vol. of vapours at NTP
pieces of glass. ;'
Calculations : = 0.5335 x 22400= 86.59
138
(i) Mass of bulb + air = ffJ. g
(c) Hofmann's method: The method is applied to
(ii) Mass of bulb + vapours = ~ g those substances which are not stable at their boiling points,
(iii) Mass of bulb + water = ~ g but which may be volatilised without decomposition under
Mass of water in bulb = (W3 - ffJ. ) g reduced pressure. A known mass of the substance is vaporised
So Voluine of bulb = (W3 - ffJ. ) mL above a mercury column in a barometric tube and the volume
(iv) Room temperature = TI K and pressure after . of the vapour formed is recorded. It is then reduced to NTP
deducting vapour pressure of water = PI nnn conditions. The molecular mass of the organic substance can
Volume of the air in the bulb at NTP be calculated by the application of following relationship:
mass of the substance 22400
= (~ - ffJ. ) X PI x 273 = V mL 1
M o.mass= x
TI 760 I
volume of the vapours at NTP
MolecUlar mass of the salt = 2E + 2 + 195 + 213 volume ofthe acid solution used, the mass of the organic base
=2E +410 which will require 1000 mL of a normal acid solution for
2E + 410 w MaSs'ofplatinum salt complete neutralisation can be calculated. This mass will be
So, =-= the equivalent mass of the base.
195 x Mass of platinum
,
1000 mL N acid solution == One gram equivalent of the base
I
.
E=!2 [wx x 195 - 410]
Problem 13. 1.575 g ofan organic acid was dissolved in
250 mL of water. 20 mL of this solution required 16 mL of N/8
Mol. ~'of the base = Eq. mass x acidity of the base alkali solution for cf!mplete neutralisation. If the basicity of
. the acid is two, find its molecular mass.
=Exn
Solution:
where n is the acidity of the base.
16 mL N /8 alkali solution == 20 mL of acid solution
Problem 12. 0.49 g of the chloroplatinate of a diacid
2 mL 1 N alkali solution == 20 mL of acid solution
base gave on ignition 0.195 g of platinum. Calculate the
molecular mass of the base. 2 x 250 mL 1 N alkali solution == 250 mL of acid sOlution
20
Solution:
25 mL 1 Nalkali solution == 1.575 g acid
Mol. mass of chloroplatinate Mass of chloroplatinate taken
At. massofplatinum Mass of platinum left 1000 mL 1 N alkali solution == 1.575 xl 000 g acid'
25
0.49 Eq. mass of the acid = 63 g acid
=0~195 MoL mass of the acid = 63 x 2 = 126
Let B be the equivalent mass of the base. Problem 14. 2.65 g of a diacidic base was dissolved in
2B + 410 0.49- . .' N
=-- 500 mL of water. 20 mL of this solution required 12 mL of -
195 0.195 6
Hel solution. Calculate the equivalent mass and molecular
or '2B = [. 0.49 x 195 - 410] =80 mass of the base. .
0.195 .
Solution:
or B=40
Mol. mass of the base = Eq. mass x acidity = 40 x 2 = 80 12 mL N Hel solution == 20 mL of base solution
6
(iii) Volumetric method for acids and bases: The or 2 mL 1 N Hel solution == 20 mL of base solution
molecular mass of an. acid can be determined by dissolving a
known mass of the acid in water and titrating the solution or 2.
20
x 500 mL 1 N Hel solution == 500 mL of base solution
against a standard solution of an alkali using phenolphthalein
or 50 mL 1 N Hel solution == 2.65 g of base
as indicator. Knowing the volume of alkali solution used, the
mass of the acid, which will require 1000 mL of a nonnal 1000 mL 1 N Hel solution == 2.65 xl 000 = 53 g base
alkali solution for complete neutralisation can be calculated. 50
This mass of the' acid will be its equivalent mass. Eq. mass of the base = 53
J000 mL 1 N alkali solution, == One gram equivalent of the acid Mol. mass of the base = Eq. mass x acidity = 53 x 2 = 106
Qne grain equi~alent of alkali
ILLUSTRATIONS OF OBJECTIVE QUESTIONS
Calculafjolis: .Suppose wg of the organic acid requires
.9. Molecular mass of a volatile organic solid can be
V inL N 1 alkali solution for complete neutralisation. determined by:
V mL N 1 aIkali solution == w g acid (a) silver chloride method (b) platinichloride method
(c) Victor Meyer's method (d) Kjeldahl's method
So, lPOOmL Nl alkalisolution w xl000g acid [Ans. (c)]
. . . VxN 1 10. Molecular mass of a non-volatile organic solid can be
== one gram equivalent acid deteimined by:
(a) Victor Meyer's method
Equivalent mass of the a~id == w x 1000'
, -. VxN (b) elevation in boiling point
.. ,. .' • . . 1
(c) silver salt method
Thus, MolecUlar mass of theacid=Eq. mass x basicity (d) depression in freezing point
In the case of organic bases, the khO\tmnlasS of the base is [Ans. (b) and (d)]
titrated
.
against
- . of ~ acid. Knowing the
a standard solutio.
.
-'
Molecular Analysis o{Or~anic Compounds 51
11. Equivalent mass of an organic acid can be determined by: Thus, the simplest formula of a substance capable of
(a) silver salt method (b) cryoscopic method expressing its percentage composition can be called its
(c) ebullioscopic method (d) platinichloride method empirical formula.
[Ans. (a)] Calculation of empirical formula: Empirical formula
U. Equivalent mass of an organic base can be determined by: is calculated from the percentage composition. The steps
(a) silver salt method involved in the calculation are as follows: .
(b) depression in freezing point Step 1: The percentage of each eli~ment is divided by
(c) elevation in boiling point its atomic mass. This gives the relative number of different
(d) platinichloride method atonis present in the molecule.
[Ans. (d)]
Step 2: The relative numbers of different atoms
2.5 EMPIRICAL FORMULA AND MOLECULAR obtained in Step I are divided by the lowest one amongst them
as to get simple ratio of atoms present in the molecule. .
FORMULA
Step 3: .The values obtained in Step 2 mayor may not
The empirical formula of a compound is the simplest be whole numbers. In case one or more values are fractional,
formula which expresses the simple whole number ratio of these are multiplied by a suitable integer to get" simplest ratio
the atoms of constituent elements present in the molecule. in whole numbers. Minor fractions are neglected.
For example, CH 20 is the empirical formula of acetic acid. It Step 4: . The symbols of each element .present are
expresses that the simplest whole number ratio between written side by side in a line with the number of atoms as
carbon, hydrogen and oxygen atoms present in one molecule determined in Step 2 or Step 3 as subscripts to the lower
of acetic acid is I :2 : l. The empirical fOmiula does not tell us corner of each. This gives the empirical or simplest formula.
the exact number of various atoms of different elements Knowing the empirical formula, the molecular formula
present in one molecule of the substance. However, the exact can be ascertained if the molecular mass of the substance is
number of atoms of different elements present in one molecule known. It may be the same as the empirical formula of the
is always a simple multiple of ratio of atoms in the empirical substance or an exact multiple of it.
formula. The formula which gives the actual number of
Molecular formula;;;: n X (Empirical formula)
atoms of various eh~inents present in tbe molecule of the
substance is termed the molecular formula. The value of 'n' can be determined if molecular mass of
Thus, Molecular formula =n X [Empirical formula] the substance is known.
where n is a whole number. Molecular mass
n=--------
Molecular formula of acetic acid = 2 x Empirical formula Empirical formula mass
=2xCH 20 An alternative method of molecular formula·
=C 2H 40 2(CH 3COOH) determination. ..
In this method, molecular formula can be determined
The value of'n' can be obtained by dividing the molecular
without determining empirical formula. It is very simple
mass by empirical formula mass. . .
method and comparatively less time taking.
Molecular mass Following relation is used to calculate number of moles of .
n=--------
Empirical formula mass an element in the compound.:". ..Jtt.~
Solution : .. ' Cal~ulation of eml2irical formula : Problem 18. Haemoglobin is a chromoprotein having
four atoms of Fe in each molecule. AnalysiS showed 0.35%
Jlemeot ~t Relative number8lmplest ratio
Percentage mass of atoms. . ofatoms Fe. Whatis the molecular weight of haemoglobin?
. Solution: Atomic mass of iron =56 amu
34.62 12 34.62 =2.88 . 2.88 ~ I X 3 = 3 ' Mass of iron in a molecule of haemoglobin
12, ' 2.88
. ..,. = 56 x 4 = 224 anru
'Hydrogen 3.84 1 3.84 = 3.84 3.84:::: 1.33 x 3 =4
1 2.88 ': 0.35 amu of Fe is present in 100 amu of haemoglobin
61.54 .16 .61.54 = 3.84 3.84 = 1.33 x3= 4 :. 224 amu of Fe will be present in 100 x 224 amu. of
Oxygen (by difference) . 16 2.88 . 0.35
. Empiri~al fopnula of the acid = C 3 H 40 4 . .... haemoglobin, i.e., 64000 amu
Thus; molecular mass of haemoglobin = 64000 amu
. 'Empiricalf~rmulamasS=" (3 x 12)+ (~ ~ l)'if- (4 x 16}
=104, '
2.6 MOLECULAR FORMULA OF GASEOUS
Calculation of molecular mass: HYDROCARBONS
, 20mLO.l NNaOHso..1075g,acid
20xO.l mL I, N NaOH =O.I075g acid . The molecular formula of g~seous hydrocarbons caribe'
'. " . '0.1075 ; - . determined even without knowing their percentage
So·,·1000mL1 N NaOH= 20 Xl000g acid composition. A .known volume of hydrocarbon is taken in
, xO.l eudiometer tpbe and exploded wit~ an excess of known
Molecular Analysis of Organic Compounds 53
volume of oxygen. The carbon and hydrogen of the 25 mL On adding a concentrated solution of potassium
hydrocarbon are oxidised to carbon dioxide and water hydroxide, the volume -forther diminished to 15 mL, the
respectively according to the following general reaction : residual gas being pure 'oxygen. All volumes have been
+(X+~)02 ~ ~
reduced to NTP. Calculate the molecular formula of the
CxHy xC0 2 + H 20 hydrocarbon gas. .
Solution: Letthe formula of the hydrocarbon beCxHy-
After explosion, the tube is allowed to cool to. room
temperature. The volume of the gaseous mixture is reco~ded. Its combustion can be shown by the following equation:
The volume corresponds to unreacted oxygen ang carbon
dioxide. The volume of carbon dioxide is determined by the CxHy + (X+~)02 ~ xC0 2 +fH 20
decrease in volume of the gaseous mixture when caustic
potash solution is introduced into the eudiometer tube. The 1 vol. x vo!'
caustic potash solution absorbs whole of carbon dioxide. The
gas left behind is the unreacted oxygen. Volume of oxygen 5 mL S(x + i) mL 5x vol.
used is then calculated by subtracting the volume ofunreacted
oxygen from the total volume of the oxygen taken initially. Volume of carbon dioxide produced = (25 - 15) = 10 mL
The molecular formula of the hydrocarbon can be 5x =10 .
evaluated by knowing (i) the volume of gaseous hydrocarbon or x=2
taken, (U) the volume of oxygen used, and (iii) the volume of Volume of oxygen used = (30 -15) = 15 mL
carbon dioxide produced.
y] Y15
ILLUSTRATIONS OF OBJECTIVE QUESTIONS [ 4 =15
5 x+ or x+ 4 ="5=3
Y
4
(x+~)o~ ~
(c) C6 H12 (d) C6 HI4
[Ans. (a)] i.e., Hexa-I,3,5-triene CxHy + xC0 2 +fH 20
t (H2C=CH-CH=CH-CH=CH2 )
lBint : Moles of H2 taken up
3
IOxmL
: 8.40 X 10- == 3.75 X 10-4
The first reduction in volume after explosion
22.4
Moles of compound:
10.02 x 10-3
22.4
: 1.253 x 10-4 : 10 + 10 [x + : J-lOx =20
Thus, moles of H2 taken up by 1 mole of compound
: 3.75 X 10-4 =3 =10+. lOy
4
=20
1.253 X 10-4
10x4
Therefore, molecules has three double bonds and it may be Thus, y==--=4
10
hexa-l ,3 ,5-triene.]
Volume of carbon dioxide produced =20 mL
Problem 19. :;'mL of a gas containing only carbon and
Thus, lOx == 20
hydrogen were mixed with an excess OJ 'oxygen (30 mL) and 20
the mixture exploded by means of an electric spark. After the x=-=2
10
explosion, the volume of ihe mixed gases remaining was-
... . Henc,e, the molecular formula. of the hydrocarbon: C2 H4
":
. \
54 G.R.B. Organic Chemistry for Competitions
2.7 MODERN METHODS OF STRUCTURE Most ofthese ions carry a unit positive charge. The parent
ELUCIDATION molecular ion possess so much excess energy that' they often
brea~ up to give new smaller positive ions called fragment
Several new techniques have been designed during the ions through various bond cleavages.
last three or four decades which help in complete elucidation ABC+
of the structure of an organic compound. These techniques not
only help in determination of the molecular mass and various .ABC electric beam-E AB+C+
functional groups present in the molecule but also help to A+BC+
detemrine the complete three-dimensional structure of the . For example, a molecule of 2,2-dimethyl propane
molecule including bond length and bond angle, etc. These (neo-pentane) may break up as:
methods are broadly divided into two groups:
CH 3
. roscopic methods: These methods are based
either on the absorption or radiation or the emission of I
(CH3)4C or CH 3 -C-CH 3 C SHt2 +e-,
radiation. The molecular mass is easily determined by the use
of Mass spectrometry. The infrared(IR), ultraviolet (UV),
I Parent ion
(Mass 72)
CH 3
and nuclear magnetic resonance (NMR) techniques are used 2,2-Dimethyl propane (CSH12)
these days to detect the presence of functional groups in the
molecule. C4H; (Mass 57)
~hifraction methods: X-ray diffraction, neutron CSH12 C 3 H; (Mass = 43)
diffraction and electron diffraction techniques are
commonly used to determine the three-dimensional structure. - E C 2 H; (Mass = 29)
These methods also help in the measurement of bond lengths . Energy required to knock ion from an electron (ionisation
and bond angles. potential) is only about 10-15 eY. Since, energy of the
electron in practice is approximately 50-75 eV, the molecular
. Mass Spectrometry ion is fonned with an excess energy which is large enough to
Mass spectrometry is the most accurate method for further break it down into a mixture of neutral and positively
determining the molecular mass of a compound and its charged fragments. '
elemental composition like molecular formula and molecular Each kind of ion has a particular mass-to-charge ratio or
structure of an unknown compound. When the vapour of a mlZ value. For most of the ions, the charge (Z) is (i- 1), so that
compound in high vacuum is bombarded with a moving beam mlZ usually represents the mass of the ion. All positive ions
of high energy electrons (::::. 70eV), ionisation of some are accelerated in an electric field and then passed through a
molecule occurs with the formation of a radical cation. magnetic field when these get separated. Ions having the same
Molecule+e- ~ (Moleculet +2e- mass to charge ratio are, thus collected into beams.
(M) Radical cation (or M+) Gases, liquids or solids may be used in the determination
of mass spectra.
4
Molecular Analysis of Organic Compounds 55
J
Molecular Analysis ofOrganic Compounds 57
silver nitrate is heated at 300°C for six hours in the (g) Estimation of carbon 7. Kjeldahl's method
estimation of halogens. and hydrogen in an
(r) In Kjeldahl's method, during digestion of the organic organic compound
compound with conc. H 2S04, potassium sulphate and 5. Complete the following:
sodiuni' sulphate are also added.
H+
(s) An organic compound containing nitrogen, on heating (i) (CH 3COOhPb+Na 2S ~ ...... + ..... .
strongly with H2 SO4 gives ammonium sulphate which
(ii) Fe3+ + 3NaCNS ~ ...... + ..... .
on treatment with excess ofNaOH liberates ammonia.
(t) The simplest formula that shows the ratio of the atoms (iii) NaI + AgN03 ~ ...... + ..... .
of the various elements present in the molecule is (iv) 4FeCl 3 + 3Na4Fe(CN)6 ~ ...... + ..... .
called the molecular formula. (v) FeS0 4 + 6NaCN ~ ...... + ..... .
(u) The molecular mass of a non-volatile organic com-
(vi) Na2S+Na2Fe(CNhNO ~ ..... .
pound is determined either by the Victor Meyer's.
method or Duma's method. (vii) (NH4 h S04 + 2NaOH ~ ...... + ...... + .... ..
(v) The gas displaced in Victor Meyer's method is air.. (viii) 5CO+I20 5 ~ •••.•. + ..... .
(w) The gas estimated in Duma's method is nitrogen. (ix) RCOONH4 + AgN03 ~ ...... + ..... .
(x) A Lassaigne's solution is boiled with dilute HN0 3 ,
cooled and AgN03 .added. It gives a yellow precipi- (x) CxHy +(X+~)02 ~ ...... + ..... .
tate, sparingly soluble in ammonia. This indicates the
presence of iodine in the organic compound. ~ SH"OaT AN,SWER TYPE
(y) A black precipitate is formed when lead acetate 6. Describe the following:
solution is added to acidified sodium extract of an
(i)' Chemistry of Lassaigne's test for the detection of
organic compound containing sulphur.
. nitrogen in an organic compound.
(z) Copper wire is used in Beilstein test.
(ii) Chemistry of Lassaigne's test for the detection of
3. Give reasons:
sulphur in an organic compound.
(i) During the test for nitrogen in Lassaigne's filtrate,
(iii) Chemistry of Lassaigne's test for the detection of
sometimes red colouration is' obtained when ferric
halogens in an organic compound.
chloride is added.
(iv) Chemistry of Kj~ldahl's method for the estimation of
(ii) Why is sodium extract made acidic with acetic acid
nitrogen in an organic compound.
before the addition oflead acetate in the test of sulphur?
(v) Platinichloride method of determination of molecular
(iii)' In the test of nitrogen, freshly prepared solution of
mass of an organic base.
ferrous sulphate is always used.
(vi) Silver salt method of determination of molecular
(iv) During the test for halogens, why is sodium extract
mass of an organic acid.
first boiled with a few drops of conc. HN0 3 ? (vii) Principle of Duma's method for the estimation of
(v) Why the organic compound is fused with sodium metal nitrogen in an organic compound
during detection of nitrogen, sulphur, halogens, etc.? (viii) Liebig method for the estimation of carbon and
(vi) What is the role of copper sulphate and potassium hydrogen in an organic compound.
sulphate in Kjeldahl's process for the estimation of (ix) Carius method for the estimation of sulphur in an
nitrogen in an organic compound?
organic compound.
(vii) Is Beilstein test a satisfactory test for detection of
(x) Carius method for the estimation of halogens in an
halogens?
organic compound.
4. Match the following:
fl.'operty to be Method used for (xi) How is molecular formula of a hydrocarbon derived
determined determination by eudiometry?
(xii) The difference between empirical and molecular
(a) Molecular mass of a I. Silver sMt method formula and the relationship between them.
volatile organic solid (xiii) Layer test for bromine ana iodine in an organic
(b) Molecular mass of a non- 2. Liebig method compound.
volatile organic solid (xiv) Aluise's method for the estimation of oxygen in an
(c) Estimation of chlorine 3. Platinichloride method organic compound.
in carbon tetrachloride (xv) Beilstein test or copper wire test.
(d) Estimation of nitrogen 4. Victor Meyer's method
""".. j:_liiliMANSWERS·:ish· - =!t'_':,'1,~~
in l;Uliline
.
1. (a) nitrogen; halogens; (b) sodium su1phide', (c) sodium cyanide;s..
(e) Equivalent mass of an 5. Depression in freezing
. u1 hate' (f) HCN and H 2 ,
organic acid point (d) sulphur; (e) ammoruum s p. ' d' (k) acidity"
(f) Equivalent mass of an 6; Carius method (g) H 2S04; (h) nitrogen; (i) AgN0 3; (j) blu~coIO:. (0) simp';
(I) silver salt; (rn) equivalent mass; (n) eu orne •her ..
organic base ratio of atoms of constituent elements; (P) actual num
58 G.R.B. Organic Chemistry for Competitions
(q) Molecular mass . (r) CH; (s) CH 20; (t) 30; (ii) Lead acetate is hydrolysed by NaOH present in sodium ex-
Empirical formula mass' tract. It is neutralised first with acetic acid before the addi-
(u) phosphorus; (v) CO 2 , S02; (w) NaCNS; (x) 75; (y) mass of tion of lead acetate.
platinum salt; (z) two. (iii) Ferrous sulphate gets hydrolysed if its solution is stored.
2. (a) False-hydrogen is not always present; (b) True; (iv) As to decompose NaCN or NazSifpresent in the sodium extract.
(c) False-sometimes the test fails; (d) True; (v) As to convert nitrogen, sulphur or halogens present in an or-
(e) False-molecular mass of an acid = equivalent ganic compound into ionisable substances.
mass x basicity; (t) False-used for a volatile compound; (vi) Copper sulphate acts as a catalyst white potassium sulphate
(g) True; (h) True; (0 False-the fmal product formed is raises the boiling point of H 2S04,
ferri-ferro cyanide; (j) False-not applicable to pyridine, (vii) It is not always reliable. Substances such as urea, thiourea,
compounds containing N-N, N-O, etc. bonds; (k) True; pyridine, organic acids, etc., also impart colour to flame.
.(1) False-dry CuO is used; (m) True; (n) True; (0) False-for 4. (a-4); (b-5); (c-<i); (d-7); (e-l); (f-3); (g-2) .
the determination of equivalent mass of organic acids; (P) True; 5; (i) 2CH 3COONa + PbS 0:) Fe(CNS)3 + 3Na+
(q) True; (r) False-potassium sulphate and copper sulphate are
(iii) AgI + NaN0 3 (iv) Fe4[Fe(CNk;h+ 12NaCI
added; (s) True; (t) False-is called empirical formula;
(v) Na4[Fe(CNk;] + Na2S04 (vi) Na4[Fe(CN)sNOS]
(u) False-determined by either elevation in boiling point method
(vii) 2NH3 + Na 2S0 4 + 2H 20 (viii) 12 + 5C02
or depression in freezing point method; (v) True; (w) True;
(x) False-indicates the presence of bromine; (y) True; (z) True. (ix) RCOOAg + NH4N03 (x) xC0 z + ~ H20
3. (i) When nitrogen and sulphur both are present in an organic 2
compound, sodium thiocyanate is formed which gives red
colouration with FeC1 3•
1. 0.45 g of an organic compound gave on combustion 0.792 g 6. 0.33 mole cholesterol gives 9 mole CO 2 on combustion. It
of CO 2 and 0.324 g of water. 0.24 g of the same substance was observed that cholesterol contains 83.85% C; 12% H
was Kjeldahlised and the ammonia fonned was absorbed in and 4.15% 0. Find its molecular fonnula and molecular
50 mL of 0.25 N H 2S04 , The excess of acid required mass.
77.0 mL of 0.1 N NaOH for complete neutralisation. IAns. C z7 H 4P; 386)
Calculate the empirical fonnula of the compound.
7. An automobile antifreeze consists of 38.7% carbon; 9.7%
(Ans. C4HsNzOl
hydrogen and remaining oxygen by weight. When 0.93 g of
2. A compound contains 40% C, 6.66%. Hand 53.33% 0.
it are vaporised at 200°C and 1 atm pressure, 582 mL of
An examination reveals that 9.0 g of the compound
vapour are formed. Find molecular fonnula of antifreeze.
dissolved in 500 g of water raises the boiling point of
(Ans. C zHp zl
water by 0.051°C. What is the molecular fonnula of the
8. The compound [Pd(CxHyN z )](CI0 4 h contains 30.15%
compound? [Kf =0.51Kmor l kg]
carbon and 5.06% hydrogen. The compound
(Ans. CJllz061
3. Tyrosine is one of the amino acids present in protein. Its [Pd(CXHyN z )](SCN)2 contains 40.46% carbon and 5.94%
content in the protein is 0.22% and its molecular weight is hydrogen. Calculate x, y, Z.
181 g mol-l. What is the lowest molecular weight of the IAns. x=14,y=ZS,z=4)
protein? 9. Methyl orange, an acid base indicator, is the sodium salt of
(Ans. 82272) an acid that contains C, H, N, S and oxygen. Quantitative
4. A molecule was known by its mode of synthesis to contain analysis gave C = 51.4%, H = 4.3%, N = 12.8%, S = 9.8%
10 atoms of carbon per molecule, along with unknown and Na = 7.0%. What is the empirical fonnula of methyl
number of chlorine, hydrogen and oxygen. Analysis orange?
indicates that it contains 60.5% carbon, 5.55% hydrogen, IAns. CI4HI4N3S03Nal
16.1% oxygen and 17.9% chlorine. Derive molecular 10. The sulphur content of cystine is 26.7%. Given that cystine
formula. contains two sulphur atoms, what is the molecular weight of
(Ans. CloHnO:zCI) . cystine?
5. A w~lding fuel gas con~carbon and hydrogen only. IAns. 239.7 g)
Bummg a small sample of It m oxygen gives 3.38 g carbon (Bint: Atomic mass of sulphur is 32, hence for two sulphur
dioxide, 0.690 g of water and no other products. A volume atoms, the molecular formula will have 64 g sulphur.
of 10 litre (measured at STP) of this welding gas is found to Thus, if 26.7 g sulphur, then molecular weight = toO g.
weigh 11.6 g. Calculate (i) empirical formula (ii) molar and if 64 g sulphur is present, molecular weight
mass of the gas (iii) molecular formula. 100x64 .
= ~-- = 239.7 g morl]
[Ans. (i) CH z (Ii) 26 (iii) CzH z) 26.7
1m!'
MolecularAnalysis o/Organic Compounds 59
;:-""~ ~ ~
_~~~~08JEClIVE
- < - , • .. • - ,
'.
OUESIIOIS I,,~
.-
_. _ _ _ _~~.~:
SET I ! This set contains the questions with single correct answer. (a) nitrogen 0 (b) phosphorus 0
1. Carbon and hydrogen are estimated in organic compounds by: (c) sulphur 0 (d) chlorine 0
(a) Kjeldahl's method 0 (b) Duma's method 0 11. Which of the following compounds gives blood red
(c) Liebig's method 0 (d) Carius method 0 colouration when its Lassaigne's extract is treated with
2. Lassaigne's test is used for the detection of: alkali and ferric chloride? [DPMT 2009]
(a) carbon only 0 (a) Thiourea 0 (b) Benzamide 0
(c) Phenyl hydrazine 0 (d) Diphenyl sulphide 0
(b) hydrogen only "\ • 0
12. Copper wire test of halogens is known as:
(c) oxygen only 0
(a) Liebig's test 0 (b) Lassaigne's test 0
(d) nitrogen, sulphur and halogens 0 (c) Fusion test 0 (d) Beilstein's test 0
l. In Lassaigne's test, the organic compound is fused with 13. Duma's method involves the determination of nitrogen
sodium metal as to: .
content in the organic compound in the form of :
(a) hydrolyse the compound 0 [BBU 2005]
(b) form a sodium derivative 0 (a) NH3 0 (b) N2 0
(c) convert nitrogen, sulphur or halogens if present into
soluble ionic sodium compound 0 (c) NaCN 0 (d) (NH4)2S04 0
(d) burn the compound 0 14. In Lassaigne's solutio!1. pink/violet colouration is produced
4. Nitrogen containing organic compound when fused with when sodium nitroprusside solution is added. It indicates
sodium metal forms: [CET (Karnataka) 2006) the presence of:
(a) NaN0 2 0 (b) NaCN 0 (a) sulphur 0 (b) nitrogen 0
(c) chlorine 0 (d) none of these 0
(c)NaNH 2 0 (d) NaNC 0 IS. An organic compound on heating with CuO produces CO2
S. The sodium extract of an
organic compound on treatment but no water. It may b~ ,
with FeS04 solution, FeCl 3 and RCI gives a red solution.
The organic compound contains:
(a) CR4 0 (b) C2RsI 0
(a) both nitrogen and sulphur 0 (c) CRCl 3 J 0 (d) CCl 4 0
(b) nitrogen only . 0 16. In an organic compound, Kjeldahl's method is used for the
(c) sulphur only 0 estimation of:
(d) halogen 0 (a) halogens 0 (b) sulphur 0
6. The prussian blue colour obtained during the test of (c) nitrogen 0 (d) oxygen 0
nitrogen by Lassaigne's test is due to the formation of: 17. In Lassaigne's test for the detection of halogens, the sodium
[AIEEE 2004; AFMC 2010) . fusion extract is fIrst boiled with concentrated nitric acid.
This is : [PET (Kerala) 2010)
(a) Fe4[Fe(CN)6h 0 (b) Na3[Fe(CN)6] 0
(a) to remove silver halides 0
. (c) Fe(CN)3 0 (d) Na4[Fe(CN)sNOS] 0 (b) to decompose Na2Sand NaCN, ifpresent 0
7. Which of the following sodium compound/compounds are
,
(c) to dissolve Ag 2S 0
formed "when an organic compound containing both
nitrogen and sulphur is fused with sodium? (d) to dissolve A-gCN, if formed 0
(e) because Ag 2S and AgCN are insoluble in nitric acid
(a) Cyanide and sulphide 0 (b) Thiocyanate 0
o
(a) benzaldehyde 0 (b) benzoic acid 0 31. In the estimation of carbon and hydrogen, if the substance
(c) aniline 0 (d) chlorobenzene 0 also contains both halogen and SUlphur, then near the exit, it
21. In organic compounds, halogens are estimated by: is placed:
(a) Carius method 0 (b) Liebig's method 0 (a) a roll of silver 0
(c) Kjeldahl's method 0 (d) Duma's method 0 (b) a layer of lead chromate 0
22. In the estimation of sulphur in an organic compound, (c) a bright copper gauge spiral 0
fuming nitric acid is used to convert sulphur into: (d) none of the above 0
(a) S02 0 (b) H 2S 0 32. In carbon and hydrogen estimation, the saphnolite (a resin)
(c) H Z S0 3 0 (d) H 2 S04 0 absorbs:
23. Schiff's and Piria method is used for the estimation of: (a) N2 0 (b) water vapours 0
(a) nitrogen 0 (b) sulphur 0 (c) both COz and H 20 0 (d) only CO2 0
(c) halogens 0 (d) oxygen 0 33. Catalyst used in Kjeldahl's method for the estimation of
24. Prussian blue colour is obtained by mixing together aqueous nitrogen is:
solution ofFe 3+ salt with: tCET (J&"K) ~OO11 (a) sodium 0 (b) magnesium 0
(a) ferricyanide 0 (b) ferrocyanide 0 (c) mercury 0 (d) copper 0
(c) hydrogen cyanide 0 (d) sodium cyanide 0 34. Formula which represents a simple ratio of atoms of
2S. The blood red colour in the combination test of nitrogen and different elements present in a molecule of the substance is
sulphur in organic compound is due to the formation of: called:
(a) ferric sulpho cyanide 0 (a) molecular formula 0 (b) empirical formula 0
(b) ferric acetate [J (c) structural formula 0 (d) none of these 0
(c) ferrous sulpho cyanide 0 3S. An organic compound contains carbon, hydrogen and
(d) ferric cyanide 0 oxygen. Its elemental analysis gave C, 38.71% and H,
9.67%. The empirical formula of the compound would be:
26. The violet colour obtained during the test of sulphur by
, (CME (M~~ a_I
,'M'f
Lassaigne's test is due to the formation of:
(a) Naz[Fe(CN)sS]
(K~ftliij 1M\ CM(; (V@U{)f'@) 1-1
0 (b) Na2[Fe(CN)sNO] 0
(a) CHzO
(c) CH 3 0
0 (b) CH4 0
0 (d) CHO
0
0
36. An alkaloid contains 17.28% of nitrogen aiid its molecular
(c) Naz[Fe(CN)6] 0 (d) Na4[Fe(CNhNOS] 0
mass is 162. The number of nitrogen atoms present in one
27. Chloro acetic acid is heated with fuming nitric acid in molecule of alkaloid is: ('''\\jiD CiT (bg.) I . ,
presence of AgN03 in Carius tube. After filtration and (a) 3 0 (b) 2 0
washing, a white precipitate is obtained. This precipitate is:
(c) 5 0 (d) 4 0
(a) AgN03 0 (b) Ag 20 0 37. A hydrocarbon contains 10.5 g carbon and 1 g hydrogen. Its
(c) AgCI 0 (d) CICHzCOOAg 0 0.36 g has I litre volume at 1 atm and 1270 C, the
28. Mark the incorrect statement in nitrogen Kjeldahl's method hydrocarbon is: (U'.ftAT ""l
of estimation: (a) C6H7 0 (b) C 7Hg 0
(a) nitrogen gas is collected over caustic potash solution
. 0 (c) CSH6 0 (d) None of these 0
38. Which of the following reagents is used for the separation
(b) potassium sulphate is used as boiling point elevator of
H 2 S04 0
of acetaldehyde from acetophenone? . 'An~ I..)
(a) NH 20H 0 (b) NaOHIz 0
(c) copper sulphate or mercury acts as a catalyst 0
(d) nitrogen is quantitatively decomposed to give
(c) NaHS0 3 0 (d) C6 H sNHNH z 0
ammonium sulphate 0 39. The formula of gas is [CO]x' If its vapour density is 70, the
29. In the estimation of carbon and hydrogen, if the substance value of x will be: tOCll ~l
also contains nitrogen, then near the exit, it is placed: (a) 2.5 0 (b) 3.0 0
(a) a roll of silver 0 (c) 5.0 0 (d) 6.0 0
(b) a bright copper gauge spiral 0 40. The ammonia evolved from the treatment of 0.30 g of an
(c) ammonium sulphate 0 organic compound for the estimation of nitrogen was passed
(d) a layer of lead chromate 0 in 100 mL of 0.1 M sulphuric acid. The excess of acid
30. In the estimation of carbon and hydrogen, if the substance
" required 20 mL of 0.5 M sodium hydroxide solution for
also contains halogens, then near the exjt, it is placed:
complete neutralization. The organic compound is:
(a) a roll of silver 0
~liU*,,'
(b) a layer oflead chromate 0
(c) both, a roll of silver and a layer of lead chromate 0
(a) urea o (b) thiourea 0
(d) a bright copper gauge spIral 0
(c) acetamide o (d) benzamide 0
Iiiiir---'--------------_______________________--'-
Molecular Analysis of Organic Compounds 61.
41. How will you separate a solution (miscible) of benzene 49. Match the fo!19wing:
+ CHCl 3? (AFMC 200S) Property to be Metbod used for
(a) Sublimation 0 (b) Filtration 0 determined determination
(c) Distillation 0 (d) Crystallisation 0
42. An organic compound having molecular mass 60 is found to (A) Estimation of carbon and hydrogen (i) Lassaigne's test
contain C = 20%, H = 6.67% and N = 46.67% while rest is in an organic compound
oxygen. On heating it gives NH3 along with a solid residue. (B) Estimation of nitrogen in aniline (H) Carius method
The solid residue gives violet colour with alkaline copper (C) Estimation of chlorine in carbon (Hi) Liebig's method
sulphate solution. The compound is: tetrachloride
. (AIEEE 2005; PMT (Kenta) 2008) (D) Detection of nitrogen, sulphur and (iv) Kjeldahl's method
(a) CH3NCO 0 (b) CH3 CONH2 0 halogens .
(c) (NH4 hCO 0 (d) CH3CH2 CONH2 0
ABC D
43. A compound containing only carbon, hydrogen and oxygen,
(a) (i) (ii) (iii) (iv)
has a molecular weight of 44. On complete oxidation it is
converted into a compound of molecular weight 60. The (b) (iv) (iii) (i) (ii)
original compound is: (KCET 200S) (c) (ii) (i) (iv) (iii)
(a) an aldehyde 0 (b) an acid 0 (d) (iii) (iv) (ii) (i)
(c) an alcohol 0 (d) an ether 0 SO. Match the following:
(A) Equivalent mass of an organic acid (i) Depression in
44. 29.5 mg of an organic compound containing nitrogen was freezing point
digested according to Kjeldahl's method aildthe evolved
(B) Equivalent mass of an organic base (ii) Victor Meyer's
ammonia was absorbed in 20 ml of 0.1 MHCI solution. The
method
excess of acid required 15 mlofO,1 MNaOH solution for
(C) Molecular mass of a volatile or- (iii) Platinichloride
complete neutralisation, The percentage of nitrogen in the
gamc solid method
compound is': (AIEEE 2010)
(a) 29,S 0 (b) 59.0 0 (D) Molecular mass of a non-volatile (iv) Silver .salt method
organic solid
(c) 23.7 0 (d) 47.4 0
45~ An aromatic hydrocarbon with empirical formula C SH.4 on B C D
A
treatment with concentrated H2 SO 4 gave a monosulphonic (a) (iv) (iii) (ii) (i)
acid. 0.104 g of the acid required 10 ml of N/20 NaOH for (b) (i) (ii) (iii) (iv)
complete neutralisation. The molecular formula of (c) (iii) (i) (iv) (ii)
hydrocarbon is: (PET (Kerala) 2007]
(d) (ii) (iv) (i) (iii)
(a) CSH4 0 (b) ClOHg 0
SET II: This set contains the questions with one or more correct
(c) CI5 H 12 0 (d) C2o H16 0 answers.
(e) C 1s H 20 0 51. Which of the following compo,unds may give blood red
46. When 20 g ofnaphthoic acid (CII Hg O2 )is dissolved in 50 g colouration while performing Lassaigne's test for nitrogen?
of benzene (K f = 1.72 K kg mol-I), a freezing point (a) (NH2)2CO 0 (b) (NH2hC=S 0
depression of 2K is observed. The van't Hoff factor (0 is: (c) p-NH2 C6H4 S0 3H 0 (d) C6HsS03H 0
(lIT 2007) 52. The desiccants used for absorbing water during Liebig's
(a) 0.5 0 (b) I 0 method for estimation of carbon and hydrogen are:
~2 0003 0 (a) Anhydrous CaCl 2 0 (b) Anhydrous Na2S04 0
47. Sodium fusion extract, obtained from aniline, on treatment
with iron (II) sulphate and H2 SO4 in presence of air gives a
(c) MgS04 ·7H20 0 (d) Mg(CI0 4 h 0
prussian blue precipitate. The blue colour is due to the 53. The empirical formula of a compound is CH 2. To which of
formation of: [liT 2007) the hydrocarbon series does it belong?
(a) Fe4[Fe(CN)6h 0 (b) Fe3 [Fe(CN)6h 0 (a) Alkanes· 0 (b) Alkenes 0
(c) Fe4[Fe(CN)6h' 0 (d) Fe3[Fe(CN)6h 0 (c) Alkynds 0 (d) Cydoalkanes 0
48. CamphOr is often used in molecular mass determination . 54. An organic compound contains about 52% carbon. Ii could
because: (UGET (Meet) 2007) be:
(a) it is readily available 0 (a) ethanol 0 (b) dimethyl ether 0
(b) it, has a very high cryoscopic constant 0 . , (c) acetic acid 0 (d) phenol 0
(c) it is volatile 0 55. Presence of halogen in a compound is tested by:
(d) it is solvent for organic substances 0 (a) Iodoform test 0 (b) Millon's test 0
(c) Silver nitrate test 0 (d) Beilstein test 0
62 G.R.B. Organic Chemistry for Comvetitions
56. The weights of carbon, hydrogen and oxygen in an organic (c) C6H 5 CI o
compound are in the ratio 6: 1 : 8 respectively. The (d) 2,6,6-Trinitrochlorobenzene o
molecular formula of the compound may be: , 58. Violet coloured complex obtained in the detection of
(a) CHzO D (b) CZH40Z 0 sulphur is: [AFMe 2010]
(c) CHzOz 0 (d) C3 H 6 0 3 (a) Naz[Fe(NO)(CN)sl D
57. Which of the organic compounds will give white precipitate (b) Na3[Fe(ONSNa)(CN,s] D
with AgN03?
(c) Na4[Fe(CN)sNOS] o
(a) C6HSNH;CI- 0
(d) both (b) and (c) Cl
(b) NaCI 0
,ANSWERSJ
OBJECTIVE QUESTIONS
1. (c) 2. (d) 3. (c) 4. (b) 5. (a) 6. (a) 7. (b) 8. (d) 9. (c) 10. (b)
11. (a) 12. (d) 13. (b) 14. (a) 15. (d) 16. (c) 17. (b) 18. (c) 19. (a) 20. (d)
21. (a) 22. (d) 23. (c) 24. (b) 25. (a) 26. (d) 27. (c) 28. (a) 29. (b) 30. (c)
31. (b) 32. (d) 33. (c) 34. (b) 35. (c) 36. (b) 37. (b) 38. (c) 39. (c) 40. (a)
41. (c) 42. (c) 43. (a) 44. (c) 45. (c) 46. (a) 47. (a) 48. (c) 49. (d) 50. (a)
51. (b,c) 52. (a,d) 53. (b,d) 54. (a,b) 55. (c,d) 56. (a,b,d) 57. (a,d) 58. (d)
1. (d) 2. (a) 3. (a) 4. (c) 5. (c) 6. (b) 7. (a) 8. (a) 9. (d) 10. (b)
11. (a) 12. (b)
64 G.R.B. Organic Chemistry for Competitions
1. Which among the following is not correctly matched with 7. 9.9 g amide with molecular formula C4H sN x O y on heating
their colour? with alkali liberated 1.7 g of ammonia. If the pe1:Centage of
Compound Colour oxygen is 33.33% then the ratio of 'N' and '0' atoms in the
(a) Na4[Fe(CN)sNOS] purple o compound is:
(b) Fe4[Fe(CN)6h blue 0 (a) 1 : 1 0 (b) I : 2 0
(c) Fe(CNSh blood red 0 (c) 2 : 3 0 (d) 3 : 2 0
[Hint: Amide C4HS NxO y will give x mol NH 3•
(d) AgCI light yellow 0
2. In case, nitrogen and sulphur both are present in an organic :. Molecular mass of amide = 9.9 x 17x 99x
1.7
compound, sodium thiocyanate is formed. If sodium fusion
is carried out with excess of sodium, sodium thiocyanate % Nitrogen in the amide = 14x x 100= 14.14
decomposes. Which of the following compounds is/are 99x
present in the extract after decomposition? % Oxygen in the amide = 33.33
(a) NaCN 0 (b) Na2S 0 Ratio of number of atoms of 'N' and '0'
(c) Both 0 (d) None of these 0 = 14.14 : 33.33 = I: 2]
3. 0.0833 mole of a carbohydrate of empirical formula CHzO 14 16
contains 1.00 g of hydrogen. The molecular formula of the 8. Lassaigne's test is not shown by diazonium salts because
carbohydrate is: . . they:
(a) CSHlOOS 0 (b) C3H40 3 0 (a) form NH3 gas on heating much before the reaction with
(c) C12H22011 0 (d) C6H12 0 6 0 sodium . 0
1 (b) form N2 gas on heating much before the reaction with
[Hint: 'I mole of carbohydrate will contain --gof
0.0833 sodium D
hydrogen, i.e., 12 g hydrogen.
(c) are highly volatile and evaporate before the reaction
:. The molecular formula of the compound will be C6H 120 6] with sodium 0
4. Select the organic compounds, which will give red colour in (d) all of the above D
Lassaigne's test? 9. 0.28 g of a nitrogenous compound was Kjeldahlised to
(a) NaCNS 0 produce 0.17 g of NH 3 . The percentage of nitrogen in the
organic compound is:
~
(b) NH2-C-NH2 0
(a) 5
(c) 50
D (b) 30
(d) 80 o
0
0
S [Hint: 0.17 g NH3 will contain (!~ x 0.17) g of nitrogen, i.e.,
11
(c) NH2-C-NH2 o 0.14 g of nitrogen
. Mass of
% Nitrogen = ~~~~~~ x 100
(d) H2N-{ )-S03Na+ . Mass of compound
o
= 0.14 x 100 50%]
5. The desiccants used for absorbing water during Liebig's 0.28
method for estimation of carbon and hydrogen are:
10. Kjeldahl's method cannot be used for estimation of nitrogen
(a) CaCl 2 0 (b) Na2S04 0 in:
(c) MgS04 ,7H20 0 (d) Mg(CI04 )2 0 (I) C6H s CONH2
[Hint: . Anhydrous CaCl 2 and Mg(CI04)2 are used as desiccants (II) Pyridine
because they are efficient absorben~ of water.] (III) C6Hs-N=N-C6Hs (IV) C6HsNHCOCH3
6. Kjeldahl's method can not be used for estimation of (a) I, III 0 (b) II, III 0
nitrogen in: (c) III, IV 0 (d) I, II D
(a) pyridine o (b) azobenzene o
(c) nitrobenzene o
(d) all of these D
•
G.R.B. Organic Chemistry for Cmnpetitions
7.
True (a) False (b)
Cyclo alkanes and alkenes have same empirical formula.
(c)N, (d) °
2. What is the petcentlge' composition of carbon in the
True (a) False (b) compound?'
Passage 2 (a) 16% (b) 8%
(~)28% . (d) 48% .
Combustion of 0.42 g of a compound gave 0.924 g CO 2 ahd
3. Percentage composition of nitrogen in the compound will
0.243 g H 2 O. Due to. distillation of 0.208 g of compound with ~: " "
N
NaOH, ammonia evolved required 30 ml.:of H S04 for (a) 16 (b) 61
, , ' " 20 2- ,
'.(c) 6 ' , (d) 28
complete neutralization. Vapour density of the coriipoUnd is -69.5.' 4. Which among the following is the empirical formula of the
Answer the following questions: compound?
1. The compound has empirical formula: (a) CgH:4N02 (b) C 4 H g N 2 0
(a) C 7 H 9 0 2 N (b) C6 HSN02 (c) C 4 H gNO (d) C g H 4 NO'
will
(c) C 3 H 7-CONH2
°II
(d) NHr -;;.·C-NH 2
5. Molecular formula of the compound
(a) CgH 4 N0 2
be:
(I:» C4 H gN 2 0
(c)' C4 H g NO (d) CgH4NO
1--------::----------,
ANSWERS: LINKED COMPREHENSION TYPE QUESTIONS!-
Passage 1 1. (a) 2~ (b) 3. (b) 4. (a) 5. (b) 6. (b) 7. (a),
Passage 2 1. (a) 2. (c) 3. (b) 4. (a) 5. ,(c)
Passage 3 1. (a) 2. (d) 3. (d) 4. (b) 5. (b)
3
CLASSIFICATION AND
NOMENCLATURE OF
ORGANIC COMPOUNDS
3.1 CLASSIFICATION OF ORGANIC COMPOUNDS more closed-chains or rings may be present in the molecule.
Organic compounds have been classified on the basis of The compounds with only one ring of atoms in the molecule
carbon skeleton (structure) or functional groups or the concept are known as monocyclic but those with more than one ring of
of homology. atoms are termed as polycyclic. These are further divided into
two subgroups:
(A) Classification Based on Structure (a) Homocyclic or Carbocyclic, (b) Heterocyclic.
.All the known organic compounds have been divided into (a) Homocyclic or Carbocyclic: These are the
two main types: compounds having a ring or rings of carbon atoms only in the
1. Acyclic or Open-chain compounds: These are the molecule. The carbocyclic or homocyclic compounds may
compounds in which the carbon atoms are linked to each other again be divided into two types: (i) Alicyclic compounds and
in such a manner that the molecule is having an open-chain (ii) Aromatic compounds.
structure. The chain of the carbon atoms may be straight or (i) Alicyclic compounds: These are the compounds
branched. These compounds are also called as aliphatic which contain rings of three or more carbon atoms. These
compounds. The term aliphatic has been derived from "the resemble with aliphatic compounds than aromatic compounds
Greek word aieiphatos meaning fats, since the earliest in many respects. That is why these are named alicyclic, i.e.,
compounds to be studied were fatty acids or compounds found aliphatic cyclic. These are also termed as polymethylenes.
in fats. Some of the examples are: Some of the examples are:
CH)
I
CH)-CH-CH) H 2C=CH 2
Isobutane Ethylene
Examples are: H H
H H H
HC""""C'-.,C/C~CH
HC~C'CH H~ ' C / 'CH
C C I I I
HC~C/C~N""""CH
I I I I I H
HC~ /CH HC'C/C~C~CH Quinoline
. ~ H H
Naphthalene
The classification may be summarised as follows:
Benzene
(Monocyclic) (Bicyclic) ORGANIC COMPOUNDS
H H H I
C C C
H~ ' C / ~C/ ~CH Open-chain, Closed-chain
HC
I C C
I
CH
I. 1
acyclic or aliphatic
compounds
or cyclic
compounds
~C/ ~C/~C/ I
H H H
Anthracene Homocyclic Heterocyclic
(Tricyclic) compounds compounds
I
. COOH NO z OH
I I. I Alicyclic Aromatic
C C " #C, compounds compounds
HC~ 'CH H~ 'CH HC~ CH
I
I I I I I
HC~ /CH H~C/CH HC~ /CH Benzenoid Non-benzenoid
C C
H H " H
aromatic
compounds
aromatic
compounds
Benzoic acid Nitrobenzene Phenol
The above compounds are also known as benzenoid (B) Classificatiou Based on Functional Groups
aromatics as their molecules consist of benzene ring or rings. The compounds of only carbon and hydrogen are c~lled
However, there are aromatic compounds, which have hydrocarbons. Hydrocarbons are considered as the parents of
structural units different from benzenoid type, and are known all the organic compounds. All other compounds are obtained
as non-benzenoid aromatics. Tropolone and azulene are the from hydrocarbons by the replacement of one or more
examples of non-benzenoid aromatics. hydrogen atoms with o!her atoms or groups.
-H
R-H +X
R-X
Hydrocarbon Derivative of hydrocarbon
Class Functional group Certain compounds contain more than one functional
groups. Such compounds are called polyfunctional
OlefinslAlkenes )C=C( compounds. The properties of each functional group may be
Acetylenes!Alkynes -C===C- modified by the presence of the others.
Halides -F, -Cl, -Br, - I (Halo) Homologous series: Organic compounds belonging to
Alcohols .-OH (Hydroxy) a main class can be divided into different families, known as
Thiols '-SH
homologous series, on the basis of similarity in structure and
chemical properties. All compounds having same carbon
Aldehydes -~:-H (Aldehydic) framework (skeleton) and same functional group in their
molecules possess similar properties. Such compounds when
° arranged in order of their molecular masses constitute a series
Ketones
°II
- C - (Ketonic)
called homologous series and the individual members are called
homologues. The property by virtue of which a number of organic
S compounds fonn a homologous series is tenned 'homology'.
Thioketones
II A homologous seri~ can be defined as a group of
-C- compounds in which the various' members have similar
I I structural features and similar chemical properties and the
Ethers
-f-o-f- (Alkoxy)
successive members dift"er in their molf'Cuiar formula by CH 2'
The general characteristics of a homologous series are:
I
-G-S-C-
I (i) All compounds in the series are composed of same
Thioethers
I I elements and contain the same functional group.
(ii) All compounds in the series can be represented by
°II
-C-OH (Carboxyl)
one general formula, e.g., the homologous series of
monohydric alcohols can be represented by the general
Carboxylic acid
formula* C n H 2n + I OH. The formula of various homologues
-S-OH
°II can be written by giving the values 1,2, 3, .. ; to n.
S~lphinic acid n CIIH2Ir+ IOH 1The molecular formula of
CH 30H ~CH2
°I
-C-NH2 (Amide) 2 C2H sOH .
) each member differs from
the members above and
below it by one CH 2
Amides
3 C3H7 0H CH 2 group.
Amines _N<H (Amino) 4 C4H9 0H CH 2
H (iii) The molecular mass of every two adjacent members
differs by 14 (CH 2 =12+2xl=14).
CyanideslNitriles -C===N (Cyano)
(iv) All compounds in the series have similar chemical
Nitro compounds -N<O (Nitro)
properties because of the presence of same functional group.
(v) The members of the series show a gradual gradation
° in their physical properties like solubility, density, melting and
°I I
boiling points. The physical properties generally increase as
the molecular mass increases.
Esters'" -C-O-C- (Ester)
. I· (vi) Thehomologues can be prepared by almost similar
methods. These are known as general methods of preparation.
, °I There are a number of homologous series in organic
Acid halides -C-X (Acylhalide) compounds. Some important series of aliphatic compounds
are Jisted below:
°
Contd.
Classification and Nomenclature of Organic Compounds 69
H
-NH-,
(sec.)
~N
(tert.)
(pri.)
10. Amides
W
II. Esters C"H2n°2 -C-O-R
12. Nitriles C}l2n+lCN -CeeN
13. Thiols C,;H2n+ I SH -SH
H
)c=c <H.;
H H
H-e' C-H;
Acetylene
which they w~ obtained. Quite frequently, the names chosen
had Latin or Greek roots. The following examples justify the
above statement: .
(a) Acetic acid derives its name from vinegar of which it
Eth~lene is the chief constituent (Latin: acetum vinegar).
(b) Formic acid was named as it was obtained from red
H H
ants. The Greek word for the red ants isformicus.
1 I (c) The names oxalic acid (oxalus), malic acid (pyrus
H-C=C-OH;
Vinyl alcohol malus), citric acid (~:'''Us) have been derived from botanical
. sources given in parentheses.
Acraldehyde (d) Urea and uric acid have derived their names from
Note: The double bond between carbon and oxygen atoms is not a urine in which both are present.
sign of unsaturation as in acetaldehyde_ or acetone. (e) The liquid obtained by the destructive distillation of'
wood was named as wood spirit. Later on, it was named
methyl alcohol (Greek: methu =spirit; hule =wood).
i
70 G.R.B. Organic Chemistry for Competitions
(1) Names like glucose (sweet), pentane (five), hexane (b) Prefix iso- is used for those paraffins in which methyl
(six), etc., were derived from Greek words describing their group is attached to the second last carbon atom or the
properties or structures. continuous chain.
(g) Methane was named as marsh gas because it was CH 3
produced in marshes. It was also named as fire damp as it
formed explosive mixture with air.
I
CH3-CH-CH3
The IUPAC names have become very popular these days . lsobutane
. but certain common or trivial names are so familiar that their (continuous chain)
use could not be completely discarded. A few of these CH 3 CH 3
common names have become a part of the IUPAC system I
while some others continue to be used along with the
I
CH 3-CH-CH 2-CH 3 CH 3-CH-CH z-CH 2-
corresponding IUPAC names~ These common names may lsopentane lsopentyl
include simple compounds such as acetone, acetic acid, glycol, (continuous chain)
glycerol, benzene, toluene, phenol, etc; or complex compounds (c) Prefix neo- is used for those paraffins in which two
such as penicillin, streptomycin, qumme, morphine, methyl groups are attached to the second last carbon atom of
vitamin-A, etc. A student must be familiar with both the continuous chain.
common and IUPAC names of organic compounds as both
the names are generally used in the standard text books on CH 3 CH 3
organic chemistry. A brief description of important members I I
of various families with their comnion names has been made CH3-C-CH3 CH 3-C-CH 2-
here. I I .
(1) Saturated hydrocarbons: Hydrocarbons are CH 3 CH 3
compounds that contain only carbon and hydrogen. The Neopentane Neopentyl
saturated hydrocarbons contain only single bonds between (continuous chain)
carbon, atoms. These are also .called paraffins (Latin:
parum small, and affinis affinity) as these are chemically
less reactive and represented by the general formula C n H 2n +2 •
The first four members are known as methane, ethane,
propane and butane. The names of the higher members have
. Greek prefixes indicating the number of carbon atoms in the Neohexane Neohexyl
molecule. (continuous chain)
There are four types of carbons in the carbon chain.
(i) Primary carbon: A carbon atom attached to one (or
Methane CH 4 ' no) other carbon atom is tenned prinwy carbon or 1° carbon
Ethane C 2H 6 atom.
Propane (n) Secondary carbon: A carbon atom attached to two
C 3Hg
other carbon atoms is termed secondary carbon or 2° carbon
Butane ".
. C 4H IO atom.
Pentane C S H12 (iii) Tertiary carbon: A carbon atom attached to three
Hexane other carbon atoms is termed tertiary carbon or 3° carbon
C 6 H14 atom.
Heptane C 7 H 16 (iv) Quaternary carbon: A carbon atom attached to
Octane CgH 1g four other carbon atoms is termed quaternary carbon or 4°
Nonane C 9 H 20 carbon atom.
Decane CH 3 CH 3
CIOH22
I I
Chain isomerism (see chapter 4) starts from butane. All
isomeric paraffins have same parent name. The names of
various isomers are distinguished by prefixes.
(a) Prefix n- is used for those paraffins in which all the
CH C
3-~3
CH
-1' L3
CH CH (2,2,3-Trimethyl pentane)
Primary (1°)
carbon atoms are in one continuous chain. The prefix n-stands
Secondary (2°)
for normal or straight chain.
l...------Tertiary (3°)
CH 3CH 2CH 2CH 3, Cil3CH2CH2CH2CH3, '-----,-------Quatemary (4°)
n-Butane n-Pentane [The hydrogen atoms attached to primary, secondary and
CH3CH2CH2CH2CH2CH3 tertiary carbon atoms are correspondingly termed as primary,
n-Hexane secondary and tertiary hydrogen atoms respectively.]
j
Classification and Nomenclature of Organic Compounds 71
Normal hydrocarbons contain either only primary or paraffin, i. e., there is one double bond between two carbon
both primary and secondary carbon atoms. No branching " atoms in their molecules. They have the general formula
is present. C n H 2n . The first member of the series is C 2H 4 • These
Iso-hydrocarbons contain a tertiary carbon atom, i.e., "unsaturated hydrocarbons are named olefins (Latin: oleum
(CH 3 hCH-. = oil; fiant = making). The names are derived by substituting
Neo-hydrocarbons contain a quaternary carbon atom, the suffix -ane of the corresponding paraffin by -ylene.
i.e., (CH 3 hC-. H 2C=CH 2 Ethylene
The isomers of butanes (2) and pentanes (3) can be named CH3---CH=CH2 Propylene
by using prefixes (n-, iso-, neo-) but it will be difficult to name CH 3-CH2---CH=CH 2 Butylene
properly all the hexanes (5), heptanes (9) and decanes (75) by CH34=CH2 Isobutylene
this method.
Alkyl groups: These are univalent groups or radicals CH 3
obtained by the removal of one hydrogen atom from a
molecule of a paraffm. The symbol 'R' is often used to - Alkene -H ) Alkenyl Alkenyl
represent an alkyl group. (-e+ yl)
-H
-H H 2C=CH 2 ~ H 2C=CH- Ethenyl (Vinyl)
(Alkane) C n H 2n +2 --~) C"nH2n+l (Alkyl group) Ethene
(R-H) (R-) -H
H 2C=CH-CH 3 ~ H 2C=CH- CH 2-
Alkyl groups are named by dropping -ane from the name
2-Propenyl (Allyl)
of corresponding paraffm and adding the ending -yl.
-H
Parent saturated " Name. of the H3C-CH=CH2 ~ H 3C-CH=CH- I-Propenyl
hydrocarbon _ aIkylgroup Structure
(3) Acetylenes: These are unsaturated hydrocarbons"
Methane Methyl CH 3- containing four hydrogen atoms less than corresponding
Ethane Ethyl CH 3-CH 2- paraffin. There is one triple bond between two carbon atoms.
Propane n-Propyl CH 3-CH 2-CH 2- These have general fOrnlula-C n H 2n - 2 • The first member of the
Butane n-Butyl CH 3-CH2-CH 2-CH 2- series is C 2H 2. The various homologues are considered to be
Alkyl groups derived from saturated hydrocarbons having derived from acetylene by replacement of one or both
three or more carbon atoms exist in isomeric forms. hydrogen atoms by alkyl groups.
HC==CH
/c~7)3CH2CH2- n-Propyl
Acetylene
CH 3-C==CH Methyl acetylene (Allylene)
CH 3CH 2CH 3~ CH- Isopropyl CH 3-C " C---CH 3 Dimethyl acetylene (Crotonylene)
Propane CH 3
Alkyne -H) Alkynyl
CH 3CH 2CH 2CH 2- n-Butyl (-e+ yl)
or -H
HC=C-CH 3~ HC=C-CH 2- 2-Propynyl
(Propargyl)
(4) Alkyl halides: These are monohalogen derivatives
of paraffms and are obtained by the replacement of one
Isobutyl =
hydrogen atom by halogen atom X (X F, CI, Br or I). These
have the general formula C n H2n+lX, Common names are
obtained by naming the alkyl groups and adding the name of
Tertiary butyl the halide as separate word. The position of the halogen atom
(Tert. butyl) is indicated by primary, secondary or tertiary prefix.
Beyond butyl, the number of isomeric groups derived Br
from each paraffin becomes so great that it is impracticable to I
CH3Br CH 3CH 2CI; CH3---CH---CH3
designate them all by various prefixes. Ethyl chloride Isopropyl bromide
Methyl bromide
(2) Olefins: These are unsaturated hydrocarbons
containing two hydrogen atoms less than the corresponding
Classification and Nomenclature ofOrganiC Compounds 73
<
COOH COOH anhydride
I CH 2 (11) Amines: They are the derivatives of ammonia and
COOH COOH are obtained by the replacement of hydrogen atoms of
Oxalic acid ammonia by alkyl groups. They are called primary. secondary
Malonic acid
and tertiary arnines depending on the number of hydrogen
<
CH 2COOH CH 2COOH atoms of ammonia replaced. The common names are obtained
I CH z by adding the names of alkyl groups to the suffix amine.
CHzCOOH . CHzCOOH CH 3
Succinic acid Glutaric acid I.
(10) Acid derivatives: These are the . compounds CH 3NH2 CH 3 -NH-CH 3 ; CH 3-N-CH 3
which are obtained by the replacement of hydroxyl part of the Methyl amine 00) Dimethyl amine (20) Trimethyl amine W)
carboxyl group with other groups. CH 3
o I
I CzHsNHz ; CH 3 NHC zH s ; C zH s-N-CH 3
(i) Acid cblorides : OH part ofthe -C-OH group is Ethyl amine 00) . Ethyl methyl Ethyl dimethyl
replaced by Cl atom. These are named by removing the ending amine (2°) amine (30)
-:ic acid of the carboxylic acid and adding -yl chloride. CH 3CH 2CH 2 NH Z ; C 2 H sNH-CH(CH 3 )2
CH 3COCI Acetyl chloride n-Propyl amine Ethyl isopropyl .
CzHsCOCI Propionyl chloride W) amine (2°)
66 0 00
NH2 COOH S03H structures. These rules underwent further modifications in
1979 and later revised in 1993 (A Guide to IUPAC
~ I.~. ~ I Nomenclature of Organic Chemistry by R. Panico, W.H.
Powell and J.C. Ricber). The name assigned on the ba~is of
Toluene
(Methylbenzene)
Phenol· Aniline Benzoic
. acid
Benzene
sulphonic acid
latest IUPAC rules to an organic compound is known as its
systematic name.
CI CHO
0 (5
Chlorobenzene
CH3
Nitrobenzene
CH3
0
Ethylbenzene
0
Benzaldehyde
Salient Features of IUPAC System
1. A given compound can be assigned only one name.
2. A given name can clearly direct in writing of one and
only one molecular structure.
3. The system can be applied in naming complex organ~c
.
0
OCH' OCH' OCOOH
~ COOH
compounds. . .
4. The system can be applied in naming multifunctional
organic compounds. .
CH3 5. This is a simple, systematic and scientific method for
o-Xylene m-Xylene . p-Xylene Phthalic acid nomenclature of organic compounds.
Basic rules of nomenclature: For naming simple
CH(CH3)2 CH=CH2
6 6 0
aliphatic compounds, the normal saturated hydrocarbons have
been considered as the parent compounds and the other
compounds as their derivatives obtained by the replacement of
one or more hydrogen atoms with various functional groups.
Cumene Styrene Cyclopropyl Each systematic name has two or three of the following parts:
(Isopropyl benzene) (Vinyl benzene) benzene (i) Root word, (ii) Primary suffix and (iii) Secondary suffix.
(i) Root words: The basic unit is a series of root words
The following names are given to certain aromatic which indicate linear or continuous chains of carbon atoms.
hydrocarbon residues formed by the loss of one or more Chains containing one to four carbon atoms are known by
hydrogen atoms from the parent hydrocarbon. special root words while chains from C s onwards are known
by Greek number roots.
00=0
CJIs-
(Phenyl)
C 6H4(
(o-Phenylene)
CH3CJI4-
(o-Tolyl)
Chain length
CI
Cz
C3
Root word
Meth-
Eth-
Prop-
Chain length
Cil
C IZ
C 13
Root word
Undec-
Dodec-
Tridec-
'0- 0
C4 But- C I4 Tetradec-
CH( C~ • Cs Pent- ·Pentadec-
CIS
CJI5CH
. .a 2- C6H sCH(
r 0
C6H5C~
~
C1
Cg
C9
Hex-
Hept-
Oct-
Non-
C I6
Czo
C30
C40
Hexadec-
Eicos-
Triacont- .
Tetracont-
(Benzyl or (Benzalor (Benzo;or. Pentacont-
C Dec- C
Phenyl methyl),' Benzylidene) Benzylidyne)
Classification and Nomenclature of Organic Compounds 75
In general, the root word for any carbon chain is alk-. Alcohols
(ii) Primary suffixes: PriIruuy suffixes are added to the (unsaturated) Alk -yne -01 Alkynol
root words to show saturation or unsaturation in a carbon chain. one triple bond
Aldehydes
NIlPlreof carbon Primary IUPAC (saturated) Alk -ane -al Alkanal
e~aiD· ·sul'fix name
Ketones
(saturated) Alk -ane -one Alkanone
Saturated (C-C) -ane Alkane
rnsaturated (C=C) Carboxylic acids
-ene Alkene (saturated) Alk -ane -oic acid Alkanoic acid
with one double bond
{unsaturated (C==C) Acid chlorides -oyl
-yne Alkyne (saturated) Alk -ane Alkanoyl chloride
with one triple bond chloride
? J
76 G.R.B. Organic Chemistry for Competitions •
Homologous series Struetural formula Root word Primary sumxSeeondary suffix • IUPAC name
S.No.
(1) (%) (3) (4) • • (5) • ,. (6)
I. I
Paraffms or Alkanes (C~2ni-2) Meth ~ane Methane
CH4
2 1
CH3 CH 3 Eth -ane Ettume
3 2 I
CH3 CH 2CH3 Prop -ane Propane '
432 I
But -ane Butane
CH) CH 2CH2 CH 3
2. Olefins or Alkenes (C~2n) 2 I
Eth -ene Bthene
H 2C=CH2
3 2 I
. Prop -ene Propene
CH 3 CH=CH 2
4 3 2 I
CH 3 CH 2CH=CH2
But -ene But-l-ene
4 3 2 I
But -ene But-2-ene
CH3 CH=CHCH3
3. Acetylenes or Alkynes (CnH~2) H~-CH Eth -yne Ethyne
3 2 I
Prop -yne Propyne
CH 3 -CE!!CH
4 3 2 I
But -yne But-I-yne
CH 3 CH 2-C -CH
4 3 2 I
But -yne But-2-yne
CH 3-C-C-CH3
4. Monohydric Alcohols 1
Meth -ane -01 Methanol
CH 30H
(C~2ni-IOH)
2 1
CH 3 CH10H
Eth -ane -01 Ethanol
3 2 I
Prop -ane -01 Propan-I-ol
CH 3 CH2 CH 20H
3 2 1
Prop -ane -01 Propan-2-ol
CH3 CHOHCH 3
4 3 . 2 1
But -ane -01 Butan-l-ol
CH3 CH2 CH2 CH20H
4 3 2 1
But -ane -01 Butan-2-01
CH3 CH2 CHOHCH 3
5. Aldehydes (C~2nO) I
Meth -ane -a1 Methanal
HCHO
2 I
Eth -ane -al Ethanal
CH3 CHO
3 2 1
Prop -ane -al Propanal
CH3 CH 2 CHO
432 I
But
CH3 CH 2 CH2 CHO -ane -al . Butanal
3 2 I
Prop -ane -one Propanone
CH3 COCH)
4 3 2 I
But -ane -one Butanone
CH3 CH 2 COCH 3
5 4 3 2 I Pent -ane -one Pentan-2-one
CH3 CH 2 CH2 COCH3
5 4 3 2 I Pent -ane -one Pentan-3-one
CH 3 CH 2 COCH2 CH3
7. Carboxylic acids (Mono) I
Meth -ane -oic acid Methanoic acid
HCOOH
(C~2n02)
2 1 Eth -ane -oic acid Ethanoic acid
CH3 COOH
3 2 I
Prop -ane -oic acid Propanoic acid
CH)CH 2 COOH
4 3 2 1 But ~ane -ole acid Butanoic acid
CH 3 CH2 CH£COOH
8. Acid chlorides (RCOCI) 2 I
Eth -ane -oyl chloride Ethanoyl chloride
CH3 COCl
3 2· 1
Prop -ane -oyl chloride Propanoyl chloride
CH 3 CH2 COCI
432 I
But -ane -oyl chloride. Butanoyl chloride
CH) CH2 CH 2 COCl
Contd.
Classification and Nomenclature ojOrgahic Compounds 77
Homologous series Structural formula Root word Primary sufra Secondary sufra IUPACname
S.No..
(1) (%) (3) (4) (5) (6)
9. Acid amides (RCONH 2 ) 2 I
Eth -ane amide Ethanamide
CH 3CONH2
3 2 I
Prop -ane amide Propanamide
CH 3 CH2 CONH2
4 3 2 I But -ane amide Butanamide
CH3 CH2 CH2CONH 2
I
10. Amines (R-NH2) Primary Meth -ane amine Methanamine
CH3NH2
2 1
Eth -ane amine Ethanamine
CH 3 CH2NH2
3 2 1
Prop -ane amine Propan-l-amine
CH3 CH2CH2NH 2
3 2 1
Prop -ane amine Propan-2-amine
CH3 CHNH2 CH 3
II. Cyanides or nitriles 2 1 Eth -ane* nitrile Ethane nitrile
CH3 CN
(R-CN)
3 2 1
Prop -ane* nitrile Propane nitrile
CH3 CH2CN
4 3 2 1
But -ane* nitrile Butane nitrile
CH3 CH2 CH2CN
12. 1
Alkyl halides (C"H2n+ IX)
CH3CI
Meth -ane • Chloro Chloromethane
2 1
Eth -ane Chloro Chloroethane
CH 3CH2CI
3 2 I
Prop -ane Bromo I-Bromopropane
CH 3 CH2CH2Br
3 2 1
Prop -ane Bromo 2-Bromopropane
CH 3 CHBrCl:h
13. Ethers I Meth -ane Methoxy Methoxymethane
CH 3OCH3t
2 1 Eth -ane Methoxy t+=
;..!
Methoxyethane
CH3 CH 2OCH 3t <I)
2 I ~
Eth -ane Ethoxy Ethoxyethane
(15) Esters: The esters are formed when the hydrogen (16) Anhydrides: Anhydrides are derived from acids
atom in the carboxyl group is replaced by an alkyl group. by replacing OH with OCOR. Anhydrides are named by
-H , changing the suffix .acid of the parent acid to anhydride.
RCOOH ~ RCOOR, [--COOR']
Carboxylic acid +.l\. Ester Functional group 0 0 0
These are named as the alkyl salts of the parent acid. Their I
.R-C-OH
OH 1/
) R-C-O-C-R'
I
names consist of two words. The first word is the name of the
alkyl group attached to 'oxygen atom. The second word is derived ~
+O--C-K
from the carboxylic acid name with -ic acid changed to -ate.
o 0 o 0 o 0
II I I I 1/ II
H-C-OCH 3 CH3-C-OC2Hs CH 3-C-O-C--CH 3; C2H5-C~-C-C2Hs
Methyl methanoate Ethyl ethanoate Ethanoic anhydride. Propanoic anhydride
o 0
C2Hs-C~C2H5
?! II
CH3-C-O-C-C2Hs
1/
Bo.nd Line Notations of Organic Molecules (ii) Carbon atoms are represented by lines drawn in a
It is a simple, short and convenient method of zig-zag fashion and carbon atoms by line ends and
representing organic molecules. The main points of this intersections. It is assumed that required number of hydrogen
notation are as follows: atoms are present wherever they are necessary to satisfy the
(i) The bonds (C-C) are shown by lines: Single bond by tetravalency of carbon. Terminal denotes CH 3 groups and
a single line (-), double bond by two parallel lines ( ) and a unsubstituted intersection, a CH 2 group.
triple bond by three parallel lines
IUPAC Nomenclature of Organic Compounds in Bond Line Structures
Series Name· Structural formula Series Name Stmctural·formula·
I. Alkanes Ethane 4. Alcohols Propan-I-ol
(Mono) (I-Propanol) ~OH
Propane ~
Propan-2-o1
OH
Butane ~ (2-Propanol)
A (>-OH)
Pentane ~ Butan-I-ol
(I-Butanol) "~OH
~
2-Methyl
butane Butan-2-o1 OR
(2-Butanol) . ~
~
2,2-Dimethyl
butane 2-Methyl
propan-2-o1
OH
~. (rOH)
~
(2-Methyl-
2, 3-Dimethyl
2-propanol)
butane
2,2-Dimethyl
~OH
propan~I-ol
~ ()-)
2,2-Dimethyl (2, 2-Dimethyl-
propane I-propanol)
~
2. Alkenes Ethene -- ~H
5. Aldehydes Propanal
Propene ~ 0
0
~
~H
But-I-ene Butanal
But-2-ene ~
2-Methyl
~H
~
3-Methyl propanal
but-I-ene
0
~
~H
2-Methyl
but-2-ene 2, 3-Dimethyl
butanal
~
3-Methyl
pent-I-ene
6. Ketones . Butan-2-one. 0
3. Alkynes Ethyne
=== (2-Butanone)
~
Prop-I-yne ~ (- ) Pentan-2-one 0
But-I-yne . ~ ~)
(2-Pentanone)
~
3-Methyl 0
( =)
~
~
But-2-yne butan-2-one
,
(3-Methyl-2-
"- - butanone)
Pent-I-yne ~
3-Methyl
but-I-yne ~
Pentan-3-one
(3-Pentanone) ~
0
Contd
Classification and Nomenclature of Organic Compounds 79
~OH ~NH2
Butanoic acid 3-Methyl
butanol-amine
~Cl ~C==N
8. Acid Ethanoyl 4-Methyl pentane
chlorides chloride nitrile
Butanoyl
0
propane
A . (>-Br)
chloride·
~~Cl
~CI
3-Methyl
l-chlorobutane
0
)~NH2
2-Chloro
~
9. Acid amides Ethanamide
2-methyl
()-CI)
propane
~
CI
~~NH2
3-Methyl
butanamide Ethoxy ethane ~O~
0
Ethyl N02
ethanoate
~O~ 2-Nitro butane
~
0
~~O~
N02
2-Methyl-2-nitro
~
Ethyl
butanoate propane
()-N02) .
ii&'"
80 G.R.B. Organic Chemistry for Competitions
~--------------~t-----------------~ (I)
CH 3 Three substituents
(Derivative of pentane)
_ CH 3
(b) The horizontal straight chain consists six carbon atoms
while the longest zig-zag chain consis(s eight carbon CH 3-C-CH 3
I .
atoms. Hence, the longest chain consists eight carbon
atoms and the compound is a derivative of octane. The
r --'--- - - - - - - - - --1 ----- --------~.----,
:CH_______________________________
L_~
3-CH 2-CH-CH 2-CH 3J :
various substituents are methyl groups.
. CH 3 CH 3 (II)
One substituent
r-~-------------------J---------
CH 3 +-C-CH 2-CH 2-C-CH 3 ! The chain of (1) is chosen as the parent chain because it
: I :--------------t--------- has three substituents.
: CH : CH 3 Example:
:, I 2 :, rCH~--=---CH=CH=CH=ciT--cii;i
i CH i Derivative)
( of octane '--------i------t-----1------t---------- J
:,, I 2 :,, (c) CH 3 CH 2 CH 3 CH 3 .
: CH 3 :
1______ - ,
I
CH 3
(c) The horizontal chain consists six carbon atoms while the
longest zig-zag chain consists seven carbon atoms. It is, thus, (I)
Four substituents
derivative of heptane. The substituents are ethyl and methyl
groups. CH 3 -CH -+cif=cii=cif=ciI-;]
;CH 3 I i I :-+----+-----:-----'
CH 3 iCH2i CH 3 CH 3
i--------t----------------i , I
: CH 3-CH-CH 2-CHt--CH 2-CH 3 1
I :
, I.
!..---------------------, :CH 3 :
, _ _ _ _ _ _1
iCH~=CH~--=-CH;j (II)
(Derivative ortreptaney---------- Three substituents
Note: It is possible that sometimes there may be two or more carbon The chain of (1) is chosen as the parent chain because it
chains of equal lengths in the molecule. In such a case the has four substituents.
selected chain should (a) contain maximum number of side 2. Numbering of the carbon atoms of the longest
chains (substituents) or (b) have the least branched side chains.
chain: The carbon atoms of the longest continuous chain
(parent chain) are numbered by arabic numerals I, 2, 3, 4 ...
~ la~s~sl~'fi~c~a~tio~n~a~nd~M~o~m~e~n~cl~a~ ~r~e~o~{~O~r~g~a~nl~c~C~o~m~p~o~u~n~d~s
C ______________________ ~ ______________________ ~81"~
etc., from one end to the other. The number that locates the preferred which has a lower number at the first point of j
position of the substituent is known as Locant. difference even, if it violates the lowest sum rule (First point
(a) The carbon a"toms carrying the first substituent getthe of difference rule).
lowest possible number Oowest individual number rule or Correct munbering -_~
lowest locant rule). The positions of the substituents (side 10 9 4 3 82 7 6 5 ,J
chains) are indicated by the number assigned to the carbon CH3-CH2-CH-CH-CH2-CH2-CH;r-CH2-CH-CH3
atom to which it is attached. , ' 2 31 41 5 6 7 8 91 ~,o
5 4 3 2 , 1 2 3 4 5 CH3 CH3 CH3
CH3-CH2-CH:r-CH-CH3; CH3-CH2-CH2-CH-CH3; Wrong numbering
1 ' " 1' The correct name is 2,7,8-trimethyldecane and not
CH3 CH3 3,4,9-trimethyldecane, because at the first point of difference
2-Methylpentane ' 4-Methylpentane 2 is less than 3. Thus,the lowest set of locants rule is mo"e
(Correct) . (Wrong) •
general and preferred over the lQwest sum rule. Other example
(b) In case, there are two or more similar substituents .
IS,
attached to the parent chain, their positions are indicated CH3
separately by the prefixes such as di, tri, tetra, etc. I " 2 3 4 5 61 7 8- Correct
CH3-CH-CH2-CH2-CH-=C-CHz-CH3 numbering
(Lowest set of locants rule). 8 71 6 5 41 31 2 . ' i
CH3 CH3 CH3 CH3 I
Wrong numbering
1 2 3 4 S S 4 3 21 1
CH3-.:cH-CH-CH2-CH3; CH3-CH-CH2-C-CH3 ; The correct name is 2,5,6,6-tetramethyloctane and not
1
CH3 CH3
1 ' .ICH 1
CH3
3,3,4,7-tetramethyloctane, because 2 is lower than 3 when we
' 3 ' compare the locants in the two names term by term.
2,3-Dimethylpentane (Correct) 2,2,4-Trimethylpentane (Correct)
(d) If there are different alkyl substituents attached to the
3,4-Dimethylpentane (Wrong) , 2,4,4~Trimethylpentane (Wrong) parent chain, their names are written in the alphabetical order
(Alphabetical order of simplesubstituents).1t may be noted
(c) When many substituents are present, the numbering is , that prefixes such as di, tri, etc., are not considered while
done from the end where upon the sum of 16cants is the lowest arranging the substituent alphabetically.
(Lowest sum rule). CH3 •
I 2 3' 4 5 6 I 234 S 5 4 5"1 2 I
CH 3-CH-CH-CH 2-CH-CH 3 CH3-CH-CH-CH2-CH3; CH3-CH2-C--CH-CH3
I I "I 1 1 I I
CH 3 CH 3 CH 3 CH3 C2Hs C2H s CH3
2,3,5-Trimethylhexane (Correct) 3-Ethyl-2-methylpentane 3-Ethyl-2,3-dimethylpentane
Sum of locants = 2 + 3 + 5 = 10
CH3
2,4,5-Trimethylhexane (Wrong) 6 5 41 3 2 I
Sum of locants = 2 + 4 + 5 11 CH3-CH2-C-CH2-CH-CH3
" 1 1 '
CH3 CH 3 C2HS CH3
61 5 4 3 21 1 4-Ethyl-2,4-dimethylhexane
CH3-C-CH2-CH2-CH2-C-CH3
1 1 . 2 1
, 1
CH 2 CH3 CH2-CH3
31
S6H3 " CH3-=CH-CH-CH2-CH3
4
2,2,6,6-Tetramelhyloctane (Correct)
I
CH 2-CH2-CH3
5 6 7
Sum oflocants =2 + 2 + 6 + 6 =16
4-Ethyl-3-methylheptane
3,3,7,7-Tetramethyloctane (Wrong)
Sum of locants 3 + 3 + 7 + 7 20 CH3 CH3
I . 21 3 . 4 51 6
Thus, it is evident from the above examples that both the ," CH3-C--CH-CH2-CH-CH3
lowest set of locants rule and lowest sum rule give the same 1 I
results when the length of the carbon chain is not very long. CH3 CH z-CH3
However, when the length of the carbon chain is long, the two 3-Ethyl c 2,2,5-trimethylhexane
rules often give different results. Hence, that set of locants is
-
82 G.R.B. Organic Chemistry (or Competitions
I I I 1 .
CH 3-CH 2-C-CH 2-CH 3 CH . . I'CH-CH CH
I 3 1 3 3
CH 3 CH2
3-Ethyl-3-methylpentane 1
CH3
(f) Naming the complex alkyl substituents: When 2,7-Dimethyl-5-(I'-Methyl propyl)nonane
the substituents on the parent chain has itself branched chain, or 2,7-Dimethyl-5-Sec. butyl nonaqe
it is named as substituted alkyl' group and its carbon chain is
Alphabet'd' of dimethyl group as a complete substituent
separately numbered in such way, that the carbon atom a comes before' m' of methyl propyl group.
directly attached to the parent chain is given number 1'. The
name of this complex substituent is written in brackets. to C2H 5 , CH3 .
avoid confusion with the number of carbon atoms of the 1 2 31. 4 s '6 11 8 9 10
CH3-CH2-CH-CH-CH2-CHz-~H-CHz-CH2-CH3
parent chain.
1234567 1,1
CH3'--CH2-CH2-CH-CHz-CH2-CH3 CH3-C-CH3
I' - I
, ,l'CH-CH3 CH3
, , 1 '
4-(1 ',1'-Dimethyl ethyl)-3-ethylc7.methyldecane
CH3
, 4-( I ~-Methyl' ethyl) heptane or 4-Isopropylhep):ane • The numerical prefixes 'bis-' (for two), 'tris-' (for three),
etc., are used to indicate a murtiplicity of substituted.
Note: AccordIng to IUPAC system ofnomenCl~ture, certain trivial or substituent. . ' .
semi-systematic names may be used for unsubstituted radicals.
For example, the following names may be us.ed:
, (CH3)2CH- Isopropyl
Classification and Nomenclature of Organic Compounds 83
CH3
. that it includes maximum number of such bonds even if it is
)CH--CH not the actual longest chain.
3
6 5 4 3 2 1
I 2 3 41 5 6 7
CH3--CH=CH--CH--CH=CH2
CH~H--CH2--C--CH2--CH2--CH3
I. 1,1 I .
CH2--CHz--CH3
CH3 CH---CH3
I The name of the compound is:
CH3
3-Propylhexa-l,4-diene
2-Methyl-4,4-bis(I'-methyl ethyl)heptane
(2) A primary suffix is added to the root word to indicate
(Bis is used for two same complex substituents.) the presence of double or triple bond in the parent chain.
CH2CI
For one double bond =Root word + locant + ene
1 2 I 4 5
CICH~HT2c--cH2--CH2CI For one triple bond = Root word + locant + yne'
I In case the parent chains contain two or more double
CH2CI bonds (two or more triple bonds), the prefixes di-, tri~, tetra-,
3,3-Bis-(cWoro methyl)-I,5-dichloropentane etc., are used before primary suffix.
SOME WORKED EXAMPLES For two double bonds = Root word + locant +diene
For two triple bonds = Root word + loeant + diyne
CH 3
(3) Numbering of carbon cbain; The parent carbon
I chain is numbered in a manner so as to give lowest number to
Example 1. CH 3--CH 2-C--CH 3
4 3 12 I that carbon atom linked by double or triple bond even if it
CH 3 violates the rules of saturated hydrocarbons.
CH 3 CH3
The name of the compound is : I I
2,2-Dimethylbutane CH3--CH=CH--CH--CH2--CH-CH3
1234567
Br (A)
I The name of the compound is: 4,6-Dimethylhept-2~ene.
Example 2. CH 3-CH 2-CH-CH-CH 3
5 4 3 12 I The position of the multiple bond (double or triple) is
CH 3 placed immediately before the suffIX ene or the yne and not
before the root word as was the practice being followed
The name of the compound is : earlier. For example,
3-Bromo-2-methylpentane, ' 4 3 Z I
CH3 CH 3 CH 2 CH=CH 2
I But-I-ene
CH3 CH2 CH3 (Formerly I-butene)
1 21 31 1 5 6 5 4 3 2 I
Example 3. CHr -::CH--=CH-t:H--CH2--CH3 CH 3-CH 2-CH=CH-CH 3
Pent-2-ene
The name of the compound is: (Formerly 2-Pentene)
3-Ethyl-2,4-dimethylhexane. I 2 3 4 5 6
CH 3 -C=C-CH 2 ---,CH z-CH 3
[BJ Rules for Naming Complex Unsaturated Aliphatic Hex-2-yne
Hydrocarbons (Formerly 2-Hexyne)'
(1) Longest chain: In the case of unsaturated Note: Whenever the word formerly his been used, it implies that this
name is still being used but the one given outside the bracket is
hydrocarbons, the longest chain of carbon atoms (parent
preferred.
chain) is so selected as to include the double or triple b,ond
even if it is not the actual longest chain of carbon atoms. (4) Alkyl groups or other substituents' are numbered,
765432 I . named and placed as prefixes in alphabetical order.
CH3--CHz--CH2--CH2--CH--CH CHz - Parent chain Examples:
. 1 CH3
CH2--CH2--CH3 I .
(a) C--CH~H--CH3
The name of the compound is: 3 4 5 6
3-Propylhept-I-ene 5-Methylhex-2-yne
When more than one double or triple bond is present in
the molecule, the longest chain of carbon atoms is so selected
..
84 G.R.B. Organic Chemistry tor Competitions
432
'1
!
2-Ethylpentan-I-ol I 11 I
CH 3 CHO CH 3
(2) Numbering of. parent chain: The numbering of 2( r -Methyl ethyl)-4 -methylpentanal
the parent carbon chain is done in such a way thatthe carbon or 2-Isopropyl-4-methylpentanal
linking to functional group gets the lowest number even if
there is violation of saturated hydrocarbon rules. SOME MORE WORKED EXAMPLES
CH3~H2~H2~H-CH2-CH3
6 S 4, P Example 1. (CH3hCH-CH2~OOH
CH2~H20H
2 1 Rewriting the structure of the compound,
3-Ethylhexan-I-ol 432 1
6 Is' 4 3
CH 3
2 1
CH3~H~H2-COOH
. I
CH 3
. (H0yY)
CH3-C-CH2~H2-CH-CH3
I
CH .
. OH
I. The name of the compound is :
3 3-Methylbutanoic acid.
5,5-Dimethylhexan -2-01 I 2 3 4
(~)
Note: When Ii chain terminating group such as -CHO, -COOH, Example 2. CH 3COCH 2CH 3
~R, -CONHl , -C==N, etc., is present as the functihnal The name of the compound is :
group, it must be assigned number I. This does not apply to Butan-2-one
non.,.terminalgroupssuch as >CO, -NHl and ~H which
mayor may not be assigned I.
15q
,
. f~2 ( OH)
functional group is made on the basis of the folloWing order of
preference.
Example 5.
.
CH3-C/~ °
""oCH 3
Seniority Table for Principal Groups
(Highest Priority Group at the Top)
chosen as the principal funetional group (secondary suffix) 1.-The first step in the naming of polyfimctionalcompounds
and the remaining functional groups (secondary functional is the selection of principal functional grOup. The' "principal
groups) are treated:as substituents and indicated by prefixes. functional group gives the class name of the structure: "
For example, in the following structure: 2. The second step is the selection of Parent ch8in. The
OH - Substituent parent chain is so selected that it includes the maxlmuin number
1 - '
CH:;-CH-CHz-CHz-COOH - Principal functional group of functional groups including the principal group. c
The -COOH group is the principal functional group,. 3. The third step is the nUmbering~f parent chain. The
while the -oH group is a substituent. The principal parent chain is numbered from the side of principalJwictioQal
functional group is mentioned with its suffIX name while group; i.e., it gets lowest number. The following decreasing
secondary .fimctional groups are mentioned oniy with their order of preference for giving the !owest numbers i~ followed. ..
prefix name. .
_,'$t, , . en .
I"
CH 3 4-Bromo-3-chloro-6-nitro octane
81 CH 0
12 II 10 9 7 6 5 4
(d) CH 3 -S-CH 2-S-CH-CH 2-S-CH 2- S -
16 5 II
Example 12. CH3--C--CH-C--CH3
3 2' 1 5 14 31 2 I
CH 2-S-CH 3 CH3 CHCI
8-Methyl-2,4,6,9,11-pentathiadodecane . 1'1
(e) 0 o
Oxacyclobexane
CH3
.3-( I'-Chloroethyl)-4-methyl-4-phenylpentan-2-one
o 0
(I) 0 Thiacyclohexane
Example 13. CH 3-C-CH 2-CH 2-C-OH
5
~
4 . 3
4-0xopentanoic acid
o 0
2
~
I .
4-(2'-Butenyl)-non-6-enoic acid
88 G.R.B. Organic Chemistry for Competitions
CH 3
I .
. Example 21. N=C-CH 2 -C-COOH
3 21 I'
CH 3 1,2-Dimethy\ I-Ethyl-3-methyl
cyclopentane cyclohexane
3-Cyano-2,2-dimethylpropanoic acid
CH3
o CH 3
I I,! OCH'CH'
Example 22. CH 3 CH 2 -C-O-CH
3 2 I 1
CH 3 CH3
2-Ethyl-I,4-dimethyl- 3-Ethyl-l, I-dimethyl-
(l'-Methylethyl) propanoate or Isopropylpropanoate cyC\ohexane cyclohexane
I 2. 3 When the ring contains more or equal number of carbon
Example 23. CH2--CH--CH2 atoms than the alkyl group attached to it, then it is named as a
I I I derivative of cycloalkane and the alkyl group is treated as
COOH COOH COOH substituent.
Propane-I,2,3-tricarboxylic acid
(Formerly named as 3-carboxy pentane-l,5-dioic acid)
CN DCH'CH,CH'
5 4 31 2 I
Example 24. CH 3 -CH 2-CH-CH 2 --CONH 2
Propylcyc\obutane Butylcyclohexane
3-Cyanopentanamide
H'C\/CH'
C
H2
00 Cyclohexyl
Cyclohexane
CH3(CH')'O(CH')'CH3
1,3,5-Tris (hexyl)
Cyclopropane Cyclobutane
. Cyclohexane
Note: In case, the alkane chain contains greater number of carbon
H2C--CH2 . atoms than present in the ring, the compound is corisidered as
the derivative of alkane and the ring is designated. as substituent.
1 I·
H2C CH2 .D CH,CH,cH,CH,cH3
··~C/
H2
l-Cyclobutylpentane
CYclopentalle
CH3-CH-CH2CH3 ". "CH3-CH2-CH-CH2CH3
These are also represented by si~ple geometrical fi~es. .~ ."
V 0 0 2-Cyclopropylbutane D
3-Cyclobutylpentane
Cyclopropane Cyclobutane Cyclopentane Cyclohexane . (2) Cycloalkenes and cycloalkynes: The word cyclo
is prefixed before the name of alkene and alkyne having the
Substituted cycloalkanes are named as alkyl
o
same number of carbon atoms as in the ring. .
o
cycloalkanes. The numbering of the carbon atoms in the ring
. is done in such a way that the substituent which comes first in
the alphabetical order is given the lowest possible number
provided it does not vIolate the lowest set oflocants rule.
Cyclohexene
0,'
Cyclopentyne Cyclobutene
Classification and Nomenclature ofOrganic Compounds 89
:0: H~D~
Cyclobutane carbonyl Ethyl cyclohexyl
chloride methanoale
6 3 .
.3-Methylcyclohexene 3-Methylcyclobutyne
(3) Alicyclic compounds containing functional group:
Alicyclic alcohols, amines, aldehydes, ketones, acids, etc. are
3-Ethylcyc1opentene
UO
Methoxy cyclopentane
CH3
N-Cyc1ohexyl prop!lIlamide
named in the same fashion as corresponding aliphatic
compounds by prefixing the word cyclo before the name .. In case of cyclic ketones any functional group present in
OOH U NH
'
CJ
the ring is treated as substituents (even -CHO, -COOH
etc.) and keto group is always treated as principal functional
group. This is because carbon of the keto group is a part of the
ring. This rule is applicable till the number of carbon atoms in
Cyclopentanol Cyclobutane- Cyclohexanone substituent is less or equal to the number of carbon atoms
amine present in the ring e.g.,
~COOH ~HO
If however, the side chain contains a multiple bond or a
functional group, .the alicyclic ring is treated as substituent
·5
irrespective of the size of the ring.
4 3
H
,.-CH""'CH2
2 1
6
3
CH=CH-COOH
3-Cyclopropyl
2 1
6c
21
3.
o
4 5
6
5,6-Dimethyl cyc10
CH3
CH
3
Methyl (2-hydroxy cyc1opentane)
6
2-0xa cyclohexanone
Go
2-0xa cyclopentanone
hex-2-en-I-one carboxylate' .
2 1 Nomenclature of Bicyclo and Spiro Compounds
COOH
a
4
Bicyclo compounds contain two fused rings with the help
~,
o
"
heads, and each bond or chain of atoms connecting the bridge
2-Cyclohexyl ethanoic acid 3-Cyclohexyl butan-2-o1
q
head atoms, is called a.bridge.
CH CH
2 l
. . OH
1,3-Dimethyl cyclopent-I-ene 2-Ethyl cyclobutan-I-ol
90 G.R.B. Organic Chemistry (or Competitions
Two
carbon
bridges
! /CI~ on~;:;~on
CH2 ( 'YH21 Two
I
CH
CH2 carbon-
I
CH bridges
I l 2~6
3~S
1
the longest bridge to the other bridge head, then along the next
longest bridge back to the first bridge head. The shortest
bridge is' named the last.
e.g.,
~/ 2 4 7 1 2
CH CH2-CH-CH2
/CH"
(2) H2C CH2 I BicycJo [1.1.0] butane
"'C~
2
(4) '9C0
s
10
7
6
2
S
3
"
Bicyclo [4.4.0] decane
(Decalin) 6
S
2-Ethyl+iodo bicycJo [2.2.1] heptane
4 3
cxr
lO
I 2. C 2Hs
(6) _I BicycJo [2.2.0] hexane 9 3
(6) • 3-Ethyl bicyclo [4.4.0] decane
1 I s 6 4
(7)
0) BicycJo [3.3.1] nonane
7 S
7 2
1,1'-Bicyclopropane
t>d
4' 3'
1,1';l', 1"-Tercyclobutane
(3) Spiro [2.2] pentane
3 i 3' 2" 3"
5 2
(3)
,<:=)<J'
4
7 8 2 1,1',4',1"-Terphenyl
(5) 7002
6
8
5 1
3
Spiro [3.4} octane
3.6 WRITING THE STRUCTURAL FORMULA
FROM THE GIVEN IUPAC NAME
The IUPAC name of an organic compound consists two, three
or all the following parts:
Nomenclature of Tricyclic Compounds: The (a) Root word, (b) Primary suffix, (c) Secondary suffix,
nomenclature of tricyclic compounds is similar to bicyclo (d) Prefixes.
compounds. Tricyclic compounds have four bridges. The (a) Root word indicates the longest carbon chain. Thus,
largest ring and the longest bridge make the bicyclic system the first step is to locate the longest chain from the root word.
whose numbenng is done as per rules of the bicyclic systems. Write the number of carbon atoms in a straight chain and
The loc~tion of the fourth bridge (secondary bridge) is shown
number them from one end.
by superscripts following the number indicating the number of
(b) Primary suffix (-ane, -ene or -yne) indicates the
carbon atoms intbe fourth bridge. While the superscripts
denote the lowest set of locants of the carbon atoms holding nature of the chain. IQ case multiple bonds are present, place
that bridge. them at proper places in the chain and rest by single bonds.
e.g., . (c) Secondary suffix indicates the principal functional
7
group. Place it at proper place in the chain. In case the
::!:;;e principal functional group is the chain terminating group, put
d5
4 '"
it at carbon-I. (If the functional group does not carry any
Second
, bridge
[5 6 2
31 b'd
First
n ge
numerical number, it is assumed that it is located at carbon-I.)
(d) Prefixes are the substituents or secondary functional
groups. Place them at the proper places with the help oflocants.
/
Fourth (e) Skeleton formula is obtained by considering the above
bridge steps: Now add hydrogen atoms to satisfy four valencies of each
Tricyclo [2,2,1 0 2,6] heptane carbon atom to get the structural formula.
Example 1. Write the structural formula of 2-methyl
IUPAC Nomenclature of unbranched identical pentan-I-oL
bydrocarbon units joined by a single )ond. Root word =Pent, Primary suffix =an(e)
These systems are named by placing a suitable numeral Thus, the chain consists five carbon atoms, all linked by
prefix: as bi, ter, quater, quinque for two, three, four, five single bonds.
respectively before the name of hydrocarbon unit. Starting 5 4 321
. from either end, the carbon atoms of each repetitive C-C-C-C-C
hydrocarbon unit are numbered with unprimed and primed Functional group = -01 = -OH at carbon-l
arabic numerals such as 1, 2, 3... , 1',2',3'...... ,1",2" , 3"...... , 54321
etc. The connecting points of hydrocarbon units are indicated C-C-C-C-C-OH
by placing the appropriate locants before the name.
e.g., Substituent = methyl group at carbon-2
92 G.R.B. Organic Chemistry for Competitions
CH 3 o OH
S 4 3 _zl I I zll 3 41 5
C-C-C-C-C-OH CH 3 -C-CH z-C-CH 3
Satisfying four valencies of carbon atoms, the structural I
CH 3
fonnula obtained is:
H H H CH 3 H Example 7. Write the structural formula of the
I I I I I compound 2,3,4-trimethylhexan-3-ol.
H-?-?-?4-?-OH
H H H H H
(~OH)
I
CH z 4 -s ~H
6
3 -CH-C-CH-CH z-CH 3
I I I
(u)
HO
Example 2. Write the structural fonnula of the compound
4-methyl pent-2-ene
CH 3 CH 3 CH 3 .
/!~ Example 8. Write the structural fonnula of the
compound 4-fonnyl-3-methylbutanoic acid.
4-methyl Pent 2-ene
4 3 Z I
(H~OH)
(Substituent (Root (Double bond
with locant) word) at carbon-2)
CH z -CH-CHzCOOH
I I
H CH 3 H CHO CH 3
51 41 3 z II
H-C-C-C=C-C-H Example 9. Write the structural fonnula of' the
I I I I 1 compound methyl-2-ethylbutanoate.
H H H H-H
o
III
(?:::J
Example 3. Write the structural fonnula of the compound 4 3 z
3-methylbutanoic acid. CH 3CH z-CH-C-QCH 3
. H CH 3 H I
CH z
I I I /0 I
H-C-C-C-C( CH 3
41 31 Zl I OH
H H H Example 10. Write the structural fonnula of the
compound 6-ethyl-5-methyl dec-5-enoic acid.
Example 4. Write the structural formula of the compound 10 987654-;3 Z I
5-chloro-7-hydroxy-3-methoxyoct-5-enaJ. CH3CHzCHzCHz-C=C-CHzCHzCHzCOOH
. . I I
H OH H CI H OCH 3 H CzHs CH 3
H-1-1-b=b-b-1--b-c(O
Is 17 14 1 Iz
6 S 3 I H
H H H H H
I~
41 31 zl 1 Cl
H H H
(c) 2-Chloro-3-methyl hexa-l,4-diene
Example 6. Write the structural formula of the
~
~.
compound 4-hydroxy-4-methyl-2-pentanone.
-,
!::C!!:.la!2:ss~ifil1lC~a~tl!!!·o:!!n.!!a!!!nd~M:.!:!o!.!.!.m~en~c:;!la!!!tu~re:....:o~[..!;Or~g.::;an:!!i~C.:;;C;.:::o:.:.:;m:to:p;.:::.ou:::n;.:;::d~s_ _ _ _ _ _ _ _ _ _
w _ _ _ _ _ _ _ _ _ _ __
~ .!9~3]
~I
(e) 3-Cyclohexyl butan-2-o1
U hH (q) 1,3-bis (bromomethyl) benzene
&
(r) 1-(2-butenyl) cyclohexene
Me 4
3
2 COOH
I
BrV'
~O (u) 3-Ethoxy carbonyl cyclohexane carboxylic acid
(i) 2,3-Dimethyl cyclohexanone
:U6 5
COOH
(D 1,3-Dicyclohexylpropane
0;yC) 0COOC2 H5
o
[>-cH -<J
0
)V~OC2H5
(k) Dicyclopropyl methane 2 (v) Ethyl-3-oxobutanoate
©--O
(w) 5-(l,2-dimethyl propyl) nonane
(I) Cyclohexyl benzene
© C=N
.
.
(y) 2,2-Dimetbyl cyclobutane carl"mitrile QCH 1
CH3
cxY
U C H2-C-CH
(P) Metbyl-2(chlorocarbonyl) benzoate
(z) I-Isobutyl-2-metbyJ cyc10hexane
rATCOOCH3
~COCI'
94 G.R.B. Organic Chemistry fOr Competitions
C-O-C, -S-OH, -NH2' >NH, ~N, -C==:N, -N~, -N~, -O-N=O, etc.
oI °
o Homologous series is a group of compounds in which the various members have the SImilar structural features and similar
chemical properties and the two successive members differ in their molecular formula by CH 2 (molecularlnass 14).
o Nomenclature of organic compounds: Their common names (Trivial system) are generally based on the source from
which they were obtained.
o IUPAC System: The complete IUPAC name of an organic compound consists of the following parts: ..
Secondary prefix + Primary prefix + Root word + Primary suffix + Secondary suffix.
The IUPAC names of some simple aliphatic organic compounds are as follows :
Alkane, Alkene, Alkyne, Haloalkane, Alkanol, AlkaDal, Alkanone, Alkanoic !lcid, Alkanoyl chloride, Alkanamide,
Alkylalkanoate, Alkanoic anhydride, Alkanamine, Alkane nitrile, Alkane isonitrile, Alkoxy alkane, Nitroalkane and
Alkanethiol. etc. .
IUPAC system has framed a set of rules for nomenclature of various types of organic compounds such as :
o Nomenclature of complex branched chain alkanes. •
o Nomenclature of complex unsaturated aliphatic hydrocarbons.
o Nomenclature of complex aliphatic compounds containing one functional group, multiple bonds. and substituents.
o Nomenclature of aliphatic compounds having polyfunctional groups. The order of preference for the choice of principal -
functional group is:
Sulphonic acids' > carboxylic acids> acid anhydrides> esters> acid chlorides> acid amides > cyanides> aldehydes
> ketones> alcohols, phenols, thiols > amines > ethers> alkenes, alkynes > halo, nitro, alkyl.
o Nomenclature of polyfunctional compounds containing more than two like functional groups .
. 0 Nomenclature of organic compounds in bond Line structures.
o Nomenclature of alicyclic compounds.
CJ Nomenclature of bicyclo and spiro compounds.
o Nomenclature of simple aromatic compounds.
i:I Nomenclature of di and poly functional aromatic compounds.
"
Classification and Nomenclature of Organic Compound... 95
(vii) A functional group is an atom or ...... in a CH3 -CH2 -CH 2 -CH-CH2 -CH - CH3
molecule that gives the molecule its characteristic . I . 2
CH3 -CH-CH 3
(viii) All members of homologous series are composed of
is ......
· ..... elements and contain the same ...... group.
State, whether the following statements are True or False :
(ix) The general formula of the alkenes is ..... .
(i) Homologous series can be· represented oy a general
(x) Thiophene is a ...... compound. formula.' .
(xi) The trivial names of organic compounds are called
(ii) Chemical properties of an organic compound depend
on the functional group.
(xii) Wood spirit waS named ..... .
(iii) In homologouS series, all members have the same
(xiii) Systematic names of organic compounds are
physical properties.
obtained from ...... system.
(iv) Cn H 2n is the general formula of alkanes.
(xiv) Full form of IUPAC system is ..... .
(v) Groups ootained by the removal of one hydrogen
(xv) ...... system of nomenclature of organic
atom from the alkanes are called as alkyl radicals:
compounds is universally accepted system.
(vi) IUPAC means International Union of Physics and
(xvi) The functional group in an alcohol is ...... and its
Chemistry.
suffix in IUPAC system is ..... .
(vii) Propane consists two primary carbon atoms and one
(xvii) Paraffins are ...... aliphatic hydrocarbons.
• secondary carbon atom.
(xviii) The systematic names of the alkanes ar(( based on
(viii) Alli:ynes consist of one double bond in their molecules.
· ..... . . of carbon atoms in the ...... continuous
(ix) Acetic acid is the systematic name of vinegar.
chain of carbon atoms.
(xix) Maximum number of functional groups must be o
included in the carbon atoms chain selected even if it (x) CH3 - C < is an unsaturated compound.
does not satisfy the . . . . . . ' . OH
(xx) In the case pf compounds containing more than one. (xi) Prefixes like n-, iso-, sec-, tert-, neo-, etc., are used in
functional group, the most important functional IUPAC system.
group is considered as ...... and the rest are (xii) The systematic names of the acids are formed by
considered as . . . . . . . dropping the -e of the name of parent alkane and
(xxi) In case a carbon compound consists two functional adding suffix -oic acid;
groups one of which is -COOH "group, the (xiii) Primary suffixes are added to the root word to show
numbering of the chain should start from carbon saturation or unsaturation in a carbon ~hain.
atom linked to . . . . .. . (xiv) Neohydrocarbons contain a tertiary carbon atom.
(xxii) The name of compound with the structural formula, (xv) The common name of2-propanol is isopropyl alcohol.
(xvi) The IUPAC name of CH 3 COOCH3 is methyl acetate.
CH 3
(xvii) 'The IUPAC name of HCHO is methanal.
I (xviii) The IUPAC name of CH 3 CN is methyl cyanide.
CH 3 -CH 2-C-CH 20H is ..... .
. I (xix) Methane was named as firedamp as it formed explosive
mixture with air.
CH 2
(xx) The IUP~C name of dimethyl ketone is propanone.
I
CH 3
3. Match the following: 8. Give the IUPAC names of the following compounds:
[A] (a) Benzene (l) Alicyclic CH 3
(b) Pyridine (2) Aliphatic
(c) Cycloalkane (3) C 2 H sCHO
I
(i) CH 3-CHr -CH-CH-CH,-CH,-CH.
(d) Anthracene (4) Aromati,c (Monocyclic) I - - .'
(e) Glycerol (5) Aromatic (Tricyclic) CH-CH,-CH 3
(f) Next homologue of (6) Heterocyclic I -
CH)CHO CH 3
[8] (a) Acetic acid (I) 2-Butyne
(b) Wood spirit (2) Trichloromethane CH3 CH 2-CH3 CH ,
(c) Acetone (3) Ethanoic acid I I I .
(ii) CH3-CH-C-CH2-CH=C-CH]
(d) Dimethyl acetylene (4) Dichlorodifluoro • I .
methane CH '
(e) Chlorofonn (5) Methanol I 2
(0 Frcon (6) Propanone CH 2
(1) Alkynes
[C] (a) C" H ZII + 2
(2) Nitrites
I
(b) C"H z" CH-CH 3
(e) C"H 2,,_2 (3) Carboxylic group I
(0) C"H 2J1 + I CN (4) Alkenes CH 3
~ (e) Principal functional (5) Cyclohexane
(iii) CHr-CH2-C~C-CH-CH=CHi
group
(0 C(,.112 (6) Paraftins or alkanes
I
CH2
4. Select the principal functional group when the following I
groups are present in the molecule: CH-CH3
(a) Oil. COOH. -NO z I
(h) N0 2 • NH 2 .-CONH z CH3
(e) Hr. Cllv·_·CHO
(iv) CH 2 =CH-CH{CH 3 h
(d) CI. CIl~.-OH. . CH
5. Name the Ii.lllow"ing alkyl groups: 3
. CH 1CHJ)
I
(v) ,·LC-N--C-CH,-CH,
(u) (,11,CII 2 (e) ('II " .' 1 I - .'
CH) CH) C2HS
(b) (CI11h(' (f) CH ,-CH--CH,
, . 1 - Me
(e) (Clld 2 CII CHI (vi) Me~Me [PMT (Kerala) 2006)
(tI) CII,('II,CII, Me~Me
6. What is 'the n~lIure-orearbon alom marked with astcrisk(*) sign or
in the lollowing compounds'!
CH CH
1* 3 1* )
(a) CH~-C--CH~ (b) H-C-CH,CH]
'I - 1 _.
CH) CH)
.
(c) CH)-CHz-CH1-CH) (d) CH3-CH2-CH2-CH~
. CI
I
7. Answer the following: (vii) CH2=CH-CH-C=CH 2
(i) What would be the molecular formula for a straight I
chain hydrocarbon having 8 carbon atoms with (a) all CH 2
C--C single bonds; (b) One C--C double bond, I
CH3
(c) One C--C triple bond?
,(ii) What is the structural unit that is added to one normal
alkane in order to form the next member in the ho- (viii) (CH 3 h COH
mologous series? (ix) CH3HC=CHCH2 NH 2
~ ~
(iii) What is the minimum number of carbon atoms in,
(a) a branched alkane, (b) cyclo-alkane?
(x) H-G-C-OH
(iv) Name the isoradical that does not have a correspond-
ing isoalkane. (xi) CH3~CH-CH-CH3
(v) What system of nomenclature of organic compounds 1 I
are universally accepted? CI Br
Classification and Nomenclature of Organic Compounds .. 97
.
~
4 5 . . gCH
0
3
(t)
(n\
~'
(e) [CBSE (Med.) 2005)
1
±
;:YaH
(h)U CN~.
(y)
~. . I (z)
61
(0) N-N- Dimethylbutanamide;
(P) 4-Phenylbutanal;
(q) 3-Ethenylpenta-l,3-diene;
(j) (r) 4-Hydroxy-4-methyl-2-pentanone;
(s) 2,6~Dimethylhepta-2,5-dlenoic acid;
(t) l-Cyclopropyl-3-methylpent-l-ene;
~H
be given to it. The correct name of the compound. is
4-amiIiobutan-2-one. .
(i) (j)
14. (a) No, it should be pent-2-yne; (b) No, Tert. word is not used in
IUPAC system. It is 2-methylpropan-2-ol; (c) No, it should be o
hexa-I,5-diene; (d) No, it should be 3,4,4-trimethylhex-l-)ine;
If~O~
(e) No, Keto is not used. It is the principal functional group. It is
I-hydroxy propan-2-one; (t) No, it should be 2-methoxy H
~N<
]:
ethan-I-ol; (g) Yes; (h) Yes. (k) / (I)
15. (a) 3-Methylbut-l-ene (b) 2-Methylbuta-I,3-diene
(c) Butane-I,4-dioic acid (d) 2,3-Dihydroxybutane-l, o
(e) Trichloro nitro methane
(g) Ethane nitrile
4-dioic acid
(t) 2,2-Dimethyl propane
(b) Methoxy methane
(m)A '-....N~
(n) ~NH;
(i) Ethanamide (j) Cbloroethane H
16. (a) 2-Hydroxy-l,2,3-propane tricarboxylic acid; o o
(O)~N/
(b) 3,7-Dimethylocta-2,6-dienal;
(c) 3-Methyl cyclohexyne; ; (P) H·,
(d) Methyl-3-chlorobut-2-enoate.
(e) 2-Bromo-6-methyl cyclohexane carbaldehyde.
(t) Cyclohexane carbonylcbloride.
(g) Cyclopentane carboxamide.
'" o
. )lJ<?H
(h) Cyclobutane carbonitrile.
(i) Propyl cyclopentyl methanoate. (q)~ (r)
(j) 3-Bromo-4,4-dimetbyl cyclohexanol.
17. (a) 3-Metbyl hexane; (b) 3,3,4-Trimethyloctane;
(,) X
(c) Cis-2-butene; (d) Trans-2-outene;
(e) Hexa-2,4-diyne; (t) 4-Isopropyl-oct-2-ene; NOOH ; (t)
(g) 3,3-Diinethyl pent-l-en-4-yne; (h) Octa-l-en-4-yne; .
(i) Cyclo dodecane; (j) 3-Methyl-I-cyclohexyne;
(k) Trans-l,2-dimethyl cyc1ohexane;· .
6.
(I) Cis-l,3-dimethyl cyclobutane; .
",
(m) 4-Ethyl-2-cycloPropyl-hex-l-ene; (u)
~ ; (v)
(n) 1,2-Ethanedioic acid; .
(0) 2-(2'-Chloropropyl)hexa-l,3,5-triene; 0
(P) Propanoic anhydride;
(q) 4-Ethyl hex-4-en-2-01;
(r) 3-Methyl bexa-I,3,5-triene;
(s) l-Chloro-3-ethyl-2-pentanone;
(t) 3,7..Dimethyl octa-I,3,6-triene;
(u) 3,4-Dimethyl pent-l-en-3-01;
(w)
Lx 0
; (x)
ft:
~CI
(v) 3-Hydroxy-3-methyl butanoic acid;
(w) 2-Carboxy-5-formyl cyclohexanone;
(x) 5-Ethyl-4,6-dimethyl octa-l,4-diene; ~OH;
(QY 61
(y) (z)
(y) 2~Ethenyl-3-methyl cyclohexa-I,3-diene;
(z)3,3,5-Trimetbyl hex-l-en-2~01.
~
18. (a) (b)~
19. (a)
o (b) IT (c) L
(c)
T=< (d)
~
(e)
(g)
~•
~H
(t) H A H
(b) C I - G .
,
;
"'''''''CI
.)
Classification and Nomenclature of Organic Compounds 101
r
I 1
6. The IUPAC name of (CH3 h CHCH3 is: [BHU(S) 2008] . GH 3- CH2-CH-CH3
(a) isopropyl methane 0 (b) 2-methyl propane 0 CH3
(c) trimethyl methane 0 . (d) dimethyl ethane 0
7. The IUPAC name ofCH30C2H s is: (a) 1,1-:dimethyl-l,3-butandiol 0
(a) ethoxy methane 0 (b) methoxyethane O. (b) 2-methyl-2,4-pentandiol 0
(c) ethyl methyl ether 0 (d) methyl ethyl ether 0 (c) 4-methyl-2,4-pentandiol 0
8. The IUPAC name of CH3CH(OH)CH2CH:iCOOH is: . (d) 1,3,3-trimethyl-l,3:propandiol 0
(a) 4-hydroxy pentanoic acid 0 14. The IUPAC name ofCH 3-rH-CH2-CH(OH)-.,-CH31s:
(b) l-carboxybutan-3-01 0 CH 2CH3
(c) l-carboxybutan-4-01 0
(d) 4-carboxybutan-2-01 . 0 (a) 2-ethylpentan-4-01 o
9. The name(s) of the following compound is:
(b) 4-ethylpentan-2-01 o
(c) 4-methylhexan-2~ol o
pH (d) 4-methylpentan·2-01 o
CH2--C-'-CH2 15. The IUPAC name of the following compound is:
1 1 'I H 2C=C-CH 2 - CH3
COOH COOH COOH ·1 .
CH~CH3
(a) 2-hydroxypropane-1 ,2,3 -tricarboxylic acid 0 I
(b) 3-carboxy-3-hydroxy-l,5~pentanedioic acid 0 CH 3
(c) citric acid 0
(d) all of the above EJ
,!.!i,.+.f:b<@~ ~1i¥f
'.--:
. I.·
CH3 -CH
S-
O
>. c=o is:
[]
35. The IUPAC name of the following compound is: (c) methyl isopropyl acetylene
.l
o
O=C-CH-CH2 (d) 2-methylpen~4-yne o
I J I 42.' The IUPAC lJame of (CH3 h C-CH=CH 2 is:
OH NH2 OH IAMU (Med.) 2005]
(a) 2,2-dimethylbut-3-ene 0
(a) 3-amino-2-hydroxy propanoic acid o (b) 2,2-dimethylpent-4-ene 0
(b) 2-amino-propan-3-ol-l-oic acid , o (c) 3,3-dimethyibut-I-ene .. 0
(c) 2-amino-3-hydroxy propanoic acid o (d) hex-I-ene 0
l· (d) amino hydroxy propanoic acid o 43. The IUPAC name of,CH2 =CH-:-CN is: [NSEC 2001]
H
I '(a) ethenenitrile 0 (b) vinyl cyanide 0
36. The IUPAC name oflhe compound CH,~CH,CH, j" (c) cyano ethene 0 (d) prop-2-enenitrile 0
OH
SO. The IUPAC name of the given structure H is : 58. The IUPAC name of the compound (DPMT 2004)
(a) 2,2-dimethyl butane 0 (b) isohexane 0 Cl ~ /CH2CH3 "
(c) 2,3-dimethyl butane 0 (d) disohexane 0 /C=C"" IS:
51. The structural formula of 2~oxo-3-methyl-(N-bromo)
butanamide is : . H3C 1
(a) CH3 CH 2-CO-CO-NH-Br o (a) trans-2-chloro-3-iodopent-2-ene 0
CH 3 (b) cis-2-chloro-3-iodopent-2-ene 0
·1 (c) trans-3-iodo-4-chloropent-3-ene 0
(b) CH3 -CH-CO-CO-NH-Br o (d) cis-3-iodo-4-chloropent-3-ene 0
CH3 59. The IUPAC name of the compound
I COOH
(c)' CH3-CH-CO-CO-NOBr o I
(d) (CH 3 )3 C-CO-CO-NH-Br o CH3-CH2-CH2-r-CH2-CH3 is:
52. The IUPAC name of the given structure A is: COOH
(a) 1,2-dimethyl cyclopropane o (a) 2-propyl-2-ethylpropanedioic acid 0
(b) cyclopropane-I,2-dimethyl o (b) 2-ethyl-2-propyl propanedioic acid 0
(c) I-methyl-I-methyl cyclopropane o (c) 2-ethyl-2-carboxy pentanoic acid 0
(d) cyclopentane . o (d) 2-carboxy-2-ethyl pentanoic acid 0
CH3
Of6
60. The IUPAC name of the following compound is:
lOT 2009)
~
53. The IUPAC name is: (AIIMS 2003)
Br
(a) 3,3-dimethyl-5-carboxy pentanoyl chloride 0 (a) 4-bromo-3-chloro-I-cyc1ohexen-5-yne 0
(b) 4-chloroformyl-3,3-dimethyl pentanoic acid 0 (b) 5-bromo-6-chloro-I-cyc1ohexen-3-yne 0
(c) 5-carboxy-3,3-dimethyl pentanoyl chloride 0 (c) 6-bromo-5-chloro-3-cyclohexen-l-yne 0
(d) 5-chloroformyl-3,3-diIDethyl pentanoic acid 0 (d) 6-bromo-5-chloro-I-cyclohexen-3-yne 0
56. The IUPAC name of the compound 62. The compound which contains all the four 10 , 20 , 30 and 4 0
CH3-CH2-CH-C~OH is: (BHU 2004) carbon atom is: (CET (J & K) 2005)
.' I . (a) 2,3-dimethylpentane 0
. OCH3 (b) 3-chloro-2,3-dimethylpentane 0
(a)2-methoxy-I-butanol 0 (b) 3-methoxy-I-butanol 0 (c) 2,3,4-trimethylpentane 0
(c) I-methoxy-l-butanoID (d) 1,2-methoxybutanol 0 (d) 3,3-dimethylpentane 0
Of~(CI is:
.57. The IUPAC name of the compound
'HoD
63. TheIUPAC name
o
i" lAIEEE 2004) (CBSE (Med.) 2006; AIEEE 2006)
(a) 2-ethyl-3-methyl"butanoyl chloride ' 0
. fa) 3,3~dimethyl-I-hydroxy cyclohexane D· (b') 2,3-dimethyl pentanoyl chloride . 0
(b) 1, l-dimethyl-3-hydroxy cyclohexane o . (c) 3,4-dimethyl pentanoyl chloride 0
. (c) 3,J-dimethyl-l-cyclohexanol o (d) l-chloro-I-oxo-2,3-dimethyl pentane 0
(d) 1,1,-dimethyl-3-cyCiohexanol o
, .
Classification and Nomenclature of Organic Compounds 105
64. The IUPAC name of the compound shown below is: 71. The IUPAC name of the following compound is:
[UGET (Moo.) 2007)
OBr
(a) 2-bromo-6-chlorocyclohex-l-ene
(AIEEE 2006)
o
(a) bicyclo [2.2.0] octane '.
(b) bicyclo [0.2.2] hexane
(c) bicyclo [2.1.1] bexane ,
o
o
o
(b) 6-bromo-2-chlorocyclohexene o (d) bicyclo [2.2.0] bexane ' o
(c) 3-bromo-I-chlorocyclohexene o 72. The IUPAC name of the compound
(d) I-bromo-3-chlorocyclohexene o (CH3)2 CH--CH=CH--CHOH--CH3 is:
6S. The IUPAC name ofC6 H s COCI is:(lIT 2006) [EAMCET (Engg.) 2007)
(a) benzoyl cbloride o (a) 5-methylbex-3-en-2-o1 o
(b) benzene cbloroketone o (b) 2-methylbex-3-en-5-ol o
(c) benzene carbonylchloride o (c) 2-bydroxy-5-methyl-3-hexene o
(d) chlorophenyl ketone o (d) 5-hydroxy-2-methyl-3-hexene o
66. The IUPAC name of CI-CH2-CH=C-CH2OH is: 73. The IUPAC name of
I H3
CH 2CH3 , V
(DPMT 2006) CH3 --C-C--CH2 --CH20H is: [AIIMS 2007]
. (a) l-chloro-2-ethyl-4-hydroxybut-2-ene o (a) I-hydroxy-4-methylpentan-3-one o
(b) 4-hydroxy-l-chloro-2-ethylbut-2-ene o (b) 2-methyl-5-hydroxypentan-3-one o
(c) 4-chloro-2-ethylbut-2-en-l-ol o (c) 4-methyl-3-oxopentan-l-ol o
(d) 2-etbyl-4-chlorobut-2-en-l-ol o (d) hexan-l-oI-3-one o
o
Q--1-NH-C
74. The correct IUPAC name of the compound
CHO
67. The IUPAC name of 6H 5 is:
(c) N ,N-dimethyl cyclopropane carboxamide o (d) I-D, 2-C, 3-B, 4-A, S-E. D
(d) none of the above o (e) I-E, 2-D, 3-A, 4-C, S-B . D
78. The IUPAC name of the following compound
SET II: This set contains the questions with one or more correct
?H3 answers.. A
CH3 - N - C-CHz -CH3 is: (DPMT2008]
, I I 84. The compound CH 3-CH2 - C - - CH2 may be named as:
CH3 C2 H S I
r CH 3
(a) 3-dimethylamino-3-methyl pentane o
(b) 3-(N,N-trimethyl)-3-aminopentane o (a) 2-ethyl-2-methyloxirane D
(c) 3-N,N-trimethyl pentanimine o (b) 1,2-epoxy-2":methylbutane D
(d) 3-(N,N-dimethyl) arnino-3-methylpentane o (c) 1,2-oxapentane D
79. The IUPAC name of the following compound is: (d) 2-methyl-2-butoxide D
CH3--rn-CHz-CH3 (AFMC2008] 85. Which of the following names are not correct for the given
compound? . .
C6 HS CH2 -CH-CH
I I I •
(a) 2-cyclohexyl butane 0 (b) sec.-butyl benzene 0 2
'00
(d) Ifassertion is incorrect but reason is correct. pent-3-en-I-yne and not Pent-2-en-4-yne.
(R) CH2 =C 0 is called ketene. (R) It is named as derivative of cyc10pentane because the
number of carbon atoms in the ring is more than the side
chain. .
108 G.R.B.Organic Chemistry tor. Competitions
I ANSWERS I
OBJECTIVE QUESTIONS
1. (b) 2. (b) 3. (a) 4. (c) 5. (b) 6. (b) 7. (b) 8. (a) 9. (d) 10. (c) .
11. (e) 12. (b)
21. (a) 22. (d)
13. (b)
23. (d)
14. (c)
24. (a)
.
15. (a)
25. (d)
16: (b)
26. (b)
17. (d)
27. (c)
18. (c)
28. (a)
19. (b)
29. (b)
20• (c)
30. (c).
31. (d) 32. (b) 33. (a) 34. (d) 35. (c) 36. (d) 37. (a) 38. (b) 39. (c) 40. (a)
.
41. (a) 42. (c) .43. (d) 44. (c) 45. (c) 46. (a) 47. (b) . 48. (d) 49. (a) SO. (c)
51. (b) 52. (a) 53. (a) 54. (b) 55. (d) . 56. (a) 57. (c) 58. (a) 59. (b) 60. (b)
61. (b) 62. (b) 63. (b) 64. (c) 65. (c) 66. (c) 67. (d) 68. (a) 69. (c). 70. (a)
71. (d) 72. (a) 73. (a) 74. (c) 75. (b) 76. (c) 77. (c) 78. (d) 7'. (d) 80. (a)
•
81. (c) 82. (a) 83. (b) 84. (a,b) 85. (b,e) 86. (e,d) 87. (a,b,e) 88. (a,e,d) 89. (a,e) 90. (b,d)
91. (a,b;d) 92. (a,b) 93. (a,b,e) 94. (a,b) 95. (d) 96. (d)
1.
7
Ans. I, r, 3', f'-Tercyclobutane.
6 3 4
1
CH2 N-CH3 CONH2
Ans. 2-(3'-Oxobutyl) cyclohexan-I-one
II· I I
4. CH3-CH-CH=CH-C--C=CH-CH:z----(:-COOH
~CH3
.
Ans.
1
COOC~7
. 1
COCl
2-Amide-2-chlorocarbonyl-5-(N-ethyl, N-methyl) amino-
11. s0J
. 7 6 4 .
6-methylene-9-propoxycarbonyldec-4, 7-diene-I-oic
Ans. 2-Methyl spiro [4.5] deca-I,6 diene
:60,
acid
5. n-~-o-rH-CH3' 12.
y
OH
0 CH3 o5 3
6. CH3(CH2)~H
X 13.
H (CHZ)9CH3
6
eN
Ans. 1,3,5-Trisdecylcyclohexane
A,ns. Bicyclo [2.2.2] oct-5-ene-2-nitrile
~
HOCH2CH2-O>
7. CH-COOH 14• .
HOCHzCH 2 -O
Ans. 2,2-Bis (2-hydroxy ethoxy) ethanoic acid Ans. 3, 3-Diethylpentane
110 G.R.B. Organic Chemistry tor Competitions
25·0C=O
15. Ans. Cyclohexylidene methanone
4 3 2 I
26. CH2 -CH 2 -CH- CH 2
Ans. 7-Ethyl-2,4,5,6-tetramethyldec-I,8-diene . I I I
CHO . CHO CHO
CH 3 CH3
I I Ans. Butane-I, 2, 4-tricarbaldehyde
27. CH2--CH--CH 2
16. CH3-CH-CH-CH(CH2CH2CH2CH3h
Ans. 5-( 1',7.-dimethyl propyl) nonane I I I
CONH2 CONH2 CONH 2
Ans. Propane-I, 2, 3-tric¢oxamide
.
CH'NH-@-@NHCH'
17. o 0
"6 S 4 3 2 III
,28. H-C-CH2-CH 2 -CH-CH 2 -C-H
Ans. 3, 4'-Bis (N-methylamino) biphenyl" I .
2:' I" S 4 I' 2' CH 2 CHO
18. BrCH2-CHCI---.:.cH-CH-CHBrCH2CI
Ans. 3-(Formyl methyl) hexane-I,6-dial
I I I
CH3-CHz-CHz CH2-CH2-CH3
8 7 6 3 2 I
29. 2N!S.
Ans. 4-(1'-Bromo,2'-cbloroethyl).5-(2"-bromo-I"-cbloroethyl) 3~5
octane. 4
Ans. Bicyclo [3.2.1] octane
>t:Y
9 10 1
30. 8( 7 6 4 3
CH3
.~
31. ~ •
Ans. Ethyl-2-methyl~2-(3'-nitro phenyl) propanoate 2 3 4
OH Ans. Bicyclo [1.1.0] butane
32.
CH3 s 3
Ans. 5-methyl-3,6-octadien-4-ol 4
21.~
Ans. 7,7-Dimethyl bicyclo [2.2.1] heptane
'Cl
Ans. 2,3,3,7,7-Pentamethyloctane
22. Cl zCH-fH-fH-CCl3
33·,W 764
Ans. 2-Chlorospiro [4.5] decane
3
CzHs C2 H S
'0'
Ans. 3-(Dicbloromethyl)-4-(trichloromethyI) hexane
34.
23. SHC-@-COOH 7C1J4
S •
24. :C) 4
2[>A<J2".
3
1.
I'
ADs. I,4-Dioxacyclohexane
Classification and Nomenclature of Organic Compounds. 111
(a) 2-iminobutan-I,3,4-tricarboxamide 0
(d) CH3-fH-CH2CHO o
(b) 3-imino-4-carbamylhexan-I,6-diamide 0 CH 3
(c) 6-amino-2-imino-4-carbamylhexanamide 0 3-methylbutanal
(d) none of the above 0 42. Match the List I and List II; seiect the correct answer from
37. The nJPAC name of· (:2:J ,i.:
the given code:
List I List II
RCO
(c) bicyclo [2.2.2] decane. 0
(d) bicyclo [3.3.0J nonane . 0 2. bridged bicyclic
38. The IUPAC name of the compound
~H3'~'
(a) 3-(3-methylcyclopentyl) benzene 0
C.~ 3. spirocyclic ~
D
3
39. I. . CH3 CH3 CH 2CH3
C2HS The IUPAC name of the above compound will be:
The nJPAC name of the above compound wili be: (a) 5-ethyl-l-methyl-2-propylcyclohexane 0
(a) l-ethyl-4-(5-methylhexyl)cyclohex-l-ene 0 (b) l-ethyl-3-methyl-4-propylcyclohexane 0
(b) l-ethyl-4(l,4-dimethylpentyl) cyclohex-l-ene 0 (c) 4-ethyl-2-methyl-I-propylcyclohexane 0
(c) 5-( 1,4-dimethylpentyl)-2-ethylcyclohex-I-ene 0 (d) l-propyl-3-ethyl-2-methylcyclohexane . 0
(d) 4-(1,4-dimethylpentyl)-I-ethylcyclohex-I-ene 0 44. The IUPAC name of the compound
40. The IUPAC name of the compound (CH3 )3 c-Q-<1 is :
(a) 3-Thiabutanoic acid 0 51. Which of the following is the correct IUPAC name for the
(b) 3-Sulphobutanoic acid 0 compound given in above question?
(c) 3-Thiobutanoic acid .0 (a) 6-mercapto-4-cyclohexene-l,3-diol 0
(d) 3-Thioxobutanoic acid 0 (b) 4;mercapto-5-cyclohexene-l,3-diol 0 •
47. Select the correct IUPAC name of the following compound: (c) 2,4-dihydroxy-5-cyclohexene-l-mercaptan 0
(d) 4,6-dihydroxy-2-cyclohexene-l-mercaptan 0
(a)
cY>
l,l-cyclobutyl heptane o
53. The IUPAC name of which of the following compounds is
not correct?
Compound IUPAC name
(b) Bicyclo [6.3.0] nonane o
(c) Spiro [3.6] decane o (a) Q-cOOH cyclohexanoic acid
(d) Spiro [6.3] decane o
COOH
•
(b) I-methyl-3-cyclobutylcyclohexane.ift
(c) l-cyclobutyl-5-methylcyclohexane
[]
0 (d) Br~OOH 4-bromobenzoic acid
(d) l-cyclobu~I-3-methylcyclohexane 0
54. Select the correct priority for citation as principal group:
ro
~ CH CH 2
49~ . ~ ~
(a) -C-OH >-C- >-C-H :::f-OH >-SH
~. 0
~
<)1-CH3 o
¢
S~ S6. TIie IUPAC name of is:
(a) 51
6
3
2
OH
(b) :Q:OH (a) phenylethanone o (b) methylphenylketone 0
I (c) acetophenone o (d) phenylmethylketone 0
OH OH
~
g
SH SH
1'
6g 2
0H OH
.57. CH3 -CH-C-CH-OCH2 -CH 3
OCH3
I I
'CH 3
(c) (d) 21 6
5 3 3 5 The IUPAC name of this compound is:
4 4
OH OH
Classification and Nomenclature of Organic Compounds 113
(a)2-ethoxy-4-methoxy-pentan-3-one
(b) 2-methoxy-4-ethoxy-pentan-3-one
[]
0 [Hlni: Th, IUPAC nrun. of ~ ;, b;,yolo (2.2.2) h'","'I
(e) 2-ethoxy-3-methoxy-pentan-3-one []
(d) none of the above 0 60. Select the correct IUPAC names among the following:
58. The IUPAC name of BrCH2 CHCOCH2 CH 2 CH 3 , is: Compound IUPAC name
I
CONH 2
(a) 2-bromomethyl-3-oxohexanamide 0 3,7 -dimethyloct -2,6-dienil
(b) I-bromo-2-amido-3-oxohexane 0
(c) l-bromo-2-amido-n-propylketone 0
(d) 3-bromo-2-propyl propanamide 0
59. Which name is incorrect?
2. c:)<) Spiro (3.6) decane
The ~int of attachment of two rings are caUed bridge head atoms
.. Some bicyclic compounds· like camphor are commonly C. OJ (iii) [404.0]
found in plants. Others like norbomane can be synthesized in the
DO~
laboratory. The formal names ofbicyclic and related ring systems
are based on: (iv) [3.2.0}
(I) Total number of atoms in the molecule.
(2) The number of atoms in each bridge conilecting the
bridge head atoms. These numbers are Written in square bracket
in decreasing order. Codes:
Spirocyclic compo~ds have two fused rings, but only one (a) (A-H); (B-iii); (C-iv); (D-i)
bridge head atom. Spirocyclic compounds are named like (b) (A-i); (B-ii); (C-iii); (D-iv)
bicyclic compounds, but have the. prefix spirocyclo. (c) (A-iv); (B-iii); (C-ii); (D-i) .
Answer the following questions: (d) (A-ii); (B-iv); (C-iii); (D-i)
5. Which of the following is the correct structure of bicyclo
[1.1.0] butane?
(a) [3.2.1] (b) [3.1.0] If the organic compound contains more than two similar
(c) [1.3.0] (d) [2~1.0] terminal groups and all of them are directly attached to the
3. Select the correct statements about the following principal chain, then none of them forms a part of the principal
compounds: chain. Special sufftxes are used to name these.
Functional group Suffix
. -CONH2 Carboxamide
-CN Carbonitrile
-CHO Carbaldehyde
-COOH Carboxylic acid
(a) it is a tricyclic compound Carbon atoms of these terminal groups are not counted in the
(b) it is bicyclo compound principal chain. If anyone of these terminal groups is not directly
(c) it is spiro compound attached to the parent chain and forms the part of side chain, then
. (d) its IUPAC name is bicyclo [2.2.2] octane the longest chain is selected containing two such similar groups at
4. Match the List I with List II and select the correct answer its two ends. The groups present in the side chain-are treated as
from the given codes: substituents and are indicated by suitable prefixes.
List I List II Indicate whether the following IUPAC names are true (a) or
(Compounds) (Number of carbons false (b).
in the bridges)
(i) [3.2.1]
Classification and Nomenclature of Organic Compounds 115
1. BOOC-CH2 -CH-CH2-COOH
f Propane-l,2,3-tricarboxylic acid
True (a) False (b)
CN
I
2. NC-CH2-'-CH-CH 2 -CN 3-cyanopentane-l ,5-dinitrile
True (a) False (b)
CH2 -COOH
, I
3. HOOG-CHz-CH-CHz-COOH" 3-(carboxymethyl) pentane-l ,5-dioic acid '
True (a) False (b)
CH 2CHO
, I
4. OHC-CH 2 -CH-CHz-CHO 3-(formylmethyl) pentane-l,5-dial
,True (a) , False (b)
CONH 2
I
5. H2NOC-CH2-CH-,-CH2~CONIf2" ,Propane-l,2,3-tricarboxamide
True (a), False (b)
Passage 3
, 0
II S* 6
COOH"
'
The priqrities for citing principal groups in a carboxylic acid
derivative areas follows: (a) CI-C 4f_\~\, 02CH3
acid > anhydride > ester > acid halide > amide > cyanide 3 2
All of these groups have citation priority over aldehydes and CN
"*1
ketones as well as the other functional groups. o C02H
Name ,of' carboxylic acid derivatives when used as
substituent groups are : (b) CI-C, Sf_'2 OzCH3
Group Name
4 3
-COOH carboxy
CN
o
I
'-C-OCH3
V
-C-OC2Hs
methoxy carbonyl
ethoxy carbonyl
?!*I
(c) CI-C, 3
CN
f_' 6,
4 5,
C02H
02CH3
"
o
I
-CH2-C-OH carboxy methyl
-0-G-CH3 '
V acetoxy
o o
II
-C-CI chloroformyl 2. Cl-QJ--NH-CH'
o
I Which of the following is the correct IUpAC name of the
---'C-NH2 carbamoyl above compound?
Answer the' following questions: (a) p-acetamido chlorocyclohexane,
1. Which ofthe following structures has the correct locants? (b) 4-chloro-N-methyleyclohexane carboxamide ,
(c) N-methyl amido chlorocyclohexane
(d) none of the above '
";
118 G.R.B. Organic Chemistry tor Competitions
Cyclohexaneoyl chloride
V
(a) CH)-C-NH- group is principal group
(c) Q CN
CH)
2-methylcyclobutane
carbonitrile
r .
(b) CH3-C-NH- will be considered as substituent
Br .
~COOCH3 Methyl,2-bromocyclohexane
group (d)U carboxylate
(c) Locant number 1 will be assigned to -COOH
(d) p-acetamidobenzoic acid -is its systematic name
4. For which of the following compounds, the IUPAC name is
wrong?
r
5.. CH3-fH-Clll-C-O-CHz-fH-CH3
Compound IUPAC name
CI Br
Select the correct IUPAC name among the following:
(a) 3-chlorobutyl-2-bromopropanoate
2-methyl .:yclopentane (h)· ::!-chl .. robutyl-3-bromopropanoate
carboxamide I,'j ..., -hl\liilopropyl-3-chlorobutanoate
l d I ,I-bromopropyl-Jl-chlorobutyrate
=
4
ISOMERISM
(
4.1 INTRODUCTION
The molecular structure of the organic compounds plays a very important role in the study of organic chemistry. There are
numerous examples where it is observed that the same molecularformula can represent more than one compound having different
properties. For example, ethyl alcohol and dimethyl ether have the same molecular formula (C 2H 60) but show different physical
and chemical properties.
CH 3COOH HCOOCH 3
Acetic acid Methyl formate
CH 3-CH-CH3
CH3CH 2CH 20H CH3-0-C2lfs
n- PropylalooooJ 6H
lsopropylalcohol
Ethyl methyl ether
H2r-TH~
CH 3-CH 2-CH =CH 2 CH 3CH=CHCH 3
But-I-ene H2C-CH 2 ,But-2-ene
. Cyclobutane
CH 3-C=CHz
3
H C> C=C <H H)C) <CH3
C=C I
H CH3 H H CH3
Trans-2-butene . Cis-2· butene 2-Methylpropene
118 G.R.B. Organic Chemistry for Competitions
c5
or skeletal isomerism. The isomers showing chain isomerism'
belong to same homologous series. The simplest compound
exhibiting this type of isomerism is of molecular formula, (iii) ~
(iv)
C 4 H lO (butane). It exists in two forms,
CH 3
'I
CH 3CH 2CH 2CH 3
n-J.3utane (Butane).
(StraIght carbon cham)
CH3-CH-CH3
lsobutane (2-Methylpropane)
(Branched carbon chain)
(V)'~OH (W) ~OH
o o
&
Pentane (C s HI2) exists in three isomers,
CH3CH2CH2CH2CH3 CHi-CH-CH2--CH3
n-Pentane (Pentane) 1
(vi,) (viii)~
CH 3
lsopentane (2-Methylbutane)
"J
Isomerism 119
Solution: (ii) and (iii) ; (iv) and (vii); (v) and (vi);
(i) and (viii).
'Example 2. Write down all structural isomers ofC 6 H 14 .
CgHlO OCH3; OCH; 0
CH3 CH3 CH3
oCI
Solution: p-Xylene
~
(a)
(c)
~
~
n-Hexane
3-Methylpentane
(p)
(d)
2-Methylpentane
~
2,2-Dimethylbutane
CsHgCh
CC 1,2
CI CI
Dichlorocyclopentane
1,3
OCl; OCl; 0
Cl Cl ,Cyclob!ltane propane
Cl
C~4C12
Q-Dichloro- m-Dichloro~ CI
benzene benzene' p-Dichlorobenzene .
120 G.R.B. Organic Chemistryfor Competitions
CH3CH2CH2CH2CH=CH2
Hex-I-ene
It can be included in functional isomerism, if ring chain
isomerism is not mentioned.
Cyclobutene 3-Methyl
If\,
I-Methyl
CH
3
4.5 FUNCTIONAL ISOMERISM cyclopropene . cyclopropene
Compounds having same molecular formula but different (v) Cyanides and Isocyanides (-CN and -NC)
functional groups in their molecules s.how functional
isomerism and are called functional isomers. As the functional C 2 H3N CH 3CN CH3~C
Methyl cyanide Methyl is('cyanide
group determines largely the properties of a compound, such
isomers differ in their physical and chemical properties. (vi) Nitro alkanes and Alkyl nitrites (-NO z and
Examples: -O-N=O)
. (i) Alcohols and Ethers (C n H 2n +20)
C2H 60 CH 3CH 20H H3C-O-CH 3 C 2H s-O-N=O
Ethyl alcohol Dimethyl ether Ethyl nitrite
CH 3CH 2CH 20H C 2H s-O-CH 3 Nitroethane
n-Propyl alcohol Ethyl methyl ether (vii) Amines (Primary, Secondary and Tertiary)
C 4 H lOO CH 3CH 2CH 2CH 20H C 2 H s-O-C 2 H s
n-Butyl alcohol Diethyl ether C3H9N CH 3CH 2CH 2 NH 2 CH 3CH 2-N<H
(ii) Aldehydes, Ketones and Unsaturated alcohols, Propanol-amine CH
3
Ethers and other Cyclic compounds .•• etc., (C n H 2n O) N -Methylethanarnine
-0
<
CH 3
I CH 3CHCH 3 CH 3-N
C3 H 6 0 CH 3CH 2CHO CH3-C-CH} ;
Propionaldehyde Acetone I CH 3
NH2 N • N -Dimethyl-
CH 2-CH-':"CH 3 H 2C=CH-CH 20H Propan -2-arnine methanamine
"-:/ Prop-2-en-I-ol
(viii) Alcohols and Phenols
°
1,2-Epoxy propane
(Allyl alcohol)
CH20H
OCH,
OH
O
~I
(2-Methyloxirane)
o
1,3-Epoxy propane
(Oxetane)
Methyl vinyl ether Cyclopropanol
C7HsO ~
Benzyl alcohol
(ix) Oximes and Amides
o-Cresol
OCH OCH; 0
Solution: (ii) and (iii) ; (iv) and (vii); (v) and (vi); CH3 CH3 CH3
(i) and (viii).
CSHIO 3;
-Example 2. Write down all structural isomers ofC 6 H 14 .
Indicate chain and position isomers among them. CH3
fJ-Xylene m-Xylene
Solution: p-Xylene
(a) ~
n-Hexane
(b) ~
2-~etbylpentuie
c(1 5JP
(c) ~ (d) ~ Cl Cl
3-Methylpentane 2,2-Dimetbylbutane l~ l~
Dichlorocyclopentane
4.3
_Cham isomers: (a), (b),(c), (d), (e)
Position isomers: (i) (b) and (c);
POSITION ISOMERISM
(ii) (d) and (e)
0,2
CH -
"
Propan-2~01
(Isopropyl alcohol) CH 3-"-C=CH ; HC=CH
Propyne Cyclopropene
C 4H lOO CH 3CH 2CH 2CH 2OH; CH 3 CHCH 2CH3
Butan-I-ol I CH3
OH
Butan-2oOl I
CH
Note: Aldehydes, carboxylic acids (and tbeir derivatives)_ A
cyanides· do not exhibit position isomerism. C4H~ CH 3CH 2CH=CH 2 ; H 2C-CH2
But-l-ene Methylcyclo-
OCI; OCI; 0
CI CI Cl propane
C6~C12
~ .
CH2-CH2)
o-Dichloro-
benzene
m-Dichlol;Th-
benzene
Cl
. I CHCH 3
p-Dichlorobenzene CH 2 -CH 2
Methylcyclopentane
120 G.R.B. Organic Chemistryfor Competitions
°I
<
CH 3
CH 3CHCH 3 CH 3-N
C 3H 60 CH3CHzCHO CH 3 -C-CH 3 ;
Propionaldehyde Acetone I CH 3
NH2 N, N -Dimethyl-
CH z-CH-CH 3 H 2C=CH-CH 20H Propan -2-amine metha.ne
~ Prop-2-en-l-ol (viii) Alcohols and Phenols
° (Allyl alcohol)
CH20H OH
1,2-Epoxy propane
(2-Methyloxirane)
0?71 O CH
o
1,3-Epoxy propane Methyl vinyl ether Cyclopropanol
C7H gO ~
Benzyl alcohol
(ix) Oximes and Amides
o-Cresol
3
(Oxetane)
(iii) Acids, Esters and Hydroxy carbonyl compounds CH 3CH=NOH;
°I
CH3-C-NH2
... etc., (C"Hz"Oz) Acetaldoxime Acetamide
C 2H 40 CH 3 COOH HCOOCH 3 (x) Thio alcohols and Thio ethers
2
Acetic acid Methyl formate C 2H(jS C 2H 5SH CH3-S-CH3
Ethyl thioalcohol Dimethyl thioether
CH 3CH 2COOH CH 3COOCH 3
Propionic acid Methyl acetate
4.6 METAMERISM
o It is the isomerism in the same homologous series. It is due to the
I presence of different alkyl groups attached to the same
CH 3 CHCHO CH 3 CCH 20H
polyvalent functional group or atom (i.e., -S-,
I I-Hydroxy-
propan-2-one -NH- and -CO---). So, the compounds having same
OH
2-HydroxypropanaJ .molecular formula but different structural formulae due to
(iv) Alkynes Alkadienes and cycloalkenes (C"Hz,,_z) different (size or nature) alkyl groups on either si!ie of the
functional group are called metamers and the phenomenon is
C4 H 6 CH 3CH 2-C==CH H 2C=CH-CH=CH 2 known as metamerism.
But-I-yne Buta-I,3-diene Examples:
CH 3-C==C-CH 3 H 2C=C-:-CH-CH 3 C 4 H IOO C 2 H 50C 2H 5 ,. C 3H 70CH 3
. But-2-yne Buta-l,2-diene Diethyl ether Methyl propyl ether
•
Isomerism
6 6
(Pentan-2-one) (Pentan-3-one)
are metamers and not position isomers. They can be included
~
. in position isomerism, if metamerism is not mentioned.
(b) CH 3-C---CH 2CH2 CH 3 ; CH 3 -C-CH-CH 3 Cyclohexanone eye lohex-l-en-I-ol
(Keto form, 99%) (Enotie form, 1%) .
I I I
o o CH 3 The greater stability of keto form than the enol form in all
(Pentan-2-one) (3-Methyl butan-2-one) these examples is due to greater strength of C-O, 1t-bond
are metamers and not chain isomers. (87 kcaUmol) as compared to C-C, 1t-bond (60 kcaUmol).
2. Triad system :
(i) Keto-enol system:
and two carbon atoms.
Polyvalent atoms are oxygen (d)\ rH ---"-
~
~ ~ ~"~~~~"
resonance and hydrogen bonding than their corresponding
keto forms.
, Enolisation is in order: CH3~C-CH2-:C-CH3 ........- CH 3-C=CH----:C-CH 3
Acetyl acetone ' , Enol fonn, (76%)
, CH3COCH3<CH3COCH2COOC2H5 <C6HsCOCH2COOC2Hs Keto form, (24%)
, < CH 3COCH2CO<;:H 3 < CH 3COCH2COCH 3 O---H-O
« >=0 f----7
I
CH 3-C-CH=C-CH 3
I ,
Percentage of enol content in some compounds Iftheenolic form besides H-bonding is also stabilised by ,
conjugation, (i.e.; enolic double bond is in conjugation with
Ci!Dipound " Enol (in %) , another double bond or amuItiple bond or a benzene ring) the
o enol contentfurther'tncreases. Thus, the only form which is
II 0.00025 exhibited in phenol is enolic form.
CHr~C-CH3,
b
o OH'
~ 4.8
" I, '
" ,
CHr
,~ ", '
100.0
(Keto) .
& (Enol)
Isomerism '123
.0,'. n--Qf.'"
-
-C.
-
, 0 0 .0 ;
Br
2-Bromobutane
CH 3 .
Benzophenone p-Be~quinone
I
(iv) .. CH3-C- CH 3
I .
Br
2-Bromo-2-metbyJpropane
(iii) HCOOC 2 H s (iv) CH 3CH-CHO [Hint: ( )-oH will be most stable enol fonn due to
Ethyl methanoate I resonance. 1
OH
2-Hydroxypropanal 7. Which of the following is( are) an isomer of compound (i)?
(i) CH z -CH-CH3
o "-/
II o
(v) CH 3 -C--CH 20H
I-Hydroxypropan -2-one
o
(ii) CH3 -CH z
I
-C-H
ILLUSTRATIONS OF OBJECTIVE QUESTIONS o
1. Which of the following is a dynamic isomerism? II
(a) Metamerism (b) Geometrical isomerism (iii) CH 3 -C-CH3
(c) Tautomerism (d) Optical isomerism (iv) CH3 -CH=CH-OH
[Ans. (c)] (a) (ii) (b) (iv)
3. Enol content is maximum in: (c) (ii) and (iii) (d) all of these
(a) acetone (b) acetophenone . [Ans. (d)]
(c) acetic acid (d) acetylacetone [Hint: All are structural isomer to each (ll",:']
(3) Acyclic isomers carbon atoms (two groups linked to each carbon atom utilising
hybrid orbitals) fixed in space and is responsible for space
o o isomerism known as geometrical isomerism.
II I So, in genera l. the geometrical isomerism is shown by
CH 3-C-CH 3 ; CH 3-CH2-C-H
Acetone Propanal alkenes or their tkrivatives in which two different atoms or
groups are attached to each carbon containing double bond
CH 2=CHCHPH; CH 2=CH-O-CH 3 and carbon atoms joined by double bond cannot rotate freely.
Prop-2-en-l-ol Methoxy ethene Let us consider now the various groups linked to two
(Allyl alcohol) (Methyl vinyl ether) carbon atoms joined by a double bond.
1st Case: When two groups attached to a carbon
(b) Cyclic isomers
atom are same,
X
H
Ci 1\
0
CH3
a-C-a
a-C-b
II or
a-C-a
~C--a
I
Oxetane Propyleneoxide Cyclopropanol .
(I)
or or
Both the structures are identical
~CH2 CH3~C~H2 a-C-a a-C-a
o o
1,2-Epoxypropane
I or II
1,3-Epoxypropane b-C-d d-C-b
Thus, there are total seven isomers.
.
(II)
Both the structures are identical
Note: For writing the structural isomcl's for any given molecular
formula, tautomers are neglecl(',1 unless otherwise asked for. Geometrical figures in (I) and (II) will be identical, hence,
no geomdrical isomers are possible.
4.8 GEOMETRICAL ISOMERISM 2nd Case: When two groups attached to 3 carbon
A double bond between two carb(>n atoms consi~ts one sigma atom are different,
(0) bond and one pi (re) bond. Both the carbon atoms are sp2_ b-C-a b-C-a
hybridized, giving thre'c hybrid orbitals each. One p-orbital of I or II .
each of the carbon atoms is left as such, i, c., it does not take b-C-a a-C-b
v
part in hybridization. The sigma bond between the two carbon (III)
atoms is formed by overlap of one hybrid orbital of each of the Non-identical
carbon atom, while 1t -bond is formed by the overlap of one b-C-a b-C-a
p-orbital of each carbon atom.
Like the p-orbitals, a re -bond has two lobes. One half of II or I
d-C-e e-C-d
the 1t -bond lies above the plane containing the two nuclei and
other halflies below the plane (The two carbon atoms a!1d four "
(IV)
hybrid orbitals lie in ihl! same plane while the lobes of 1t-bond Non -identical
lie above and below this plane). Rotation around 1t-bond is ~C-a ~C-a
not possible. If any attempt is made to rotate one of the carbon II or II
atoms, the lobes of p-orbitals will no longer remain coplanar, d--,-C-a a-C-d.
i. e., no parallel overlap will be possible and thus, 1t-bond will v
break and it requires the energy ofthe order of 251 kJ. This is (V)
Non -identical
known as concept of restricted rotation~ In other words, the
presence of 1t-bond makes the position of two carbon atoms The two geometrical figures [as shown in (m), (IV) and (V)]
rigid, i.e., fixed with respect of each olIK'!'. The restriction in will be different and hence, geometrical isomers are possible.
rotation makes the position of four groups attached to two Such isomers, which possess the same molecular and
structural formula but differ in the arrangement of atoms
or groups in space due to hindered rotation around the
Hybrid Hybrid
, orbital orbital double bonded atoms, (i.e., )C=C, )C=Nand
-N=N) are known as geometrical iS01ners and the
phenomenon is known as geometrical isomerism. The
Hybrid isomer which has similar groups on the same side of the
orbital double bonded carbon is called 'cis' isomer (Latin: cis = same
side) and the isomer which has similar groups on the opposite
p-orbital p-orbital side of the double bond is known as 'trans' isomer (Latin :
Fig. 4.1 Formation of double bond trans = across). However, in cases where all the four groups
,:126, ' G.R.B. Organic Chemistry fOr Competitions
are. different (abC=Cde), it'is notpossible to decide the cis ' In aldoximes;when -H and ~H groqps are, on the
and'transisomers. ' . ' ' ," same side of the, double bond, the isomer is known as'syn'
" The compounds· like" 1,2-qisubstituted "alkenes and, , ,(analogous to cis) and When these groups are on opposite sides
uns'aturated dibasic acids are capable ofshowtng geometrical of the double bonq, the isomer is known as 'anti' (analogous to
, isomerism. trans).,' '
, Examples: (a)Ctsand1.hins:' .(i) "CJIs--C,--H
" '
CJI~~H
(i) 1,2-Dichloroethene' " II
:)cc<:·
'11 '
H)' C=C'<CI, "
N---OH
Syn-benzaldoxime
(a),m.pt~ 35°C
HO-N
Anti-benzaldoxime
(~), m.pt. 30~C
CI H' ,
(Cis) (Trans) ,(ii) Similarly, azocompounds are also named
(ii) But-2-ene (CH 3CH,:....-CHCH 3) CJIs
N N N N/
C
H3 ) _ <CH 3 H3C~_ ( , CJIi' =, "Ct;Hs CJIi'
C-C , /v-:C, Syn-azobeniene Anti~azobenzene,
'<'H ",
(iii) C6Hs--G-CH3
, II
HOOC) <COOH HOOC) , N---:-OH'
C=C ' c=c' '
Syn-methyl,phenylketoxime
H H H COOH Anti-phenyl methylketoxime
Maleic acid Fumaric acid
(Cis) (Trans) , CJIs--C--CH3
(iv) Crotonic acid and isoCrotonlc acid II
HO-N
Syn-phenyl methylketoxime '
H)C=C<H H)C=C<'COOH, Anti-methyl phenylketoxime
H3C " ' COOH H3C '' , H '' (iv) , p;-CH3-C6H4-C-C6H5
'~ ,
Isocrotonic acid CrotClnic acid ,
H H
OOH
containing C N (aldoxime and ketoxime) and N = N (azo
compounds) bonds also ~how geometrical isomerism.
However, in these cases~ 'syn' (for cis) and 'anti' (for trans) COOH COOH COOH H
are more commonly used. (Cis) (Trans)
Isomerism 127'
(ii) Cycl~tane 1,2 and Cyclobutane 1, 3-dimethylderivative (iv) dipole moment : In general cis-isomer has higher
.lQl fHf
dipole moment than trans-isomer as cis-isomer of an: alkene IS
found to 'be more polar than the tfans-:-isomer. .
(v) Stability: Ingeneral,trans~isomer is more stable
but less reactive than cis-isomers. The stearic repulsion ofthe
"
Hrl
f-l
CH3
~J H3
H)
C
C=CCH
"<H
b.pt. = 277 K
3 H3C
H) C=C"<CH
H
3
CI). /Cl
(Cis) (Trans)
n}--ItH ~=r 3
b.pt. 333.3 K
(Cis)
1l=1.85D
Maleic acid and fumaric acid :
H
b.pt. = 320.5 K
(Trans)
·1l=O.OOD
Cl
t:=r
1,3-Dimethyl cyclohexane H). C=C <H C=C
HOOC COOH HOOC H
.t-\f Maleic acid (cis-) Fumaric acid (trans-)
d~tH3 CH3 . H
,mpt. =403 K
(Solubility 79 gil 00 mI H20)
mpt. = 575 K
(Solubility ofO.7g1100ml H 20)
(Cis) (!,:ans)
Cis-trans isomers are configuration isomers and called
1,4-Dimethyl cyclohexane diastereomers as they are not mirror images of each other.
(d) Alkadienes: For example, hexa-2,4-diene shows Cis-trans isomers have similar but not identical
different cis and trans isomers. chemical properties. For example, maleic acid (cis-isomer)
forms anhydride on heating while fumaric acid (trans-isomer)
cis cis trans does not give anhydride. This means that in maleic acid, the
\!~.
FvV~ two-COOH groups are on the same side of double bond and
trans
~ on this basis the configuration of maleic and fumaric acid can
be established. '
Physical properties 'of cis-trans isomers: H-C-COOH 403K H-C-CO) ,
(i) melting point: m.p. of trans-isomer" is more than II ) II ," O+H 20
H~C-COOH (Heat) H-C-CO
that of cis-isomer. "
(Cis) Maleic acid Maleic anhydride
(ii) boiling point: b.p. of cis-isomer is more than that of
trans-isomer. Further ciS'- and tranS'- isomers behave differently towards
(iii) solubility: The solubility viscosity and refractive alkaline KMnO 4 and Br2 water.
index of cis-isomer is more than the trans isomer in a given
solvent.
G.R.B. Organic Chemistry for Competitions
Br2 water
H-C-Br
rOOH
.•
But-2-ene
I
CH 3
(addition to trans side
but on available site)
(Anti-addition)
I Determination of configuration of aldoxime and
H-C-Br
I ketoximes: The two fonns 'syn' and 'anti' of aromatic oximes
COOH resemble each other in many ways but differ in the behaviour of
(meso) their acetyl derivatives towards sodium carbonate solution.
I
H Ar.........C/H
\I Na2C03..
r
C + AcOH
CH3-C-OH N
Alk.KMn04
I Acb/ m
CH3-C-OH (Anti) Cyanide
CH 3 -C-H I
CH3-C-
I f'
H
(meso) Ar......... /H Ar......... /H
Cis-2-b\u C . C
Br2
~ d-and/- \I \I + AcOH
(Anti-addition) (racemic) N N .........
2,3~Dibromobutane ......... OAc OH
H (Syn) Aldoxime
I
CH 3 -C-OH Configuration of ketoximes is determined by Beckmann
Alk:. KMn04 rearrangement.
- I
HO-C-CH 3 R
CH3-C-H I ) C=NOH H2S0 4 ) R'CONHR or RCONHR'
H
I R' Acid amide
H-C-CH 3 d- and /- Ketoxime
Trans-2-butene (racemic)
Br2
(meso)
(Anti-addition)
Isomerism
The two different amides can be identified by their (i) The symbol 'E' is assigned to an isomer in which the
hydrolysis to different acids and amines. In this rearrangement atoms or groups of higher precedence are on the opposite
the migration of groups is always trans (anti) to the leaving. side (E from German word, Entgegen;:;: across or opposite).
group (-OH). (ii) The symbol 'Z' is assigned to an isomer in which the
~ atoms or groups of higher.precedence are on the same side (Z
(
HO-N
R-C:JR'
. II
Ketoxime
- from German word, ZuSitfhmen :;;: together) ..
In such cases, E and Z system of nomenclature is used. the group> C=O is equal to >C-O
This system is based on a priority system developed by Cabn, I
Ingold and Prelog.
o
In this system, the two atoms or groups attached to each of N
the doubly bonded' carbon are put in order of precedence I
and the group -C=N is equal to -C-N.
(priority) on the basis of sequence rules. . . I
N
130 G.R.B. Organic Chemistry (or Competitions
Example 6. Give the E-Z designation of each of the The senior groups are on the opposite side. Hence, it is the
following: 'E'isomer.
(iv) Precedence order :
(i) F)c=c<Br C6HS->-B; -COOH>C 6 HS
CI I (i) G:i (j) cy
HOOC) <H
~c=c(G)
(ii)
H
C=C
COOH
ar" CD
The senior groups are on the opposite side. Hence, it is the
Cl COOH 'E'isomer.
(iii) )c=c< (v) Precedence order: CH 3 > H
. HO I CD @
6H H ~C=_fl
(iv) C S)C=C<:6 S (if" L~G>
H . COOH The senior groups are on the same side. Hence, it is the 'Z'
isomer.
H3C) <CH 3 (vi) CI> H, Br > C~ hence, it is ' Z' isomer.
(v) C=C (vii) It is 2,4-hexadiene. At position 2(CH3 > H,
H H -CH =CHCH 3 > H), it is ' Z' isomer and also at position 4, it
is ' Z' isomer. Thus, it is (2Z, 4Z) isomer.
H <CI (viii) It is hexa-2,4-diene. At position 2, it is 'E' isomer
(Vl) )C=C
and so at position 4. Thus, it is (2E, 4E) isomer.
CI Br
(ix) 'E' isomer.
(vii) \ /. \ (x) 'Z' isomer.
Example 7. .Indicate the configurations ofthe following
geometrical isomers:
(vlb) /
(a)~ (b);=U
or~
Rotated Rotated
to right to left
Fig. 4.2
The measurement of optical activity is done in terms of
specific rotation which is defined as the rotation produced
by a solution of length of-l0 centimetre (one decimetre) Chiral Achiral
(two unequal halves) . (Two equal halves)
Fig. 4.3 Chiral and achiral objects
G.R.B. Organic Chemistry (or Competitions
P q
I I
I
optical activity.
,,,
A A
I
I
'I.. CH 3 CH 3 CH 3
.,,, ,, I
,, ,, 1* 1 I
I , H-C-OH H-C-CH3 H-C-H
Chiral Achiral 1 . I I
(Non-superimposable) (Superimposable) COOH COOH COOH
. Lactic acid Isobutyric acid Propionic acid
The cause of optical activity was put forward by van't (Chiral) (Achiral) (Achiral)
Hofland Le Bel in 1867. According to them, the four optically active optically inactive optically inactive
valencies of carbon atoms are directed towards. the four When an interchange of two ligands bonded to an atom
corners of a regular tetrahedron. If there are four different results . in a new stereoisomer, the atom is termed as
atoms or groups a, b, c, d attached to four corners of a stereogenic centre (stereocentre).
tetrahedron, then two different arrangements are possible' . It is true that most of the compounds which contain
which are not· superimposable and bear the mirror-image chirality centre show optical isomerism. The formulae of a
relationship, i.e., act as enantiomers. (Fig. 4A). Hence, a few compounds are given below and each has atleast one
compound which consists of atleast one asymmetric chirality centre (stereo genic centre) and hence, optically
carbon atom is capable of showing the phenomenon of active. It is marked by asterisk sign (*).
optical isomerism.
CH 3 H3 C
.Mirror 1* I
d (i) H-C-OH HO-C-H
I 1
COOH HOOC
b c Lactic acid (Two enantiomers)
(v)
COOH
I
H-C~H
HOOC
HO-C-H
1
b
~x --x
+y
'~Y
'b
,
HO-C-H
I ', 1
H-C-OH
.'
I
CH 3
-----+
H-C-OH
------- Plane of Symmetry
Three forms of lactic acid are known. Two are optically
active and third is optically inactive. ,I \
: COOH;
t ____ .:.. _______,
A)C=C=C,
B
<A A)c=c=c<X '
B B Y
---\B;. ~B}m-<B; \O}m
H)C=C=C<C Hs , 2 B B B
(Both rings have no plane of symmetry) .
B
>
H3C H
--'~\~; ~Otm
N 2
o2 C=C=C<NH
.
Et Et
2. Alkylidenes: When one of the C-C double bonds in A B
allenes is replaced by one cyclohexyl ring, the (Both rings have plane of symmetry)
compound is known as alkylidene cycloalkane. Such
compounds will be optically active if two groups 4.12 NUMBER OF POSSIBLE STEREOISOMERS
attached to each terminal carbon atom are· different. IN COMPOUNDS CONTAINING DIFFERENT
Examples are : NUMBER OF ASYMMETRIC ATOMS
The number of optical isomers of a compound depends on
its structure and number of asymmetric carbon atoms present
in its molecule. The number of optical isomers is calculated by
the application of the following rules:
(i) Wheri the molecule cannot be divided into two equal
halves, i.e., the molecule has no symmetry (unsymme-
trical) and (n) is the number of asymmetric carbon atoms, then
3. Spiranes : When both the C-C double bonds The number of d- and 1-(optically active) forms, a 211
(C=C=C) in allenes are replaced by two cycloalkanes
(same or different) rings, the system is known as and The number of meso-forms, m = 0
spiranes. Examples are : • Total number of optical (stereo) isomers =a + m =2 11
AXXXA A~X *
For example, CH 3 -CHOH-COOH (Lactic acid)
B B B~Y
=21 =2, m =0, r =2 =I
CI>ocxH
where, n =: I, a
2
Br NH2 So, total optical isomers =: 2 + 0 =: 2
4. Biphenyls: They show optical isomerism when the (ii) When the molecule can be divided into equal halves,
following two conditions are satisfied : . i.e., the molecule has symmetry and the number (n) of
(i) Each ring in biphenyl should have two different ortho asymmetric carbon atoms is even, then
substituting groups or the minimum number of The number of d- and l-(optically active) forms, a =2(11-1)
substituents should be two i.e., one substituent in each
and The number of meso-forms, m = 2 (11/2)-:1
ring. The two substituents must have a large group
(bulky) like -N0 2 or-S0 3Hgroups. Examples are: Total number of optical isomers =a + m
=2(111) +2(n/2)-1
<()~A~(» N~ F *
For example, HOOC-CHOH-l-CHOH-COOH
I *
BD
Where,n= 2 ,a= 2 n-1 =22-1 =2'1 =2
m =2(nI2-1) =2(212-1) =2° =1
So, total optical isomers =: 2+ 1= 3
G.R.B. Organic Chemistry (or .Competitions
. (iii) When the molecule can be divided into two equal halves
(symmetrical) and the number (n) of asymmetric carbon
atoms is odd, then
(i) t)f'
Cl H K:j'
CI H
and
The number of d- and I-forms, a =2(11-1) _2(n-I)12
The number of meso-forms, m =2(n
Total number of optical isomers = a + m = 2(n-1)
For example,
1)/2
(ii) ~a
CH3
avo CH
I
I 3
H--~C,C H
'" '" I '"
CH 20H-CHOH-dHOH-CHOH-CH 20H (iiz) C H /C---H
I
2 5 "'Br Br'" 2 5
where, n == 3, a == 2 (n-I) - 2(1l-1)/2 - 21 == 2
m==2(n-l)/2 =2(3:"'1)/2 =2 1 =2
CH2Cl CH2Cl
So, total optical isomers 2 + 2 4
In all the above three cases, the number of race,mic
I I
H-:-C-OH HO-C-H
forms will he al2 (iv) I I
Example 9. Mark the asymmetric carbon atoms and give HO-C-H H-C-OH
the number of optical isomers in the following compounds: ' I \'
(i) CH 3-(CHOHh-COOH CH2CI CH2Cl
(if) HOCH2-'---(CHOH)4-CHO OH OH
. (iii) HOCH2-(CHOH)4-CH20H I I
, Solution: (v) CH/C~-H H---C,C H
H H 2 5. CzH 5 /
C2H5
2 5
L I.
(i) CH.3-C- C-,-COOH Solution: Enantiomers (i), (li), (iii) and (iv); Identical (v).
. I I .. Example 11. Calculate the d- and I-isomers formed by
OH OH the follOWing compound and also give the number of meso
forms. .. .
The compound cannot be divided into equal halves and it
consists of two asymmetric carbon atoms, HOOC-CH(CH 3)-CHOH-,- CHBr-CHOH-
Hence, the nurriber of d- and 1- (optIcally active) isomers, CH(CH 3 )-COOH
a =211 =2 2 =4 SoIWi'jil: The compound can be divided into two equal
and Number of meso forms, m = 0 halves and it consists of five asymmetric carbon atoms, i. e.,
odd number of asymmetric carbon atoms.
So, Total' optical isomers = a + m = 4 + 0 = 4
Hence, the number of d- and I-isomers
H H H H H H = 2(n-l) _ 2 (n-I)/2
II I I I I
(ii) HO-C-C~~-·-C~=O (Glucose) =2(5-1) _2(0.5X5-0.5)
~
6H 6H 6H 6H
=2 4 _2(2.5-0.5) =2 4 _22
. 16 =16-4 =12
where n=4 a =2 4 =16, m=O r= ::::8 Number of meso isOmers == 2 (n-I)/2
. " , 2
So, Total optical isomers = 16 + 0 =16 =2(2.5-0.5) = 22= 4
IH H H H H H So, total number of configurational isomers =12 + 4:::: 16 .
II I I I I Example 12. Calculate the number of geometrical ..
(iii) HO-C-C~~~~-OH (Sorbitol)
, I \ I I I I isomers in the following polyenes~
. H OH OH OH OH H (i) H 3C-CH=CH-CH=CH-CH=CH-CH
where,n=4,a=2(4-1) ::::2 3 =8,m=2(4/2-1) =2(2-1) =2, r =CH-Br
(Ii) H 3C-CH=CH-CH=CH-CH=CH-CH
8 =CH-CH 3 '
r =4
·2 (iii) C6H5 -CH=CH-CH=CH-CH=CH-C6H s
So, Total optical isomers =8 + 2 =10 (tv) C6Hs-CH=CH-CH=CH-C1
Example 10. Indicate whether the following pairs are Solution: (i) The molecule has four double bonds and
identical or enantiomers : can not be divided into two equal halves (unsymmetrical).
Isomerism
( }-b=O+NH2-0H~ ( >--:ob.
(ii) The molecule has four double bonds (even number)
and the end of polyene are same (symmetry). N-OH+H20
The number ofgeometric~l isomers =2(n-l) +2(n/2)-I, X1me
It shows 'sYn' and 'anti' isomer.
=2 3 +21 =8+2=10
~H5",/H
(iii) The molecule has three double bonds (odd number). c
(n+l) _I
The number of geometrical isomers =2(n-l) + 2 2
II and
N-OH
=2 2 +2 2- 1 =4+2=6 13. Which of the following alkenes shown below· has the
.(iv) The moh:icule has two double bonds and is Z-configuration of its double bond?
unsymmetrical.
The number of geometrical isomers =2 n
2
(a)~ (b)~
=2 =4
~
example, the reduction of pyruvic acid (CH 3-C-C00H) in
reaction the configuration of the new compound may be
opposite to that of the original, i.e., .
presence of nickel catalyst gives (±) lacpc acid (racemic COOH COOH COOH
mixture). H--1-OH PCls .. CI--1-H AgOH.. HO-C-H
I
(i) On the other hand, pyruvic acid is reduced to (- ) lactic
I I I
acid only by yeast or to (+) lactic acid with NaBH4 CH2COOH CH2COOH CH2COOH
(+) Malic acid (-) ChIoro succinic (-) Malic acid
acid
1 PCls
COOH COOH
I AgOH I
H-C-OH '" H-C-CI
I I
CH2COOH CH2COOH
(+) Malic acid (+) Chloro succinic
acid
Isomerism 139
I
I
HO-C-H
COOH
H-C-OH
HOOC
I
HO-C-H
I
H--C-OH
CH
H
>
geometrical isomers.
3
C=C<CH
H
3
CH
H
>
3
C=C <H
CH 3
(Cis) (Trans)
I I The important characteristics of diastereomers are:
COOH HOOC
Mirror (i) They show similar but not identical chemical
(I) (II)
• properties. The rates of reactions are different.
One pair of eoantiomers
$
(ii) They have different physical properties, such as
melting points, boiling points, densities, solubilities,
.,COOH HOOC
refractive indices, etc.
I I (iii) They can be easily separated through fractional
H--C-OH HO-C-H
crystallisation, fractional distillation, chromatography, etc.
I I
H-C-OH HO--C-H Erythro and threo system
I I This nomenclature is used only for two. adjacent chiral
COOH HOOC
Mirror carbon compounds and have the following structure:
(III)
.
Second pair of enantiomers
(IV)
R '-Cab-Cbd-R"
Out of six substituents, the two substituents (i.e., group b)
(I) is mirror image of (II); similarly (111) and (IV) are on two chiral centres should be same.
mirror images of each other. Thus, the four isomers are two When Fischer projections are drawn for stereoisomers
pairs of enantiomers. Now compare (I) with (III); they are with two adjacent chirality centre the pair of enantiomers with
neither superimposable nor they are mirror images. They are similar groups on the same side of carbon vertical chain is
called diastereomers. (I) and (IV) are also diastereomers, as called erythro form. The pair of enantiomers with similar
are (ll) and (111) arid (II) and (IV). groups on the opposite side is called threofor·m.
Another example is 2-bromo-3-chlorobutane. It has two
R'
chiral centres (2n) and can have four stereoisomers or two
:+:
pairs of enantiomers.
• •
CH 3 -CH-CH-CH 3
~- - ~-..-------- ~ b- sign. of rotations. Lactic acid and its ester having same
configuration possess opposite sign of rotation.
~ I COOH COOCH 3
(iii) Vertical lines are used to represent bonds going away
from the observer, i. e., groups attached to the vertical lines are
I I
HO-C-H HO-C-H
understood to. be present behind the plane of the paper. I I
(iv) Horizontal lines represent bonds coming towards the CH 3 CH 3
observer, i..e., groups attached to the horizontal lines are (+) Lactic acid (-) Methyl ester
understood to be present above the plane of the paper. of lactic acid
The Fischer projection formulae of enantiomers of lactic Two systems have been developed for studying the
acid and butan-2-01 are as given below: Chi r configuration of stereoisomers.
CH ' H C / ra lty
. I._ 3 1 3 / • centre (i) Relative configuration (D, L-nomenclature): . Before
1
I
y
H~rH~H ~ r~r
CHO CHO
I I
H-C-OH HO-C-H
I I
COOH CH 3 CH 20H CH 20H
Fischer projection of Fischer projection of D-form L-form
one of the enantiomers one of the enantiOiners (-OH group on the right side) (-OH group on the left side)
. of tartaric acid of 2,3-dibromobutane
Any stereoisomer which can be obtained from or
Along with Fischer projection formulae, the enantiomers converted into D-glyceraldehyde will belong to D-series.
of a compound can also be represented by the given \vays: Similarly, any stereoisomer which can be obtained from or
(a) Perspective Formulae: For example, converted into L-glyceraldehyde wifl belong to L-series.
The sign (+) or (-) added after D- and L-Ietters indicates the
direction of the optical rotation. An optical active substance
having D-configuration can be dextro (+) or laevorotatory
(-). Similarly, an optical active substance having
L-configuration can be dextro (+) or laevorotatory (-).
- (Enantiomers of 2-bromo-l-propanol) Now, the comparison can be made with the absolute
(b) Projection Formulae : For example, configurations of glyceraldehyde as given below:
I
CHO CHO
CH3 H3C
H-C-OH
I
,
:,
,
,
1I HO-C-H
,
I
H I OH HO I H
I CH 20H CH 20H
I
I
I
I D (+) Glyceraldehyde L (-) Glyceraldehyde
!
(Enantiomers ofbutan-2'-ol)
Isomerism
For Example, the most oxidised carbon attached to the chiral The formula ofbutan-2-01 can be represented in a number
centre is placed on the top of vertical line and the group with . of ways, e.g., .
carbon atom forming a part of the chain is kept at the bottom OH H
of vertical line. The horizontal line represents the remaining I I
atoms or groups projected towards the observer. H-C-'--CH3; CH 3-C-OH'
I I
.,...---Cru:bo~ in the higher I I '
-C- I -
' -'-C- OXldationstate C2 HS CzH s
, (bOnded to more oxygen)
X _ C~Chiral centre . C2 HS
V~Carbon in the lower I
-C - CH 3 -C-OH'
-C- Oxidation state
, I '
I I(bonded to less oxygen)
H
Other examples are lactic acid, glyceric acid, glucose and
The above formulae represent either configuration (1) or
fructose, etc.
configuration (II). In order to designate these configurations,
CH 3 CH 3 · a system of nomenclature called Cahn-Ingold-Prelog system'
H . I OH HO+H has been developed. The important features of the system are:
Step 1. Order of Priority: The four diflerent groups
COOH COOH
attached to the chiral caJ;bon atom are assigned a priority or
D (+) Lactic acid L (-) Lactic acid order of precedence I, 2, 3 or 4 on the basis of sequence rules
CH20H (see Sec. 4.8). 1 is the highest priority group and 4 is the
I lowest, (i.e., 1 >2 >3 >4).
CHO C=O Sequence Rule I. If all the four atoms attached to
. I I , chirality centre are different, their priority numbers are
(CHOHh (CHOH)2 decided on the basis of their atomic numbers. The atom of
,------~- ------, ,-- ----~-------, higher atomic number gets the higher priority.
:H-'--C-OH: : H-'--C-OH:
,,
,
I ,' I :,, I' .:,, For example, in the compound,' bromochloroiodo
'
methane (CHClBrI), the order of decreasing priority is
L____ ~g~2!"!j L____ ~g~2!"!] I (1), 13F == (2), CI == (3) and H == (4).
D(+) Glucose D(-) Fructose If two of the atoms attached to chirality centre are
isot{)pes of the same element, then atom of higher mass
(In sugar series, the letters D- and L- are related to the nhmber gets higher prioritY.
. configuration of the last but one C-atom in a moleoule.) For example, in the compound, a.-deuterio ethylbromide
Example 13. Which of the following compounds, are [CH;CH(D)Br], the order of decreasing priority is: Br (1),
erythro and threo enantiomers?
CH 3 ~ (2), D== (3) and H == (4).
+
CH 3 CH 3 H3 H3 , 4H
H CI H CI H OH H OH 2
Br I
3el
Br Br H CI H H Rule II. ,If two of the atoms attached to chirality centre
are same and their priority sequence unable to be decided on
CH 3 the basis of rule I, in such cases the relative priorities can be
(iii) decided by comparing the second (or even third) atom of the
Solution: Structures (i) and (iv) are erythro respective group. .
enantiomers because the two like H -atoms are on the same For example, in butan-2-01, the chiral carbon is attached
side in Fischer projection formula., . to OH, H, CH 3" CH 3CH 2 groups; The priorities of CH3 and
Structures (ii) and (iii) are threo enantiomers. CH 3CH 2 -groups cannot be decided·by rule LIn CH 3 group,
(ii) Absolute configuration (R and S systems of the second atoms are H, H, H while in CH 3CH 2 group, the
nomenclature): Butan-2-01 molecule can have the second atoms are C, H, H. Now by comparison, C has higher
following two different contigurations: atomic number than H, therefore CH 3CH z group gets priority
over CH 3 group. Hence, the sequence of priority for
butan-2-01 is; OH= (1), CH 3CH 2 -= (2), CH 3 = (3) and
H == (4). The other example is 2-bromobutane.
142, G.R.B. Organic Chemistry tor Competitions
x R-(Clockwise) S-(Anticlockwise)
I .
-C;::;;;:;X is equivalent to ~ C - X (ii) Bromo chloro iodomethane: (CHClBrI). The
, XI sequenceofpriorityisI=(1), Br=(2), Cl=(3)andH (4).
and -OH has the highest priority of all the substituents in'
I, Br, CI, S03H, SH, F, OR, OH, N0 2 NR 2 , NHR, NH 2,
glyceraldehyde. Thus, 0, 0, H of -CHO gets priority over 0,
H, H of -CH20H Hence, the order of decreasing priority is: COOR, COOH, CONH2, COCH 3 , CHO, CH 20H, CN,CR 3 ,
C6Hs,-C;::;;;:;CH,-:CH=CH2,CHR2,CH2R,CH3,DandH.
-OH = (1), -CHO = (2), -CH 20H = (3) and -H =(4) (iii) When the molecule contains more than one chiral
In case of phenyl (C6HS) group centre, the same procedure is applied to each.
I Note: (i) A racemic mixture is designated as (R, S).
H ...... /
t<CH
C
(i) When atom or group of lowest priority is at the Ifa molecule contains two or more chiral carbon atoms,
bottom of vertical Hne. Move the eye in order of decreasing then configuration (R or S) of each of the chirality centre is
priority to detennine the configuration. assigned separately following the sequence rules as discussed
~
earlier. For example,
I
(~l CH3
1
(4)H H-=C!-OH
R -BromocbJoroiodometbane 1 or
(Clockwise) H~!-OH
41
H3 C ,
~) rH,,)
(Z)
NH2
/(;\
HsC z Br
r
CII
( 3 ) . / + ..(I)
C Hs 2
For chiral carbon 2,
~
(3)
CH ..........
(4)H (4)H
H+OH Without changing CH3 • (I)~~) 1
S -(Anticlockwise) S -(AntiC\ockwise) HO CH(OH)C2HS
\ ./ Cbange.otherp~sitions
(ii) When atom or group oflowest priority is at the top '-CH(OH)CzHs anticlockwise ~,
of vertical Hne. In such a case rotate the entire molecule S-(Anticlockwise)
through 180°, so that the atoms or groups of lowest priority
come at the bottom. Now, move the eye in order of decreasing For chiral carbon 3,
~H)C] ,.~H(OH)CH3
priority to determine the configuration.
Wi_ohM"'"
(1)~(3)
(4)
R-(Clockwise)
'
~
2)
~
2) I
(4)
, CHO
H
~(I)
OH
CHO
Without Changin,g -CHO
Chan th '. " ..
~(3)
(I),
HO CHzOH
(c) HsCz-C-H
I
(€I) H 2 :N-f- 1
H
positions of other atoms or groups till the group of lowest ,\ 1(3) , (4)H
priority comes at the bottom of vertical line. Now, determine '-CH20H
the configuration in a usual manner. ConfigUration R (clockwise)
~
~ ,
2) Note: The lowest priority group is positioned at the bottom and away
(1)
CHO
~4) "~\9H~~
Without changing~HO. HOH C~bH
from the observer. This is done by interchanging groups bonded
to the asymmetric carbon. The interchange opemtion is always
H~(3) HJ Change other POSItiOns' 2 ;, I done in pairs to avoid a configUration change.
CH20H clockwIse H
(b) Order of priority is -Br>-CI>-COOH>-H
S-Glycemldehyde (2)
(Anticlockwise) CI
Assigning of Rand S configurations from Fischer (I)~ ~
projection containing two chiraHty centre. BryOOH Configuration R (Clockwise)
H
(4)
G.R.B. Organic Chemistryjor Competitions
(b):~:
--OH>-C 2H s >-CH 3 >-H
rn
H4-0H
(I) (a)HO~H
(l)OH ·OH
(2) .
H5C~-H
I (4).'_
-
(3)
H3Cy2HS
1 c;! COOH
Solution: (a) Order of priority for both chiral centres
C1hOH
+
(1)
C2H5 C2HS === H0:-r-CH(OH)COOH
(4)H
Br Configuration R (at C2)
(c) I + H (d) HO' CHO
(Clockwise)
Cl . CH 3
For chiral carbon 3,
CH 3 H
Q
(e) H+CH=CH2 (f)CH 3+ C H O (3)
CH(OH)COO mCH(OH)cOOH
C6HS C2HS
, H CH 3 H~(l)! (4)H HootLoH
(g) H 2N + H2Cl (h) H~OH
(2)
COOH
./'
(40H
CH 3 CH 2CH 3 Configuration R (at C 3)
(Clockwise)
Solution:· (a) R, (b) S, (c) S, (d) R, (e) R, (f) R, (g) R,
(h) S. Thus, the compound is (2R,3R)-2,3-dihydroxy
Example 16. Assign the priority order number to the butanedioic acid (Tartaric acid).
following atoms or groups: (b) Order of priority for cool carbon 2, is:
(a) --OH, -CH 20H, -CHO, -H --OH>-CHO> -CH(0H)CH 20H> H
(b) -CHO, -CH 20H, -CH 3 , --OH .
(c) 'C 6 Hs-c, -CH(CH 3 h, -H, -NH2
(d) -CH(CH 3 h, -CH=CH 2, -C~H, C 6H s-
(e) -CH 3 , -CH 2Br, -CH 2 0H, -CH 2Cl
f5i)
I,
H(,4), (lbH .
(j) ~H3' -N(CH 3 h. -CH 3 ,-H l (3)
~CH(OH)CH20H
./
Isomerism ~~5
H
H,
t,H",0,c", ',OH _
<,
CH20H
OH'
(.) B~ r:'.
CH 3
CH
(ii)
H
3
CH
6 5
C(~l)~p:(z:t..)_-uH
H 3C""4)'----'FL--H
OH'
" (2)Ca(OH)CHO
~
(1) .. (3)
CI$3 3
'H
== HO, ," CH20H
(4)
(iiI) H , "
,H
H 1
R-(Clockwise) C 2H S
Thus, the compound is (2R, 3R)-2,3,4-trihydroxy butanal. Solution: (i) 2R,3S (ii) 2S,3R
Example 18. Assign the configuration of each chirality (iii) 2R,4R (iv) IS,3R
centre in the following struCtures: Example 21. In the following reactions, assign Rand S
r
configuration to the products formed:
CHO
(a) HO-t-H (b)<f}f (C)~ ~
< H-f-OH
CH20H" Br Br H Br
Anti-addition
(Hi)
H Br
Solution: (a) 2S,3R (b) IS,2R (c) IS, 2S.
__
(A)
Example 19. Draw enantiomers of each of the
following compounds using Fischer projectionformula:
(I) Cl-?H-F O +-___H_C_O~3_H__-+
Anti-addition
~
(Hi)
Br Cyclopentene
H OH
(iz) CH 3 -CH-CH 20H (B)
" I
(iii) CH 3 -CH -CH-CH3
OH ' ColdKMn04
8yn-addition
.~.
I I " HO OH
CH 3 Br (C)
Solution: (A) (i) -R, (ii) -R, (B) (i) -R, (ii) -R,
(iv) CH3CH 2 -CH-CH 2CH zCl
"I ', (C) (i) -R, (ii) -So
CH 3 Example 22. The following compound has only one
chirality centre, why then does it have four stereoisomers?
F F *
CH 3CH2 CH CH zCH=CHCH 3
Solution: (i) Br+Cl CI+Br . I '
H H Br
CH 3 CH 3 Solution: Along with one chirality centre, it also have
(ii) H O + - H H I OH one unsymmetrical (C=C) bond. Thus, there are:'
(i) two optical stereoisomers
CHzOH CHzOH
CH zCH 3 CH 2CH 3
CH(CH 3 h CH(CH 3 h I I .
(iii) Br I H H I ,Br Br-C-H
I
and H-C-Br
I
CH 3 CH 3 CH 2CH=CHCH 3 CH2CH=CHCH 3
C ZH 5 C ZH 5
(iv) H I CH 3 H3C I H
(ii) and two geometrical isomers
Br
CHzCHzCI CHzCHzCl
I
Example 20. Assign R "and S configurations to each CH3CH2CHCH2~ <CH 3
chiral centre in the following Fischer projection: /=C and
H c'IS H
\
G.R.B. Organic Chemistry (or Competitions
: rooc~: H~OH
(W)
H+-,OH,OH
H - t - 0H H0-t-H
COOH COOCH) COOCH 3
(A) (B) (C)
CH 3 cn . [UPSEAT 2004]
H I. CH 2CI
H2
~ H I) CH 2CI (a) (A) and (B) are identical
(b) (A) and (B) are diastereomers
CH=CH 2 CH 2CH 3
(X) (c) (A) and (C) are enantiomers
(Z) (d) (A) and (B) are enantiomers
CH 3 CH 3 [Aus. (b)]
II~ CICH 2 [Hint: They are neither superimposable nor they are mirror
or CICH 2
I
CH=CH 2 CH 2CH 3
H
I images.]
16. The number of isomeric pentyl alcohols possible are:
(X) (neE 2009]'
(Z)
(a) two (b) four
CH 3 CH)
(c) six (d) eight
or H CI~ H
I
CH=CHCH 3 CH 2CH 2CH 3
Cl
I [Ans. (d)]
[Hint: Sec Art. 9.4, problem 2]
(X)
(Z)
17. Which of the following will form two
isomers with
semicarbazide?
Example 24. Identify the pairs of enantiomers and (a) Benzaldehyde (b) Acetone
diastereOmers from the following compounds (I), (II) and (III): (c) Benzoquinone (d) Benzophenone
[lIT 2000] [Ans. (a)]
r
H~ ~H :~=F:
CH 3
(D
CH3
(n)
[Hint: <;HsCH=O + H 2 NNHCONH2 ~
Benzaldehyde Semicarbazide
and
<;HsCH = NNHCONH 2
Semicarbazone
CJIS'"'-c/H
Solution: Structures (I) and (III) are enantiomers . N
II
because these are mirror image of each other; H2NCOHN/ Q
Structures (I) and (II); (II) and (III) are diastereomers
because these are not mirror image of each other.
Isomerism
~
4.17 CONFORMATIONAL ISOMERISM to 60° generates one of the maqy other arrangements in
The sigma bond joining the two carbon atoms as in ethane is between staggered and eclipsed forms. These arrangements
cylindrlcallysymmetrical about the nuclear axis. This are called Gauche or Skew form. .
symmetry of the bond pennits the free rotation of the two Relative Stabilities of the Conformations of Ethane
carbon atoms with respect to each other along the bond axis The potential energy of the ethane moleCUle changes
without bre!lking the bond. If one CH 3 group is kept stationary somewhat with rotation arOund the C-C bond on account of
and other methyl group is allowed to rotate through G-C the distance between hydrogen atoms of the two carbon
axis, an infinite number of atomic arrangements are possible atoms. The potential energy of staggered form is minimum
depending upon the angle through which the CH 3 group is and of, eclipsed form is maximum. The difference in the
rotated.· The different arrangements of atoms in space tbat energy content between the two extreme conformations is 3
result from the free rotation of groups about C--C bond kcaUmol (or 12.5 kJ mol-I). This small barri~r of rotation is
axis are called conformations or conformational isomers also called Torsional barrier. This energy is not large enough
or, rotational isomers and the phenomenon as to prevent rotation. Even at ordinary temperature, the energy
conformational isomerism. The .basic structure of the barrier is overcome through collisions and thus, the
molecule and various bond lengths and bond angles, however, conformations keep on changing from one form to the other.
remain the same in all these arrangements or conformations. The variation of energy with rotation about C-C bond in
Conformations of Ethane (Sawhorse Projection) ethane has been shoWn in figure.
Of the infinite number of possible arrangements of Eclipsed
(Lesss\able)
ethane, two conformations represent the extremes. These are
called the eclipsed conformation (I) and the staggered
conformation (II). In the case of eclipsed conformation, the ,
hydrogens of one carbon atom are directly behind the other,
consequently, the repulsion in these atoms is maximum. While 1
in the staggered conformation, the hydrogens of the two
carbon atoms are staggered with respect to one another. As a !
~o
result, they are at maximum distance apart and have minimum ,
repulsion between them. Any other arrangement which will be _ staggered Staggered·
between these two extreme positions as shown in (III) is (stable) :
known as Gauche or Skew form.
Angltiof Rotation '
H
Fig. 4.6
H~~
HH
. ,~HH.. conformational analysis.
.~ ~
........... Conformations of Propane
H ' H .. The conformations of propane are similar to those of
H HH II ,ll ..:thane except that one of the hydrogen atoms is replaced by a
H
. \r ,
methyl group. The two extreme conformations of propane are·
(i) Eclipsed form (ii) Staggered form (iii) Gauche or skew form
shown below (NewD1an Projections):
(Newman Projection)
The difference in the potential energy between these
A rotation of 60° converts a staggered conformation into extreme
. .
conformations
1
is about 3.4 kcal mol- 1 (or
an eclipsed confOimation, or vice-versa. Rotation between 0° 14.2 kJ mol- ).
148 G.R.B. Organic Chemistry for Competitions
methyl groups are so closed that they repel each other (ill and
V are mirror images). This' repulsion causes Gauche
HyfyCH' conformations to have about 3.8 kJ mol-I more energy than
H~H'
anticonformation. The conformations (II) and (VI) are
partially eclipsed and unstable because of repulsion. Their
·H potential energy is 14.6 kJ mol-I.
EclipSe9 Staggered In conformation (IV) (Fully eclipsed), the steric strain is
~------~------~
Conformations of propane
maximum, hence, this conformation is most unstable and have
potential energy 18.4 kJ mol-I. This is because of repulsion
Even then, this energy barrier of rotation about C-C between methyl-methyl group which are very close together.
bond is so small that it cannot prevent rotation. As a result, the The order of stability of these conformations is:
two conformations are readily interconvertible by rotation Anti> Skew or Gauche> Partially Eclipsed> Fully Eclipsed
through an angle of 60° and thus, it is not possibl~ to separate The energy difference between various conformations is
these two conformations. shown below:
COJ)formations of Butane
n-Butane molecule can be considered as a dimethyl
derivative of ethane in which one H-atom of each carbon is Eclipsed Fully Eclipsed Fully Eclipsed
replaced by a methyl group as shown below: (IT) (IV) (VI)
H H
I 21 31 4
H3 C - C - C-CH 3
1 1
H H
If uow one of these central carbon atoms (C 2 or C 3) is
fIxed and the other is rotated round the ceutral (C 2 -C 3 ) bond
60· 120· 1800 240· 300° 360°
throu&h au angle of 360°" we get many conformations. Out of
Angle ofl'Otation _ _
these 'only six conformations (60° each time) are important
and their Newman Projectious are given ahead: . Fig. 4.8
~
CH3H Conformations of Cycloalkane
Conformational isomerism has also been shown in
CH3 . cycloalkane molecules. Cyclopropane arid cyclobutane are
n·. H H planar molecules having bond angles of 60° and 90°
respectively..
Staggered (Anti) Eclipsed Skew or Gauche
(I),
CH
(II) (III)
EJ
H~' H~H
CH3
Amount of deviation (d) =~ (109° 28' Valency angle) Relative Stabilities of Chair and Boat Conformations of
Cyclohexane
e.g., In cyclopropane, d = ~ (109°28' -60°) =24°44'
The chair conformation of cyclohexane is more stable
In cyclobutane, d = ~ (109° 28' - 90° ) = 9°44' than the boat conformation due to the following reasons:
(i) In chair conformation, the adjacent hydrogens on
In cyclopentane, d = ~ (109° 28' -108° ) = 0°44' C I - C 2 , C 2 -(;3, C 3 -C 4 , C 4 -Cs , Cs -C 6 and C 6 -C) are
quite staggered (more stable) and the force of repulsion in
and in cyclohexane, d = ~ (109° 28' -l20° ) = - 5°16'
them is minimum. On the other hand, in boat conformation,
Thus, strain is minimum in cyclopentane and hence it is the adjacent hydrogen atom on C 2 -C 3 and C s C 6 are in the
more stable and less reactive than cyclopropane and less stable eclipsed orientations. .
cyclobutane. As a result, cyc10hexane is free from angle of The two forms have not been. isolated so far, because the
strain and hence is quite stable and unreactive. Therefore, energy difference between the two forms is too small (29.9 kJ
cyc10hexane adopts a non-planar structure. mol-1) while 37.710 46.0 kJ morl is the energy of barrier and
According to Sachse and Mohr, the cyclohexane exists in one form readily changes into the other.
two non-planar or puckered (or folded) conformations called (ii) The two hydrogen atoms (marked as Hf) called the
the.chair (Z form) and the boat (C form) conformations as flag pole hydrogens and in chair forms, C-H flag poles at
shown in the figure. C1 and C 4 are in the trans side (distance 2.29A or 229 pm)
having minimum strain and thus' more stable. While in boat
form the C-H flag poles at C 1 and C 4 are on the same side
H (distance 1.83 A or 183 pm). and so sterlc hindrance is
increased and thus stability is decreased.
H H
The following diagram shows the conformations of .
cyclohexane (and their relative energies) as one chair
H conformation interconverts to the other chair conformation.
Cyclohexane with methyl group in the equatorial position
H
Chair conformation Boat confonnation half chair
.'Z' form (staggered form) 'C' form (eclipsed form)
Methyl group in
equatorial position
,. .
D Dextro-tartaric acid (d-form): This rotates the plane plane of the page, resulting· in a cross with asymmetric
polarised light to right. The rotation due to the upper half carbon atom at its centre.
is strengthened by rotation due to lower half. It has no D Relative configuration (D,L-nomenclature)
plane of symmetry and occurs in !lature. D D- form: The enantiomer having hydrogen (H) atom on
D Laevo-tartaric acid (I-form): This rotates the plane the left and another group (X or -OlI) on the right was
polarised light to left. Here again rotation due to upper half given D-configuration.
is strengthened by rotation due to lower half. It also has-no D L- form: The enantiomer with (X) or -OH group on the
plane of symmetry and does not occur in nature and hence, left' and hydrogen atom on the right was given the
it is prepared by resolving racemic tartaric acid. configurational symbol 'L'.
The d- and I-tartaric acids are mirror image of each other D Absolute configuration (R and S system _of nomen-
(enantiomers). clature): Actual spatial arrangement of atoms or groups
D Racemic (r-) tartaric acid: It is an equimolecular (absolute configuration) of each chiral centre in a
mixture of d- and I-forms. The rotation of the d- form is molecule was devised by Cahn, Ingold and Prelog (CIP).
compensated externally by I-form and hence, it is optically D The four ligands (atoms or groups) attached to the chiral
inactive due to external compensation. It can be resolved centre are assigned a sequence of priority according to
into d- and I-forms. sequence rules. '
D Meso (m-) tartaric acid: It possesses a plane of sym- D R (Rectus = right) is given to the isomer if sequence is left
metry and is consequently optically inactive and to right (i.e., the eye travels in a clockwise direction).
superimposes on its mirror image (i.e., they are identical). D S (Sinister = left) is given to the isomer if sequence is right
The optical inactivity is said to be due to internal to left (i.e., the eye travels in the antic10ckwise direction).
compensation as the rotation due to upper half of the D Conformational isomerism (conformers): The
molecule is balanced by tlte equal, but opposite rotation different arrangements of atoms in space that result from
due to lower half. It cannot be resolved into active d- and 1- the free rotation of groups about C-C bond (O'~bond) axis
isomers. are called conformational (rotational) isomers and the
D Resolution of racemic mixture: The process of phenomenon is known as conformational isomerism.
separation of racemic mixture (dl-) into d- and I-forms (its D Out· of the infinite number of possible arrangements of
enantiomers) is called resolution. ethane, propane and butane, two conformations represent
D Racemization: It is reverse of resolution, i.e., _the the extremes. These are called (i) eclipsed conformation
process of converting d- or I-form of an optically active (ii) staggered conformation.
compound into dl- (racemic) mixture is termed D Various other structures in between eclipsed and staggered
racemization. Since the rotation of d-form is cancelled by conformations are called Skew or Gauche
equal but opposite rotation of I-form, so a racemic mixture conformations.
(r-) is always optically inactive. D The small increase in electron-electron repulsion
D Asymmetric synthesis: The synthesis of an optically (difference in the energy content) upon rotation between
active compound (chiral centre) from a symmetrical the two extreme conformations (i.e., from staggered to an
molecule (having no asymmetric carbon) without eclipsed) is referred to as torsional strain (barrier) ..
resolution to form (+) cir (-) isomer directly is termed 'D The eclipsed conformation is least stable while the
asymmetric synthesis. For example, synthesis of(-) lactic staggered conformation is most stable. The order of
acid from pyruvic acid. stability ofthese conformations is :
D Walden Inversion (Optical inversion): The conversion Anti > Skew or. Gauche > Partially eclipsed > Fully
of d- form of an optically active compound into 1- form of eclipsed.
the same or different compound or vice-versa is known as D Conformations of cyclohexane: Sachse and Mohr
Walden inversion. For example, the conversipn of d-malic assumed two non-planar or puckered (or folded) forms of
acid into I-malic acid (or I-chloro succinic acid). cyc1ohexane. These are chair and boat conformations
D Diastereomers are the stereoisomers that are not mirror which are free from angle strain. Both forms are inter-
images (enantiomers) of each other and have different convertible into each other.
physical and chemical properties. D Chair conformation or Zform (staggered form}is more
D Fischer projection is a planar representation of the three- stable than boat conformation or C form (eclipsed form).
dimensional structure as the bonds are projected into the
G.R.B. Organic Chemistry for Competitions
! , .ii
,~;V.flt'Sh9rt~Answer Type (iv) Isomers which are ...... mirror images are known
1. Fill in the blanks: as ......
(a) The number of possible isomers ofC sH12 is ..... . (v) Optical activity of a compound is measured in terms
(b) CH 3 COC3 H 7 and C2HsCOC2HS show. . . . .. ' of .....,.
(c) An organic compound with the formula (vi) 'Irans-forms are ...... stable than ciY-forms.
(vii) Geometrical isomerism is not observed in a molecule
CH 3 CH 2 CH2 0H shows functional isomerism with
if either of the doubly bonded carbon atom has two
compound of the structural formula ..... .
. ..... groups.
(d) Alkenes can exhibit position, chain and ...... isomerism.
(viii) Geometrical isomers have ...... physical
(e) Tautomerism is also known as ...... isomerism.
properties but almost the same ...... properties.
(f) Hexane has ...... chain isomers. (ix) Optical isomers have same physical and chemical
(g) There must be minimum ...... carbon atoms to properties but differ with resp,ect to rotation of
exhibit chain isomerism. ...... light. ,
(h) Carboxylic acids and esters are examples of (x) A molecule is said to be chiral if it possesses at least
...... isomerism. . ..... carbon atom.
(i) Ketones must contain at least ...... carbon atoms in (xi) ...... cannot be resolved into d- and I-forms.
order to exhibit metamerism. (xii) A reaction where diastereomerically different starting
(j) n-Butane and isobutane are •..... isomers. materials give diastereomerlcally different products
(k) The structural formula of the compound isomeric with is called •...... reaction.
acetone is ..... . (xiii) d- and 1- lactic acids are known as ..... .
(1) The chain isomers of n-pentane are isopentane and (xiv) If the replacement of one group at an achiral centre
by a new substituent generates a chiral centre, the
(m) n-Propyl alcohol and isopropyl alcohol are ...... isomers. original molecule is said to be ..... .
(n) Metamers belong to ...... class of compounds. (xv) Number of stereoisomers of HOOCCH(OH)COOH
(0) But-2-ene and but-I-ene are ...... isomers. is ......
(P) But-I-ene and cyclobutane are .' ..... isomers. (xvi) Enantiomers have asymmetric carbons of different
(q) The number of isomers of molecular formula CgHIO
containing benzene ring are ...... . (xvii) 'E' and 'Z' system of naming geometrical isomers is
(r) The two extreme conformations of ethane are called based on ...... rules.
. . . . . . and ...... conformations. (xviii) Maleic and fumaric acids are a pair of ..... .
(s) Staggered form of ethane is ...... stable than eclipsed (xix) The stereoisomers which are not mirror images to each
form. othpr are called ......
(t) Ethyl cyanide and ethyl isocyanide are ..... :isomers. (xx) Fischer projection is a ...... representation of the
(u) The possible number of dichloro derivatives of propane three dimensional structure.
are ...... 3. State whether the following statements are True or False:
(v) At room temperature, the eclipsed and the staggered (a) Members belonging to same class of compounds are
forms of ethane interconvert rapidly and ...... be called isomers.
isolated as separate conformers. (b) Isomers have same molecular formula.
(w) Which conformer of butane has highest energy ..... . (c) Can isomer be homologues of each other?
and which one has lowest ..... . (d) m-Chlorobromobenzene is an isomer of m-bromo-
(x) Two or more organic compounds having same chlorobenzene.
molecular formula but different properties are known (e) Ethyl alcohol and dimethyl ether are position isomers.
as ...... and the phenomenon as ..... . (f) All alkenes show cis-trans isomerism.
(y) Ethyl benzene is ...... isomer to xylenes. (g) 2-Butenedioic acid exhibits ciY-trans isomerism.
(z) The structure of enol formofCH 3 COCH 2 COCH3 with
CH 3
intramolecular hydrogen bonding is ... '...
2. Fill in the blanks: (h) The alkene CH3-CH2 -C C
I <C2 Hs
exhibits
(i) Stereoisomers possess ...... molecular and C2HS
...... structural formula.
(ii) Thecompound CHCI=CHCl can show geometrical isomerism.
• isomerism.
0 ••••
(i) Cis-trans isomers possess different physical properties.
(iii) Geometrical isomerism is due to ...... rotation of G) Cis-trans isomers have different dipole moment.
0 bond.
•••••
(k) Optically active compounds may exist in four forms.
Isomerism 163
(1) 2,3,4-Trichloropentane has three chiral carbon atoms. (u) The first accepted explanation for optical isomerism by
(01) Tartaric acid has two asymmetric carbon atoms. certain compounds was given by Le Bel and van't Hoff
(n) Every optically active compound has a racemic form. in 1874.
(0) d-form and I-form of ali optically active compound (v) Only organic molecules can be optically active.
have same specific rotation with opposite sign. (w) The direction of rotation is denoted by the prefix (+) for
(P) All forms of compounds containing asymmetric carbon dextrorotatory and (-) for laevorotatory enantiomers.
atoms are always optically active. . (x) The arrangement in space of the atoms or groups that
(q) The compoundCH 3CHOHCOOHcan have four optical characterizes a stereoisomer is called its configuration.
isomers. (y) Sign of rotation of an enantiomer is related to its
(r) In ethane, both eclipsed and staggered forms have same
configuration.
stability.
(z) Diastereomers have different physical properties and
(s) Propanone does not exhibit the phenomenon of
similar but not identical chemical properties.
tautomerism.
(t) The specific rotation of a compound is measured by an
apparatus called polarimeter..
4 •. Match the following:
CH3 CH3
I I
[A] (a) A pair of functional isomers (i) H-C-OH HO--C-H
I I
COOH COOH
(b) A pair of geometrical isomers (ii) H2 C=CHOH CH3CHO
CH3
I
(c) A pair of optical isomers (iii) CH3 CH2 CH 2 CH3 CH3-CH-CH3
. H) <CH 3
[B](a) d,l-mixture (i) . C=C
H3C . H
(b) Cis-iSomer (ii) Eclipsed and staggered forms.
(c) Trans-isopler (iii) Polarimeter
(d) Meso form (iv) Enantiomers
HOOC> <COOH
(e) Conformation (v) =C
H H
(t) Non-superimposable mirror images (vi) Optically inactive
(g) Specific rotation (vii) Racemic
'.~-,~ ';
.,<', ~-._.>, ,vF>:~f .,
.",~~,' ,::'iL:~~~;~
f:'-"~2' ~'.--
<~:,:..;.:;{6""~'4,,,,'/,---____________________________G..;;;..;.;;;..R:;.:.B:...;•....:O:...;r.liil~~an;.;,.;l..;;..·c.....;C;.;.;h..;;..em;=.;;is~try"-Lfo:..;.r_C::..:o;.;.;m.;;.!,;;p...;.e.;.;.ti;.;.tio.;.;.n;.;;;..s
H> COOH
and (ii) C=C<
HOOC H
F> <CH2CH 3
6. Mention the specific type of isomerism exhibited by each of (iii) C=C
the following pairs: ' H CI
(a) 1,2-Dibromoethane and l,l-dibromoethane
(b) n-Butylalcohol and . diethylether
(c) Propionic acid and' methylacetate
(d) o-Methylphenol and benzylalcohol
(e) Maleic acid . and fumaric acid
(f) n-Butane and isobutane
(g) o-Nitrophenol and m-nitrophenol
(h) Acetic acid and methyl formate
7. Write structural formulae of:
(a) Two enantiomorphs (b) Two homologues
(c) Two functional isomers (d) Two geometrical isomers
(e) Two position isomers (f) Two metamers
8. Write down the name and structure of one isomer of each of
the following compounds:
(a) CH2=CHCH2CH3 (b) CH3 CHC1 2
(c) (CH 3 )2 CHOH (d) CH 3COCH 3
(e) CH 3 COOH (f) CH3 0CH 2CH 2CH3
(g) maleic acid (h) d-lactic acid
9. Which of the following compounds are optically active
compounds? Cl~Br.
~
(i) Butan-I-ol, (ii) Heptan-4-ol, (iii) 2-Chlorobutane,
(iv) 3-Chloropentane, (v) Pentan-2-ol, (vi) 2-Bromo-2- (ix) , (x) ;===L-
methylbutane (vii) Penta-2,3-diene.
[Hint: Write down the structures and find out which compound
has asymmetric carbon atom. The compound having CI\ /
asymmetric carbon atom shows optical activity.]
10. State which of these exhibit stereoisomerism and of what type?
(xi) (xii) /\-'0_
. Br
Br Br
I I (xiii) ~
(a) CICH2 -C=C-CH2Cl
, (b) CI-CH2-~-CH2-fH:-CH3 (CH 3 h CH > <COCH3
(xiv) . C-C
o CH3 C2HS COCl
Isomerism
(i) 0
Cyclopentane
(ii)
r-I
U
Metbylcyclo Etbylcyclo
(iii) CH3CH2CH2CHzOCH3
I-Methoxybutane
(iv) CH3CH
2T
HOCII3
CH3
butane propane 2-Methoxybutane
. CH
I 3
I,I-Dimethyl
(v) A (v) CH 3THC H zOCH 3
CH3
(vi) CH3-r-O-CH3
CH3
cyclopropane
CH3 CH3 I-Methoxy-2-methyJpropane 2-Methoiy -2-methyl propane
1,2-Dimetbyl cyclopropane
CIS (meso) Thus, there are total six isomers.
(vii) /'\.
H-C-COOH
19. (A) Fumaric acid II
H3C~ ' CH3 (trans) HOOC-C-H
Structure (vi) and (vii) are trans-isomers and are same. It can exist H-C-COOH
in d, 1 form. _ (B) Maleic acid II
So, total nomber of cyclic as well as stereoisomers possible are (cis) H-C-COOH
seven.
(C) Ethene dicarboxylic acid-
(B) The possible cyclic isomers of the compound with molecular
<
COOH
formula, C4~ are five.
<
HzC==C H~t)
CH3
COOH
H2C-CH H~-CH 6H <
o
I II 1/1 /"-
H C-CH, HC-CH2' HC=CH, (D) Cyclic ester of oxalic acid and glycol.
O=C/ 'CH2
I I
2
<
o c.,0 /CHz
20. (A) C7 H 16 has nine isomers.
17. (i) Penta-2,3-diene:
(i)~ (ii)
n-Heptane 2-Metbyl hexane
(iii)
A(V
3-Metbyl hexane
(iv)~
2,2-Dimcthyl
pentane
(v)~
3,3-Dimethyl
pentane
(vi)
~
2,3-Dimethyl
pentane
23. lli+=H H+=lli
.H
CH 3
CH)
Br' Br
CH3
CH 3
H ' . H+:
H
CH 3
eH 3
r
(v) D (vi)
/
/\
"""-
I-Methyl cyclopropene
CH3
O.)~';
Cyclobut-l-ene
CH)
(vii)
6 3
3-Methyl cycloprop-l-ene
(viii)
Methylene cyclopropane
27. There occurs breaking and reforming of C-I bond. This results
into two enantiomers which form racemic mixture which does not
show optical activity due to extemal compensation.
(ix) <I:> I
H--C-I
I
CH3
(i) -I-
(ii) +1-
)
I
CH3
H--C-I
I
+
CH3
I
I--C-H
I
Bicyclo (1.1.0) butane C2H S C2H S C~s
(Racemic mixture)
Thus, there are total nine isomers.
21. It is due to intramolecular H-bonding in enolic form which reduces CH3 CH 3
intermolecular aSsociation and lowers the boiling point. I I
O-H---O 28. (A)
H-] H-C-Br
I
I I C-H Anti -addition H-C-Br
CHr-C~/C-OC2H5 I I
CH 3 CH 3
I
H But-2-ene (trans) (Meso)
H H
CH3
I. I. CH3
22. The reaction is Ph-{;-C-Ph Ph-C-C-Ph I 1
. II I I 1 (B) H-] Br2 H-<;":-Br
I
.
+ Enantiomers
ij-1
---=----'?)
°°
Thus, two asymmetric carbon atoms are created in the reduction
OHOH
Anti-addition Br-?-H
product. There are three stereois~mers of the reduction product. CH3 CH3
Ph Ph Ph But-2-ene (cis) (Racemic)
I I I Br
H--C-OH HO-C-H H--C-OH I
I I I ,
CH 3--C-CH:zBr
H--C-OH H--C-OH HO-C-H
I
Ph
I
Ph
I
Ph
CH 3
(Achiral)
::.:Is~o;:;:.m:;;;:e;:,.:n::::.;·sm:.:.:;... _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _....;.;.·. ·.:.tlj59!C:;';·~~~~·
Br2 ...-H-_
(D)·O ~ No reaction o 0' 0' D
Cyclobutane
II (a) II I 1\
CH~-CH-C-CH3 ~ CH3-C~C/C-CH3
...-H-_ I
o 0 0"'" -0 CH3 I
CH3
a-Methyl acetyl acetone
II I
.11 II (Ketofonn) Enolisation (smaller)
29. CH~-CH2-C-CH3 ~ CH~~C/C-CH3
due to highly strained
BX
Acetyl acetone
(Ketofonn)
~
Enolisation (greater)
due to less strained
30.
U (R)
. 1'88 G.R.B. Organic Chemistry (or Competitions
c
0 (d) 5 0
. . CH 25) (c) 4
[ 6 "' 6c",; 6;
OH OH OH
Alcohols: CH 3CH:zCH2CHPH, . CHOH,
H3C
H3C~T
/"nCH20H, (CH3)3 COH
Hint: "- I ;
H3C . "~1; CH3
~.R:B.'organir: Che11iistryjorCompetitions
(b) CH 3-CH-CH CH-CH2---"CH
, t ' ," , 3 ,
o (a) 4 ' 0 , (b) 3 o
'
CH
3 " ' (c) 2 ,,' 0 (d) 5 ' o
, ' \ 56. Consider the following Qrganic compound;
" ·'~·(ct,CH~:-CH.=CH-dH3, 0 CH3-CH2-'-CH2-CH2-CH2-CH2-CH3
I ,21 4 S 67
" (d) CH3-CH2-CH , CH-CHi-CH~ 0
• '46. How many primary, ai'nines are possible for the formula ,To make ita chiral compound, the attack should be on
carbon : ' ' " (DeE 2001)
C 4 Hll N? ,
(a}.l 0 (b) 2 0, (a) I 0 (b) 3 0
, " (c) 3 ' ,". 0 (d}A ' ' ",.,' 0 (c) 4 ',," ,0 (d) 7 0
47• How many optlcaliy ,active stereoi'somers are possible for 57. A compound withmolecula:r formula C 7 H16 shows optical
, butane-2,3,.diol? ' isomerism, the ,compound will be : [eBSE (Med.) 2001]
(a) 1 ' .' 0 (b) 2 ' 0 (a) 2, 3-dimethyl pentane 0
(c) 3 . 0, (d) 4 , \ ' 0 (b) 2, 2-dimethyl pentane 0
48., The number of' possible enantiomeric pairs ~at ,can be (c) 2~methylhe~ane 0
" ' produced during,monochlorinationof 2-methyl butane is: ' (d) none of the abOve 0
(a) 2
, (c) 4
0 (b) 3
0 (d) I
,.49. Tautomerism will be expla~ed by:
'(~) (CH3hNH ' CJ, (b) (CH 3h CNO
0
0
0
·58. M.;xrtH
, H ,,'
(c)R 3CNt>z 0 (d) RCH2NOi O. Hydrogenation of the above compound in the presence of
, 50. ". 4n'enantiomerically pure acid is treated with racemic \ \ poisoned palladium catalyst gives: ,'(lIT (S) 2001)
.~ ,. - .
(a) optically active compound 0
nuxture of an alcohol haVing one chiral' carbon. The ester \
fomiedwiU~e: ,', (lIT 2003) \ (b) an optically inactive compound 0
(a) optically active mixture 0 " (c) a racemic mixture 0
(b) pure enantiomer ' , 0 (d) a diastereomeric mixture" 0
, (c) meso compound 0 59. The number of isomers for the compound with molecular
formula.C4;arC~I is: (PET (Kerala) 2007)
',,(g), r~cemic'tnixture ' " 0
51.~-Methylpenta-2,3-diemds aehiral because it haS: '
(a) 3 0 (b) 4 0
(a) a plane of sytrnnetry , 0 (c) 5 0 (d) 6 0
(6) a centre of symmetry 0 (e) 7 0
60. The tWo compounds shown 'in figure l:!elow are:'
(c) a c; axis of symmetry 0
" ,(d),bothiplane and a centre ofs~etry, 0
'52. 'The racemizationofopiicalJy acti:ve compounds is driven and
'by:,"""
" ,.,:(a), ellth~lpy, , o
(b) entropy . 0
" (c)"¢nthalpy andentiopy 0 (d) element of symmetry []
'53. ,The follow,~rig cOIllPound can show: l a)
diastereomers 0 (b) enantiomers o
. SIh)c C(H ,H (c) epimers 0 (d) regiomers o
61. The compounds given below are :
CH3' )c(·,
, ' " CI:h' , eOOH
(a) opticalisomerism ' 0
HO-@--COOH ~d HO--@-COOH,
'. .H
3'),
,C' ··. C· <.
,.,.' ",
CH
'. '. H
3
. ,(IIT(S}2(f()21"
' . .
(a) 2 .'
.' (c) 6 ' '. .
0 (b) 5 '
0 (d) 3 '.
,J]" , . 71. On~onoch1orination: 2-methylbutane, th.e total nmnb.f;ir, .'
of chiral compounds 1S:
of
. "
"0
.0 .
(IlT(S} 1~041: "..
(b) CHi-C==C-:CH3 0 (a) 2: '; " o
(b) 4 .. . <'[1 '
. • ,(c) 6 , · . ,0 (d) ,8', . '.<0
(c)CH 3- CH:i;"':"'C C-H 0 12•.... Which type ofisomerismis shown by 2,3~dichlor6butane? .
(d) cH .' Ca~cS='CH ' ' ' ,D ,",' ' [AI£EE100S] ..
2
66•. Among the folloWing four ,structures I ,to IV: (a) D i a s t e r e o O (b) Geometrical 0,
.
fH3' 3
(c) Optical
'.73. Correct configuration of the following is:' [ADMS200s)
C2 Hs--'-CH-C 3 H7 , CH3',--C--;-CH-C2Hs
(I) , (II),:: .
'H+OH
. H .
1"
·.·CH3
I,
CH 3 TH OH
'H-c-f' C2Hs~~~-C2Hs
(a) lS,2S 0 (b) 1S,2R
.
0
'. H (c) lR,2S 0 (d) lR,2R 0
. (III) (AIEEE2003)
74. Which of the following is optically active? (BHU 2005).. ,.'~
(a) all four are chiral compounds' . ·0 (a) Butane 0 (b) 4-Methylheptane 0
(b) only (I) and (II) are chii'alconipounds . 0 (c) 3-Methyl heptane 0 (d) 2-Methyl heQtane 0 '
(c) only (III) is a chiral compound 0 75. Maximum enol content is in: (nCE 2005; AIIMS 2008)
(d) only,(II) .and (IV) are chifal compounds 0 0 0 0
67. '~ich~of the following is most . likely to· show optical ';
.' Isomensm? . . " [UPSE~TZ004] (a)A 0 (b»)~.D
....... •. H'.. •..... . . · H · .... .
(C)~H O(d)~i~
. '.' . 1 " .. 1 '
. (a)HC==C-f~C==CH 0 (b) HC==C-f-CH3 0
CI .. CI'
eOOH ..COOMe.'..: ! ..
H CI
(c) HC==C-r-H
1
o (d) HC=C-C=CH2
1
o 76.. :+=~: :~4=;.,
COOMe"COOH~i'; ,,'
Cl (I) . (II}" .... '. t' i,,'
68. The molecular formula of diphenylmethane, Structures (I) and (II) are: , '., ' :f~PMr200S] .
(a)enantiomers 0 (b)diaSter.eomei's· . . D. .
(c) meso compounds 0 (dfid~iicrtl:'" ',' .', 0 '
77. The two structures of D-glucopyranose forms are: ' . ,
. • . . [UT(S) 2005]
How many structural isomers are possible when one of the
hydrogen is replaced by a chlorine atom?
(a) anomers o (b) enantiomers D'
. [CBSE (Med.) 2004] (c) epimers, . 0 ,(d) diastereoisomers' ,- []
. ~. Which of the following will show~,!!.metricaliSOinerism
.. ?
(a) 6 0 (b) 4 0 '. . LJK,:ECE (Med.)200S} :
(c) 8 0 (d) 7 0 (a) C 2 H s B r , O (b) CH2 (COOHh'" .'[j.
69. Which one of the follQwingwill have a meso-isomer also?
, .' . (AlEEE 2004; JCECE (Med.) 200S) (c) (CH)i(COOHh 0 ,(d)O:2H6 ......:',: ,,'p
....
., :
.
- " .
G.R.B. Organic Chemistry/or Competitions
~: H~H
(c) 3 o (d) 4 o
".~. ©H mW,~CHO = \
[AMU (Med.) 2006] \
:=f:COOCH
.. : .\
;
'COOH COOCH3
(I) (Ill)
(a) position isomers 0 . (b) chain isomers 0
(c) functionalisomers 0 (d) stereoisotners 0 (a) I and II are identical 0
87. Number of structural isomers for C6H 14, is: [lIT 2007] (b) I and II are diastereomers 0
(c) I and III areena:ntjOl~ers 0
(a) 3 0 (b) 4 0
- (c) 5 0 (d)'6 0 (d) I and II are enantiomers []
88. CH3-CHCI-CH 2 -CH3 has achiral centre. Which one (e) II .and III are enantiomers .0
93. Geometrical isomerism is.possible in: [JEE (WB)2007)
. of the following represents its R-configutation?
. [eBSE (Med.) 2007]
(a) isobutene 0 (b) acetone-oxime 0
(c) benzophenone-oxirne 0 (d) acetophenone-oxirne 0
Isomerism
94. Which of the following will have a meso-isomer also? 100. The total number of isomers in C6H3 Cl 3 is:
[UPSEE (Engg.) 2007; AFMC (Med.) 2007] [DPMT 2007]
(a) 2:3-Dichlorobutane 0 (a) two 0 (b) three o
(b) 2-Chlorobutane 0 (c) four 0 (d) five o
(c) 2,3-Dichloropentane 0 101. How many stereo isomers does this molecule have?
(d) 2':'Hydroxy propanoic acid 0 H 3 C-CH=CHCH2CHBrCH 3 [CBSE (Med.) 2008]
95. Which of the following molecules will not show optical (a) 2 0 (b) 4 0
activity? [PMT (Kerala) 2007] (c) 6 0 (d) 8 0
CH 102. The absolute configuration of the following:
7,
¥(, 3
CH 3
W '00 0
HO...,.... ,
H3 C
H Cl-i- H
H + . Cl,is:
C2 HS
[DCE(Engg.) 2008]
(c)
COOH
H~~~
COOH
,
o H~:X7<::2H
HH
, is: [AIEEE 2008)
(a)S,R 0 (b)S,S 0
(c) R, R 0 (d) R, S 0
(d) B r A H o 104. C g H 16 that can form cis-trans geometrical isomers and also
H . Br
has a chiral centre, is: [AIIMS 2008]
(e) H3~-CH2-CH3 o
(a)~ 0 (b)~H 0
CI
96. Pick out the correct statements: [PMT (Kerala) 2007] (c) both of these 0 (d) none of these 0
(i) if a compound has no asymmetric carbon atom, it is 105. Which of the following is chiral? [DPMT 2008]
always achiral. (a) CICH2CH2CH2CH2CH3 0
(ii) if a compound has just one asymmetric carbon atom, it (b) CH3 CH2CHCH 2 CH3 " 0
is chiral. I
(iii) if a compound has more than one asymmetric carbon CI
atoms, it mayor may not be chiral. (c) CICH=CHCH 2 CH 2 CH 3 o
(a) (i), (ii) and (iii) are correct 0 (d) HC=C=CHCH 2 CH3 ,0
(b) (i) and (ii) only are correct 0 I
(c) (ii) and (iii) only are correct 0 CI
(d) only (ii) is correct 0 106. Of the isomeric hexanes, the isomers that give the minimum
(e) only (i) is correct .0 and maximum number of monochloro derivatives are
97. The chirality of the compound respectively: . [PET (Kerala) 2008)
(a) 2,3-dimethylbutane arid n-hexane 0
(b) 3-methylpentane and2,J-dimethylbutane 0
(c) 2,2':'dimethylbutane'and 2-methylpentane 0
(d) 2,3-dimethylbutane and 2-methylpentane 0
(e) 2-methylpentane and 2,2-dimethylbutane 0
IJIPMER (Moo.) 2007]
107. How many chiralcarbon atoms are present in
(a) R 0 (b) S 0 2,3,4-trichloropentane? [MGIMS (Wardba) 2008]
(c) Z 0 (d) E 0
(a) 1 0 (b) 2 0
98. Different structures generated due to reaction about C-C (c) 3 '0 (d) 4 0
axis of an organic molecule, are examples for:
108. The total number of acyclic isomers including the
ICET (J & K) 2007]
stereoisomers (geometrical and optical), with the molecular
(a) geometrical isomerism o formula, C~H7Cl is: IGGSIP (Engg.) 2008]
(b) optical isomerism o (a) 12 0 (b) II 0
(c) conformational isomerism o (c) 10 0 (d) 9 0
(d) structural isomerism , o 109. Which of the following will exhibit cis-trans isomerism?
99. The number of geometrical isomers in [JEE (WB) 2008]
[DPMT 2007]
CH3CH=CHCFhCH=CH2 is:
(a) two 0 (b) three o (a) CH2Br-CH2Br o (b) CBr3~3 0
(c) four 0 (d)five o (c) CHBr=CHBr o (d) CBt2 =CH2 0
.... '
' ': .. ..
'
;', '.
110. Whichooo','Iof the follbwing ·compounds is capable ·of. List I' ListH'
..e.xistin~,~ameso form? . .,' (PET (Kerala)2008) o
. ,.·(a) ),~~Dlbromopentane 0 (b) 4-Bromo.:.2-pentanol 0 " . II ..
.·',(c) 3~BroQlo-:2-pentanol 0 (d) 2,3-Dibtomopentane [] (i) l. Apaiiofchainisomers:{1) CH3":--C-CH2CooC2H s;'
: (e) .2A~Dib!omopentaneD i " ',=i?' OH
J.
CH 2 0H Codes /;.a) I~A, 2-B, 3-C, 4-D, (b) I-D, 2~C, 3-B, 4-A
(c) l-B, 2-D, 3-A, 4-C, (d) I-C, 2-A, 3-D, 4-B
, {i}.:pair of diastereomers [JEE (WB) 2~) (ii) 1. A pair of optical
'.' ;'(b) pair of en~tiomers ,0 isomers
(c) same mol~cule [j
(d) both are optically inactive D
-~
.113. Which of the following compounds will show geometrical
. isomerism? [DPMT 2009)
(a) Cyclohexene 0
(b) 2-Hexene 0
. . (c) 3-Hexyne . 0
COOH
I. HOOf
(d) 1,I-Diphenyl ethylene D 2. A pair of geometrical (B) H-C""":OH ,H-r-OH
, 114.A C?mpound is formed by substitution of two chlorine, for
two hydrogens in propane. The nu.rtlber of possible isomeric
isomers 1
HO-f- H H-1- 0H
Isomerism
±:I H±HI
COOH
4, Fischer projection
I .....'
(D) HO-C-H 0 ' HO-C-H 0
! ~
(d)
<o8~> , '. []
~HI H~HI
COOH CQOH
127. Which of the following compounds will show' g~metricaJ
. I· 1 isomerism?"
H~ H--€
1 .1 (a) 2-Butene 0 (b) Propene .0'
CHzOH CH20H (c) I-Phenyl pr6pene 0 (d) 2-Methyl-2-butene 0
Codes :(a) I-C, 2-A,3-D, 4-B, (b) I-A, 2~B, 3-C,4-D
<)-CH~CH"--oH
128. Tautomerism is exhibited by:
(c)1-D,2-C, 3-B, 4-A, (d)l-B, H), 3-A:. 4-C
1l0~Cis-2-butene and trans~2-butene are : (a)
o
(a)· geometricalisom~rs P (b). diast(!reomers .;'; . . 0
o
(b},O~>=o o
(c) enantiomers. . ' . (d) position isomers 0
yo·
121. Whichoftbe foliowingcan.existin 'sYJ?' and 'anti; forms?
. (a)C6HS-,--N N:":':"OH' . . . "0-
- ':.. ',', - -\
.
o
C3H 7-C::'....-C 2H s C2Hs-:-c-C3H7
129. Geometrical isomerism is exhibited by; . . . ....... .....
(I).. (II)
. [BHU (Mains) 2008] .
Cl-C-Br CI-:-c-Br (a) 2-chlorobut;'2-ene 0 (b) but-2.:.ene .. :,':.- ·tJ
I II' (c) 3~methylpent-2-ene 0 (d) 2-methYl but~2-ene·tl\
H-C-F F-C-H
130. The correct statement(s) about the compound given below"
(Ill) (IV) is ( a r e ) : ' . . .. (lIT 2008]
(a) (I) [] (b) (II) 0
'H.:~·
l'~
(c) ( I I I ) . 0 (d) (IV) 0
123. Keto-enol tautomerism is observed in:
.CH3
(a) C6Hs-CHO 0 (b) C 6H 5 COCH 3 0 . 3 '"~H .
(c) C6HsCOC6HS [J (d) C 6 H s COC1I2COCH3 b Cl
124. Which of the following statement(s) is/are. correct about· (a) the compound is optically active .
tautomers? (b) the compound possesses centre of s)'l:111i1etry
(a) They possess·different electronic aI\d atomic arrange- ( c) the compound possesses' planeof"synimetty
ments . 0 (d) the compound possesses axiS:-Qf synimetry
(b) They possess different .electronic but sa~e atomic 131. The correct statement(s) concemingthe sttfiCtures E,Fand
airangement ' 0 G is (are); . . - - ' \. .j ·.[nT2008]
(c) They have different atomic arrangements but same
electronic arrangement' [] H3C~O H3C~OH H3C:>==<CB.
(d) They exist in equilibrium \, .,' 0 H3C .CH3 H3C CH3 . H3C OH
125. The lowest molecular weight alkanes, which arc: optically (E) (1') -(0)
active, are:
(a) 3-methylhexane 0 (a) E, F and G are resonance stntctnres ·0
(b) 2,3-dimethylpentane 0 (b) E, F and E, G are tautomers , ','0
(c) 2,3,3-trimethylbutane
(d) 2-methylhexane
[J
0
(c) F and G are geometrical isomers
Q.
o
(d) F and G are diastereomei:s
126. Which of the following compounds are chiral and resolvable? 132. The correct statement(s) about the compound
+
(a) [C6HS N(CH2CH2CH3)(C2Hs)(CH3)]Br- 0 H 3C(HO)HC-CH=CH-CH(OH)CH3 (X)is(arel: .'
. .,lnT1009)
(b) C6 H 5 N(CH 3 )(C 2 H s ) 0 (a) the total number of stereoisomers possible for (X) is 6
(c) CH3CH2CH(CH3)N(CH3J(C2Hs) 0
G.R.B. Organic 'Chemistry (Or Competitions
(b) the total number of diastereomers possible for (X) is 3 (d) if the stereochemistry about the double bond in (X) is
. ,0 .cis, the number of enantiomers possible for (X) is 2 0
(c) if the stereochemistry about the double bond in (X)' is "
trans, the number of enantiomers possible for (X) is 4 0
H3)C~C-N<CH H3)C~C-N H
.' H . CH
3
<
3.. (A) Following amide exist in two StruCturlll forms:
3
structures.
10. (A)All the hydrogen atoms in but-2-ene lie in one plane.
(R) All the carbon atoms in it are sp2 -hybridized.
11. (A) Benzaldehyde forms two oximes on" reacting with
(1) (II) NH2 0H.
(R)The two oximes arise due to geometrical isomerism
(R) Rotation about carbon nitrogen bond is restricted due to around C N bond.
resonance.· 12. (A)Cyclobutane is less stable than cyclopentane.
4. (A)Dextro-isomers rotate the plane of .polarised light . (R) Presence of 'bent bonds' causes loss of orbital overlap.
towards right. .
13. (A) Ethyl acetoacetate gives reddish violet colour on
(R)Dextro-isomers are represented by putting (D) before treatment with ferric chloride.
their name. (R) 'Keto' form is dominant in it.
5. (A)Trans-l-chloropropene has higher dipole moment than 14. (A) The boiling point 6f cis-l,2-dichloroethene is higher
.cis- t -chloropropene.
than corresponding trans-isomer.
(R)The resultant of the two vectors in trans-l-chloro (R)The d~pole moment of cis-l,2-dichloroethene is higher
. propene is more than injis-l-chloropropene. than trans-isomers.
6. (A)Meso tartaric acid i~ptically inactive. 15. (A) Molecules that are not superimposable on their mirror
(R)Meso tartaric a>i«has plane of symmetry. images are chiral. (lIT 2007]
(R) All chiral molecules have chiralcentre.·
Isomerism 161-
_J ANSWERS I
OBJECTIVE QUESTIONS
-.
1. (e) 2. (e) 3. (b) 4. (d) 5. (a) 6.· (d) 7. (b) . 8. (d) 9. (e) 10. (b)
11. (b) 12. (a) 13. (a) 14. (e) 15. (c) 16. -(c) 17. (d) 18. (a)· 19. (e) 20. (c) .
21. (a) 22. (e) 23. (a) 24. (e) 25. (d) 26•. (d) 27. (d) 28. (d) 29. (b) 30. (a)
31. (a) 32. (d) 33. (b) 34. (b) 35. (c) 36. (c) 37. (c) 38. (d) 39. (b) 40. (a)
41. (b) 42. (d) 43. (a) 44. (c) 45. (al. 46. (d) 47. (b) 48. (a) 49. (d) 50. (a)
51. (c) 52. (b) . 53. (a) 54. (c) 55. (d)'. 56. (b) 57. (a) 58. (b) 59. (d) 60. (a)
61. (b) 62. (a) 63. (c) 64. (c) 65. (b) 66. (b) 67. (b) 68. (b) 69. (b) 70. (d)
71. (b) 72. (e) 73. (a) 74. (e) 75. (e) 76. (d) 77. (a) 78. (c) 79. (c) 80. (d)
81. (b) 82. (a) 83. (d) 84. (d) 85. (d) 86. (c) 87. (c) 88. (b) 89. (b) 90. (e)
-91. (a) 92. (a) 93. (d) 94. (a) 95. (a) 96. (c) 97. (a) 98. (c) 99. (a) 100. (b)
101. (b) 102. (b) 103. (c) 104. (a) 105. (d) 106. (d) 107. (b) 108. (a) 109. (c) 110. (e)
111. (d) 112. (c)- 113. (b) 114. (d) 115. (c) 116. (d) 117. (b) 118. (c)
119. (i-b), (ii-a), (iii-il), (iv--c) 120. (a,b) 121. (a,b,c) 122. (a,c) 123. (b,d) 124. (a,d) 125. (a,b) 126. (a,c)
127. (a,c) 128. (a,e,d) 129. (a,b,e) 130. (a,d) 131. (b,c,d) 132. (a,d)
..
G.R;B. Organic Chemistry fOr Competitions
alkaline KMn04
.(r.
OHOH
Cis-I,2-cyciopentandiol . [Ans. (I), (II), (III), (~Enantiomei:s
(land III); (II and III); (I and IV),
. (II and ~Diastereomers]
'. q ..
.
€r +<8f
. HCOOOH
(Ans. S. Indicate optical configuration in following compounds:
~
Cyclopenrene H OH OH H 5 ·.3 - .
1rans-I.2-cyclopentandiol (a) Br---,. 2 -"fI. (b) Br.-~·· .. ---Br
H- .Br '. H H
+~l
... (A~s~ (a) (lR,2R) 1, 2-dibromocyclopentatie
.. (b) (lR,2S) 1, 2-dibromocyclopentane]
6. .Specify chiral-enantiomers .and achiial';identical pairs
Br H
Trans-! ,2-·dibromocycloiJentane
following compounds: . . ~ . .~
DH
N~N
HO~~DH
(ii) H>·.
.H
~·-2.~
(I.
..
"H
......
o
...HN·ANH (iii)
HO~mrlO·
Tautomer
(iv)
3. Give the ring-chain tautomers of4-keto pentanoic· acid
(Laevulic acid): .
CH3 CH3
. I: I
cH2-C=O~ CHz-'-C-OH
(Ans. I ,;-.,) ~. I '" 0
.CH2-~-0' HI CH 2-c/ . [ Ans. (i) Chiral-enantiomers
II '-, II (ii) Chiral-enantiomers
o 0 (iii) Achiral-identical
(Ring-chain tautomerism) . (iv) Chiral-enantiomers
(v) Achiral-identical]
4. Identify enantiomers and diastereomers among the following:
7. Pu~ star mark to the chirality centre of the following
(a) CH''-..cD CH
',
H CH3 CH3 H
II
CH2
Carvone (Speannint oil)
"
" .. -,,'
Isomerism'
(b)
o
.
.&.
. CH3
.*
C.H3
.-:::P
.
..
..
. CH2
~~
...
. C H3
. . '.
U. Which of the following havea'm~so~f~rm?'
(a)2,3 ..Dibtomobutane
(c) 2.4-Dibromopentane ..
(b) 2,37Dibrornop<mtane
?
(ela
8. Assign 'R' and '8' configuration for the following:
H ~HO N' 0
-::?, ,', 0
HOY"(,
I HO,t~H (f) . 'V
(a) CHf':F''-CH2CH3(b) I OH
CI H~<?~OH I " OH
'L9'.' .'.
,~C=CH2' I.
I
!
.. .CH3. )
CH20H
(Ans. (a) (b)CH" ..•. C=C---':H
COOH
, 3 .
. !
(c)
H'C~NH2
I (c) CH2=C-O~CH3
fH (d) CHr:-C-CH-CH2
~..
HO~<?~H
,,
CH3
[ Ans. (a) (S)-2-chlorobutane
(b) (2S, 3R)-2, 3, 4-trihydroxybutanal
(c) (2R, 3S)-2-amino-3-hydroxy butanoic acid]
9. Assign Cahn~Ingold Prelog priorities to the following sets
. cr
(e) ",""-
,"""-.
"I,"
OH
'.'
.. (f)
of substituents:
(a)--:-H, -Br, -CH2CH3,-CH2CH20H (a). N~ /N~
(b) -COOH, ~COOCH3 , --:-CH20H, -OH R 'R H 'R
(c) -CN,-CH2NH2,-CH2NHCH3,-NH2
(d) -Br,-CH2Br,-CI,-CH 2CI
( Ans.(a) -Br > - CH2CH 20H > - CH2CH3 > --'- H
(b) -OH > - COOCH 3 > - CoOH > - CH20H.
(c) -Nlf 2 > CN > - CH2NH CH3 > CH2NH2
(d) -Br > -CI > -CH2Br > -CH2Cl]
10. Which of the following structures represent 'meso' form?
(a)~~H
• I
~l ~~H •
H,
Br
Br,t~CH3
(d) I (dl ~.
CH3~<?~H
. ,,
Br
U CH3
.[ Ans. (a) and (d) are meso forms.]
GrR B. Organic Chemisl1Jl for Cqmj2¢tJtions.
o
;
. ,aoo'1/\«OOH o· (d)
(c) ',H.
H H HOOC
f6r COOH
o 10':
Syn-acetaldoxime Anti-acetaldQxime
.36. Wmch'of the f'Oll'Owing cycl'Oalkanes involves I)'l8XmlUm
t'Orsi'Onal strain?
Trans~o-aminocinnamicacid
' , N H ,., .. ' " ',.
2
",,37. The m'Ost stablec'Onf'Orlnati'On 'Of 1,2-.diphenyl ethane is:
Cis-o-aminocinnamic acid' . *H
. . C~
.~.
cils
(d)
H3C )
C=C
'<. C;H2CH2CH3. C,IC.H2)··.. , . .-.
and ' '. C=C
<
. . C~,l" 6 5
(a} C H ' . . . . ,'
.' C~5 .
. Ho
H'"
(b) H "
H',
,,"'.'
H
0
H CH3 ' BrCH2 , ' , CH3 .
Z-isomer E-isomer 0 H,
o
(a) 0:: o (b) CH3-CH=N.,......;()H 0
o '~
0, (C)'VV o .(d) All 'Ofthese " D·
.
o 39. Which 'Of the f'OlI'Owing is/are correctmatchingS?
Column 1· . Column 2
(a)(~~.)
CH3 -C==C-CH 3 ' " P'Ositi'On is'Omer o
o (c) CH 3CH 2CH 2NH2 arid
. CH3.;....,fH~CH3 , taut'Omers o
N02 COOH NH '
2
(b) CH2=C=CH2 o
Isomerism
40. Consider the following structures and pick up the right 45. Which of the following cyc10alkanes will show cis-trans
statements: isomerism?
U""-C"p-o .
. I
H;.,.i' CH20H
HO
C~ (')0 ·0 (b) c1~:: o
(II) (III)
C~
... CH3.
o (d) ~ D.
(a) I and II have R-configuration 0
. (b) I and III hiwe R-configuration 0 . .
. (c) onlyIIlhas S-connguration ·0 46. Match List I with List II and select the answer from given
(d) both (a) and (c) are correct 0 codes:
41. Which of the following will not show optical activity? List I ListII .
Structure of the Name of g~metrical
HOOC COOH compound isomer
(a) H,,~.. H· o (b). CH:;---GH-CD o
.J \ I 3.
, L S-cis .'
OH H· OH
o (d) BrA·'Br
H
H· o 2. Trans
6·. D. ,
H/C~CH2 '.
4. S-trans
(a)
(b)
(c)
A
1
4
2
BCD
2
3
3
3
2
1
4
1
4
represented by: . (d) 3 2 4 1
. 9H3 "COOH 47. Which of the following is correctly matched?
. Compound Number of geometrical .
(a),H2N~COOH 0 (b)H+-NH2 o isomen
H CH 3 (a) CH 3-CH=CH-CH . CH-C2HS 4
COOH (b) CH3-(CH=CH)4--:-CH3 2
o (d) CH3- f - N H2 ' 0 (c) H 2C=CH-CH=CH2 23 +i =10
'H (d) CH3 (-CH=CH)s-CH 3 24 +22 = 20
48. Match List I with List II and select the correct answer from
44. The IUPAC name of the compound,
the given codes:
CHI . \ \' /CH3 is: List I List II
Number or optical
Compound
isomen
(a) (2E,4E, 6Z)-octa-2,4,6-triene o A. A symmetrical compound ,L 2n-~
(b) (2E, 4E, 6E)...octa-2,4,6-triene o with •n' chiral carbon.'
(c)· (2Z, 4E, 6Z)-octa-2,4,6~triene o n--1
(d). (2Z,4Z, 6Z)-octa-2,4,6-triene o B. Symmetrical molecule with
'n' chiral carbon when n is even. 2.211-1_22
CH3
OCb} , 0
0 (d) 0
H H Br
H ,H
OH OH
(II) (iII) , 59. Thetkjorproduct frofu the reaction ofBr2' withZ-3-hexene
is:
OH
'(a) optiCally active D~
·ORC . (b) raeemicmixture D
'. (c) llleSo f o n n . 0 '
(d) both racemiclllixtUre and meso fonn . 0,'
H 60. Which one of the following statement(s) is/are true for
OH . , threo-:butane-2,3-diol regarding their population of different
confonners?', ' ". ' '. , . " , ,
(IV) ,
, (a) The most populated confonner will have the hydroxyl
Which of the above represents erythfo isomer?
groups of the gauche position. .' . 0
(a) I and I i I ' 0 . (:b) 1 and iv . 0 . '(b) The most populated confo,nner will have the hydroxyl
, '(c) I and II ' , ' 0 (d) II and IV .0 . groups at the anti position. , ' , 0
'58, In the dehydrohalcigenation of 2-bromobutane, which (c) All staggered conformations will be equally populated.
confonnation leads to the formation of cis-2-butene? , .,'" 0
:(d) Relative populations of different 'confotmers is not
pt:edictable. , ' ' ',' , ", ','.,' 0
, , [Ans,(a:)Iit~olecular hydrogen bonding iiI possible in
gauchecoriforinarlon which makes it more stable ,than
, allti fonn,] , ' ,
[V-m,
~ ).
rotation abOu~- sigma ~onds, are conformational isomers' whife
.
those, which can be converted only by breaJdng and remaking of 1. The compound acetophenone shows
bonds and not simply by rotation, are called configurational
isomers.
the 'keto' - 'enol' tautomerism. .
The angle betweeI,l C-C and C-H bonds on adjacent
(a) True (b) False
carbon aionls in any conformation is' called· dihedral· angle. ,lint : Compounds having at least one hydrogen at a-position
The cYclic co:tDpounds most tommonly found in nature
with [oc tO'
~~6)ShO~"thde tautomerism.]
0I
P
containing 'six membered rings can exist in a conformation that is reS
aimostCbmpletely free of strain. The most stable conformation of
cyclohexane.is chair form,
2. Benzaldehyde V au benzophenone
According to Bayef strain theory, the greater deviation from
the normal tetrahedral angle;. greater is the angle strain or
torsional strain and hence lesser is the stability ofthe.cycloalkane.
Answer the fol,lowing questions:
1. Dihedralangle in staggered and eclipsed conformations are:
(a) 60° and 0° - (b) 0° and 60°
[cr~'O] bosh pos~ss wuromffi_
(c). 60°, 120° _ (d) 120°, 60° . (a) True (b) False
. 2. Dihedral angle between two methyl groups of n-butane in
the gauche and anti forms are:
(a) 60°, 0° . (b) 60°, 1800 3. Phenol is more stable than
0 0
(c) 0 ,60 (d) 180°,60°
3. Which among the following conformations of cyclohexane
is the most stabl~ form?
(a) Chair form (b) Half chair form
(c) Twist boat form (d) Boat form
4. Which of the lollowing molecules has the highest deviation
from .tetrahedraH10nd angle?
(a) Cyclopropane (b) Cyclobutane (a) True (b) False
. (c) Cyclopentane (d) Cyclohexane
5; The energy barrier _between eclipsed and staggered forms is:
(a) 44 kJ/moi " (b) 6.7 kJ/mol [ -. O-H
I 9I 1
(c) 12.55 kJ/mol (d) 29.7 kJ/mol 4. Acetylacetone CH3 -C=CH-C-CH 3 is more
6. Select the correct sequence of decreasing order of stability:
[CH,-r~!-m,]
(a) g~uche > staggered> partially eclipsed> fully eclipsed .
(b) .staggered> gauche> partially eclipsed> fully eclipsed
(c) fully eclipsed> partially eclipsed >gauche > staggered stable than a..methyl acetyl
(d) partially eclipsed> fully eclipsed> staggered> gauche
CH3
Passage 2
acetone.
Tautomerism arises due to 1,3-migration of a proton from (a) True (b) False
otie polyvalent atom to the other within the same molecule. Two 5. 'Enol' form of acetoacetic ester is more stable than 'keto'
isomers thus o~tained exist in 4ruamic equilibrium with each form.
· other .are called tautomers and' the phenomenon is called OH 0
- tautomerism or allelotropism or dynamic isomerism. . I I
FOr an aldehyde or ketoneto'exhibit keto~enol tautomeri{lm, CH3 -C=CH-C---OC2 H s
· it is essential that it must have at least one a-hydrogen atom.' In (MOf(: stable)
siinple-aldehydes and. k,efones the 'en:olic' form is negligibly o 0
small. This is due to .greater stability of the 'keto' form with I
CH -:-C-CH
I
· respect to 'enol' form. Strength of (C=O) bond in keto form has 3 2 -C-OC 2 H s
greater energy than (C C) bond in enol form. . . (Less stable) .
Isomerism
-: ED~C=C=C<AB
~
:
I
A)C
B' ,
C''c~D
'~E,
'
I
1. H3Cu"
~c=c=c
<H
It is optically active:
H3C " H
(a) True (b) False
4. Ph::> C=c=C~r .
Ph " Bi-
All the terminal groups of this molecule be in the same
plane:
(a) True ' ; ~(b)False .
5.
(53c=ccc~'
CI' CI
•. 180·· V R B Organic Chetjlistr)llor Competitions
.. AIl tbe.tet11$ial groups of it are in the same plane: [Hint: When odd no. of cumulative double bonds~xists, orbital·
. (a) True. (b) False overlapping causes the four groups to occupy one plane
and cis~trans iSomeiism is Observed.]
.!
MECHANISMOF-ORGANlC
REACTIONS'
'. sharing o.f the electro.n pair. Fo.r example, in the bo.nd _/ Effect :' Ato.ms o.r gro.ups (Eled:ron:"attracting o.r
1 .
withdrawing) in th¥ decreasing o.rder is:
· -.C-Xif X is mo.re' electro.negative than C, the electro.n pair NR3 >-N0 2 >-S02R >-CN >-COOH >-F
'I . . , >-Cl>-Br >':"'1 > '-OR >-COR >-OH
is attracted to.wards X .. With the result· o.f this shifting, X >-C6HS >-CH=CH 2 >-H .
acquires Ii partial negative charge deno.ted by 0:- and C attains +I Effect: Gro.ups (Electron-releasing o.r repelling) in
, a partial po.sitive charge deno.ted by 0 + the decreasing o.rder is:
(CH 3 h C-> (CH 3 h CH ":' >CH 3CH r >CH 3-> D>H
·-C-;-
'I'. X '.... I ..•...
o.r -C-.X o.r
" C10 -X
+ 0-
.
I
o.r -C --+-X '
Important Features of Inductive Effect
, 1 I" I 1 (i) It is a permanent effect in the mo.lecule o.r io.n.
The polarity thus'produc~d in the molecule as a result (ii) The shared pair of electro.ns altho.ugh. permanently
shifted to.wards mo.re electro.negative ato.m, yet remains in the
ofhignerelectronegativity of one atom compared to other
same valence shelL,
is termed inductive effect. It is impo.rtant to. no.te that the (iii) As a result of electro.n shifting, the mo.re
electro.n· pair" although permanently displaced o.r· siillply electronegative end acquires partial negative charge and the
.shifted, but remains in the same valence shell. The·in~uctive o.ther acquires partial po.sitive charge. . .
effect ·is· always transmitted. alo.ng a' chain o.f ·carbo.n ato.ms. (iv) The inductive effect is no.t co.:p.fined to. the
.wli~!1e'veJ:anelectron withdrawing ato.msuch as halogen(l:') po.larisatio.n o.f o.ne bo.nd but is transmitted alo.ng a chain o.f
ot-group (-N0 2 ~N, -COOH, etc.) is attached to. the end
, carbo.n atoms" thro.ugh a-bo.nds. Ho.wever, the effect .. is
o.f. a ((arbo.n ,chain, the aelectro.ns o.f the G-X 'bo.ndare insignificant beyo.nd seco.nd carbo.n in the chain. .
slightly' displaced to.wards themo.re 'eiectro.negative halo.gen . ,(v) hiductiveeffect brings changes in physical pro.perties
ato.m.. Ho.wever, its intensity. decreases as distance from the such as
dipo.le mo.ment, so.lubility, etc. It affects the rates o.f
the reactio.n. . '
source ato.ms increases.
(vi) Carbon,.,hydro.gen bo.nd is taken as a standard o.f
-C4 --+--C 3000+ --'-~)_I·C 200: --+-~c 0+' -+-CI 0- inductive effect. Zero. effect is assumed fo.r this bond. Ato.ms.
" o.r gro.ups which have a greater electron-withdrawing capacity
The po.sitive charge on C 1 attracts the electro.n pair shared. than hydro.gen are said to have -1 effect whereas ato.ms o.r
between C r and C 2 towards, itself. This will cause C 2 to.. gro.ups which have a greater electron releasing po.wer are said
acquire a small po.sitive charge b'!lt this charge o.nC 2 will be to. have +1 effect.
,smaller than o.n C 1 . Siririlarly; C 3 will. acquire positive charge . The pkeno.mel)o.n o.f inductive.effect is very important in
that will be still smalk~r; ThisefIect is 'still relayed further. In organic chemistry as it is helpful in explaining a number o.f
, fact, inductive effect t~nds to. be insignificant beyo.nd the fl!cts. So.me o.f them. are discussed belo.w:
seco.nd carbo.n ato.m.It is,a.per~iutn~n,t effeciin the molecule <a) Reactivity of alkyl halides: The presence o.f
· . and can be o.bserved practiCaUy:in the furm of dipo.le mo.ment. halo.gen ato.m in the mo.lecule of alkyl halide creates a centre
: "This type'o.f,electron:displa¢emen,t ruotrg a carbo.n chain due is
of lo.w electron density which readily attacketi by the
negatively charged" reagents. Fo.r example, C1hCI is mDre
to the presende o.f a :source ,is called Inductive effect o.r reactive than CH 4 as inductive effect is present in CH 3CI and
·1)-anSmissim..'~ffect." This effect is represented by an'afrow no. inductive effect in methane. .
. headjn tWUriddle. of ~o.valent bo.rid Po.inting in the directio.n ' '0+ 0'-
o.f'electfoiCdisplacement (--+-)~ . Dr H3 C - CI ..
J .....
The,.carbM-hydro.gen>bo.nd is used as a standard fDr . Site for the attack by
co.mparing theJendency of electron attractio.n and repulsiDn~ electron-rich reagent
. .- ,
Ther~,~r¢JWDJypesoflnductiveeffects, i.e., -.:-1 effect ,and,
The act.iwtyalso increases from primary to secondary and
+1 effect/(i)'fbe: atOJn~or,:~gr6Upwhich, has mpre po.wer.t~ . frDm Secondary to tertiary halides as the +/ effect o.f methyl groups'
attracte16Cti'ons"in oomPaPsontDhydrogen is said to- have":'J'.' enhances "-1 effect o.f the halogen atom by repelling the electrons
. effect. .The:l'J ,electrons:are:;displacoo towards the 'substituent X. , towids .the tertiary carbon atDm. The reactivity Drder fo.r" alkyl
(ib .
i~ .. ' Th~ at4m.'or grDUp. whichj:'nas .less PDWer to.. 'attratt the lialldes .is: .
...elec:trons:t~"hydiogenis;i~M to. have +I ~ffeCt.' The a .. CH 3 CH 3
.• electrcns are displaced awaY,frDm the substituent 1':
. ".'.' ~r0'-,-+.,-c:F'-+-Cr -+- y 0+
+ > +
H 3C-+-C-+- X > H 3C-+-CH-+-X>CH 3 -+-CH2 -+-X
. .' . -- . ~
. CH
t .
>CH -+-X
3
...
';l;el~~tFp~l,Wit:n.ihawi~g While th~ secDnd type ele(!tro.n repeili~g 3
Tertiary > .Secondary > Primary >. Methyl
,~ orelecftorri:eleasing atDm org..Dup (IngDld ~DnventiDn). '. .
(b) DipoiemomeDt: As the inductive effect increases,
.'.,soifi~.co.mm!ln'ato.msor gro.ups which cause and -+- 1
··the dipole mo.ment increases.
etfuc~' aie~Sho{Vn below' in' decreasing o.rders:
" '. .' ".: :.~ .. - . -' .
Mechanism of Organic Reactions .183
o 0
I I .
Iiiductive effect increases F-+--CH 2-+--C-+--O-, CI-+--CH2.-+--C~O-
Less - ve charge More - ve charge
(c) Relative strength of the acids (Acidic nature of (More acidic) (Less acidic)
-COOH): An acid rruiy be defined as a species that has the
Furthennore, the inductive effect in 'di- and
tendency to lose proton. Furthennore, the strength of an acid
tri-halogeno substituted acids is stillmore marked with the
depends on the tendency 'to release proton when the acid is
result that these acids are progressively more stronger than the
dissolved in water.
corresponding monohalogeno substituted 'acids~ Thus, acidic
o o nature decreases in the order:
II II _ +
R-C--OH ~ R ---,-C--O + H , CCI 3COOH> CHCI 2COOH> CH 2ClCOOH> CH 3COOH
o o Trichloro Dichloro Monochloro Acetic acid
II I acetic acid acetic acid acetic acid. •
H-C-OH ~ H-C-O- +H+,
(- Inductive effect increases, SQ acid strength increases)
o o
II I _ + Thus, the group or atom having -1 effect increases the
CH3 -C-OH CH 3 -+-c-o + H , strength as it decreases the negative charge on the.carboxylate
o ion. Greater is the number of such atoms or groups (having-1
I effect), greater is the acid strength.
C2H s -C--OH Since, the inductive effect decreases with increase in
So, (i) stronger is acid, weaker is its conjugate base. distance of halogen atom from the carboxylic group (so~rce),
(ii) More negative is the charge on carboxylate ion, the the strength of the acid is proportionally decreased. Thus, the
more is its reactivity and more is basic nature, i.e., lesser is chlorobutyric acids follow the following acidity order:
acidic nature. CH 3CH 2CH(CI)COOH > CH 3CH(Cl)CH 2COOH
o 0 o a-Chlorobutyric acid ~-Chlorobutyric acid
I
H-C-O- , CH 3 ~C-O-
I ,
I Ka x lOs = (14.0) (8;2)
C2Hs~C-O
> CH 2 (CI)CIf2CH 2COOH; > CH 3CH 2CH 2COOH
Less - ve. c~ge More - ve charge Most - ve charge y-Chlorobutyric acid. n-Butyric acid
(Most aCidic) (Less acidic) (Least acidic) (3.0) (1.5)
Thus, acidic nature is: This fact can be shown by the following table that higher
HCOOH > CH 3COOH > C 2H sC<?OH > C3H 7 COOH > C4 H 9 COOH the Ka values (dissociation constants); more·stronger will be
(+ Inductive effect increases, so acid strength decreases)
• the acid .
Measurement of Acid Strength
Among isomeric carboxylic acid, acidity decreases with (K a values of some acids x 10-5 )
increase in branching of alkyl group attached to carboxylic
HCOOH= 17.7
group. CH 3CH 2CH 2CH2COOH> CH3CH 2?HCOOH >
CH 3COOH = 1.76
CH 3
CH 3 CH 3CH 2COOH = 1.60
I (CH3)2CHC-OOfl = 1.38
CH3-C-COOH CH 2COOH
I .
CH 3
(CH3)3CCOOH = 0.89 I. =365
CICH;COOH= 136 CN
Any group or atom showing +I effect decreases the acid
Cl 2CHCOOH = 5330 HOOC-COOH = 5400
strength as it increases the negative charge on the carboxylate
ion which holds the hydrogen firmly. Alkyl groups have +1 C13CCOOH = 23200
effect. FCH2COOH = 217
Further, the halogenated fatty acids are much stronger
acids than the parent fatty acids and the acidity is increpsed
The relative strength of acids are measured in their ionis-
almost proportionately with the increase in electronegativity
ation constants (Ka or pKa vaiues).
of the halogen present which helps in repelling the proton
from the hydroxy group of acid. HA ~H+ +A-
Acid .
Greater the value of K a or lower the value ofpKa' . , explained on the basis of inductive effect. The +1 effect
stronger will be the acid. increases the electron density while -1 effect decreases. The
pKa values of some 'acids ate: amines* are stronger bases than NH3 as the alkyl groups
increase electron density on nitrogen due to +1 effect while
HCOOH=3.77 .·CH2CQOH'> CINH z is less basic due to -1 effect. "So, more is the tendency
CH3COOfI =4.76 I '.......... :: 2A7 to donate electron pair for coordination with proton, the more
CN .:
C2H sCOOH = 4.88 is basic nature, i.e., more is the negative charge on nitrogen
CJ:lsCOOH == 4.17 ." •• C1CH2COOH=2.86 .' . atom (due to +1 effect of alkyl group), the more is basic
. "C12CHCOOH "';1.29
nature":
N02CH2COOH = l.68 . . ."
ICH2COOH73.16
(See also Section 12.6, the acidity of carboxylic acids)
Ka{ionisation constant of acid.) "
.!(5\,
~henol
OH > H-OH ,> CH 3
Water
~OH
Methyl alcohol H
As compared to water, phenol is.moreacidic (-1 effect) I
but methyl alcohol is less acidic (+1 effect). . and Cl--+-N:
The decreasing order of acid strength in alcohols is also . I
H
due to +1 effect of alkyl groups. .'
CH30H > CH3CHzOH > (CH3}zCHOH > (CH3)3 COH Thus,the basic nature decreases in the order:
Methyl Ethyl Iso-propyl Tert-butyl (C2HshNH>CH3CH2NH2 > CH 3NH 2 :>NH3 > CINH 2
alcohol alcohol aJcohOl alcohol Diethyl Ethyl Methyl Ammonia Chloro
Acidity of some important inorganic acids used in organic amine amine amine amine
chemistry are given below: The order of basicity is as given below:
HF < HCl < HBr < Hi (Acidity) Alkyl groups (R-) Relative base strength
F- > cr > Br- > C (Basicity) (i) CH 3 R2NH>RNH2 >R3 N > NH 3
H 20 <HiS <H 2Se (Acidity) (ii),C 2H s R 2NH> R3 N >RNH2 > NH3
No(e:, (i) In gas phase, tertiary afulnes are more basic than secondary
OH- > SH- > SeH- (Basicity)
amines which are more basicthanprimaryamines.
CH 4 < NH3 <: H 20 < HF (Acidity). "'(ii)' In !lqueous medium baSicity of ethyl amine' is:
"./" . . . '., ". .
Relative acidity of hydrocarbons may be.given as: (C 2 Hsh NH > (C 2 HshN> C2HsNH2 >NH3
HC=CH >CH 2=CH 2 >CH 3 - 'eH 3 The relative strengths ofbases are measured as Kb or pK b
pKb = ' 25 44 50 values.
Asthe hybridisation changes from sp3 in ethane to sp2 in BOH·~B+ +OH:"
Base
ethene and to sp in ethyne, the acidity increases and the pKa
K _ [B+ ][OH- ]
decreases. This is because of the relative' stability of the
b - [BOH]
unshared electrons in the conjugated bases of each of these
compounds. In other words, energy of hybrid orbitals is in the pKb=-logKb"
order: sp < sp2 < sp3 . . . Greater the value of K b or lower the value of pK b'
Or being. the mO,st electronegative, the sp-hybridized stronger will be the base.
carbon atom in ethyne polarizes its C-H bond to the greatest Amine (CH 3hNH CH3NH2 (CH3hN
extent, causing its hydrogens to be most positive. Therefore,
ethyne. donates a proton to a base more·. readily. Relative pKb 3.23 3.32 4.2
,basicity of corresponding carbanions is given below: (See also Sec. 16.13)
- - - Kb (ionisatiori constant of base) , .
CH 3-CHi >CH 2 =CH > CH=C
.
,
H
CH3NH2 > NH3 > C 6 SNH2 > (C 6 Hs h NH> (C 6 Sh N H
(d) Strength of bas~: A compouI!d is said to be basic
in pature, ifit is capable of accepting a proton. Base strength is As compared to ~onia, methylamine is more basic (+1
defined as the tendency to donate an electron pair for sharing. effect) but aniline is less basic and diphenylamine is still more
The difference in base strength in various amines' can be weaker (-1 effect).
• It is important to note that the rela,tive basic character of amines is not in tQtal accordance with inductive effect (t > s > p ) but it is in the following
.; o r d e r : ' Secondary; Primary> Tertiary
The reason is believed to be steric factor. .
""'.":
Mechanism oj Organic Reactions t"1~~;(>:; .
The decreasing order of base strength in alcohols' is due to . DUe ,tQelectron repelling nature of methyl group, the
+1 effect of alkyl groups. . electronic shift occurs according to eq. (i) way and not by
(CH3 hCOH> (CH3 hCHOH> CH 3CH 20H>CH30H" eq. (ii)way.
(3°) (2°) (10) methyl . ".'C\ . .
In Lucas test of making distinction betwet:n three types CH3-+-CH=CH-H-CH2CH3.~ .
(1°,2° andJO) of monohydric alcohols, , . Pent-2-ene - + .
C.H~CH-CH-CH2CH3
2
R-,'OH+ HC1(conc.) Anhyd. ZnC1 ) .R-Cl+ H 20] +1 effect ofCH3CH2~ is largerthari that ofCH 3--, hence
[ (Base) (Acid) . (Wbi~e ppt.)
n-electrontransfer is from (;3 to C 2.
the basic character of alcohols is in the order, benzyl In the case of carbonyl group, the shift is always towards
>3°>2°>1° a!"1 hence, the strongest base (30) will be
oxygen, i.e., more electronegative atom.
reacting f"st:ost with cone. HCl in presence of anhydrous
ZnCl 2 (LUI-as reagent) and gives white turbidity immediately.
2. Electromeric effect: It is a temporary effect. It , )C r:O ~>t-.8
comes into play instantaneQusly at the demand of the [In cases where inductive effect and electromeric effect
attaclcing reagent and as soon as the attacking reagent is , simultaneously operate,. usually. electromeric 'effect predomi-
removed the original condition is restored. nates.] . .
A mUltiple bond (double or triple) consists of sigma and Since,the electromericeffecttakes place only at the time
X-bonds. The electrons of the x-bond are loosely held and of' attackhlg reagent, it' always fadlitates the reaction and .
easily polarisable. When a compound having a mUltiple bond
never inhibits .it.T-bis effect is of common occurrence dUring
is approached bya charged reagent, the x-electrons of the
. bond are completely polarised, i.e., shifted towards one of the additionofpolarreagentson' )C~C(and )C=O bonds .
constituent atoms. Thus, '
There 'aretwo types of electromeric effects, i.e.,
o Reagent added + ••
>C .c<"'" '...
Reagent removed
>. )C-C< +E effect ot -E effect.
(a) When the transfer of electrons takes place towards the
The atom which acquires the electron· pair becomes attacking reagent,the effect is called. +E effect, e.g., the
negatively charged while the other atom gets the positive addition of acids to alkenes. .
charge. ' ) c "C<· + H+ ---? )c+-y(
The effect involving the complete transfer of a shared .. . I
pair of electrons toone of atoms joined by a multiple bond H
. (double or triple) at the requirement of attacking reagentis ~ . +
CH 3 ~CH=CH2 +H+ ---? CH 3-.CH-.CH3
known as electromeric effect. It is indicated by E and· Propene .
represented by a curved arrow (r\). showing the shifting of
Since, -CH3 group is electron repelling, the el~oD:s
electron pair.
are transferred in the direction shown. . .' .
Direction of the shift of electron pair: The direction
The attacking reagent is attached to that atoin on which
of the shift of electron pair can be decided on the basis.. of .
electrons have been transferred. "
following points:
(b) When the transfer of electrons takes place away from
(i) When the groups linked to a multiple bond are similar,
the shift can occur to either direction. For example, in ethylene the attackiI~g reagent, the effect is called -E effect•. For
the shift can occur to anyone of the carbon atoms. example, the addition of cYllnide ion to carbonyl cotrlpounds.
r---..... .
H 2e 0 CH2 ~ H2 C- CiI2 ' . )C \.9+CN- ---? >?-o-
n . .;-. + " Both are similar CN
H 2C=CH 2 ---? H 2C-CH 2
J The attacking reagent does not get attached to .:that atom
on which electrons have been transferred.
(ii) When the. dissimilar groups are linked on the two 3. Resonance and Mesomeric effect: For resonance
ends of the double bond, the shift is decided by the direction (See section 1:12). If the single and double bonds are present
of inductive effect. For example, in propylene the shift can be alternately in a molecule, it is said to contain double bonds in
shown in the following ways: conjugation and the molecule is called a conjugated
o + •• molec~e. For example, butadiene is a conjugated molecule.
CH 3-CH=CH 2 ---4 CH 3-CH-CH2 ... (i)
CH2 =CH-CH=CH 2 ·
" 0 .. + . Following are some of the c~njugated systems:
CH 3-CH=CH 2 ---? CH 3-CH-CH 2 ... (ii)
G.R.B. Organic Chemistry for Competitions
a-
chloride a conjugated system.)
In such compounds, the 1t-electrons are .delocalised and
polarity in the molecule is developed. The same thing also
happens when an atom or group with lone pair of electrons is
situated in conjugation with a conjugated double bond. The
mesomeric effect refers to the polarity produced in a
..
:CI:
molecule as a result of interaction between two 1t-bonds or
a 1t-bond and lone pair of electrons. The effect is transmitted
in the chain in a similar manner as the inductive effect.
In a carbonyl group ()C=O), the oxygen at~m is more
. electronegative than carbon atom. The 1t-electrons' of the
double bond get displaced towards the oxygen atom. The
shifting 'of electrons is shown by a curved arro~ «()). This
........
6
This effect extends the degree of delocalization and
. imparts stability to the molecule. Phenoxide ion gets
stabilized by resonance (See section 16.15). Lone pair on
will give an ionic structure. The actual structure seems to lie in nitrogen in aniline gets delocalized and thus the basic nature
between the structures (i) and (ii) which can be best of aniline is less than that ofNH3 (See sectlon 16.13). Thus,
represented as structure (iii) in which 1t-electrons are drawn +Meffect activates benzene nucleus for electrophilic
preferentially towards oxygen. substitution (S E) reaction at 0- and p-position.
)C=O )C 0a ~ )
+
C-O
••
) . . _--=-O Note: X (--CI, Br, -1) groups are ortho-para directing due to
(+M) effect but these groups are deactivating due to FI) effect.
'(i) (ii) (iii)
- Mor -R effeet groups:
NQw if the carbonyl group is conjugated with C=C type o
system, the above polarisation is transmitted further through II .
1t-electrons.·· . -N0 2 , . -C-,-CHO,-COOH,-COOR,etc.
() ~- + ..
.
H 3C---CH=CH---CH='=O
C J
(i) .
~
.'
H 3C---CH==CH---CH-0
'.
+
t. . ..
For example, in -.\1 effect the x-electron displacement
takes place towards such groups (-N02' -CHO,
-COOH). So, electrophile attacks at the m-position in ..
nitrobenzene (See section 16.12). Thus, - M effect deactivates
H3C-CH-CH-CH-0 or H3C-CH-CH=CH-0 benzene nucleus for S E but activates for S N reaction.
. C J
(iii) (ii)
Salient Features of Mesomeric Effect
The polarisation also occurs when an atom or group (i) 1t-electrons and lone pair of electrons are involved.
having lone pair of electrons 'is present in conjugation with the This effect .operates through conjugative mechanism.
(ii) It is a permanent effect present in the molecule in the
.., .
:Sr:
..
double bond (conjugated system) as in bromobenzene..
+Br:
' .. +Br:
. ..
+Br:
ground state.
(iii) It affects the physical properties such as dipole
..
6-9~Q-,6n
moment, solubility, etc. Rate of reaction of the substance is
also affected. .
(iv) It is denoted by M. Groups which have the capacity
to increase the electron density of the rest of the molecule are
said to have +M effect. Such groups possess lone pairs of
Like inductive effect; mesomeric effect may be + M or electrons. Groups which decrease the electron density of the
- M. It is + M when the transference of electrons is away from rest of the molecule by withdrawing electron pairs are said to
the atom or group and- M when transference of electrons is have"';'M effect, e.g.,
towards atom or group (but away from conjugate system). In (a) The groups which donate electrons to the double bond
general, . or to a conjugated system are said to have +M effect or +R
effect. For example,
.:;) n·
X-C=C-.
+M effect
and
-M effect
H2 6J CHJ:'CI:
••
~ CH 2-CH=CI: (+R effect)
••
Vinyl chloride
Mechanism o/Organic Reactions 187
In vinyl chloride, C-CI bond has double bond character unsaturated carbon atom, (i.e., having )C=C<) or positive
due to resonance. charge (as in carbonium ion) or a negative charge (as in
(b) The groups' which withdraw, electrons from the carbanion) or odd electrons (as in free radical, etc.) are able to
double bond or from a conjugated system towards itself due to release electrons by .a mechanism similar to that. of
resonance are said to have -M effect or -R effect. For electromeric ,effect, e.g.,
example, H ,
~
-b~c rt(
(\ , + '
H20=CH~ N: ~ CH 2- 'CH=C=N: (-Reffect) ~ -C=C-C-(
••
Vinyl cyanide I I
Simnaritles between Inductive and Mesomeric Effects This type of electron release by alkyl group attached to
the unsaturated system (H-C-C=C) is known as
(i) Both (Xc permanent effects.
hyperconjugatlon (involving de localization ofo and x-bond
(ii) Both affect the physical properties of the molecule.
(iii) Both can either hinder or facilitate a particular
orbitals, i.e., a- x conjugation) or the kind of delocalization
reaction. Buth affect the rates of reaction, the strength of acids involving sigma bond orbital is called hyperconjugation.
and bases, the reactivity of halides and the substitution of There should be atleast one H-atom at a-carbon with
different aromatic species. respect to Sp2 -hybrid carbon (C=C) and greater the number
The two effects differin the following points:
of C-H bonds at a-carbon to the unsaturated system, greater
will be the electron release and thus greater the
hyperconjugation effect. Thus, electron release due to the
I. It is operative in saturated 1. It is operative in unsaturated presence of three alpha H-C bonds in methyl group is greater
compounds. compounds especially having
conjugated systems.
than that by an ethyl group (CH3CH2~) in which there are
oniytwo alpha H-C bonds. Similarly, the effect is still,
2. It involves electrons of signla 2. It involves electrons of
smaller in case of isopropyl group (CH 3 hCH- having only
bonds. x-bonds or lone pair of elec-
,- trons. one alpha H~ bond and the effect is zero in tert. butyl as it
has no hyperconjugated H-C bond.
3. The ele.ctron pair is ,slightly 3. The electron pair is completely
displaced from its position and transferre!! and thus full posi- H H
I
thus partial charges are devel-
oped~ ,
HO·I."~H
, '~'
...... +-too'
...••.
.',
H'O·I c:. e
.'
....
;;::::;",
1(6','.·,H
+-too. '.
: ..', ...
.+-too
.'
,'~
~6c.,H
2,3-D1n1ethyl but-2-ene . 2-~ethyl but-2-ene
(1)
But~l-ene
(IV)
. (II)
CH3 CH 2 CH=CH2 > CH 3CH=CH 2
Propene
(V)
2-Methyl propene
(III)
H
I '. H-C+
I
~ H-C
I
2
"
Mechanism wOrganic Reactions
~,
~.H_ A~+
bility of alkenes.] ..
S. The decreaSing order of basic strength in .
V .•~.• .
..
C6H sNH2' (C6HshNH. CH3 NH 2 , NH)is:
. (I) . . (II) . (III) (IV)
Toluene (a) IV>III>I1>I (b) I>II>III>IV
(c)III>IV>I>II (d) II>I>UI>IV
[ADS. (c)]
[Hint: As compared to ammonia, methylamine is more
basic (+1 effect) but aniline is less basic and diphenylamine
. is stin more weaker (-1 effect).]
G.R.B. Organic Chemistry (or Conwetitions
CH3-
CH 3CH2-
105
101
110
111
85
84
70
70 56
93
94
84
85 ct W ; H3C ; H3C- C -
f
CH 3CH 2cH2- 101 110 85 70 56 92 84
Chlorine
free radical
Hydrogen
free radical
Methyl
free radical
I
H
Ethyl free
radical
Mechanism of Organic Reactions ·,91; ••.
The formation of free radical is initiated by heat, light or Reactions Involving Free Radicals
catalysts. (i) Wurtz reaction giving alkanes.
Energy . (ii) Substitution reactions of alkanes.
(a) Cl·CI . ) CI· + CI·
• sunlight . (iii) .Kolbe's electrolytic reaction giving alkanes, alkenes
. and alkynes.
• 102 kcal • • (iv) Anti-Markownikoff's addition or peroxide effect or
(b) H 3C.H . ) H3C + H
Kharasch effect.
Relative stablHties of free radicals : The tertiary alkyl
free radicals' are most stable and methyl free radical is least
stable, i.e., the free radical formed easily has greater stability.
R R H H
I•
.R-C . > R-C
I• > R-C
I• > H-C·.
I•
I I I I
R H H H
Tertiary Secondary Primary Methyl radical
free radical free radical . free radical
Benzyl and allyl free radicals are resonance stabilized
86kcal . • . .
hence are more stable than alkyl free radicals.
.< >=
-'
(f) H 2 C=CH-CH2 -H ----; H 2 C=CH-CH2 + ~
( .)-CH2 ~ ( )= ~
(g) ( . )-CHr-H
88kcal .. o-~
'I _
(Allyl)
~CH2+ H-
(Benzyl)
· Benzyl free radical
CH2
~
0= ~ ..
•
CH2'
CH2
• •
CH 2=CH-CH 2 ~ CH 2-CH=CH 2 (Allyl)
(h) CH 3- NH2 Heatlligh\ CH 3 + NH2 Relative stability of free radicals are:
(i) 30 > Benzyl> allyl> 20 > 10 > methyl> vinyl
Chemical reaction which takes place in the presence of
• • • •
BELPR [H : Heat (.2! SOOOC), E : Electricity, L : Light (sun (ii) (C 6 H ShC> (C 6 Hsh CH>(CH3hC >C 6 H s CH 2
light, hv), P : Peroxide, R : Radical] is known as free radical • • •
. > (CH3 h CH> CH 3 CH2
>CH2=CH-CH2
reaction.
Charaeterlsties of Free Radicals
,
.
>CH 3 >HC==C
-
(i) Free radicals are generjllly electrically neutral.
(ii) They are· highly unstable.
(iii) CH30-@-CH2 > ~H3--@-CH2
(iii) They are short-lived and highly reactive on account
of the presence of odd electrons. They readily try to pair up the
odd electrons. Three types of reactions are observed in free
radicals.
(a) The mutual combination of free radicals forms neutral The stability of various free radicals can be compared
molecules. . from their bond dissociation energies (the energy required for
the homolytic cleavage of the covalent bond in the molecule
CI- +CI- ~ Cl 2 (CI:Cl)
to form two radicals). In general, the smaller the amoUnt of
• • energy required for bond breaking, the more stable is the
CH 3 +CH 3 ~
CH3:CH 3 (Ethane)
radical.
(b) The reaction between free radical and a neutral Structure of alkyl free radicals:
molecule gives a new radical.
.
C;H4 +CI ~ CH 3 + HCI - The carbon atom of alkyl free radicals
which is bonded to only three atoms or
(c) A free radical can lose a neutral molecule to forma groups of atoms is Sp2 -hybridized. Thus,
new radical.
free radicals have a planar structure with.
CH 3COO· ~ CH 3 + CO 2
Acetate radical Methyl radical odd electron situated in the unused
(iv) Free radicals are paramagnetic in nature. p -orbital at right angles to the plane of
hybrid orbitals ..
(v) Free radic~ls are generally formed either ig,presence
of UVIvisible light orin presence of peroxides. .
G.R.B. Organic Chemistry {or Competitions .
However, in the substituted alkyl radicals the's' character The three hybridized orbitals which lie in the same plane are
of these orbitals has been found to increase, thl,ls,~ending to involved in the formation of three cr- bonds with other atoms
. . .
the pyramidal shape. . .. or groups while the unhybridized p -orbital remains vacant.
CH 3 < CH 2F < CHF2 <CFj
'. The carbocation has a planar structure.
Reactions Involving Carbocations
So, CF3 is essentially pyramidal in shape. .
(ii) Carbocations (Carbonium ions) : .. When a covalent (i) Elimination reactions (EI )to form alkenes from alkyl
bond, in which carbon is linked to a more electronegative atom halides and alcohols. . .
or group, breaks up by heterolytic. fission, the more (ii). Electrophilic addition reaction of alkenes, alkynes
electronegative atom takes away the electron pair while carbon and alkadienes.
loses its electron and thus acquires a positive charge. (iii) S N 1 reactions of alkyl halides and .diazonium salts.
Such organic ions carrying a positive charge on carbon (iv) Molecular pinacol-pinacolone rearrangement.
atom are known as c.rbocations or carbonium ions.
Structllre of Carbocations
-
:;>C:x ~ ~+ :x The only .difference from free R
~Empty orbital·
Carbocation radicals which have oddelectron~
Carbocations are named by adding the words Carbocations are very reactive as
they have a carbon atom having a J20 0 . C+--R
'carbocation'to the parent alkyl group. These are also termed
vacant p-orbital (6 electrons in
as primary, secondary, tertiary, depending upon the nature of
valence shell). The positively
the carbon atom bearing positive charge ..
charged carbon atom tries to R
H H complete its octet and hence, these ions react readily with those
I I
H-C+ CH 3-· C+
species which can release two eleCtrons for the formation of
fourth bond, i. e., they react with nuCleophilic reagents.
I I Usually the order of reactivity of any chemical species is
H H
Ethyl carbocation reverse to that of its stability. Therefore, the order of reactivity
Methyl carbocation .
,
.
(primary)
of ions is:
Primary (10) > Secondary (2°) > Tertiary (3°)
H Stability: .The stability of alkyl. carbocations is·
(CH 3 hC
1+. (CH 3h C +
influenced by resonance, hyperconjugation and .inductive
ejIects. An alkyl group has an electroll releasing inductive
.Isopropyl carbocation Tert. butyl
carbocation effect. An alkyl group attached, to the positively charged
(Secondary)
(Tertiary) carbon of a carbo.cation tends to release electrons towards that
carbon. In doing so it reduces positive charge on the carbon. In
Formation of Carbocations other words~ the positive charge gets dispersed as the alkyl
(a) By heterolysis: They are formed by heterolysis of group becomes somewhat positively charged itself. Tbis
halogen compounds. dispersal of tbe cbarge stabilizes tbe carbocation. More the
. (). + "number of alkyl groups, the greater the dispersal of positive
(CH3hC-CI ~(CH3hC+Cl charge and, therefore, more the stability of carbocation is
(b) By protonationof alkenes or alcobols : observed.
. . H+ + R R H
.
H 2C=CH 2 :;:::= CH2-CH 3 .
+ .. H+ -~O
t
R-r--C+ >
t
R-r--C+
I
> R-r--C+ > H3C +
~ 'R+ + H 20
. R-O-
.. H:;:::=R-.OH 2
(c) By decomposition of diazo compounds:
t
R
I
H
·1
.H
Methyl
If a.-hydrogen with respect to carbocationic carbon has Relative stability of carbocations are:
one or more than one lone pair of electrons, then lone pair of (a) Triphenyl> 3° > benzyl> allyl >2° > 1° > methyl
electrons strongely stabilises a carbocation due to the + 1:-_ .+ +
(C6 HS h C>(C6 HS hCH> (CH3 hC>C 6 HsCHz
delocalization.
Amino (-NH2) and alkoxy (-OR) groups are
important substituents for such type of carbocations. + + +
> H2C=CH > HOs=C> C6 Hs
CH 3" " . . + . •• +.
/ N-CH2 and CH 3 -O-CH 2 are more stable
CH 3 (b) CH30--@-CH2> CH3 --@-CH2
+
. ,
than R3-C.
>@-CHz > N02--@-CH2
Allyl and benzyl carbocations are much more stable as
these are stabilized by resonance, while propylium
+ The groups like -N0 2, -.CN and, -Br (electron
(CH 3CH 2 CH 2 ) ion has no resonance. attracting) which have -/ effect reduce the stability ot
+ + carbocations.
H 2C=CH-CH 2 ~ CH 2-CH=CH 2 (Allyl) . (iii) Carbanions: When a covalent bond, in Which
+
+6
CH CH2 carbon is attached to a lesser electronegative atom, breaks up
by heterolysis the atom leaves without taking away ~
6
.~
Benzyl
carbocation
; _
.:%
_
+
bonding pair of electrons and thus the carbon atom acquires a
negative charge due to .an extra electron ..
~
/ ' C:Y ---'?
. -
?,-C:
+ y
+
[>-CH-<] > 0+
CHz""
. COOC2 H5
+ C2 H s0---'? CH",,'
Malonic ester
COOC2H5
+C 2H50H
+ + + Characteristics of Carbanions
> (C 6H ShC> (C6HshCH>C6HsCH2
(a) The carbon carrying the negative charge contains 8
Note: Stability of benzyl, allyl and tertiary alkyl carbocations are electrons in the valence shell, i. e., complete octet.
almost sam~ jn solutions. The or~r of. stability of different (b) They are highly reactive because in them the carbon
compounds in decreasing order is as follows: carrying the negative charge is electron rich and can donate its
(0
Aromatic compounds> Conjugated non-aromatic compounds>
non-bonding pair of electrons to so~e other group for sharing.
1
~)
.. (H2C=CH-CH=CH-CH=CH2) Hence, carbanions behave as nucleophiles and readily
# . attacked by electrophiles.
non-conjugated compounds> antiaromatic compounds (c) Th~ negatively charged carbon is' in a state of sp3_
(H2C=CH-CH2-CH=CH2) . hybridization. The hybrid orbitals are directed towards the
194, G.R.B. Organic Chemistry (or Competitions
o-~-&-6~
comers of a tetrahedron. Three of hybrid orbitals are involved
in the formation of single covalent bonds With other atoms while -
the fourth hybrid orbital contains a lone pair of electrons.
Thus, carbanions have a pyramidal structure similar toNH 3
molecule.
. Benzyl - . -0 - _
carbanion
(d) Carbanions are diatriagneti'c.
Relative stability of carbanions are..:. _
Reactions Involving Carbanions
Aromatic> benzyl> allyl> HC==C> H 2C=0I> alkyl
(i) Aldol condensation of aldehydes having a-H atoms. (p- > sec- > tert-).
(ii) Cannizzaro's reaction of aldehydes without a-H
atoms. (i) (C6HS hC>(C6Hs)z CH>C6HS CH z >CH 2 -'-:""CH-CH2
(iii) Perkin's reaction involves the formation of carba-
nions as intermediate. - '>HC==C>H2 C=CH:>CH3 :>CH3 CH 2 :>(CH3h CH
(iv) Knoevenagel reaction involves the formation of
carbanions' as intermediate. . -
Structure of Carbanions :
QL=~rr (ii) OZN-@- CH2 >@-cH2 :>
1\
CH3-@-CH2:> CH30 -@-CH2
I Itt
H-T> R-+-y- > R-+-y~ ~. R-+-C
(Carbocations and Carbanions)
Ions
, olitershell (electron deficient), out of which two constitute a Singlet" state has single spin multiplicity.
" lone pair and two ~re shared. So, they are divalent carbon, Spin multiplicity = (21:s+1) =2 x {(+Y2) + (-Y2)} +1 =1
" species containing two unpaired electrons and possess no
(b) Triplet: When the two electrons go into different
, charge., ,
orbitals and have same spin (parallel), i.e., the unshared
, Thus, in short, carbenes are sp2 as well as sp-
electrons are not paired. Such carbene would have a permanent
hybridized, neutral, transitory reaction ,intermediate magnetic moment and would exist in three closely grouped
containing a carbon atom with two bonds and two energy state, if it were placed in a magnetic field. Such a state is
'electrons. They can be formed: called triplet st~te and is believed to'be a linear molecule, so
(A) By the photochemical decomposition or pyrolysis of sp-hybrid carbene is always a triplet caroene,
aliphatic diazo compounds or ketenes.
, ." (fI" ~
(i) CH 2N 2
hv or Heat'
' ) :CH 2 +N 2
t ' 1800 VLY
, Diazo methane (UV) Carbene -C---'- 'CH2,:; , H~H ; R,-C-R
t '
hv or Heat CH e N With H-C-H bond angle 180° and a C-H bond length
R-CHN2 ) R e + 2
Alkyl carbene of 1.03 A, it might be considered as a free diradical and is
mote stable. It is also known as cold methylene (carbene).
hv or Heat CO CH~' N
RCO-CHN 2 ) R - e + 2 The decreasing order of stability of different types of
Acyl carbene singlet carbenes are as follows:
Substituted carbenes are simply named, as derivative of :CH 2 > :CF2 >~CC12 > :CBr2 > :C1 2
carbenes. For example:
Triplet state has three spin multiplicity.
R-C-R 'CH
, 6 5 -"CH :CCl 2 Spin multiplicity = (2D+ 1) =2{(+Y2) + (+Y2)} + 1=3
Dialkyl car bene Phenyl carbene Dichloro carbene
Reactions: . Carbenes undergo several important
(ii) H 2C=C=O ~ :CH 2 +CO reactions.
Ketene Carbene (a) Addition to alkenes: 'Formation of cycloalkane
(B) By the action of a base on suitable polyhalogen derivatives, e.g.,
compound.
(i) CHCl~ + C2H 5 0Na -----7 :CCl 2
Chloroform Dichlorocarbene
+C 2H 50H+ NaCl
(ii)CHC1 3 + (CH 3h CO- ~(CH3hC-OH+
Tert. butoxide ion
:CCl 3
(ii) R /~C=c(R + it CH2 -----7
R""
, ""C-C
/R'
H . ' ""H
Cis-alkene
Carbene
(singlet)
a/ \/
C
"'-H
H2
CHX 3 KOH (alc.)
~
ex 3 + H+ (Cis-)
Addition reaction of singlet carbenes with alkenesor
cx 3 ) :CX 2 + x- alkynes is known as chelotropic addition.
(b) Insertion reactions: Carbenes are aJso .used in its
So, carbenes are, related to carbanions through the insertion between the C-H bond, e.g.,
a-elimination reaction.
sp2 -hybrid carbene is of two types:
1 '
(a) Singlet: When both the electrons go into one -C-CH2-H (Next homologue)
orbital and have opposite spin (antiparallel), i. e., the unshared I ' ~
electrons are paired in one orbital and has a bent structure.
H
' ' "H9' ,
H
N
'-~-C~; CH2:; 103" C;"
R) ,
"", C<ID ·-1,
H-' C-H +:CH z ~
1
H-C-"CH 2-H
," "H ,R:
,IH ' 1
The singlet state is actually found to have H-C-H bond H
angle 103° (between 90° to:1200) and'a C':-'H bond length of Methane Ethane
1.12A. It is generally considered as the less stable and highly
reactive; It is also known as bot methylene.
19§. G.R.B. Organic Chemistry for Competitions
o~6-0-m"O~12
Propane n-butane
and CH 3 CHCH 3
. I .
CH 3
Iso-butane
(c) Ring expansion reactions: These involve the
addition of a halogeno cru;bene across a double bond followed
by rearrangement. . ---+
CHCl,/~HPN'. C?~~l
9
+:CCh [
Dichloro OH
carbene
-LIa C H O
(Jel
+
Pyrrole
#'
--Hel (o-Hydroxy-
benzaldehyde)
(v) Nitrenes or Imidogenes
3-chloropytidine
Nitrenes are the organic species having tqe general
Carbenes have important synthetic applications and .are ••
the reactive intermediates in some well known reactions like formula, R-N. These are the nitrogen similar to carbenes
••
Carbylamine reaction, Reimer-Tiemann reaction, Wittig
and neutral univalent nitrogen intermediates (with' one bond
reaction and Wolff rearrangement, etc.
••
Carbenes as reaction intermediates: and two nonbonded electron pairs, i.e., -N). These are
••
(a) Carbylamine reaction: By heating a mixture of defined as 'the electron deficient species in which nitrogen
primary amine and chloroform with ethanolic potassium has a sextet ofelectrons' (six electrons in the outermost shell).
hydroxide to form isocyanide (carbylamine) is known as They are highly reactive and act as strong electrophiles as
carbylaminereaction. they need a pair of electrons to complete the octet. The parent
RNH2 + eHCl 3 + 3KOH ---7 RNC + 3KCI + 3H 20 ••
Mechanism: . ...
species is N-H (known as nitrene or..imidogene or azene or
Phenol
OR
a
CRO " . ·
- , ' - ' . . +~KCI+2R;Q
Salicylaldehyde "
.
,
sp-Triplet nitrene
... ~
Mechanism of Organic Reactions
0
(vi) Benzyne (1,2-Dehydrobenzeile or Aryne)
, (e,H,)
1
In the presence of ethylene, nitrene is trapped to form
ethylenimine (a cyclic product). "Benzyne is a neutral, highly re,active reaction
..
••
HN + H 2C=CH2 '
Nitrene
-
Ethylene ,
H 2C-CH 2
\/
N
intermediate in which the aromatic character has not been
markely disturbed". It is formed as an intermediate during
nucleophilic substitution of aromatic compounds. It contains
H Carbon-Carbon triple bond in the benzene ring involving the
Ethylenimine formation of a new weaker C-C bond by si!ieways
(b) Alkyl, aryl and acyl nitrenes may be prepared by the overlapping of Sp2 -hybridizeq orbitals of two adjacent carbon
photolysis of alkyl azides, alkyl isocyanates or acyl azides atoms.
respectively. Formation of Benzyne
Light' ••
R- N 3 ) R-N +N 2 (a) When arylhalides are treated with very strong bases,
Alkyl azide •• such as sodamide, NaNH 2 or certain metal alkoxides such as '
Alkyl nitrene
potassium tert. butoxide, Me 3COK, they eliminate HX from
.
CH 3 -N 3
Light
)
••
CH 3 -N +N 2
vicinal carbons to produce a species called benzyne, wlrlch
Methyl azide •• then undergoes reaction with the available nucleophile, NH2
Methyl nitrene (liquid ammonia) rapidly to form aromatic compound, aniline.
C6H S-N3
Phenyl azide
Light
)
••
C6HS-N +N 2
••
Phenylnitrene
N CI
-,'
~+ NH2 ---,-" ~
O·II
+ NH3+ CI
-
Chlorobenzene 'Benzyne
(JCI (JC'I
Light ••
CH 3CON 3 ) CH 3C0!'i +N 2
Acetyl azide Acetyl nitrene
Ani''1'
me,
~
' (53%)
H
NH2
'
compounds and give the following reactions.
1. Addition to alkenes: Nitrenes add on alkenes to Experimentally both products are formed, hence,
form corresponding alkeneimine, a cyclic product., elfmination addition n:iec~sm
\
is.. followed. Further, ill this
reaction, there occurs vicinal rearrangement in which the
•• entering group occupies the ortho-position to the leaving
CH 3CH=CH 2 + H-N ---? CH3-CH-CH2
group. Therefore" this reaction, is also known as
Propene Nitre~: "" /
N
cine-substitution.
(b) ,Benzyne can also be obtained by the decomposition
I of benzene diazonium o-carboxylate or 9-fJuorophenyl'
H
Propeneimine magnesium bromide.
2. Addition to alkanes: Acetyl nitrene reacts with 'COO- '
isobutane to form acetyl tert. butylamine.
••
(JCI
~ ,N=N'
~ ,0""
~
II +Nz+COz
'(XI~ .
F
MgBr
.'
Heat
:0"
~
II' + Mg<Br
'. F
9. Which of the following pairs of ions is more stable?
(a) CH3 CH 2 0 8 and CH 2=CH-09
(1) (II)
·9 9
o-FluQroplienyl Benzyne (b) (CH 3 h C-CH=O and (CH3 hC-CH=CH2
magnesium broinid. (I) (II)
.• 0 1 +HOH -I
~
'
.. ( )..··OH
·
'.
and
'..
..
Me~CH=CH-CH=NMe2
.
(II)
. .
$
.
aC(c,f(,)'
Benzyne Phenol [Ans. (aY (II), (b) (I), (c) (I)]
10. Which among the following compounds behave both as
an electrophile as well as a nucleophile?
+
, CH 2=CH-CH 2
(2)
Benzyne . TriphenylmethylbertZene
(Tetraphenylmethane) o
. II
.. ' '.~HCH3 CH3-C-Cl
O
~II
""
Benzyne
+ CH3N}12 .~ (
" I
~ )..
N-Methylaniline
. .
.
Answer using the following codes:
(a) only (1) (b) (1) and (2)
(4)
o~
. II + CJIsLi
Phenyl lithium
.CX ::f(, :::J~: .
Phenyl'
lithium compound
[Ans. (c)]
11. Which of the following species is an ambident
nucleophile?
(a) CH 3 CH2
e
(b) H 2C=CH2
e •• e
·CX·'·I' CJI5
(c) ~N=O
[Ails. (c)]
(d) NH2
© (b)~
(c) ithas4n + 2nelectrons
, (d) none of the above
[ADS. (d)]
8. Heterolysis. of propane gives:
(aJ (C)~ (d)~CII'
(a) methyl and ethyl free radicals .' N0 2 CH3
(b) methylium'ion and ethyl anion [Ans. (c) because +R group present atp~ (or 0-) position
(c) methyl anion and ethylium ion increases the stability of benzyl' carbocation and -R group
,(d) methylium andethylium ions decreases· stability.]
[ADs. (c)]
Mechanism of Organic Reactions '199
5.5 NATURE OF ATTACKING REAGENTS donate.. They are' either negative ions or neutral· molecules
with free electron pairs to donate. They attack regions of low
Most of the attacking reagents carry either a positive or a
, electron density (positive centres) in the substrate molecule.
negative charge. The positively' charged reagents attack the
regions of high electron density in the substrate. mol~cule . I ,I'
while the negatively charged reagents will attack the regions .-C+ + :Nu- ~ -C-Nu
of low electron density in the substrate molecule. The fission 1 Nucleophile I
Substrate. Product
of the substrate molecule to create centres of high or low . (Electrophile) (Neutral)
electron density is influertced by attacking reagent!). Mosf of
The common nucleophiles are listed below:
the attackmg reagents can be classified into two main groups:
(i) Electrophiles or electrophilicreagents . Negatively charged Neutral molecules
(ii)- Nucleophiles or nuCleophilic reagents
(i). Electrophiles: Electrophiles or electrophilic reagents
-are electron loving species (Electro = Electron, . philic=
loving). These species carry either positive charge or neutral
molecules with electron deficient centre. So; a reagent which' ••
H-O-H,
can accept an electron pair in a reaction, is called an ' ••
electrophile. These contain, generally, two electrons less than
•• ••
the octet and attack regions of high electron density (negative R-O-:-H, R-O-:-R,
centre) in the substrate molecule as to complete the octet and
act as electrophiles,
••
...
R~S-H,
••
••
I_ I
-C: + E+ ~ -C-E [CH(COOC 2 H s hr,
• e·.
R~S-R, H-S~H,
.;.
I Electrophile . I •• ••
Substrate Product
(Nucleophile) (Neutral) [CH3COCHCOOEtr,
H-O-H ~ Electrophile
-
i
Nucleophile
Mechanism of Organic Reactions 201
Acetamide n .
HO+ -,:.""C<
CI
~ :CC1 2 +H 20+Cl-
HBr
(v) HC==CH + HBr ~ CH z =CHBr----t CH3 CHBr2 61 Y CI Dichlorocarbene
Acetylene Vinyl bromide 1,I-Dibromoethane Chloroform
(Ethylidine bromide) Dichlorocarbene is the reactive intermediate involved in
(iii) .Elimination 'reactions: The reverse of addition carbylamine reaction and Reimer-Tiemann reaction.
. reactions are termed as elimination reactions. In these H
reactions generally atoms or groups from two adjacent carbon I
R 2C-CI ~
-H+
R 2C-CI R 2C:
atoms (a,~) in the substrate molecule are removed and
multiple (double or triple) bond is formed. In the process two Carbene
sigma bonds are lost and a new n-bond is formed, i. e., state of In 'V-elimination, it is removal of two atoms or groups
hybridization of carbOn atom changes from sp3 to spz and Sp2 from a-and 'V-positions (other than from adjacent atoms or
to sp. This reaction is known as ~elimination. same atom) and produces a ring, e.g.,
202 G.R.B. Organic Chemistry for Competitions
(J.
~ ~CHz-Br
n (d) Presence of substances like peroxides which form free
H2 C '\yS
CH -Br
Zn <lust, Ll
.. .)
y-eI urunattOn
H 1 c<CH2 + ZnB'12
~ CH I
. 2
radicals readily on decomposition. I
The mechanism of reactions involving the attack of
2
Cyclopropane free radicals on the substrate molecule is referred to free
1,3-Dibromopropane
radical mechanism. The mechanism of free radical reactions
This reaction is called Freund reaction and is extensively involves three steps-initiation, propagation and termination.
used for the synthesis of three membered rings. Each of these steps, in turn, may involve tWo or more steps.
(iv) Rearrangement reactions: The reactions which Initiation step: This step involves the production of
involve the migration of an atom or group from one site to free radicals by irradiation or heating the reagent or by
another within the molecule (nothing is added' from outside carrying out-the reaction in the presence of an initiator such as
and nothing is eliminated) resulting in a new molecular peroxide. The production of free radical may be a one or two
structure are known as rearrangement reactions. The new step process. For example, the formation of bromine-free
.compound is actually the structural isomer of the original one. radical from bromine during substituting reaction is a one step
Some of the examples are: process.
Anhydrous Alel 3 hv -
WC~C~C~C~' ) CH3-CH-CH3 Br: Br ~ 2Br·
. Heat
n-Butane I A two-step process is involved in the formation of
CH3 bromine radical from hydrogen bromide during addition of
Isobutane . HBr on propylene in the presence of benzoyl peroxide.
AlCI 3 or Al 2 (S04h
(b) CH 3CH 2CH=CH 2 ) 0 0 0
But-l-ene Heat I I Heat I
(i) C6HS C-O-O-C-C6HS ~ 2C6HS C-O·
CH 3CH=CHCH 3 +CH 3-·C=CH 2
But-2-ene . I o 0
CH 3 I I
2-Methylpropene (ii) C6HS C-O· + H-Br ~ C6HS C-OH + Br·
Heat
(c) NH 4CNO -~) NH2-CO-NH2 Propagation step: The free radical formed in the first
Ammonium cyanate Urea step may generate a new free radical when it attacks the
. 0 substrate. The new free radical may react with attacking
I reagent to form free radical or may react with free radical to
OH OH
0
OCCH3 form product.
(d)
Phenyl acetate
Anhyd.AICh
(Fries. rear-
rangement)
• O 3+0 COCH
. COCH3
This process may continue in an indefinite number of
ways until there occurs an end of the chain of propagation.
•
~---~v~-~--~ Br· +CH 3-CH 3 ~ CH 3-CH 2 + HBr
(Ester)
0- and p-hydroxy acetophenone •
CH 3 CH 2 + Br2 ~ CH 3CH 2Br + Br·
Br
AlBr3 I Termination step: In this step, there occurs
. (e) CH 3CH 2CH 2Br -~) CH 3-,CH-CH3 destruction of free radicals, either by combination Of two free
Heat
n-Propyl bromide Isopropyl bromide .radicals (same or different) or by disproportionation.
• •
NOH 0 CH 3-CH 2 +CH 2-CH 3 ~ CH 3c;H 2CH 2CH 3
I pels I . (Coupling)
(t) CH 3- C -CH3 -) CH3NH-C-CH3 •
Acetoxime N -Methyl acetamide 2CH 3CH 2 ~ CH 3-CH 3 +CH 2 =CH 2 -
(Disproportionation) -
It is an example of Beckmann rearrangement.
It is also possible to teflllinate chain reaction of free
5.7 TYPES OF MECHANISM radicals by adding inhibitors like benzoquinone, phenols,
Reaction mechanisms are classified mainly into two classes: amines, nitric oxide, etc.
(i) Free radical mechanism (ii) Ionic or polar mechanism: This type of
(ii) Ionic or polar mechanism mechanism applies to those reactions in which hett;!rolytic
(i) Free radical mechanism: This type of mechanism bond fission occurs. The heterolytic bond fission is favoUred
by the following factors:' ' .
explains those. reactions in which homolytic bond fission
(a) Liquid state of reactants, (b) Presence of polar
occurs. The homolytic bond fission is favoured by the
solvents (acids or bases), (c) Inductive, mesomeric or
following factors:
electromeric effects which displace electrons in the substrate,
(a) Gaseous state of reactants, (b) Non-polar solvents,
(d) Absence of peroxides.
(c) Presence of energy in the form ofUV, sunlight, heat, etc.,
Mechanism of Organic Reactions . 203
For thermodynamic data of halogenation, the tabulated values are given below:
CI Br
..
:X.+ CH4 ~
....
.CH3 + HX:
-31 +2 +18 +34 F2 38
•CH 3 + X 2 ~
.. ..
CH 3 X: + :X •
-72 -27 -24 -21 C1 2 58
CH 4 + X 2 ~
.. ..
CH3 X: + HX:
-103 -25- -6 +13 Br2
I
46
36
l
CH2 -CO> 1]
C6 Hs -C 6 H S + N 2 + HX CH2 =CH-CHz-+NBS CH2 =CH-CH-+ I ' NH
Diphenyl Allyl I CH~-CO .
Bf
The mechanism of the reaction is as follows:
• •
Initiation C 6 f1s-N=N-X -----7 C6H5 + N2 + X
(In neutral or basic medium)
---
Heat
0 o·
Propagation (iz) + NBS
C6HS H
C6Hs C6 S Toluene Benzyl bromide
·C6HS + C6H6 -+ H +--+ H +-+ H
(:( Br
~ • # #
Termination
(iii) V +NBs~if
Ethyl benzene
Mechanism of Organic Reactions 205·
(iv) 0
Cyclohexene
+ NBS
3-Bromocyclohexene
over addition to the double bond by a low concentration of
bromine because the addition of bromine free radical to the
double bond is a reversible reaction.
•
-CH 2-CH=CH 2 + Br· ~ -CH 2-CH-CH 2 Br
~
~ . 400-600°C
(v) +NBS~ (e)CH~CH=CH2 +C1 2 ) CICH 2CH=CH 2 + HCI
Pent-l-ene Propene . Allyl chloride
Br
With branched chain alkenes, the substitution takes place
(vi) In 4,4-dimethyl cyclohexene there are two allylic
even at room temperature.
positions A and B. In presence of NBS, it gives three allylic
products. CH 3 -C=CH 2 +C1 2 CICH 2-C=CH 2
CH3X(A)
I I
CH 3 CH 3
~
CH 2-Methyl propene 3-Chloro-2-methyl-
. 3 propene (Main product)
H H(B) CI
I
fo~
+ CH 3 -C-CH 2CI
I
CH3
(Minor product)
CH H Br CH
.
Substitution by halogen is a free radical reaction.
DI +CH'U~,
3 3 ~
CH, .. CH 2CH=CH 2 + HX
All yl free rad kal
CHZ-CO)
I N-Br+HBr ~ I
. CH z-·
NH+Br z
co) H
. AIlYliC{H::)==(;. CH2-HW)
H
o
or directly presence of UV light is an example of free radical reaction.
CHZ-CO) hv or CH 2-CO>. • uv
I N-Br I ) N + Br
+B"
CH - C O ' Free radical CH -CO Light
2 initiators 2
Step 2. (g) Cyclopropane ring is opened by free halogen attack to
• form 1,3-dichloropropane.
H 2C=CH-CH 2- + Br· --7 H 2C=CH-CH- + HBr
(Chain propagation) A +CI· __ CI~.
• Cyclopropane
H 2C=CH-CH- + Br2 --7 H 2C=CH-CH- + Br·
. I
Br (h) Side chain halogenation of toluene proceeds through
(Chain propagation) a free radical mechanism.
The free bromine radical can then continue the chain
reaction. CI-CI~2Ct
206 G.R.B; Organic Chemistry (or Competitions
CH3
.
6
~
Toluene
\. ,+cr
o +HCI
Benzyl chlQride
(ii) Nucleophilic substitution: Many substitution reactions, especially at the saturated carbon atom in aliphatic compounds
such as alkyl halides, are brought about by nucleophilic reagents or nucleophiles. ' , ,
H6~1>+-xl)- ~ R-.OH+ X:' '
Nucleophile SubStrate Leaving group:
Such substitution reactions are caUednucleophilic substitution reactions, i. e;, S N reactions, (S stands for substitution and N
for nucleophjle). The nucleophilic substitution reactions are divided into tWo ,classes: ..:' .. ,
(a) SN2 Reactions: These are bimolecular reactions. When the rate of reaction dep~nds oil
theconcenirationofboth
subst:r:ate and thenucleophile, the reaction is said to be SN2, i.e., 2nd order change.
,Rate Oc [Substrate] [Nuc1eophile]
Hydrolysis of methyl chloride is an example of SN 2 reaction and high,.concentration of the nucleophile (OH-) favours
'SN 2 reaction: ,The chlorine ,atom presellt in methyl chloride is more electronegative than the carbon atom. Therefor~, C~l bond
is partially polarized. ' " " .
When the methyl chloride is attacked by OH- strong nucleophile frorq the opposite side ofthe chlorine atom, an intern'lediate.,
transition state (TS) results in which both OH and CI are partially bonded to carbon atpIn.' . '.•
,
HO
~H~"".: s_H",,)II>- . .
~ -CI~HO,---C---CI~HO-C-' H+CI-
f .
, HI. 1 1 ,', '
H H H
, ' Transition state Alcohol \, ' . ,
In transition state, chlorine starts taking !J.old ofthe electron pair through which it is bonded to carbon and the OH- ion offers
a pair 'of electrons for the formation of bond with carbon. 'Such a transition state is characterised by maximum potential energy ,
, and hence minimum stability. Fmally, chlorine leaves the molecule as a chloride ion and OH- 'hm forms a covalent bond with the
carbon givingalcQholas areactionproduct. According to this, hydIolysisis assumed to bea one stag~ process, where in two mol-
eculessimultaneously undergo covalency change and the older bond is broken and a new bond is formed simultaneously. In thjs
reaction configuration of carbon is changed, i. e.;complete inversion takes place .
.When (-) 2-bromo oct;ine is allowed to react with sodium hydroxide under conditions where second order kinetics are
followed, there is obtained (+) 2-octanol. . . ,
CoH 13 . I>~/ 6 1 3 ,
H CHI' ~C6H13 '
H~C-Br ~ HO---C---Brl>- ~ HO-,C~~ +Br-
HO- CH [ I . , · . CH 3
3.
(-:-) 2-Bromo octane
. CH3' '
Transition stafe
(+) Octan-2 col '
So, the alcohol' obtained has a configuration opposite. to that 6fthe bromide and. is said to proceed with inversion ofconfigu-
,ration. Hence, an· SN 2 reaction proceeds with complete stereo-cheIl)ical inversion called umbrella inversion which can' be
diagrall1ffiatica~ly represented as; ( , + h ----+ +,)
.
. CH3
. .. I .
I. -~-CH3.
(Benzyl and allyl carbocations are stabilized due to resonance.)
O
~ . Br
CH 3 CH 3 CH3 H
I I I I
CH3 -C-Br CH) -C-CH? Br CH 3 -C-Br CH3-C-Br CH 3 -Br
I I - I I Methyl
CH 3 CH3 H H
3° Neopentyl . 2° 1°
"
Mechanism of Organic Reactions .209
predominates. The two enantiomers constitute the racemic Solvent CH 3COOH C 2H50H CH 30H HCOOH HOH
modification. Relative <I 1 4 5,000 1,00,000
Thus, in SN I reaction, racemization as well as reactivity
(increasing)
inversion is. observed, while in case of S N2' complete
Dielectric 6 1 33 58 18 '
inversion takes place (where chiral carbon exist) .. cons~t (e)
SN i reaction is favoured by heavy (bulky) groups on the Dielectric constant is a measure of the ability of a
carbon atom attached to halogens; i.e., the order of reactivity compound. Polar solvents have high dielectric constant. The
is: positive and negative charged species are best separated in a
R3C-X > R2CH-X > RCH 2 - X > CH 3 -X medium with higher dielectri.c constant The standard
Tertiary Secondary Primary , Methyl dielectric is ,a vacuum (e =1).
Distinction between S NZ and S NI reactions
and nature of carbocation (decreasing stability) in substrate
is:
SN i order:
Benzyl> allyl> tertiary> secondary> primary
> methyl halides steps ' R : L + : Nu- ~
Allylic and, benzylic carbocations' are resonance
R '. Nu + •• L- 'R: L Slow
~ R+ +,: L-
stabilized.
y y ( ..ll,) R+ +.• N'u- ~
Fast'
(iii) .Electrophilic sub~titution :'. El:cirop~lic substitution Step 3. Carbocation loses the. proton to form
.m"olves, the attack. by ap electrophIle. It IS represented as SE (S substitution product.
stands for substitution and E stands for electrophile) . .If the
E
+0 6
order·ofreaction is 1" it is written as SEI (unimolecular) and if ,
the order is 2, it is SE2'(bimolecular). . .-
SEI Reaction Mech~nism : . . . Fast
--.---. +W
.Electrophilicsubstitution in alipijatic compounds (SE1)
are very rare; some of the, important· examples are: ~
.' (a) Repblcement of the '" metal 'atom in an The bromination of benzene in the presence of FeBr3 is
,organonietaUi~ compound. bY'hydrogen:' an example of electrophilic substitution.
o
, .. '.. . R':':;"M + H+ ~R.-.H + M+
. .-MgBr. _H+ .
e.g., CH:iCH2MgBr". ) CH~CH2 ---+CH 3CH 3 + HBr
CH3CH'2MgBr + .HBr ~ .CH3CH 3 + MgBrz
CH3tH2Na + C 6H 6 ~'CH3CH3' + C6Hs~a
Mechanism: . .
(b) D~cjlrboxYlatio,n ofsilversalt of carboxylic acid by
Step 1. Formation of elt(ctrophile takes place.
meanS'ofbromine: . . .
Br-Br+FeBr':l~ Br++FeBr;
. ' ... ' .... ". '~o+ 0'- . ~
R3C-'-C~Ag + Br-Br ~ R 3G-C-'-{) +Br-Br+Ag Step 2. The electtophile (Br'l-) !lttacks the benzene ring,
I " .. '. , II' .
• 0
. .
.. '0 .
~ R3C-'Br +COi + AgBr
(c) Isotopic exchange' ofhydr~gen for deuterium or
tritium: " , .
to form a resonance stabilized carbocation .
IA .a+'
....
#
"'<:: Br+
-
.. ,
'.
#.
H
...~.
. . f 'H
'B.r_ G
+.
B r _ .'.
~
OH +
Br
.I
benzene nucleus (aromatic cQmpounds) in which 1t-electrons the
are .highly deloc~lized.' 'and anelectrophile can attack this substitution product is formed.
'cr-.
region. of high electron density. ';._ . .
Br
Inall e1ectrophilicaromatic substitution reactions,it involves:
Step'L The fon:nation of an electrophile, E+, i.e.,
.In halogenation; ,',
>"Cl ~ Cl + FeC13 .~ C1+ +. FeCI:;
.. ~ +
Br _
0
~.
.'Oi.·~ +i>~X.I+-·0-+X
addition reactions, an electrophile approaches the double or
s=+! +!. triple bond and in the first step forms a covalent bond with one
, '#
Benzene
V,, UJ V '-_./
'.,
. + , Arenium ion
of the carbon atoms resulting in the formation of carbocation
. v which then takes up a· nucleophile to result in addition
Resonance fonns product.
Mechanism of Organic Reactions
Stability of carbocation: .
'- / Slow '- + 1
/'C-C
- " " +. E+ --~.~/--'C C E _~o > benzylic > allylic:'" 2~.> 1° > me~yl
Olefin ElectrQphile I Incase .both alkene and the add.w.g reagent are_
Caroocation .'
unsymmetrical, two products are expected.
)C-'
+ I
C-E + X- -~~
Fast "" I
/C-C-E CH3CH2CH2Br
I Nucleophile I I. CH 3-CH=CH 2 +HBr -
(n-Propyl bromide)
(10%)
X
Addition product
The addition -~f HBr on ethylene is an example of .
Propene -[
- ,CH3 H- CH3 -r
electrophilic addition. Ethylene is a symmetrical olefiri. Br
(Isopropyl bromide)
CH 2=CH 2 +HBr ~ CH 2-CH 2 (90%)
Ethylene I . I . Experimentally, it is observed that isopropyl bromide is
H Br
Ethyl bromide the major product. This can be explained on the 'basis of,'--
Mechanism: following mechanism:
Consider the addition of HBr to propene which is
Step 1. Hydrogen bromide gives a proton and bromide unsymmetrical in nature.
ion.
Step 1. Hydrogen bromide gives a proton (H+) and a
HBr H+ + : Br-
Electrophile Nucleophile bromide ion (Br - ).
Step 2. The electrophile attacks the double bond to HBr ~ - H+ +: Br-
form a carbocation. . -- Attacking electrophile
. .~ + + +
. H 2C=CH 2 + H ~ H2C-CH 3 or CH 3-CH 2 Step 2. The proton (H+) attacks the 'It-bond to give a
Carbocation stable carbocation.
Step 3. The nucleophile (Br- ion) now attacks the
carbocation to form the addition product. +
;.,. ~ {CH -CH-.CH
CH3-C~r- ~
. (Mote stable) .
CH 3-·'CH 2Br} Id . I CH 3-7--CH::dCH 2'+ H+- 3. +3 .
+ ~ . entlca _ CH 3-·CH2 - .CH 2 (I"essstable)
CH 2 -CH 3 + : Br- ~ BrCH 2-CH 3
.Note: Other reagents like HCI, HI, H 2S04 (H+ + HS04), H30+' Step,3. The nucleophile bromide ion attacks the more,-
HOCI, Br2' O 2, etc., add to ethylene similarly. The reactivityof stable carbocation to give isopropyl bromide (major product).
halogen acids is HI > HBr > HCl.while in the case of halogens,
the order is Cl 2 > Br2 > 12, Br
This clearly indicates that the reaction proceeds in two
+~ Fast .'1
CH 3-CH-CH 3 + : Br- .~ CH 3-CH-.CH 3
steps: (a) formation of carbocation (more stable) and (b)
attack of nucleophile on the carbocation. Hence, there may be 1,2-hydride shift or 1,2-methyl shift
or 1,2-phenyl shift to give more stable carbocation, than the
less stable one (3°>2°>1°). -. ,
CH 3
1
CH 3-CH-CH-CH3 (2- Bromo-3~methyl butane)
. 1
CH 3 Br
0+ 0- (Minor product)
1 +H-Br
e.g., CH3-CH-CH=CH2
'. (AR.)
3-Methyl but-l-ene CH
.' 1 3
CH 3-C -CHz,-CH 3 (2- Bromo-2-methyl butane,
I" .
Bf
(Major product)
.' fH
, 't".
CH3 -C--CH.....;-CH 3 ·
I' I
:f3, 5+ .5-
+H-Br
C 6 Hs Br
(Minor product)
'
CIt~ --C..:....CH::;:CH 2 .
. I. . .. . (A.R.)
C6Hs
3~Methyl-3-pb~nylbut-l-ene
Ii c~ be explained by ·1,2-phenylshift.
CH3 '. ' . CH ,'
. ," T":i' n...---:, ?H3 +
3
.
CH3-r~CH=CH2 +H ~ CH3
¥ ' + ' ."
-T- Cj--CH3 .
1,2-Phenyl shift '. .1 +
) CH3--C -fH--CH3+---) 3-T1-yH-CH
...
Be
CH 3
CH3
I .
Step 2.
, . H-C~Br
Br-C-H
1
I
.... eH3
Racemic mixture
;.
•
. Mechanism of Organic Reactions
I
Anti-addition H-C-Br
I
H-C-Br
I' .
CH3
1i'ans~but-2-ene
Meso- 2,3-dibromobutane
-[
CH2Br~HBrCH-cH2 '
. 3,4-.Dibromobut-l-ene . ,
. . O,2-addition)
H2C=CH---CH=CH 2 +Br2 . .
Buta-I,3-diene BrCH2---Cl:I= CH---CH2Br
IA-Dibromobut-2-ene
(lA-addition)
Mechanism: , . , " '. -.,
Step 1. The halogen molecule (Br;) undergoes heterolytic fission to give bro~um ion (electrophile) and a bromide ion.
(nucleophile).
. ~.
+
H 2C=CH-CH-'-CH 2Br + :Br- '----t H 2C=CH-CHBr-CH 2Br
(A) 3A-Dibromobut-I-ene
+
(1,2-addition)
CH 2-CH=CH-CH 2Br + :Br-:- ----t BrCH 2 -CH CH-CH 2 Br
(8) lA-Dibromobut-2-ene
( lA-addition)
Addition of halogen adds (HBr or HCI) CH3CHBr-CH=CH2
3-Bromobut-l-ene
. (l,2-addition)"
H 2C=CH-CH=CH 2 + HB r .
Buta-l,3-diene { . .
CH 3 -CH=CH-' CH 2Br,
, 'l-Bromobuh~~ene
( 1A-addition)
Mechanism:
, Step 1. HBr ionises to give a proton (H+) and a bromide ion (Br-). HBr ~ Ii+ + : Br-
Step 2. Proton attacks the double bond according to Markownikoff's rule to give a resonance stabil~zed carbocation:.
+ {\ + ,C\ +
H +H 2 C-:-CH-'CH=CH 2 ----t·'CH 3 -CH-CH=CH 2 ~ CH 3 -CH=CH-CH 2
. (A) (8)
G.R.B. Organic Chemistry for Competitions
- , . .
, ". '.' Step,3. Bro~de iQ~.Q3r-}combine~with(A) to form 3;'bromobui-l-ene (1,2-addition). It combines with (B) to form
, ,l:bromobut-2-ene.(1,4-addttion). .,' , ' . . . '
+
CH 3 -,CH-CH=CH2 + :Br- ~ CH 3 -CHBr-CH=CH2
(A) 3-Bromobut-l-ene
(l,2-addition)
+,
CH 3 -·CH=CH-·. CH 2 +:Br- ~ CH 3 -CH=CH-CH2Br
(B) , I-Bromobut-2-ene
.' ,' '., ' . ,(l,4-addition)
Thus, in such addition reactions, a mixture of two compounds' is formed. The 1,2-addition p~ominates in non-iomsing
solveD,.t like hexane, whereas 1,4-:-additionpredominates in an ionising solvent like acetic acid.'
'. ,After studying a large number of addition reactions (see also Section' 4.8 and 7.5) the Russian chemist, Markownikov,
presented a' rule known -as 'Markownikov ,rule 'or Markownikof:f's rule. According to it,
, .,"Whenan unsymmetrical reagent adds to an unsymmetrical alkene or alkyne, the negative part of reagent gets
, attached to that carbon atom ofthedouble or triple bond which is joinedto lesser number of hydrogen atoms (more
substituted carbon· atom)~"', '
• . Under, normal. conditions, always Mark0vvoikofI's rule is ,applied.
Ifthe H-atomS lfuked to a double bond ate equal in number, then negative part of the reagent to be added (addendum) goes to larger
(higher)aJkyl group. Forexample in ~t-2-en~,__tlle CH3CH2~groUP is more electron repelling than the CH 3 - group and,the
,addition of lIBr takes place as follows to giv~ 3-bromopentane:' ,
, ' . ,0+ 0"-
,CH -+--
' ' CH -+--CH=CH-:.cH
. " .0.', +H-Br
) CH3 CHz CHCHZeH)
3 z 3
Pent-2-enc; , (A.R.) I
Br'
"
, , ' , ' 3-Bromopentane
,But the addition of HBr on pent-2-ene to form 2-bromopentane can be explained on the basis of relative stabilities of the-
cai'bocation. , +
CH3 -CHz:-CH--CHz-CH3
" ' (I)
0+ 0-
+H.,-Br' ,Less stable carbocation
CH3 CH2CH-:-CHCH3
(A.R.) , +
Pent-2-ene
CH3 CHz -CH2 -CH::-CH3
, (II)
, More stable carbocation
Since:onth~ baSis o"fhyperconjugation, thecarbocation (II) is more stable than the (1), hence, the addition product will be
2-bronlopentane. '
+
CH3 -CH2-CH2-CH--CH3 ,--'-~ CH3 --CH2 -CHz-CH--CH3
(II) , '
1
Br
, , ," . ,2-Bromopentane
'. ,Addition'in alkenes and ~es(in solutions) a:~electrophilic a.d~tions,because .the positive end of the adding molecule is
more .closer to C- centre (carbaruon) and thus, ad(htlOn of electrophlle. E+ ,occurs m firsf step. '
DeViation from Mal'kownikoff'srule orPeroxideetTect or Kharasch'sefIect or Anti-Markownikoff's rule :In presence
of peroxidy, propene reacts with HBr to form n-propyl brofuideas the major prOduct and not isopropyl bromide as expected from
Markownikoff's rule.' ' ,', /'"'l. P 'd '
CH3 -CH " CHl\
'-
CH3 CHi CH2 Br
Propene '.
::re)
" n-Propyl bromide
[Ho~yer, this effect isnotobseryedill the case of addition ofHCl or HI]. The addition ofHBr has been explained via free
radical. mechanism. ' '
Chain initiation : C6~TOO~C6f1s ---1 2C l-I-CO·'
6~-'5 I
,0
° °
Dibenzoyl peroXide Benzoyl free radical
C6f1s~0- of RBr ---1 C6f1sToH+ Br-
Chain propagation:
.°
Br .'+ <;H 3 CH=CH 2 ~
°.
CH 3 CHCH 2 Br
Secondary free radical
as it is more stable
Mechanism of Organic Reactions' 2,5,
"
CH3 CHCH 2Br + HBr ---7 CH3 qH 2cH2nr + Br" Step 3. The proton (H+ 1combines with~ni()n to. fom'
Chain t~rmination: .sr + .sr •---7 Br2 ' the addition ~roduct.
• • , , ' CH 3 , '
Br + CH 3 ---7 CH3Br H3C~,.., , , ,I < H3C)',' <OH
(By disproportionation) , NC7-6 '+- H+ --'--7 NC-C-, OH?f 'C ,
In HBr, both the chain propagation steps are exothermic H3C
,
I
CH
' ,H 3C,
'
CN
, while in HCI, first step is exothermic and second step is 3
endothermic, and in Ill, frrst step is endothermic. On account In )C=O compounds, the addition of liquid HeN gives'
of this, the addition of HBr is easier. CYflnohydrin and the addendum is CN- ion (addition is
Finally, if the electron withdrawing (~I) groups such as catalysed by bases or salts of weak acids and retarded by acids
o or unaffected by neutral compounds) ,and not HCN directly.
I
-NO z, -eN, --CHO, --COR, -C-2(Z = CI,DH, OR, (5+ 5 - , "0-", OH
NH 2 ), -cx 3' etc., are attached to the unsaturated carbon )C (\0 +H-~)C_OCN-»../ ~ >C< .
(HzC=CH-X) then anti-Markownikoff's addition may (A.R.) " ' - ' " , , , CN 'CN
. "
, CH2=CH-C-H ~
~ + ?-
CHr-:.CH~C--:-,-H
and since the reaction is catalysedby CN- ion, it is'described (i) E 1 reactions, E\ stands for unimolecular elimination.
,. ..
as a nucleophilic addition: (til E'1, reactions, E2 stands for bimolecular elimination.
Ba(CNh (I) E 1 reactions: These occur in two steps.
HC==CH + HeN ) H 2C=CH-CN
. . Acrylonitrile Step 1. The alkyl halide ionises to give the carbocation.
(d) Addition of methyl alcohol to acetylene: It forms CH 3 CH 3
methyl vinyl ether and the nucleophilic reagent in this reaction 1 . Slow 1+
isalkoxide ion (-OR). C H 3 - C - X , )CH 3 -C + X
KOH . I . ,
HC~H+HOCH3 ---+) H 2C=CH-O-CH 3 CH 3 . CH 3
(iii) Free radical addition reaction: This type of addition Tert. butyl halide Carbocation
reaction takes place in vapour phase or in non-polar solvents Step.2. Carbocation loses a proton from the I'-«arbon
(i.e., Cl 2, Br2, H 2, CO 2 and CH etc.) in presence of sunlight
j.
atom by the base (nucleo~;hile) to form alkene.
or peroxides:. • '. .
. The additives are free radicals and the rate determining H3
C
)+ ~.'
.C-CH 2-H+OH- ~ .
F H 3C>..
C=CH 2 + H 20
step suggests for addition of free radicals. For example, the
H3 C , '. H3 C .
photochemicaliy catalysed addition of .chlorine to ethylene
may be shown as follows: Many secondary and tertiary alkyl halides undergo E\
hv or Heat elimination reactions when heated in an ionizing solvent.
Hl!O=CH 2 + C1 2 )
(light) CH 3
Ethylene (gas)
C2HsOH, ;l , .
.:;......;;:......:..-~) CH 3 -C=CH 2 +HBr
Ethylene (di)chlorige
328 K 2-Methylpropene .
The mechanism of the reaction involves the following
(Isobutylene)
steps:
Terl. butyl bromide
Chain initiation :
EI eliminations begin with the same unimolecular
C1 2(CI-Cl) ~ CI· + CI· ... (i)
dissociation as we saw in the SN I reaction, but the
Chain propagation :
• dissociation follows the loss of H+ from the intermediate
H 2C=CH 2 +Cl· ~ CICH 2-CH 2 ... (ii) carbocation rather than by substituti9n. In fact, the E1 and
• . SN I reactions normally occur in competition, whenever art .
[or H 2C: ~ CH 2 +ct ~ H 2C-CH 2Cl]
'-.../ '>..J ... alkyl halide is treated in a protic solvent with a non-basic
• • nucleophile. The carbocations are common intermediates for
. CICHi-CH2 +C1 2 ~ CICH 2-CH 2Cl+CI
both elfuunation and
substitution reaCtions. Thus, the best EI
.
Chain termhiation :
.
'H 2C-,CH 2Cl +Cl ~ CICH2-C~Cl
.
. . . . (iii)
substrates are also the best SN1 substrates and mixtures of
substitution and elimination products are usually obtained.
Further, the addition of HBr to unsyniri:letrical alkenes in For example,
presence of organic peroxide, R-O-O-R [like benzoyl . C~ rn3
peroxide, (C6HsCOh02] takes place according to Kharasch : 1 Hp,C2HsOH I .
Peroxide Effect (anti-Markownikoff's rule) and follows the
free radical addition reaction.
ROOR
CH 3-
r
CH 3
-Cl . 650C .) .CH 3-
r
CH 3
-bH
(potassium tertiary butoxide) and an example of a-[3 Ifbases are large, due to sterichindrance, less substituted
. elimination, e.g., alkenes are preferred (Hofinann product) .
·H
CH -CH X Alc. KOH) H C=CH
3 z z 2
1 KO-ter-Bu
(-HX) Ethene
H-. ~T CHCH zCH 3 H zC=CHCH 2CH 3
lb· ..' -----;)
~
. (large base) (Less substituted)
CH 3-CH-·CH 3 Alc. KOH) CH 3CH=CH 2
H Br·
· I. (-HX) Propene. Base
(Hofinann product)
X KOH
CH3-CH-CCH-CH3 ---~) CH 3CH=CHCH 3
CH 3CH 2CHCH 3 Ale. KOH) CH 3CH=CHCH 3 . 1~ ,I . (small base) (Zaitsev product)
. I (-HX) But-2-ene , Br ,H..., But-2-ene
·Y (Major) Base)
+CH 3CH 2CH= CH z Reactivity of the substrate depends largely on the nature
But-I-ene of leaving group (halogen atom). Thus, reactivity order is as
. (Minor)
The more substituted alkene is more stable (according to follows:
Saytzeff\ rule), hence, the fonnation of2-butene is preferred r > Br - > cr· > F- .
to I-butene. Fastest Slowest
Dehydration Qf alcohol is another example of elimina-
(a) CH1ClICH1CH~ tion reaction. When acids like conc. H 2S0 4 or H 3P0 4 are
·I - J
),
CzHsOH
CH 3 -CH=CH-.CH 3 + CH 3CH 2CH=CH 2
But-2-ene But-I-ene CH 3 -CH-CH-CH 3
(81%)
(Zaitsev prpduct)
(19%)
(Hofmann product)
I . I .
. OHH
Br Butan-2-o1
I When more than one alkenes can be form~d, atypical E J
(ii) CH]CH2-C-CH3 reaction yields predominantly, the more substituted, more·
. · . .. 1 .
stable alkene (SaytzeiT's rule)
CH 3
Conc.H 2S04
CH 3 CH 3 <;H3-C. H 2-.C.H 2-C,H-·. CH 3 )
d,-H20,
I 1 OH
CH 3CH=C-CH 3 + CH 3CH zC=CH 2 Pentan-2-bl
2-Methyl but-2-ene 2-Methyl but-I-ene
CH 3CH 2CH-CHCH 3 +CH 3CH 2CH 2CH=CH 2
(700A.) (30%)
(Zaitsev product) (Hofinann product) Pent-2-ene . Pent-I-ene
(More stable) 80010 (Less stable) 5%
G.R.B. Organic Chemistry for Competitions
Mechanism:
I,I-Dichloro-2,2-difluoro ethene
C2HsO- e
. In any elimination reaction, in which the double bond can Step 1. CF3 -CHCI 2 ) CF3 - CCl 2
be in conjugation with a benzene ring, the conjugated product Fast step Carbanion
is formed in preference to the non-conjugated product (the Here, . carbanion is strongly stabilized by d-orbital
conjugated alkene isoflower energy). resonance of CI and strong -/ effeCt of the CF3 group.
- f:\' ~ Siowstep" . _
Step 2. F-CF2 -CC1 2 ) F2C=CCI 2 + F
. - . ~HO-
I-Phenyl butan-2..QI (ii) C6HS -CH2 -CH2 -F 5) C 6H sCH=CH 2 .
(iii) C).b~OCH3
N0
ex
H
2
C2H sO-.
Heat
(XI . N02 •
Ph
I-Phenyl but-I-ene
(Ii) E 1. re.actions : .- ltis-bimolecular since substrate and base
Similarly, other examples of elimination reactions are: are involved in the rate determining step.
Dehalogenation: It is removal of halogens, e.g., Rate oc: [lJ-X][Base]
in CH30H, Heat" Substrate forms a transition state with a nucleophile from
CH2-CH2 + Zn dust . ) H 2C:-CH 2
I I. . (-ZnBr2) Ethylene which abstraction of a proton from the J>-carbon and expUlsion
of the electronegative atoms as an ion from the a-carbon atom
Br Br
Ethylene bromide occurs simultaneously. The dehydrohalogenation'of the alkyl
halides with alcoholic alkali is an example of this' type. It
Dehydrogenation: It is removal of hydrogen, e.g.,
oc~urs in one step. The rate of alkene formation is
Cu.300°C proportional to the concentrations of ethyl bromide as well as
CH 3 -CH-.CH:3 . ) CH 3 - C -CH 3
. I (-H2 ) II' that of sodium ethoxide.
. 00 0 . Rate';' k[CH 3CH 2 Br][C2 HS0- ]
Isopropyl alcohol Acetone
CH3CH2 Br+C 2 Hs (J ~ H2C CH 2 + C2 H s OH+ Br-
EI-Cb (Unimolecular conjugate base elimination)
reaction: lfthe J>-hydrogen is strongly acidic and the halide CH3 CH 2CH 2Br + C2Hs (J ~ CH3 CH=CH2 +Br- + C2H s OH
I-Bromopropane Propene
ion is a poor leaving group, E1-Cb mechanism operates, so
this is another mechanism of, J>-elimination reaction. It CH3H CH3 H
involves: 1'"\1 I Slow I .I
Step 1. Consists of the removal of a proton by a base to C2 Hs O+ H-f-y-Br ~ ~HsO---H---C-.-C---Br
fonn a carbanion. . I 1
H H . H H
Step' 2.· The carbanion loses a leaving group to give an
Transition state
alkene.
'" .
CH 3 H H
;,.'~
I· I
C=C +C 2H sOH + Br-
.yfy
. ...... ,
I
H
I I·
H
.
,
A?- X
;~mple is dehydration of primary alcohols. Anti-periplanar genmetry
{"'.:s:S~,' (staggered, lower en~)
Mechamsm:
':it H+ ' . . .+
CH3-tH-CH20H ~ CH 3 - t H-CH20H2
'. H. ,f ~'H
'.,. •. /c,. ", .'.
. ~ H /C(.". ,
1° Alcohol Carhocation ,\ Syn-periplanar genmetry
(eclipsed, higher energy) .
E2 "
~ CH 3CH=CH 2 + H 20 + H+
Propene E2 elimination is stereospecific.
So, dehydration of2° and 3° alcohols takes place by E\ CH 3
process and 1° alcohol by Eiprocess. I
E2 reaction always occurs with a periplanar geometry, H-C-' H
meaning that all four reacting atoms-the hydrogen,· the two IJ
B~-H
carbons and the leaving group-lie ip the same plane. Two such I .
geometriesarepossible;Syn-periplanar in which the' H' and
CH 3
,'X' are ontbesaine side of the molecuie,and anti-periplanar
in which 'H' and' X' are on opposite sides of the' molecule. Of
H
the two choices, anti-periplanar geometry is energetically
r: 1 H3
C""-C/ H
preferred because it allows the substituents on the two carbons H-C-CH 3 Alcoholic
to adopt staggered relationship, whereas syn-geometry . I'
-.,..----+)
KOH
" I
requires that substituentson carbon be eclipsed. CHl-C-H C
" " I] , H / "", CH
3
Br . ' 'Trans'
2-Bromobutane 2-Butene
17. Classity the following as electrophiles and nuc1eophiles: . "'. " CH3
, +
(a) ~,(b) H2O, (c) Br+, (d) N02', (e) N0 2 , CH3
(f) CH30H, (g) H2 C=CH2 , (h) RCOCI, (i) H2N-OH,
G) :CCI 2,(k) H3 0 +, (I) NH3 , (m) BF3 , . en) AICI 3,
(c) "0-.
I CH CH 2
< CH
3
(d) all of these
.~H3
CH3
IAns. (d)]
20. Which of the following alkene is most stable? (Hint: In this alkene, 12-hyperconjugative forms cari be
written, which is maximum.]
Solution: Br .: Br ~ Br+ + : Br- (ii) The formation of an olefin from an alkyl halide and
alkali, the reaction being first order in each of the reactants.
Ilt' CH+Br+
Acetylene" .
Slow
-~) CH=CH
+
Solution: (i) R-X Slow) R + + X-
\
Br R+ +OH- Fast) ROH
tarbocation
The reaction proceeds via SN1 mechanism, i.e.,
+r\ Fast
CH =CH + • Br-' ) CHBr=CHBr Rate oc [Alkyl halide]
1 • (Acetylene dibromide) (ii) Rate ofreactionoc [Alkyl halide][AlkaJi]
Br
Thus, the reaction is bimolecular. It proceeds via E 2 •
Br R H
Q CHBr + Br + ---7 CH-CH
1+ II
HO-- - H--- C-=-C---X
I 1
Br Br I \
Carbocation
H H
Transition state
Br Br Br
\. +1'\ R H
H-C-CH + :Br- ---7 ..
II
HC-CH I I
Fast
. I I I I ---7 H 20+ C=C +X
Br Br Br Br I \
(Acetylene tetrabromide) H H
'Problem 7. Explain the reaction mechanism of the Olefin
following reaction.by equations only: ' Problem 9. Calculate the pK values of the following
organic acids and bases from their given K constants:
H2S04
CH 3 -CH- CH-CH 3 . ) CH 3 -<::. CH-CH 3 . (a) CH 3 COOH, Ka =1.8 X 10-5
I ,I . Heat . I (b) CH 30H,K a =3.1 X 10- 16 .
CH s OH CH 3
(c)CH 3 NH'2 , Kb =4.5 X 10-4
3':Methyl butan-2-ol 2-Methyl but-2-ene
'Solution : •
Solution:. H2S0 4 ~ H+ HSQ4 + 5
. (a) pKa =-10g(1.8xl0- )=5-0.255=4.745
· '':H 3 -CH:-CH-'CH 3 +H+---7CH 3 -CH-CH-CH 3 (b) pKa =-log(3.1xlO- 16 )=16-0.491=15.509
· II .. +I I (c) pKb =-log (4.5 X 10-4 ) =4-0.653 =3.347
. CH 3 00 C~O~
Problem 10. Explain that, unlike other amines (RNH2 ).
(E) +
· CH 3--'CH-CH-CH 3 -~) CH 3 -CH""':'CHCH 3 guanidine, (H 2N-C-NH 2 ~ is a strong base.
I \ . -H 20 I . . . ~
CH 3 +OH 2 · CH 3 NH
20 CarOOcation Solution': The cation formed by the addition of H+ has
+ 1,2-Hydride shift + three equivalent contributing structures. This' greatly
CH 3 -CH-CH-CH 3 .....-;..---~) CH 3-C....,..CH 2CH 3 stabilizes the conjugate acid making it very weak and so a
I I strong base.
CH 3 CH 3
20 Carbocation 30 Carbocation •• •• w [.. +
(Less Stable) (More stable) H2 N-W-NH2 ---7 H2N-f=NH 2 f---)
+ . \ :NH :NH 2 .
CH 3 -C~CH2-CH3
\ .
CH 3
+
H 2N=C-NH 2
••
~
..
H2N-C-NH2 .. 1
3° Carbocation . I . II .
(More stable) +NH.. 2
Problem p. Suggest the possible pathways of converting (R)-n-C3H7CH(OH)CH3 (A) into its ethyl ether
trC3H~H(OC2Hs) CH 3 using Fischer projections and give their R, S designations.
Solution:, There are two pathways. In path I, (A) reacts first with K and then with ethyl tosylate (C 2Ms OTs) ,to form (R)
ethyl ether. [Tosyl(Ts)is p-MeC6H4SOiJ In path 2, (A) reactS frrst with tosy! chloride (TsCl) and then with C2H sOK+ to form
(S) enantiomer.
CH3 CH 3
C2HsOTs
K
n-C 3 H 7+ O K + ) n-C H 7
3 I'
OC2H S
. CH 3 . (R)H H
(R)Ether
(A)n-C 3 H 7+ O H
H CH 3 - + CH 3
(R) T~l C2Hs OK
n-C 3H 7+ O T S ) C 2H sO + t r C 3H 7
'
H H
(R) (S)
In path 1, the chiral centre is in the nucleophile and none ofits bonds are broken, resulting in retention of the configuration in
the ether. Path 2 differs in that etho1tide attacks the chiral carbon back side in an SN2 reaction with inversion of configuration.
Mechanism of Organic Reactions
Problem 14. Explain the SNJ reaction mechanism of the following by equations only.
OH
Hydrolysis I
CH 3-CH-CH-CH3 + HOH ---~) CH3-CH 2-C-CH 3 ·
I I . . I
Br CH 3 CH 3
2~Bromo-3-methylbutane 2-Methylbutan-2-o1
Solution: I .
Step 1.
. CH 3 . CH 3
I . Fast I
Step 2. CH 3 -CH2-C+-CH 3 +OH -~) CH 3CH 2-C-CH3
3° Carbocation I
OH
Problem IS. Explain a suitable mechanism for the following addition ofHBr to hexa~2,4-diene.
. Solution: CH 3CH=CHCH-CHCH3 +HBr ~ CH 3CH2CHCH=CHCH 3 +CHjCH 2CH=CHCHCH 3
Hexa-2,4-diene· . I I
Br Br
4·Bror:nobex·2~e 2-Bror:nobex-3-ene
Step 1. HBr ionises to give a proton (H+) and a bromide ion (Br-).
, HBr ~ H+ + : Br-
Step 2. PrQton attacks the double bond according to Markownikoff's rule to give a resonance stabilized carbocation.
""/
(e) H-N:,nitrene;
(e)CH3CH=CHCH 3 +--- ~ CH 3-CH-CHCH 3 ' ...•.
..
. .. .. .
N . (f)CH 3CON:, acetyl nitrene.
. Problem ·17.. Complete the following and identify the
I type for the intermediate speci'es:
H hv
(f) (CH 3hCH+ --.~'-- ~ (CH 3 hCNHCOCH 3 (a) N3H ) u--u+N2
, ,",-" .':.'~.::\.-;
,{~~,:;.. ;;_I:Il:?ti_··_________________;...-.._______~G!.:;.R~.~B:.:... .!; O:!. rgQ.1a~n! :ic~·.:.:C.: :he:; :m.: :I: : .·st: :. ryl. .f. :.(O:.:....r Co;.;:o; .;.:m;,;j..;pe_ti_ti.;;;;on=.s
••
(a) H-·
••
F·: (b) H/~H
H··
. Solution: $
••
(a) (i) H-F:
..
Nucleophile
+ H+
.
Electrophile ..
~H-F-H;
••
••
•• ••••
(ii) H-F: + OH- ~ H-O-' H + : F:-
Electro~inle Nucleophile •• H··
•• 1$
. (b) (i) H/~H + H+ ~ j N\ ;
H .Electrophile 1
NuCleophile H H H
••
Solution: (a) 0I
HN':, a nitrene; (b) ,benzyne;
(ii) H/~"H
H
+ 011·
Nucleophilc
~
(e) 01 ,benzyne; 01
(d) ,benzyne;
Electrophile
Probl~m 20. Which one of the following is a better
(a) CH 3
.0
-glo-
(b) C 6 H sO- (c) CH 3CH 20-
Problem 18. Choose the member ofeach ofthe follOwing Solution: (c) CH 3CH 20- is a good nucleophile
pairs ofcompounds that is likely to be the stronger base: because the -ve charge is concentrated 0!l one oxygen only.
e e . (a) CH 3COO- is a resonance hybnd of the followmg
(a) NH3 or NHi (b) H 20 or OH
strnctures and the -ve charge is divided on the two carbon
$ atoms. ' ' _ 0 112 -
(d) H 20 or H30
o "(
CH 3 -c(
P~ CH 3 -C" ==CH 3 -C,\_._
,/J /_-
e e
(e) OHorSH
e
(f) Aoe or /'--....0 8 -
'0- 0 . 0 1/2
(b) C 6 H 50- is not a good nucleophile because the -ve
(g) C6HS OorCsHsN (h) Ie or Fe charge is distributed at four positions.
.e e
Solution:
r ; 08
(g) C 6 H sO; (h) Ie.
Problem 19. Write equations showing ambiphilic
nature of the following molecules:
e
t)-~~ ~-&
~
-6 114~~~~4 tl4-
Inductive etTect atoms or groups which attract electrons less strongly than
When an electron withdrawing or el~tron releasing groul' hydrogen are said to have +I effect (electron releasing or
is attached to carbon chain, a permanent charge (polarity) li/iO- 1\1). s- s+ .
donating). C 3 -+- C 2 -+-C 1 -+- Y .' RelatIve
is induced all along the basic chain.. If is due to electron
inductive effects have been measured with reference to
displacement because of the difference in electronegati-
hydrogen. . .
vities. This is called inductive effect (/-etTect).
Q Due to -I etTect, the electron density decreases, hence
Q I-effect· is a permanent effect and decreases rapidly as the
basic nature is decreased and naturally acidic nature .is
distance from the source (X) increases. Any atom or
increased. For example, chlormlcetic acid is stronger than
group which attracts electrons more strongly than
acetic acid due to -1 effect and aniline is we~er base than
hydrogen is said to have -I effect (electron attracting or
oso+ (il)+ s+ . 1)- - NH3 due to electron withdrawing nature of phenyl group
withdrawing). C 3 -+-C 2 -+- C1 -+-X . The (-1 effect).
Mechanism of Organic Reactions
A :·B·~ A-: +B+ (A is moreefectronegative than B) .... .IJ Carbanions: Organic' ions containing a negatively
charged carbon are known as carbanions. For example,
.' A:,B,~' A+ + :iJ -/(B is tII.OCe,. electronegative than A)
- - - -
'So;het~rolytic fission results '.in 'the fonna~ioIi of ,catio~ .' H 3C:, CH 3CH 2 , (CH 3 hCH, (CH 3hC, C 6H 5CH 2,
and aniOn.' '~" .'
. O'Anorgatli,:: ion colltaining positively cha:fged carbon H 2C=CH-'CH 2, etc.
, '. c!lmtre is called carbbeatioil (or carbonium ion) and an Carbanions are highly reactive and'contain eight electrons
. organic ion with a' pail- of' available electrons and in the valence shell, i.e., complete octet It has a
containing negatively charged carbon centre is called. a pyramidal structure because the carbon bearing -ve
.. ' . . ,earbaQion. , .... charge is sp3 -hybridised. .
Reaction Intermediates O. The stability of carbanions is influenced by resonance,
, IJ Highly reactive and short lived fragments called reaction inductive effect and s-character of orbitals. The groups
ihtennediates result from bomotyticand heterolytic bond· having +/ effect decreaSe the stability while groups having
. fiSSIon. Examples are, . , -/ effect increase the stability of Carbanions .
IJ·· Free radical.s: Carbon free radicals have. no charge but - -
H 3C> RCH 2 > R 2GI> R3C
the central carbon atom cames odd (unpaired) electrons.
Berlzyl and allyl carbanions are. stabiiized due to
These are produced by homolytic fission of:a covalent resonance. The relative stability otcarbanions are:
bond.. For e,xample, • .
- -
i .' ,,' . ' , . ' .• • " • (C 6H s h C > (C6Hs)2CH>C6HsCH2> H 2C=CH-CH 2
. II,CH3~ CH3CH 2, (CH 3 h CH, (CH 3hC, Cl,etc.
IJ The. fonnation' of free. radical is initiated by heat, light or >CH3 >cHi~H2 >(CH 3hCH> (CH 3 )3 C
.' . . .
catalyst. Their stability is in the order:
R3C > . R 2CH > RCH 2 >CH 3
. CJ <;:arbenes: They . are short· livep, reactive,
sp2,.hybridized, neutral species and transitory reaction
intennediates in which the carbon atom has six electrons in
'. T~rtiary Secondary Primary
the outer shell, out of which two constitute a lone pair and
Benzyl and allyl free radicals are'resonance sQibilized and two are shared. So, they are divalent carbon species
. , '~"hence are ~more stable.' The relative stabilities of free containing two u.npaired electrons llfid· possess no charge.
radicals are:. . For example,
3°:> benzyl> allyl> 2° > 1° >methyl, vinyl HR·
(decreasing order) "C·
H/ • H/ •"C·
. IJ Carbocations (Carbonium Ions): Organic' ions Carberie (Methylene) Alkyl carbene Dichlorocarbene
carrying a positive charge on·carbon atoms are known as
IJ The carbon atom is Sp2 -hybridized in singlet carbene and
carbocations~ For example, .
+ + + + . has a bent structure. It is less stable and highly reactive.
CH 3 , CH 3CH2, (CH 3hCH? (CH 3 hC, Triplet carbene is a diradical, sp -hybridized and is
+ + , believed to be a linear molecule. It is more stable.
. C 6H sCHi, (C 6H shCH, etc. IJ Nitrenes (Imidogenes): These are nitrogen similar to
Carbocations are very reactive and have six electrons carbenes and neutral univalent nitrogen intennediates
(sextet), therefore, it is electron deficient species. Carbo- ••
(-N). The electron deficient species in which N has a
. cation is a planar structure and the +Vely charged carbon ••
is sp2 -hybrjdized·(trigonal planar) .. sextet of electrons are. called nitrenes. They are highly .
o The stability of .carbocations is influenced by both reactive and ~t as strong electrophiles. The parent
resonance and inductive effects ... This dispersal of the species is. : N-' II, and is fonnedwhenhydrazoic acid
charge stabilizes the carbocations. Their stability is in the . (N3H) is irradiated with UV light. In the presence of
order:' . .
C 2H 4 , nitrene is trapped to fonnethylenimine.
+ + . + + .
R3C> R 2CH> RCH 2 >GH 3 hv .. H2 C=CH 2),
N 3H ~ HN " H 2C-,CHi r
Benzyl and allyl carbocations are much more stable due to Hydrazoic acid -N2 Ni;~e" ~
reS01l<mce.· The relative stability of carbocations are:
+ + + . . + Ethylenimine
(C 6 H shC> (C 6H s hCH> (CH 3 hC>C 6H s CH 2
IJ Nitrenes can exist in the. singlet and triplet states. The
.' + . + + +
> H 2C=CHCH 2 > (CH 3hCH>CH 3 CH2 >CH3 triplet state is the ground state and most nitrenes exist in
this state. Nitrenes are highly reactive unstable compounds
.The presem;eQf electron attracting groups (-N0 2,-eN and give addition and insertion reactions.
,and Bi) which have -/ effect reduces the stability of
carbocations.
" ;
,
Mechanism of Organic Reactions
•• ••
.
,t.~
w .. ..
e.g., H-O-H +-:- electrophile, R-PH; CH~ 3 ...:-C
' ... N:
(J Acyl nitrene (R-C-N) has been proposed a:> a possible l'
••
nucleophile
intennediate in the Hofinann, Curtius and Lossen
rearrangements. ••
and H 2C=0: etc.
(JBenzyne: It is a neutral, highly" reactive reaction inter-
mediate in which the aromatic character has not been (J Nucleophiles attack electrophiles during the course· of the
r~action. The nucleophiles which can attack through two
markely disturbed. It contains carbon-carbon triple bond .
in benzene ring involving the formation of a new weaker or more atoms are called .ambident nueleophUes. For
C-C bond by siqeways overlapping of sp2 :'hybridized example, CN- can attack through N orCto givecYl,Ulide
orbitals of two adjacent carbon atoms. . (RCN) or isocyanide (.RNC). .
(J Formation of aniline from chlorobenzene proceeds TyPes of brgarllc· reactions . . .
through the fonnation of benzyne intennediate. This (J Substitution rea¢tions: ,An atom or group of atoms in a'
reaction is also known as cine-substitution. Benzyne . molecule is replaced by another atoms or groups ofthe
reacts with nucleophilic reagents and fonn addition same bonding . .capacity. Halogenation,· nitration,
product. . .
sulphonation, replacement. of halogen atotnS 'or --OH
Attacking reagents groups, etc. are some impoJ,1:a.nt examples of substitution
These are of three types: reactions.
(J Electrophiles (Eledrophilic reagents): These are (J Addition reactions: The attacking reagent adds to
electron loving species and carry either positive charge or unsaturated (n-bonded) compounds having double or
neutral molecules with electron deficient centre. These are triple bonds .without elimination to fonn saturated
Lewis adds and can accept a pair of electrons in a (cr-bond) molecule. Addition of H 2, X 2 ; HX; HOH and
reaction. Examples are: . HCN, etc. to double or triple bond compounds are some
(J Positively charged ions: H+, CI+, Br +,1+, NO;, R +, important examples of adqition reactions.
CH 3CO+, R3C+, SO;H, etc. [J Ellminationreaetions: The reverse of addition
Neutral molecules: S03' BF3, AlCI 3 • ZnCI 2, Fe~13' reactions are tenned as·' elimiruition reactions. In most
•• eliminatian reactions, the two atoms or·groups from·two
BeCl 2, RCOCI, (RCOhO, RMgX, :CCI 2, :NCOOC 2H s , adjacent carbon atoms (a,I3Yin the substrate molecule are
etc. removed and multiple (double or triple) bond is fonned.
Further, cation carriers, e.g., Br-Br, H-Br, CI--OH, Important examples are dehydrogenation, dehalogenation,
02N--OH, etc., and oxidising agents such as Fe 3+, 0 3, 'dehydrohalogenation and· dehydration reactions, etc ..
R-O-O-R, etc., also act. as electrophilic reagents. (J Rearrangement reactions: These· reactions involve
(J Nucleophiles (Nucleophilic reagents): These are transferof an atom or group from one position to apother
electron rich (donating) species and carry either negative , within the molecule forming a new compound which is
charge or neutral molecules with free eiectron pair to actually the structural isomer of the orighial one. ,
donate (N in NH 3 , and 0 in H 20). These are Lewis bases Exaniples are:
(electron-pair donor). Examples are: the change of ammonium cyanate into urea and acetoxime
Negatively charged ions: CI-, Br-, NO;, R- ,OH- ,CN-, into N-methyl acetamide, etc.
H-,NH 2, RNH-,R 2N-, R 3C-, [CH(COOC 2H s hr,
Mechanism of substitution reactions
[CH 3COCHCOOC 2H s r ,OR- ,CH 3COO-, N 3. ,S-, etc.
•• •• •• . (J Free radical mechanism: The reactions involving the .
Neutral molecules: :NH 3, RNH 2 , R 2 NH,R 3 N, attack of free radicals on the substrate molecule is referred
•• •• •• •• to:rree radicat mechanism and the reaction ipvolves three
H-O-H,. R-O-H, R-SH, R-S-R,
•• •• •• . .. 'steps:.initiatiolL, propagation and termination.
(J Halogenation, nitration· and sulphonation of 'alkanes
•• ••
...
R-0-R,R3 P:, (C6Hs)3P:, H-S-H, etc.
. .. proceed by free radical substitution. Other examples of
free radical substitution are: .
In addition, anion carriers, e.g., H*\ H, R" Mg.¥', (J Wurtz reaction (formation of higher alkanes 'from lower .
. alkyl halides). . ..
H" H3A1Li, H" C6 H s, C C, etc., and reducing agents (J.t\rylation of~rotnatic compounds (Gomberg reaction) to·
such as Fe 2+, [Fe(CN)6]4--, etc., also act as nucleophiiic . . fonn diph~nyl. by· the reaction of benzene diazonium
reagents. .. halide with benzene.-
(J AmbiphUe (Anibide~t):They behave both like electro- a Allylic bromination by NBS (N-Brom()succinimi4e)
philes (electron attracting)· and nucleophiles (electron brominates the ethylenic compounds. in the allylic
repelling) site and hence, have dual (amphoteric) nature, (CH 2=CH-CH2-) position and is. a free radical
reaction.
228 G.R.B. Organic Chemistry for. Competitions
CJ Substitution reactions of higher cycloalkanes presence m the bromide and is said to proceed with inversion of
: ofDV light is an example offreeradlcalreaction. ' configuration.
CJ Hight~mperature reaction of chlorine with propene is a CJ S N2 reaction is flilvoured by small groups on the carbon
. free radical su"stitution. ,. C , atom attached to halogen, i.e., the order of reactivity is:
CJ Cyclopropane ring is opened by free halogen attack to CH 3 - . X> R-CH 2 ,-X > R2CH-X >R3C-X
fomi l,3-dichloropropane.
CJ Increasing carbo cation stability is in the order:
CJ Side chain halogenation oftoluene to form benzyl chloride
is 'al~o a free radicai substitution reaction. Benzyl < allyr< tertiary butyl (3° ) <isopropyl (2°)
CJ N uclepphilic substitution: ' When a substitution reaction < ethyl < methyl
. is brought about by a nucleophile, the reaction is called SN CJ Higher concentration of nucleophile favours S N2 reaction,
reaction. whereas low co~centration favours the SN1 mechanism.
Neopentyl bromide shows SN2 path with ethoxide ion, but
R-X +Nu- ~R-Nu+ X-
Substrafe Product Leaving group SN 1 path with ethanol.
SN reactions are oftWo types: CJ Electropbilic substitution (S E ): It involves the attack
CJ SN1 reactions (Unimolecular): The rate of substitution by an electrophile. It can be SE1 (unimolecular) or SE2
depends on the concentration of the substrate, and the (bimolecular). The electrophile (E+) attacks to a point of
reaction is offirst order change. high electron density. The reactions like halogenation,
. Rate oc [Substrate] 'e
nitration, sulphonation, alkylation' and .:acylation of
CJ . It is a two step process in the first step alkyl haiidiionises benzene and its derivatives (aromatic compQunds) are
,to give a planarcarbo~ation (electrophile). This is a slow electrophilic substitution (S E) reactions.
proce~s and rate determining step. In the second step, the CJ SEz . is very common in benzene nucleus (aromatic
nucleophile attacks the carbocation from eit4er side to compounds). In step 1 the formation of electrophile (E+)
. form.the product: This is a fast process. . takes place that attacks the benzene ring to form an
CJ The hydrolysis of tert. butyl halide is.an example of SN 1 intermediate carbocation (in step 2) which is stabilized by
reaction. ' resonance and finally carbocation (a-complex) loses the'
CJ In another example; the<;:arboc~tion formed (in step 1) can proton, to the base (Nu -) to form substitution product
undergo rearrangement (1,2-methyl shift) to give more ($tep 3)."
stable carbocation before< attack. of the nucleophile (in CJ Att additional reagent (called Lewis acid) like Fe or conc.
step 2). H 2SO 4 is always required that can help in the formation of
CJ As a result ofS N'I reaction, there can beracemisation and an electrophile. .
inversion. ' . CJ Addition reactions: These are the reactions of the
CJ SN1 reaction is favoured by heavy (bulky)groups on the compounds containing double or triple bonds'. The 1t-bond
carbon atom attached to halogens, i.e., in addition reactions is involved with the.attacking reagent
(electrophile or nucleophile) and a-bond remains intact.
R3C-X > R2 CH-X > R-'CH 2 - X >CH 3X
CJ Electrophilic addition reactions: In stepl, an electro-
CJ Increasing carbocation stability results in increasing S'N 1 phile (E+) is added in a slow step (ratedeterminingstep)
rate of RX: . .,
to the double or triple bond to form carbo cation. In step 2,
.+ + + +
C~3 <CH 3CH 2 < (CH 3h CH < (CH 3hC the hucleophile (Nu -) is added to the carbocation (in a fast
Methylium 1° , 2° 3° step) to form addition product.
'. .' ' + +. c CJ Addition of HX to alkenes is an example of electrophilic
<H 2C=CH-.,CH2 <C6H5CH~ addition. The mechanism of such addition reactions is
Allylium Benzilium copsistent with the occurrence of rearrangement (1,2-
hydride or 1,2-methyl or 1,2-phenyl shift) resulting the
CJ S N2 reaction' (Bimolecular):'., The rate of substitution
depends oil: the' concelltration of both substrate and the formation of more stable carbocation (3° >2° > 1°).
nucIeop4il~: hence it is a bimolecular and second order CJ Addition of halogens is usually predominantly trans, i.e.,
reaction. ,i
the addition is stereoselective. Cis-but-2-ene on addition
of Br2 gives racemic mixture while trans-but-2-ene adds
Rate [Substrate] [Nucleophile]
oi:
. Br2 to give the inactive meso-product.
CJ Th~hydrolysis of methyllialide is an example of SN2 CJ ,Nucleophilic addition reaction: This addition reaction
reaction. The strong micleophile OH- attacks' from the takes place in >C=O compounds.
opposite side of the chlorine/atom to give an intermediate·
(transition state) which is unstable (carbon is pentavalent) >c0a~ >c-6=>d+-o o-
,and breaks to yield the 'product and leaving (X -) group. CN- -
. 1 ) >C-O (Oxyanion)
CJ Since, the slow step: involves ,two moles, hence it is (S ow) I
'bimolecular and called SN; reaction. The alcohol CN
(product) obtained has a configuratiori~opposite to that of
Mechanism. of Organic Reactions 229,'
The nuCleophilic reagent attacks the +vely charged carbon step 2, the carbocation 10i:les a proton frorn the, !i-earbon
to form more stable oxyanion; Hence, it is known as atom by a base (nucleophile) to form an alkene. ,
nucleophilic addition. CJ Dehydrohalogenation;' dehydration,' dehalogenation and
CJ The reactivity of )C=O compounds is in the order: dehydrogenation are some important examples ofelimina-
H" H3C" H3C" tion reaction., , "
/C=O> /C=O> /C=O CJ El reaction is favoured in compounds in which the leaving
H H ," H3C
group is at secondary (2°) or tertiary (3°) position.
CJ Important examples of nucleophilic addition reactions are CJ E 1 -Cb (Elim:ination uninio lecular conjugate base)
the addition of HCN, NaHS0 3 , R-MgX and CH 30H reaction involves:' _
etc-., on)C=O compounds. Step 1. Removalofa proton by a conjugate base to
CJ Free radical ad'dition reaction: Addition of HBr to produce carbanloll. '
unsymmetrical aIkenes in presence of organic peroxide, Step 2. The carbanion loses a leaving group, to form an
RP2 [like benzoyl peroxide (C6H5COh02] takes place alkelle and is a slow step (rate determining).
according to Kharasch Peroxide Effect (anti-Markowni- CJ E t (Elimination) Reaction: III this reaction; two
koff's rule) and follows the free radical addition reaction. O'-bonds are broken and an-bond ,is' formed
ROOR simultaneously.
CH 3CH=CH 2 + HBr. . . ) CH 3CH 2CH 2 Br
Propene (Anti-MR addition) I-Brornopropane
(Mechanism: See sec. 7.6).
CJ HF, HCI and HI do not give atiQ.-MR addition even when
peroxides are present. It is beca'llse HCl and HF do not
produce free radicals easily due to large bond energy and +H-base+L9
HI with minimum bond energy gives' free iodine. CJ It is bimolecular since substrate and base are involv,ed in
CJ Elimination reactions: The removal of two atoms or the rate determining step and,. the product obtained takes
groups, one is generally hydrogen (H+ ) and the other is a place through the formation of transition state.
leaving group (L-) resulting in the formation of CJ E2 elimination is lowest energy path in comparisontoEl
unsaturated compound (n-bond), are known as elimination and EI-Ch reactions. Hence, E2 reaction is most c~mrn.on
reactions. ' and better the leaving group, higher is the E2 reaction.
j, .'"
(a) Substitution reaction (i) A : B ---+ A +:B- '. (g) CHCI 3.+OH-:- ~ :CCI 2 +H 20+ CI
. (h) CH3 CH-CHCH3 + Zn ~ CH3CH=Cl::lCH3
(b) Addition reaction (ii) A : A ---+ A+ A I I .' . F+Ziffir
Br Br' . / ,2
"') CH3 C'I ---+CH
KOH
(c) Elimination reaction (111 3QH
.(i) CHI:i ~CH2 -CHi + Za ---+CH2 - CH~ +ZnI;i
(d) Homolytic fission (iv) BF3 '.' I I .... ~/ '
. (e) Heteroiytic fission (V) HiC=CH 2 + HBr I . I ,. ' / C H2 '
~ CH 3CH2Br (j) NH4 NCO ---+ O~C(NH;h' .' .' ..
(t)Electrophile
'.
(VI) CH3CH20H . )
' H 2 S04 (k) (CH 3 )2 NH; + ~H30- ---+((:H3 h NH + eH,OH
. H 2 C=CH2 r< 'N ,HeaL' .
.(I) H 3.....-. N-CH3~' H 3C-CH3 +Nf
(g) Nucleophile _ '.. (vii) NH3 .
(m) C2HSBr + OH- ---+/'(';2aSOH + Br-
4(A). Classify the following into electrophiltc and nucleophilic
reagents:
(a) H+., (b)CI-, (c)NH3, (d)NOi, (e)CN, (f)H2Q
(g)Br+, (h) ROH,(i) BF3,(j) ~NH2' (k) AICI 3 ,
(l) ROB., (m) Carbocatlons, (n) Carbanions, (0) S03f!; 8. (a) Arrange the following according to their stability:
(P) BeC1 2, (q) r ,(r) SnC1 4 , (s): CCI 2, '(t) : P(CH3 h, '+- • + . + '.'
(u) H 2 C=CH2 '. CH3CH2CH2 CH 2 , (CH 3 h C; CH3CH2 CH2 ,
. + .' + +'
4(B). Classify' the following as Lewis acids and Lewis bases: CH3CH z eHCH 3 , CH 3 CH z , CH3
(BCECE 2005J
(b) Arrange the follo~g aCcording' to their stability:
(a) CH3NH2 (b) CN- (c) AICI 3 (d) Fe 3+ (e) CO2
5. For the Jollowing bond cleavages, use curved arrows to C6 H S CH 2 , (CM 3 h C, CCI 3 ,till' (CJl3)2 CH .
show the electron flow and classify each as homolysis or
. .
(c) Arrange the following: aGcoiding to their stability:
. ~ .. ',. ...
.'
",
heterolysis. Identify reactive intermediate produced during (1) CH3 , (CH 3 )3 C, (C 6 H s·h C, C6 H sCH 2 , CH 3CH 2
the fission.
. ' . ' -,...-'
(iii) I
. /j'Br
~ A1+. +Br- CH 3
•
7.
(g) C 6 H S-N
.. (h) : CCI 2
Classify the follOWing reactions by type:
. reaction: CH 3 F, CH3~ CH3 Br, CH3Cl. .
. '(iii) increasin,g jlrder ofeJ\.pect~ enoL content:
(a) HCHO+ HCN· ---+ CHz(OH)CN CH3COCHzC~0, CH 3 COCH3, CH3CHO,
. Heat, eu .. CH3COPI2COCH3' . .
(b) (CH 3hCHOH . > (CHlh C=O + H 2 ' (iv) decreasing order OfS,V2 reactivity:
. . (c) CH 3 CI + KOH(aq,) ---+ CH30H + KCI
. (d) CH2=CH2.+Br2 ---+ CH 2-CH2 .
RCHiX,R2CHX,R3CX, MeX.
(v) decreasing order of SNi rel!,Cti~ity: .
I I' (i) 2-bromopentarie (A), I-bromopentane '(B),
Br Br
2-bromo-2-methylbutane (C).. . . . .
,.NOH
I
(e) CH3 -C-CH2CH 3 ---+ CH3NHCCH 2 CHl
v (ii) I-bromo-3-methylbutane(A),2-bromo~2".mef
hylbutane (B), 2-bromo-3-methylbutane (C) ..
. Ethyl methyl ketoxime N -Methyl propionamide
.; .., .
G.R.B. Organic Chemistry tor Competitions
" (vi) decreasing order of SN2 reactivity: (ii) Why formic acid is stronger than butyric acid?
, I-bromobutane (A), I-bromo-2,2-dimethyl- (iii) Why alkyl amines are stronger bases than ammonia?
propane (D), l-bromo-2-methylbutane (C), (iv) Why benzyl carbocation is more stable than ethyl
1:.bromo-3-methylblltane (D). ' carbocation?
. (vii) decreasing order of SN2 reactivity in (v) What is the effect of introduction of an alkyl group
, alkoxide nucleophiles: on the stability of the carbocation?
(vi) Why allyl cation is more stable than ethyl cation?
Me 2CHO, Me 3 CO, MeCH 2 0, MeO
(vii) Why does tert.-butyl chloride react with sodium hydro-
(e) Arrange the following as stated: xide solution by SNI mechanism while n-butyl chlo-
(i) increasing order of acid strength: ride react by SN2 mechanism? +
CICH2COOH, CH 3'CH2COOH, CICH 2CH 2COOH, (viii) In. acyliu.m ion, the structure R----C==O: is more
(CH 3 )2 CHtOOH, CH 3 COOH +
(ii) increasing order of acidity: HeIO,HCI0 2 , HCI03 , stable than R-C=O.
HCI04 : '. (lIT 2001) (ix) Why toluene reacts with bromine in presence of light
(iii) increasing strength ofH-bonding (X --;-H-X): gives benzyl bron;ride while in presence ofFeBr3' it
0, S, F~ CI, N gives p,-bromotoluene? .
9. Answer the following: (x) Why aryl halides are less reactive than alkyl halides
(a) How many types of fission are pOss$le of a covalent ,towards nucleophilic reagents?
bond? (xi) . Draw the stereochemical structures of the products in
(b) H.ow many types of ions are formed by 'heterolytic , the following reaction: '
fission and what are tlieir names? "~' C2 HS
(c) What are the ~ames and nature of the parts formed by B r + H NaOH)
homolytic ,fission? 2
CH SN
3
(d) H!lwmany electrons are present in the valence shell of
(xii) Predict the structure of the product in the following
the carbon atom of the carbonium ion? ,
(e) How many electrons are present in the valence,shell of reaction: .sr
H~Pb"
the carbon atom of the carbanion ion?
(f) Name the attacking reagents and give their nafure. ' Nal )
(g) Write'. the names of the parts' obtaineq when C~ CI Acetone
bond of ethyl chloride undergoes heterolytic fission. MeO--I-I~'- H
(h) What is the major factor that iflfluences the relative Ph
stabilities of carbocations, carbanions and free radi-
cals. '. (xiii) Which CX 2 eX = F~ CI, Br, I} is the most stable sin-
gletas compared to the corresponding triplet?
(xiv) The formation of following products (a) and (b) in
Defme the following with suitable examples: the given reaction:
(a) Substi1:tlt\on reactions . (b) Addition reactions
CH3CH=CHCH 2 CI+CN ~
(c) . Elimination reactions '(d) Markownikoff's rule
~e) HomolX!ic fission '(f) Heterolytic fission CH3CH=CHCH2 CN+CH3 -CH--CH CH 2
(g) Anti-Markownikoff's rule . ,
"
(a)
CN '
I ',
Write short n()tes on: .
(i) Inductive effect (ii) Mesomeric effect (b)
(iii) Carbocatiol.l (iv) Carbanion (xv) The formation of HOCH 2CH=CHCH 3 from the
(v) Free radicals (vi) Electrophiles hydrolysis of H2 C=CH~ CH ~CH3'
(vii) Nucleophiles (viii) SNi and SN2 reactions , I
CI
(ix) Carbenes (x) Nitrenes
(xi) Benzyne (xii) Hyperconjugation Complete the following imd identify the type for the inter-
Discuss the mechanism of the following reactions: mediate species: 'H
+ eat
(a) Dehydration of alcohols to form alkenes. (a) CH3 CH(OH)CH3 +H ~ ...... +HOH
(b) Peroxide effect in alkenes. . (b) CH3~C=C-H+Na+NH2 ~ ..... +Na++NH3
(c) Addition of HBr in alkenes.
.. (d) Dehydrohalogenation of alkyl halideS. (c) CH3 CH2-N N~CH2CH3 Heat) ...... + N2
(e) Addition of Br2 on ethylene.
(d) CH3 ~CH CH~CH3 + HI ~ ...... + r
'(f) Hydrolysis of methyl chloride.
(g) Hydrolysis of tertiary alkyl halides. (e) CH3 CHI 2 + Zn ~ ...... + ZnI 2
(h) Halogenation of alkanes. ' (f) CH3 CH 2 CI + AlCl 3 ~ ...... + AlCl 4
(i) Nitration of benzene. 1;). Complete the following and identify the type of displace-
] 3. Explain: ~.. ment reactions:
(i) Why trichloroacetic acid is stronger than acetic acid? (a) (R~CH3CH(Br)CH2CH3 + MeO- ~ ...
Mechanism of Organic Reactions
intermediate formation of stable carbocation (A): 17. What are the various alkanes obtained due to insertion
CH 3 when 2-methyl butane reacts with singlet methylene
'. I HCI' Cl- ,
(:CH 2 )?
(1) CH3-CH-CH=CH2 ~ (A) ~(B) 18. Suggest a possible mechanism for the formation of R-Li
from R - X by equation only.
ANSWERS
I. (a) homolytic, heterolytic; (b) free radicals; (c) electronegativity;
~E
(d) tert.-butyl carbonium ion; (e) six; (t) eight; (g) nucleophiles;
(h) electrophilic; (i) Sp3; (j) 1t; (k) Tert. > Sec. > Prim.; .
(iv) ·O,+E+ Heterolysis
V+
(I) conjugated molecule; (m) weaker, +I (iliductive effect); CBrbocation
(n) Markownikoff's rule; (0) free radical; (P) elimination; (Heterolysis, Carbocation intermeiliate)
'(q) diamagnetic; (r) pyramidal; (s) SN2; (t) nucleophilic;
6. (a) Onbocation, (b) Free radical, . (c) CaIbanion, (d) Free radical,
· (u) CHz-:-NO z; (v) hyperconjugation; (w)permanent, temporary; (e) Carbanion, (f) Singlet carbene, (g) Nitrene, (h) CaJ:bene.
· (x)'planar; (y) proton alkene; (z) less. . 7. (a) Addition, (b) Elimination, (c) Substitution, (d) Addition,
2. (a) True; (b) False; (c) False-.-produces -1 effect; (d) False--:is a (e) Rearrangement, (t) Allylic bromination, (g) a-elimination,
temporary effect; (e) True; (t) False--electrophilic attack; (g) True; (h) f:l-elimination, . (i) y-elimination, (t) Rearrangement, (k) Dis- .
(h) False; (i) True; (j) True; (k) True; (I) False-due to +1 effect; placement (substitution), (I) Decomposition, (m) Displacement
, (m) True; (n) True; (0) True; (P) True; (q) False--electrically neutral;
(r)False-.-Lewis bases; (s) True; (t)False-.-undergo SN1 mechanism;
(u) False-undergo hydrolysis by SNZ mechanism; (v) True; (w) True;
+
(SUbstitution), (n) Addition.
+
8. (a) (CH3 )3 C > CH3CH 2 CHCH 3 > CH3CH;zCH2 CH z
+
+ + +
(x) False--CJIs group produces -1 effect while CH3 group produces , > CH3CH zCH 2 > CH3 CH2 > CH3
+1 effect; (y) False-mesomeric effect is more powerful than inductive (b) CCh > CJisCHz > CH 3 > (CH3 )2 CH ;. (CH3 )3 C
effect; (z) True, ,
3. (a-iii); (b -v); (c~vi); (d-ii); (e--:-i);(f-iv);'(g-vii). (c) (i) (Ct;HS)3C > CJIs CH; > (CH 3)3 C > CH 3CH 2 > CH 3
4(A)Electrophilic reagents: (a), (d), (g), (i), (k), (m), (0), (P), (r), (s). (ii) II > I > 1lI
Nucleophilic reagents: (b), (c), (e), (t), (h), (j), (1), (n), (q), (t), (u). (iii) IV > III > II > I
4(8) Lewis acids: (c), (d) (d) (i) HzO < CH30H < OW < CH 30-
Lewis bases: (a), (b), (e)
(ii) CH3F < CH 3CI < CH3Br < CH31
• 5. (i) CH36\fbcH3 Homolysis ~ CHi> + 6CH3 (iii) CH 3CHO < CH 3COCH 3 < CH3COCH zCHO
Free radicals < CH 3COCHzCOCH3
(Homolysis, free radical intennediate) (iv) MeX > RCH1X >. R2CHX > R3CX,
. 0- (v) (i) C 00) > A (20) > B (10)
Heterolysis ~ )C< (ii) BOO) >C (2°) > A 00)
CN (vi) A(n-) > D(iso-) > C(sec.-) > B(tert.-)
Carbanion
(Heterolysis, carbanion intennediate) (vii) MeG> MeCH 2 0 > MezCHO > MCjCO
Heterolysis (e) (i) (CH3hCHCOOH < CH 3CH2COOH
(iii) In
..
/f'Br
A+Br- < CH3COOH < CICH2CH 2COOH < CICH1COOH
Carbocation (ii) HCIO < HCIO z < HCI0 3 < HCl04 "
(Heterolysis, carbocation intermediate)
234 . G.R.B. Organic ChemistryjOr Competitions
(iii) S < CI < N < 0 < F (xii) Br is replaced by I following SN2 mechanism. There will be
9. (a) Two; homolytic and heterolytic. Walden inversion at the place of replacement.
~±~ ~'M:±:
(b) Two; carbonium and carbanion.
(c) Parts are free radicals. These are electrically neutral.
(d) Six electrons.
(e) Eight electrons. .
(f) Electrophilic reagents-Positively charged ions or neutral mol-
ecules which have aiImity for electrons. Ph Ph
Nucleophilic reagents-Negatively charged ions or neutral (xiii) : CF2• Since, F and C are in the same period of the periodic
molecules which have the tendency to lose an electron pair.
+ table, their p AO's are about the same size permitting more
(g) CHlCH2-C1 ----+ CHl CH2 + CI efficient overlap. Furthermore, of the X-C bonds, the F-C
Ethyl chloride Ethyl carbocation Chloride ion bond length is the shortest.
(h) Any diminution of + or - charge or of electron deficiency on (xiv) Formation of product (a) .1S"obtained from the expected SN2
the carbon stabilizes the intermediate. reaction at CI. However, cN- can also bond to Cl with the
13. (i) Due to -1 effect of chlorine. nucleophile 11: i's, displacing Cl- as theallylic rearrangement
(ii) Alkyl group has a +1 effect. Hence, butyric acid gives If'" with occurs.
difficulty and therefore, weaker than formic acid.
.-~.,~ .0·
(iii) Alkyl groups increase electron density on nitrogen due to +1 effect. N=aC. CH l -CH=CH-CH2-CI ----+
and thus, the electron pair donating capacity ofnitrogen increases. \
CHl--yH-CH =CH 2 + CI"-
(iv) Benzyl carbocation is more stable due to the presence ofresonance.
CH~_ 6-0-6:
(v) Alkyl group is electron releasing group (+1 effect). It partially
(xv) (H2C=CH-&H--CHl ~ H2 I -CH=CHCH3)
CN
(b)
This is called SN2-prime mechanism.
C
The uitermediate R+ can react with H20 at either C I or d each
of which has 8+ charge. Reaction at Cl (2°) has more 8+ and
neutralises the positive charge on carbon and thus, increases the
forms HOCH2CH=CHCH3•
stability of carbocation. +
(vi) Allyl carbocation is more stable due to the presence ofresonance. 14. (a) (CH3hCH,acarbocation;, (b) CH3-C. C:,acarbanion;
. + + •
H2C=CH-CH 2 ~ CH 2-CH=CH2 (c) CHl CH2, a free radical;
(vii) Tert. butyl chloride ~eacts by S,vl mechanism because it forms + . .
(d) CH3-CH-CH2-CH3, a carbocation;
stable carbocation. "..Butyl chloride reacts by SN2 mechanism
as the reaction is non~ionic. Transition state is formed in which ••
(e) CH 3 CH, acarbene (singlet);
both OH and Cl are partially bonded to the halide carbon. +
+ (f)CH)-CH2• a carbocation.
(viii) In R-C=aO:, the octet of every atom is complete while in
+ 15. (a) (S~CH3CH(OMe)CHiCHl (SN2 invert configuration) .
R-C=O, the carbon has only 6 electrons. (b) (R~CH3CH(OMe)CH2Cfl3 (S,v2 invert configuration)
(ix) Side chain bromination of "toluene to give benzyl bromide is
favoured under photo-chemical irradiation arid involves a free
(c) (CH3)3C--0Me, an ether (SNI reaction)
(d) MC:300Me + Me:zS + MeOH (SNI reaction, methanoiysis)
.
radical mechanism.
While in presence of FeBrl. electrophilic substitution in the
(e) (R~EtOT-.J-·l"'N' (SN2 invert co~gUration)
benzene ring occurs and it forms p-bromo toluene.
(x) Aryl halides are less reactive and more stable than alkyl halideS Q JI
due to . (f) CH3CH2-0-CH2OC2Hs (SNI reaction, ethanolysis)
(Ii,). Resonance: In aryl halides, thedelocalization of electron
pair occurs (see section 16.10) and gives a partial double bond
cha:nicter to C- x bond making it stronger than C- X bond
(g) (S~I+CH2CH2CH3 (SN2 invert configuration)
in alkyl halides. H
(b) Difference in hybridization of carbon: In alkyl halides, CH) ..
the C-X bond is sl-hybridized while in aryl halides it is
(h) CH3 -b-CH2CH 3 (SNI reaction, methyl shif\)
sY-hybridized. Therefore, the C-X bond length in aryl I
halides. is shorter than"alkyl halides. OH·
(xi) In S,; reactions, the substitution occurs with stereochemical
. inversion. Hence, the reaction is:
C2HS
+uN::U, CHl
Mechanism ofOrganic Reactions ... 235:; .
(vi) (A)
Y;H5
h +, (8) .
C.H'h CI
.
CH3'-;"~-CH2--CH3
H
+ : CH2 ~ CH34-CH2CH3
CH 3
2,2-Dimethylbutane
(lnsertion on
+ tertiary carbon)
(vii) (A) CH3HC=CHCH 2; (8) CH3HC":"'CHCH2Br
(Major) 18• R - L1' _H_o_m_o..::,lY,_sis-+,, R" + Ll'"
17. ' Singlet methylene can be inserted into all C-H bonds of2-methyl (i) R-X:+Li" ~ [R-X:t + Li+
butane with equal ease.. A radical anion
(ii) [R-X:r ~ R· + X:-
(iii) R· + Li· ~ R: Li
Complete equation is RX + 2Li ~ R - Li + Li+ X-
•
G.R.B. Organic Chemistry (or Competitions
(c) CH3CH 2CH zCH 20H 0 32. Which of the following is not an electrophile?
(d) CH3-F-CH2-CH3 0
(a) AlBr3 ' 0 (b) BF3 o
(c) SnCl 4 0 (d) NH3 o
OH 33. Alkenes readily undergo:
22., Which one of the following is a free radical?
(a) . substitution reactions o
(a) H+ 0 (b) ,H- 0 (b) addition reactions , o
(c) elimination reactions O'
(c) H O ' (d) Hz '0 (d) rearrangement reactions o
23. The shape of[CH3 t is: 34. The following reaction is: ,
(a) triangular planar 0 (b) square planar 0 CzHsBr+KOH ~ CzHsOH+KBr:
(c) tetrahedral 0 (d) none of these '0 (a) electrophilic, substitution o
24. Which of the following statements is wrong? ' (b) t(linlination ' o
(a) A tertiary free radical is more stable thatl a secondary , (c) nucleophilic substitution o
free radical 0 (d) addition o
(b) A secondary free radical is more stable, than a primary 35. The following l;eaction js an example of:
, free r a d i c a l ' ,0 o , OH
(c) A tertiary carbocation is more stable, than a secoQdary . ',- 11-
carbocation
(d) A primary carbocation is more stable than' a secondary
0 - 'VC~H +HCN~ N~
V'"
carbocation ' 0
[JEE (Orissa) 2007)
25. Most stable carbocation is:
(a) nucleophilic substitution 0
o o (b) electrophilic substitution 0
+
(c) CH 2CH2Cl 0 (d) CH2-CH2N0 2 0 (c) electrophilic addition 0
26. Most stable carbocation is: (d) nucleophilic addition 0
+ + 36. Tbe reaction between ethylene and bromine.isan example
CH2 . CH2 '
of:
(a
l
©. CI
o (b)©
N02
o (a) electrophilicaddition
(b) electrophilic substitution · 0
(c) nucleophilic addition .
0
0
+ (d) nucleOphilic substitution 0
, CH2 37. In the nitration of benzene with a mixture of conc. HN03
o (d) © o and conc. H ZS04 , the active species involved is:
(a) nitrite ion
(c) nitronium ion
0 (b) nitrate ion
0' (d) nitrogen dioxide
0
0
38.
27. The shape of carbanion, [CH3 r is:
Nitration of benzene is: '
(a) nucleophilic SUbstitution
'
0
(a) linear 0 (b) pyramidal 0 (b) nucleophilic addition 0
(c) planar ,0 (d) tetrahedral 0 (c) electrophilic substitution 0
28. In carbocation, the carbon atom bearing the pOsitive charge (d) free radical substitution 0
is: 39. ' Consider the following structures
(a) sp3 ~hybridized o' (b) s~hybridized ' o +
H 2 C>=CIi, CH3 -CH2
+
,
(c) dsp2~hybridized o (d) sp2~hybridized o I II
29. An electrophilic reagent is:
(a) electron~rich species o
(b) electron~deficient species o The correct sequence 'of these carbocations in the decreas-
(c) a Lewis base o ing order of their stability is :
(dt negatively charged species '0 (a) I, II, TIl, IV 0 (b) rv,TII, II, I 0
30. A nucleophile is: (c) IV, II, TIl, I 0 (d)I, TIl, II, IV 0
(a) electron~rich species o 40. Addition of HI on the double' bond of propene yields
(b) electron-deficient' species o isopropyl iodide and notn-propyl iodide'as the major prod-
(c) a Lewis acid o uct. This is because the addition proceeds through:
(d) positively charged species o (a) a morestable carbonium ion 0
31. Which of the following is an electrophilic reagent? (b) a more stable carbanion ion 0
(a) HzO 0 (b) OH- o (c) a more stable free radical 0
(c) NO; 0 , (d) none o is
(d) none of the above a correct statement 0
G.R.B. Organic Chemistry (Or Competitions
41. Which of the following alkyl hali~es is hydrolysed by SN1 SO. Which of the following statements is correct about a car-
mechanism? bocation?
(a) CH3 Cl 0 (b) CH3 CH2Cl 0 (a) It reacts with nucleophile 0
(c) CH3 CH2CH2Cl 0 (d) (CH3 )3 CCI 0 (b) It can undergo rearrangement 0
(c) It can eliminate an H+ to fomi an olefin ,0
42. Which of the following statements does not apply to free (d) All are correct 0
radical chain reaction? 51. SNi mechanism for the hydrolysis of an alkyl halide involves
(a) It may be initiated by ultraviolet rays '. 0
the formation of intermediate:
(b) One mole of product is obtained for each mole of free
radical produced in the initiation step '0 (a) free radical 0 (b) carbocation 0
(c) It is not affected by changes in polarity of solvents 0 (c) carbanion 0 (d) none of these 0
+
(d) It is inhibited by the presence of certain reagents 0 52. Stability of CH2-CH CH2 can be explained by:
43. Which is dehydrated to a maximum extent using conc. , (a) inductive effect 0 (b) electromeric effect 0
H 2 S04 ? (c) resonance 0 (d) polar effect 0
53. Nucleophilic part of the. reagent attacks the substrate
JvOH CH3 CH2COCH3 on the:
(a) V o (b) o (a) carbon atom of carbonyl group
(b) oxygen atom of carbonyl group
0
0
9
(c) methyl group 0
. JvCH, (d) CH2 group . 0
54. Elimination reaction generally occurs with, the formation
o (d) o
(c)
U OH
of:
(a) one sigma bond
(b) one pi bond
0
0
OH
(c) one sigma and one pi bond 0
44. Which one of the following statements is wrong about SN2 (d) none of the above 0
. reaction?
55. Which of the following orders is correct for the ease of
(a) The rate of reaction is independent of the concentration electrophile addition on these alkenes?
of nucleophile 0
(b) Nucleophile attacks the carbon from the side opposite
'to where the leaving group is attached
(c) Only in one step the bond formation and bond breaking
0 (((XC(
I II III
takes place 0 (a) III> II > I 0 (b) I > II > III 0
(d) The rate of reaction oc [substrate] [nucleophile] 0 (c) I > III > II 0 (d) III > I > II 0
45. Markownikoff's rule is applicable to which of the follow- 56. Hyperconjugation is most useful for stabilizing which of
.ins reactions? the following carbocations? (PET (Kerala) 2010)
(a) ~H4 + HBr 0 (b) C3 H6 + Cl 2 0 (a) neo-Pentyl 0 (b) tert.-Butyl 0
(c) C3H6 + HBr 0 (d) C3 H6 + Br2 ' 0 (c) iso-Propyl 0 (d) Ethyl 0
46. The addition of HBr to propylene takes place opposite to (e) Methyl .0
Markownikoff's rule in presence of: 57. Which of the following explanations accounts for o-nitro
(a) sunlight 0 (b) hydrogen peroxide O' phenol to be more volatile than p-nitro phenol?
(c) platinum catalyst 0 (d) none of these 0 (a) Intermolecular hydrogen bonding 0
. 47. Anti-Markownikoff's addition is not observed in: (b) Resonance 0
. (a) propene 0 (b) I-butene o (c) Intramolecular hydrogen bonding 0
(c) 2-pentene 0 (d) 2-butene o . (d) Inductive effect 0
48. Ammonia is iso-structural with: 58. The peroxide effect in anti-Markownikoff's addition
(a) carbanion 0 (bj free radical o involves:
(c) carbocation 0 (d) carbene o (a) ionic mechanism 0
49. Which of the following statements is correct? (b) free radical mechanism 0
+ (c) heterolytic fission of double bond 0
(a) Allyl carbocation (H2C=CH--CH2 ) is more stable (d) homolytic fission of double bond . 0
than propyl carbocation [J 59. What is, the decr(asing order of strength of the bases,
(b) Propyl carbocation is more stable than allyl carbocation
o
OH- (I), NHi (II), H-C==C- (IlI),:CH 3CH (IV)? z
(a) N > II > III >, I 0
(c) Both are equally stable o (b) III > N > II > I 0
(d) None of the above [J
Mechanism of Organic Reactions
(c) 1 > II > III > IV 0 68. Heterolytic fission of a covalent bond can form:
(d) II > III > 1 > IV 0 (a) free radical 0
60. Ammge the following compounds in order of increasing (b) both carbocation and carbanion ,0
dipole moment, (c) only carbocation 0
Toluene (I), m-dichlorobenzene (II), o-dichlorobenzene (d) only carbanion 0
(III), p-dichlorobenzene (IV): 69. Reimer~Tiemann reaction of phenol with chloroform and
(a) 1 < IV < II < III 0 aqueous alkali takes place through the intermediate forma-
(b) IV < I < II < III 0 pon of:
(c) IV < 1 < III < II 0 (a) carbocations ,0 (b) carbanions. 0
(d) IV <II < I < III 0 (c) carbon radicals 0 (d)carbeneS 0
61. Which is the decreasing order of acidity in the following 70. The reaction intermediate carbenes are produced from:
compounds? (a) diazo methane '0 (b) ketene 0
CH 3 CH20H(I)
CCI 3-CH20H(III)
CF3 CH 2 0H(II)
(N°2)3 C-CH 20H(IV)
(c) CHCI3;C2HsONa 0 (d) all of these [J
71. Markownikoff'saddition product lies in the formation of
(a) I> U> III> IV 0 (b) II> I> III > IV 0
intermediate stable:
(c) IV> II > I > III 0 (d) IV> II > III > I 0 (a) carbocation 0 (b) carbanion 0
62. The stability of the following carbocation decreases in the
order: - (c) carbon radical 0 (d) unsaturation 0
72. Peroxide effect of addition of HBr to alkenes occurs
0,6,00
through a stable:
(a) carbocation 0 (b) carbanion 0
(c) carbon radical 0 (d) carbene 0
II 'III IV 13. In addition reactions of alkenes, the Markownikoff's rule
follow:
(a) IV> III > II > I 0 (b) IV> II > III > I 0
(a) ionic mechanism 0
(c) IV> II > 1 > III 0 (d) IV > I > II > III 0 (b)' radical mechanism 0
63. Order of base strength of the compounds :
° 1f7" '
0-
(c) substitution mechanism 0
~o- ~CHi ~
(d) rearrangement mechanism 0
NHi 74~ Addition ofHBr to propene in presence of peroxide (anti-
>
(a) bulky groups on the carbon atom attached to halogen
atom ' 0 stability:
(b) small groups on the carbon atom attached to halogen CH3 " +
atom, ,0 N-CH 2 (II)
(c) non~polar solvents 0 CH 3
+ .
(d) none of the above 0 CHl -y-CH 3(IV)
67. Halogenation () ran alkane takes place through the interme-
diate: CH3
(a) carbocation 0 (b) carbanion 0 (a) I > II > III > IV o (b) IV> III > 1 > II o
(c) carbon free ra,dical 0 (d) carbene 0 (c) II> IV> III > I o . (d) IV> III ;> II > I o
'240 G.R.B. Organic Chemistryfor Competitions
79. Which behaves both as a nucleophiIe and electrophile? 89. Which one of the following compounds is most acidic?
(a) CH3NH2 0 (b) CH30H 0 (a) Phenol 0 (b) Tricbloroaceu»dehyde 0
(c) CH3 CN 0, (d) CH3 CI 0 (c) Trichloroacetic acid 0 (d) Benzoic acid 0
80. Consider the following bromides : 90. Arrange basicity of the following compounds in decreasing
Me~Br ~Me Me~Me order:
CH3 CH2NH 2 (I), H 2 C=CH-NH2 (II),
Br Br
HC==:C-NH2 (III) , C6HSNH2 (IV)
(I) (II) (III)
(a) I> II > III> N 0 (b) IV> III > II> I 0
The correct order of S N I reactivity is : [AIEEE 20U))
(c) III> IT> I > N 0 (d) I > III > II> N '0
(a) I> II > III 0 (b) II> III > I 0 91. Which of the following compounds does not contain acidic
(c) II >1> In 0 ,(d) III> II> I 0 hydrogen?
81. In the, following compounds, the order of basicity is :
o
(a) Phenol 0 (b) Methylamine 0
(c) Acetic acid 0 (d) Methyl alcohol 0
0 ,0",
N
I
';;:"'N
O'~
N
I'
N
I
92. Which of the following compounds is not a Lewis acid?
(a) BF3
(c) R-OR
0 (b) SnCl 4
0 (d) R-MgX
'
~CHCI'
(a) RF>RCI>RBr>RI , 0
(b) RF~RBr>RGt>RI
(a)OgcI' o (b)
U o (c) 'RCl>:RBr>RF>,RI
0
0
. (d) RI>R,Br>RCl>RF , 0
0-'
&0~CI
118. Which of the following has the most acidic. hydrogen?
, '". . ' > ' f l l T (8) 20001
(c) o (d) CrCHCI, o (a) 3-He){anone 0 (b) 2,4-Hexanediotie 0
#
.
I·
OH
. (c) 2,S-Hexanedione'G1 . (d) 2,3-Hexanedione 0
111. Which ofllie following'aikenes will'react fastest with H2
103. In the reaction ofphen()l with CHCl 3 and aqueous NaOH at under catalytic hydrogenation c()nditions? (lIT (S) 2000)
7<1', the electrophile attackiIig the ring is:
(a) CHCl 3 0 (b)CHCI 2 0 R . R R H
(c) : CCl 2 0 (d) COCl 2 0 (a)' ~. - 0 (b) V. o
104. A solution of (+ )-2-chloro-2-phenyl ethane in toluene ':F\
H . H
' Rr \
".H
racemises slowly in the presence of small amount of SbCI s ,
X'
due to the formation of: R R • R R
. (a) carbaniob
(c) free radical
O· (b) carbene
0 (d) carbocation
0
0
105. The most unlikely representation of resonance st.(uctures of
(0) 0 (d) )=(- o
R H R R
p-nitrophenoxide ion is: 112. The set with ~orrect order of acidity is: .
. . lOT (S) 2101; CB8E(Med.) lOOS]
'-O,~/O -o,~/O-
(a) HCIO<HCI0 2 <HCI0 3 <HCI04 . 0
¢ Q
, (b) HCI04 <HCI0 3 <HCI02 <HCIO 0
(a) 0 (b) o (c) HCIO<HCI04 < HCI0 3 < HCI0 2 0
(d) HCI04 <HCI02 <HCI0 3 <HCIO 0
113. Hydrogenation of the following compound in the presence
0- o' . . ofpoisoqed,palladium catalyst gives: [tIT (S) 2GBI)
o,~/O' :. ~'Me'H
Me
~~i~VO ',# H
p.
(c)
9 0 (d)
-90
106. Which one of the given will most readily be dehydrated in
o Me
(a) optically active compound·
(b) an optically inactive compound
(c) a racenilcmixture .
(d) a distereomeric;: mixture
H .
o
o
o
o
acidic condition?' (lIT (S) 10001 114. Consider the following carbocations:
(a).U o (b) L o
o 0 The correct sequence of the stability of these is:
(c)~ 0 (d)~ o . '. [S~RA 2001.)
(a) U<I<III<IV o.-s~tLt:<I;;iv 0
". OH .OH
l07. Which of the following has the. highest nudeophilicity? (c) III<I<II<:IV ·0' (d) IV<III<I<I1' 0
(liT (S) 20001 "
"
[IIT(S) 2001)
(a) CH3CHO+ HCN ~ CH3 CH(0H)CN
©
(b) ,
CH2Cl
+ AgN02 -
©' 0
CH2N02
0
'/NH ,,' , 127. Which of the following statements are correct forcarbenes?
CH 3
.
-C.( "
"NH2
CHiCH2NH2' (CH3 hNH,
, (2) (3)
(a) ,Hybridisation of carbon in
,
Cu
2 may be sp2 as well as
[J
sp
(1) (b) sp-hybrid carbene is triplet carbene [J
o
(c) Cel 2 always exist in singlet form [J
II
car ::- C- NU2 ; (d) All are correct [J
(4) 128. Arrange the following nuc1eophiles in the order of their
(a) 2> 1 > 3 >4 O' (b) I >3> 2 > 4 0 . nucleophilic strength: [MGIMS(Wardha) 2003]
(c)3>1> 2 > 4 0 ' (d) 1> 2 > 3 > 4 0 (a) olr >CH 3 COO- >CH)O- >C6 H s O- 0
121. Which ofthe following is not a Lewis base? '
(b) CH 3COO- <C6 HsO- <CH 30- <OH- [J
, , [Pl\1T (Delhi) 2002]
{',: " - ~~X:': I:c"
(c) C6HsO~
<CH 3COO- <CH 30- <OIr o (a) Cri3..C1 o (b) CH 2 Cl 2 o
(d) CH3COO- <C6 H sO- <OH- <CH 30- o (c) CHCI 3 o(d)CCI 4 o
129•. Identify the correct order of reactivity in electrophilic sub- 135.· Which of the following represents the given mole of
stitution reactions of the following compounds: hybridization Sp2 _Sp2 -sp-sp from left to right? [lIT 2003)
[lIT 2002] (a) H 2 C=CH-C==CH 0
CH3 Cl N0 2 (b) HC=C-C=CH 0
.0
©©©©
1 2 43
(c) H 3C---:--CH:-CH-CH 3
(d) H 2 C=CH-CH=CH2
(b) H3 C-CH-e--CH3 o
I I
D CH3
.the correct order , of acidity of the poslllons
(c) H3C-e-~CH-CH3 o (X), (Y)and (Z) is: . [lIT 2004)
II (a) (Z» (X» (Y) o (b) (X» (Y» (Z) 0
D CH3
(c) (X»(Z» (Y) .. O· (d) (Y)?, (X» (Z) 0
(d)H3e-CH-CH-CH 3 ·
. I. o 141. Due to the presence of an unpaired electn;>n, free radicals
are: [AIEEE 2005; JCECE (Med.) 2008)
CH3 (a) chemically reactive 0 (b) chemically inactive 0
133. Identify the correct order of boiling points of the following (c) anions 0 (d) cations 0
compounds: (lIT 2002] 142. The, decreasing order of nucleophilicif)' among the
CH3CH2 CH2 CH2 0H, CH3 CH2 CH 2 CHO, . nucleophiles is: (AIEEE 2005)
(1) (2) (I) CHr-,-W-O- (II) CH30- (III) CN- ,
CH3CH 2 CH 2 COOH
o
. -0-.
(3)
(a) 1> 2 > 3 0 (b) 3> 1 > 2 [J
o
11
(c) 1 > 3 > 2 0 (d) 3 > 2 < 1 0 (IV) H3 C . . ~ s-o-
134. Among the following, the molecule with,highest dipole - II
moment is: .. . (UT2003] o
, G.R.B. Organic Chemistryfor Competitions
.~. ~~N~~
(a) p-Nitroaniline 0 (b) Benzyl amine 0
, (c) Diphenyl amine [J (d) Triphenyl amine 0
154. Nucleophilic addition reaction will be most favoured in:
reDSE (Moo.) 2006J
, (a) CH3CH 2CHO 0
CH3 N02 N~
(I) (II) (III) (IV) (b) CH 3 CHO 0
(a) II>I>III>IV 0 (b) m>IV>I>II 0 o
II
(c) I>IV>III>II IJ ' (d) IV>III>I>II 0 (c) CH3CH 2CH2-C-CH3 o
146. Which is most stable carbocation? [CET (J & K) 2005)
(a) n-Propyl cation 0 ' o
(b) iso-Propyl cation 0 155. The correct increasing order of the reactivity of halides for
(c) Ethyl cation 0 SN 1 reaction is: IAllMS 2006)'
(a)CH3 CH2-X < (CH 3 hCH-X
(d) Triphenylmethyl cation 0
, <Hz C=CHCH 2-':"X<PhCH2-X 0
147. W1,1ich of the following undergoes nucleophilic substitution
(b) (CH 3h CH-X < CH3CH2 -X
exclusively bySN
I
[~~~:::~.) l005; JIPMER 2007) < H2 C=CHCH2-x < PhCH 2-x 0
(a) Ethyl chloride 0 (b) Iso~opyl chloride' 0 . (c) PhCH 2-X < (CH 3 hCH-X < CH3 CH2-X
(c) Chlorobenzene' 0 (d) Benzyl chloride 0 < H2C=CH-CH 2X 0
148. Which of the following is electron deficient molecule? (d) H2C=CHCH2-X'< PhCH2-X
[CRSE (Med.) 2005; .lIpMER 2007) «CH3 h CH-X<CH3 CH2-X 0
(a) C2H6 0 (b) B2H6 0 156. 'Inductive effect involves:
(c) SiH4 0 (d) PH3 0 [CET-(Puiljab) Engg. 2007; AFMC 2008)
149. Which of the following compounds reacts slower than ben- (a) displacement of o-electrons 0
zene in electrophiIic bromination? IJIPMER 2005) (b) delocalisation of 1t-electrons 0
(a) C6Hs~CH3 o (b) C{jHs~OH 0 (c) delocalisation of o-electrons 0
(c) C~HS-NH2 0 (d)C6Hs~N02 0 (d) displacement of 1t-electrons 0
t 57. The basicity of aniline is less than that of cyclohexylamine.
150. Which one of the following resonating structures of This is due to: ..
I-methoxy-I,3-butadiene is least stabl~? IIIT(S) 20051 IKCET 2006; GGS Indraprastha Univ. (Engg.) 20071
,'" e . Ell
.-~ (a) CH2 ...:....:.CH=CH-CH-':-'O--CH3 0 (a) -R effect of -NH2 group 0
~i . e Ell
(b) -1 effect of -NH2 group 0
(b) H2C--:-CH~-CH==O--CH3 0
e Ell,
. (c) +R effect of -NH2 group 0
(c) CH2-CH-CH==CH-:-O--CH 3 0 (d) hyperconjugation effect 0
e Ell 158. In the solvolysis of3-methyl-3-bromohexane, which of the
(d)' H2C=CH~-CH-O-CH3 0 following statements is not correct?
151. CH3Br + Nu:- ----? CH3Nu + Br- IPMT (Kerala) 20061
The decreasing order of the rate of the above reaction with (a) It involves carbocation intermediate 0
nucleophiles (Nu - ) A to Dis: (b) The intermediate involves sp2-carbon 0
[Nu - =(A) PhO- ,(B) AcO- ,(C)HO- ,(D) CH30-] (c) Polar solvents accelerates the reaction 0
. IAIEEE 2006) (d) The rate of reaction depends upon 3-methyl-3- bromo-
hexane concentration 0
Mechanism of Organic Reactions . > 245
(e) It involves inversion of configuration· 0 168. Which of the following presents the correct order of the
159. Neopentyl bromide undergoes dehydrohalogenation to give acidity in the given compounds? (CBSE (Med.) 2007)
alkene. even though it has no ~ -hydrogen. This is due to: (a) BrCH2COOH>CICH2COOH>FCH 2 COOH
IPMT (Kerala) 20061 >CH3 COOH o
(a) E2 mechanism o (b) FCH2COOH>CICH2COOH> BrCH 2 COOH
(b) El mechanism o >CH3COOH· o
(c) Ilofmann elimination o (c) CH 3 COOH>BrCH 2 COOH>CICH 2 COOH
(d) rearrangement of carbocation by El mechanism o > FCH 2COOH o
(e) E 1-Cb mechanism o (d) FCH 2 COOH>CH3 C09H> BrCH 2 COOH
160. Which one is most reactive towards S N I reaction?
>CICHzCOOH o
. (CBSE (PMT) Prelims 2010]
·169. For the following
(a) C6H5CH(C6H5 )Bt 0 (i) 1- (ii)CI- (iii) Br-
(b) C6H 5C(CH 3 )(C6H5 )Br 0 the increasing order of nucleophilicity would be:
(c) C6H 5CH(CH3 )Br 0 (CBSE (Med.) 2007]
(d) C 6 H s CH2Br 0 (a) r <cr <Br-' o (b) Br- <CI- <r 0
161. Order of stability of vinyl, allyl and tertiary radical is: .
(DPMT 20061
(c) r <Br- <Cl- o (d) cr <Br- <r 0
(a) tertiary, vinyl, allyl 0 (b) vinyl, tertiary, allyl 0 170. Which one of the following is correct?
Fornrlc acid has lower pKa than that of CH 3COOH
(c) tertiary, allyl, vinyl 0 (d) allyl, tertiary, vinyl 0
because: (SCRA 2007]
162. Which of the following carbocations is most stable?
(DPMT 20061 (a) formic acid does notdiss~ciate 0
(b) formic acid does not have an alkyl group 0
~l~
(c) formic acid is smaller in size than acetic acid 0
(d) formic acid is a strong reducing agent 0
o o 171. The rate of the reaction
X R - o - C H2Br + NQ-
[R V-CHz-NO]Br-
is influenced by the hyperconjugation effect of group R. If
o o R-sequentially is: .
(i) CH3 - (ii) CH 3 -CH2 -
CH3
-rI
163. CH3 -O-CH3 is: IAMU(Med.) 2006)
(a) Lewis acid 0 (b) Arrhenius acid 0 (iv) H3 C
(c) Lewis base 0 (d) Bronsted acid 0
164. Which one is ambidentate ligand? IAMU (Med.) 2006) CH3
(a) soi- ·0 (b) CN- 0 thl increasing order of speed of the above reaction is:
(c) NH3 0 (d) H 20 0 (PMT (KeraJa) 2007)
165. Which of the following is a Lewis acid?
(a) (iv>" (iii), (ii), (i) 0 (b) (i), (ii), (iii), (iv) 0
[CET (J & K) 2006) . (c) (i), (iv), (iii), (ii) 0 (d) (iii), (ii), (i), (iv) 0
(a) AICl3 o (b) CI- 0 (e) (ii), (iii), (i), (iv) 0 .
172. The S N I reactivity of the following halides will be in the
(c) CO o order: .
16.6. Which of the following intermediates have the complete (i) (CH 3)3 C- Br (ii) (C6 HS}zCHBr
octet around the carbon atom? (iii) (C6 H s )zC(CH3 )Br (iv) (CH3)2CHBr
. IGGS Indraprastha Univ. (Engg.) 2005) (v) CzHsBr (PET (KeraJa) 2007)
. (a) Carbonium ion 0 (b)Carbanion 0 (a) (v) > (iv) > (i) > (ii) > (iii) 0
(c) Free radical 0 (d) Carbene 0 (b) (ii) > (i) > (iii) > (v) > (iv) 0
167. Which of the following is the correct order of decreasing (c) (i) > (iii) > (v) > (ii) > (iv) 0
SN 2 reactivity? (AIEEE 2007] (d) (v) > (i) > (il» (iv) > (iii) 0
(a) R 2 CHX > R 3 CX > RCH 2 X 0 (e) (iii) > (ii) > (i) :> (iv) > (v) 0
(b) RCH 2 X>R 3 CX>R 2 CHX 0 173. The correct order of case of dehydration of following is:
(c) RCH2 X>R 2 CHX > R 3 CX 0 (AIIMS 2007]
(d) R3 CX > R 2 CHX > RCH2 X (X is a halogen) . 0
,
G.R.B. Or a"ic Chemistry for Com. etitions
(a)~: (b)~.
+
(a) ·Ph 3C+ 0 (b)Ph 2CH C]
+ ;t- 0 0
· (c) Ph 2CH 2 0 (d) PhCH2 O
177. Hyperconjugation . involves overlap of the following
H E
orbitals: [lIT 2008]
NOz
(a) a-a 0 (b)a-p
(C)~: (d)~:
0
· (c) p- p 0 (d) 1t-1t 0 . D. 0
178. Mesomeric effect involves the delocalisatian of:
[CET (Karnataka) 2008J 184. Which one of the following carbanions is the least stable?
(a) protons 0 (b) sigma electrons 0 [PET (Kerala) 2008J
(c) pi electrons 0 (d) none of these 0 (a) CH3Clli 0 (b) HC==C 0
179. Which one of the following is most reactive towards (c) (C6HS h C 0 (d) CHJ 0
electrophilic attack? [CBSE (Med.) 2008J
(e) (CH 3 )3 C O.
CI
(a)rg' OH
o (b)© o
185. CH3CH 2CI undergoes homolytic fission produces:
-
(a) CH 3 CH 2 and Ct-
[BCECE (Med.) 2008J
.
0
. +
(b) CH3CH 2 and Ct- 0
. CH20H N02 + -
(C)© o (d)© o
(c)' CH3 CH 2 and Ct- 0
(d) CH3 CH 2 and Ct- 0
186. Tertiary butyl chloride preferably undergo hydrolysis by: .
[CPMT 2008; PMET (punjab) 2008J
180. Which among the following statements are true with (a) SN\ mechanism 0 (b) SN2 mechanism 0
. respect to electronic displacement in a covalent bond? (c) any of (a) and (b) O. (d) none of these . Cl
[PMT (Kerala) 2008J 187. In a S N 2 substitution reaction of the type
(1) Inductive effect operates through a 1t-bond
(2) Resonance effect operates through a a-bond
R-Br + Ct- DMF) R-,-CI + Br-
(3) Inductive effect operates through a a-bond Which one of the following has the highest relative rate?
(4) Resonance effect operates through a 1t-bond [CBSE (Med.) 2008]
(5) Resonance and inductive effects operate through (a) (OH3hC-,-CH2Br 0 (b)CH 3 CH 2B r C l
a-bond (c) CH 3 CH2CH 2Br 0 (d) (CH~)2CH-'-cH2BrCl
(a) 1 and 2 0 (b) 1 and 3 o 188. The correct stability order for the following species is:
0 (d) 2 and 4 o
)llo~ AA~o~ $~
(c) 2 and 3
(e) 3 and 4 .0
·-
181. The stability of carbanions in the following: r II III IV
(i) R-'-c-C e
O
(ii)I'.
.::::,...
e
(iv) R 3 C-,-CH 2
(a) II> IV > I> III
(c) II> I > IV> III
o
o
(b) I>II>III>IV
[lIT 2008)
189. Arrange the carbanions, SET II: The following questions have more than one correct answer(s)
(CH3)3C, CCI 3, (CH3)2CH, C6H sCH2 inorder for each of them.
of their decreasing stability: ' [AIEEE 2009) 197. Compound which shows positive mesomeric effect:
(a) C6HsCH2>CCI3>(CHd3C>(CH3hCH '0 [AMU (Engg.) 2010]
+
(b) (CH3 h CH> CCl 3 > C6H sCH2 > (CH3 h C 0 (a) H2 C=CH--CI 0 (b) C 6HS-N-Me 3 0
(c) CCl 3 > C6HS CH2 >. (CH3 h CH > (CH3 h C ' 0 (c) H2 C=CH--CH 2CI 0 (d) C6Hs --CH=CRCI 0
(d) ,(CH3 h C > (CH3 h CH > C6HS CH2 > CCl 3 0 198. Which of the following are nUcleophile7
190. Which of the following carbocations will be more stable? (a) NH3 0 (b) OH-
(JEE (WB) 2009)
+
(c) R--f>-R 0 (d) AlCl 3 o
(a) Ph 3C+ 0 (b) CH3-CH2 0 199. Which of the following are electrophile?
+ + (a) rn- 0 (b)BF3 o
(c) (CH3 hCH 0 (d) CH 2 =CH-CH2 0
191. Arrange the following free radicals in order of decreasing
(c) NO; 0 (d) AlCl 3 o
stability: (DPMT 2009] 200. Which types of mechanism take place in sec.-halides,
Methyl (I), Vinyl (II), Allyl (III), Benzyl (IV) (CH 3 hCH-X?
(a) I > II > III > IV 0 (b) III > II > I > IV 0 (a) SN' 0 (b) SN2 0
(c} II> I > IV> III 0 (d) IV> III > I > II 0 o (d) None ofthese o
192. Strongest base is: (DCE 2009)
201. Anti-Mark.ownikoff's addition ofHBr can be observed in:
H ••
<aJ 6H
0 (bJ 6 0
(a) propene
(c) but-2-ene
0
0
(b) but-I-eneO'
(d) pent-2-ene
202. 'Which gives nucleophilic addition reactions?
(a) Methanal 0 (b) Ethanal
0
[J
0:
(c) 0
N
o (d)O (c) Propanone 0 (d) Propene 0
203. Acetyl nitrene has been propesed as possible intermediate
in:
(a) Reimer-Tiemann reaction 0
193. The most easily hydrolysed molecule under S N 1 condition (b) Hofmann's rearrangement [j
is: [CET (J&K) 2009) (c) Lossen's rearrangement 0
(a) allyl chloride 0 (b) benzyl chloride 0 (d) Curtius rearrangement 0
(c) ethyl chloride 0 (d) isopropyl chloride 0 204. Carbenes are the reactive intermediates in:
194. Least active electrophile is : (DCE 2009] (a) Carbylamine r e a c t i o n ' 0
(b) ReUtter-Tiemann reaction 0
V
(a) CH3-C-OCH3 0
V
(b) CH 3-C--CI 0
(c) Hofmann's bromarnide reaction
(d) Wittig reaction
0
0
o 0 20~. Which of the statements are correct?
. Following questions consist of an A~sertion (A) and (d) If (A) is incorrect but (R) is correct.
Reason (R). Use the following keys to select an appropriate (e) Ifboth (A) and (R) are incorrect.
answer: 1. (A) SN2 reaction takes place in single, step.
(R) SN2 reaction inv~lves transition state intermediate.
(a) If both (i\) and (R) are correct and (R) is the correct
explanation of (A). ' 2. (A) Ethyl chloride is more reactive than vinyl chloride
(b) Ifboth (A) and (R) art( correct but (R) is not the correct towards nucleophilic sQbstitution reactions.
explanation of (A). (R) Vinyl chloride is +1 electron pushing group.
(c) If (A) is correct but (R) is incorrect. 3. (A) -N0 2 , -CN, -CNO act as ambident ilUcleophiles.
Mechanism of Organic ReaCtions 249
(R) These consist atoms of same period. to. (A) Allyl free radical is.more stable than simple alkyl free
4. (A) Nucleophiles attack the regions of high electron radical.
density. (R) The allyl :tree radical is stabilized by resonance.
(R) Nucleophiles act as Lewis bases. n. (A) Heterolytic fission involves the breaking of a covalent
5. (A) Cation carriers, e.g., H-Br, Cl-OH and Br-Br and bond in such a way that both the electrons ,of the shared
oxidising agents such as 0 3 an<f.R-O--O-R, etc. act pair are carried away by one of the atoms.
as electrophilic reagents. (R) Heterolytic fission occurs readily in polar covalent
(R) Electrophiles ate Lewis acids. bonds.
6. (A) Inductive and electromeric effects require polar nature 12. (A) Tertiary butyl catbanion is more stable than methyl car-
in the molecule. . banion.
(R) Polar nature in inductive effect is a must but not neces- (R) +I effect of the three methyl groups in tertiary butyl
sarily in electromeric effect. carbanion tends to make it more stable than methyl car-
7. (A) Singlet carbenes have opposite spin (antiparallel). banion.
(R) They have a bent structure. 13. (A) In SN2 reactions, complete inversion of configuration
S. (A) Carbenes act as free radicals. . takes place.
(R) Only triplet carbenes act as biradical (divalent free rad- (R) In SNI reactions, retention but not the inversion takes
ical). place.
9. (A) Tertiary carbocations are generally formed more easily 14. (A) In allylic substitution propene gives allyl bromide.
than primary carbocations. (R) NBS is a selective brominating agent and gives substi-
(R) Hyperconjugation as well as inductive effect due to ad- tution at the alpha carbon with respect to the double
ditional alkyl groups stabilize tertiarycarbocations. bond.
I ANSWERS I
OBJECTIVE QUESTIONS
1. (a) 2. (d) 3. (a) 4. (e) 5. (c) 6. (c) 7. (d) 8. (b) . 9. (a) 10. (c)
11. (d) 12. (b) 13. (d) 14. (a) 15. (c) 16. (d) 17. (b) 18. (c) 19. (~) 20. (b)
21. (b) 22. (c) 23. (a) 24. (d) 25. (a) 26. (c) 27. (b) 28. (d) 29. (b) 30. (a)
31. (c) 32. (d) 33. (b) 34. (c) 35. (d) 36. (a) 37. (c) 38. (c) 39. (b) 40. (a)
41. (d) 42. (b) 43. (d) 44. (a) 45. (c) 46. (b) .47. (d) 48. (a) 49. (a) SO. (d)
51. (b) 5Z. (c) 53. (a) 54. (b) 55. (c) , 56. (b) 57. (c) 58. (b) 59. (a) 60. (b)
61. (d) 6Z. (c) 63. (b) 64. (d) 65. (b) 66. (a) 67. (c) 68. (b) 69. (d) 70. (d)
71. (a) 72. (c) 73. (a) 74. (d) 75. (c) 76. (b) 77. (d) 78. (c) 79. (c) 80. (b)
81. (a) 8Z. (b) 83. (d) 84. (a) 85. (a) 86. (c) 87. (a) 88. (d), 89. (c) 90. (a)
91. (b) 9Z. (c) 93. (a) 94. (d) 95. (d) 96. (c) 97. (b) 98. (d) 99. (a) 1110. (d)
101. (c) 10Z. (a,d) 103. (c) 104. (d) 105. (c) 106. (a) 107. (c) 108. (d) 109. (d) 110. (b)
111. (a) 11Z. (a) 113. (b) 114. (a) 115. (a) 116. (a) 117. (c) 118. (b) 119. (d) 120. (b)
121. (a) 122. (a) 123. (a) 124. (c) 125. (b) 126. (d) 127. (d) 128. (c) 129. (c) 130. (b)
131. (c) 132. (b) 133. (b) 134. (a) 135. (a) 136. (d) 137. (b) 138. (a) 139. (b) 140. (b)
141. (a) 14Z. (c) 143. (a) 144. (d) 145. (b) 146. (d) 147. (d) 148. (b) 149. (d) 150. (c)
151. (a) 15Z. (a) 153. (b) 154. (b) 155. (a) 156. (a) 157. (c) 158. (e) 159. (d) 160. (b)
161. (c) 162. (a) 163. (c) 164. (b) 165. (a) 166. (b) 167. (c) 168. (b} 169. (a) 170. (b)
171. (a) 172. (e) 173. (b) 174. (a) 175. (d) . 176. (a) 177. (b) 178. (c) 179. (a) 180. (e)
181. (c) 182. (b) 183. (c) 184. (e) 185. (a) 186. (a) 187. (b) 188. (d) 189. (c) 190. (a)
191. (d) 192. (a) 193. (b) 194. (c) 195. (d) 196. (b) 197. (a,d) 198. (a,b,c) 199. (b,c,d) 200. (a,b,c)
201. (a,b,d) 20Z. (a,b,c) Z03. (b,c,d) 204. (a,b,d) 205. (a,b) 206. (a,b) 207. (b,c) 208. (a,c) 209. (b,c,d) 210. (a,c)
211. (a,c) 212. (a,c,d) Z13. (a,c,d) 214. (a,b,c,d) 215. (b,c) 216. (a,c,d) 217. (a,b,d) 218. (a,d) Z19. (a,b,c)
N~ ¢reI.
,~I
NO z 02~1
~ I
NO z '
,
oCI
I
o CH3 CH3 . ~
I CH3 I N02 NOz
>CH'oCH;
[Ans.
0,0,0,0,0
(I) (n) (llI) (N) (V)
00 OR CH,-CH-CH-CH,
(b) C6 H sCOC 6 H S' CH3 COC6 H5 , CH3 COCH3
,
(d)CH 3-CH=CH-CH3 OR
H3C),
H3C
C=C
<CH3
CH3
. ,)
yyyy
(0) )) CI
(b) CCI 3-(CHz)7-CH3 ]
Cl 1,1,1- Tricblorononane
Mechanism of OrganicReactions
8. Which products will·· be obtained when CCl 4 adds on The strongest acid has the smallest pKa. Therefore, its conjugate
R-CH=CH2? Give the mechanism of fonnation of the base is the weakest and is the best leaving group. Hence, the poten-
products; tial effectiveness of anions as leaving groups (fugacity) decreases
[Ans. R-CH =CH z + CCl 4 ~ R-CHCI-CHz-CCI 3 in the following order:
+ R-CHCI-CH z-rH-CHz-CCI3 CJisSOi > CI 3C-COO- > CH 3COO- > CJIsO- ]
Benzene Trichloro· Acetate anion Phenoxide anion
sulphonate anion acetate anion
R
12. Arrange the following carbocations in increasing order of
Second product is formed due toco~bination of
stability:
R-£H-CH z-C03 and R-rH-£Hz intermediates.]
o
9. Write down the dehydration products of the following
[>-cH-<J [>-c<~:, [>-K1
~a~2YH ~) cY~' (e) (j,OH lAn&C>-c<~: < [>--o>-<J < [>-!-<]I
13. Which of the following is incorrect?
0 VCH, OCR'1 .
[An, <a) (h) (0)
CI·
10. Give the major product of the following electrophilic addi-
~ +HCI o
tion reactions:
CH2CH2CH3
(e)
(f)
exI·
CH3
CH2CH3
~CH=CHCH3 + HB~
+ HBr ---:- ?
_?
o
o
[Ans.
Br
~
I
<e) -. • substitution o
VNH2
(d) none of these
'
o
II VH2 ;, an exocyelie Saytzeffproduet
<a) o Codes:
(a) I, II and III are correct 0
(b) I and II are correct 0
o (c) II and IV are correct 0
<e) ChN-Q--o-1-< )
o
o oo6
(II) (III)
In which cases will NO; be at meta-position?
(IV)
,
Ring 1 is activated (~ f_.')1'-0
o
by group, thus nitra-
(a) I < II < III 0 (b) III < ~ < I
III
0
tion takes place at para-position of the ring 1.]
(c) I = II < III 0 (d) III < I = II 0
D(d)~,
substitution reactions of the following compounds:
o
OO'~&N~
(C)OH!
V
CI + +.
()().+~
~
25. The intermediate during the addition ofHCI to propene in . .+
presence of peroxide is: (C).' . . C1 (d) 0
#' #' ~ #'
G.R.B. Organic Chemistry {or Competitions
U;, ""'"
+
CH3
[BIn" ,.,.Ie.•- ;1 ;, ""....., I o
(c) C6Hs-r-Br
allylic carbonium ion].
CH 3
33. Which of the following is least stable?
(-) (-)
o °I
6
CH2
I
{c)H~
-C-R, . -C-OR, --Ca=N, -N0 2 activates
nucleophilic addition. The order of reactivity of these
0 (d) 0
groups is:
~
rNH3
(a) \, +
000
~-"
I
I .
I I
(b) -C-H>-C-R >-C--,-OR >--O.=N>-N0 2
I
'Br+ + o
O ~.
(c) (~ . ,
NH3
CH 3 (III) (IV)
(a) I < II < III < IV 0 (b) IV < III < II < I 0
(c) IV < II < III < I 0 (d) II < IV < III < I 0
Codes:
(a) I, II, III
(c) III
(b) I, II, IV
(d) II and IV
"·
0
" I
~
+CHCI3 ~
w"~=N
~
0". I
;::?'I~
· " 1 +3HCI
fH 3
(a) True (b) False
4. Following compounds easily give Friedel-Crafts reaction:
(d) CH3 -C-Br
I"
C6 H S
4. Select the correct statements among the following:
(a) carbocation rearrangement takes place in SN 1 reaction
(b) SN2 is a two step reaction
800
256 G.R.B. Organic Chemistry for Competitions
Passage 3
Hyperconjugation describes the orbital interactions between
the n-'systems and the adjacento-bond of the substituent group(s)
in organic compounds. Hyperconjugation is also called as Baker 4. Which of the following alkenes will show maximum num-
and Nathan effect. The necessary and sufficient conditions for the ber of hyperconjugation forms?
hyperconjugation are: (a) H 2C=CH2
(i) Compound should have at least one Sp2 -hybrid carbon of (b) CH3 -:-CH-CH2
either alkene, carbocation or alkyl free radical. (c) CH3-CH2~CH CH2
(ii) a-carbon with respect to Sp2 -hybrid carbon should have CH3
at least one hydrogen, I ,
(d) eHl -CH- CH=CH2
Hypet'COtijugation are of three types:
(i) O'(C-H), n-conjugation, 5. Stability of alkyl carbocations can be explained by:
(ii) O'(C-H); positive charge conjugation, (a) inductive effect
(iii) 0' (C-H); odd electron conjugation. (b) hyperconjugation
The hyperconjugation may be represented as, (c) both inductive effect and hyperconjugation
H (d) electromeric effect
b
H-C-CH
()CH ~
H+_
H-C=CH-CH2 Passage 4
•.
2
,, HI H
I Free radical halogenation takes place in tile presence of light
or at high temperature (above 500°C). Formation of halogen free
H H radical intermediate takes place in first step called chain initiation
I 'I '
~ H+ C-CH-CH2 ~'H-C=CH-CH2
I' .H+ . Cl 2 ~2Cl·
H This reaction is mainly given by those compounds which
Number of resonating structures due to hyperconjugation have at least one hydrogen atom present at Spl -hybrid carbon.
= (n + 1), where n is the number of a-hydrogen. Greater is the
Reactivity of sp3 -hybrid carbon depends on' the reactivitY of
number of such forms, more is the stability of the species under
consideration. reaction intermediate.
The relative rate of formation of alkyl radicals by a chlorine
Answer the following questions: radical is:
1. Hyperconjugation is possible in which of the following Tertiary> Secondary> Primary
species?
(5) (3.8) (1)
(a), CH3-CH2
. ld f th ' .....t.. Relative amount x 100
Percentage yte 0 e pruuuct = - - - - - - - -
Sum of relative amounts
Relative amount = Number of hydrogen atoms on
the respective carbon x relative reactivity.
NBS (N-bromosuccinimide) is used for bromination at
2. Which of the following carbocations will show highest allylic and benzylic carbon, whereas Br21hv gives bromination at
number ,of hyperconjugative forms? benzylic, allylic and alkyl carbons.
+ ,+
(a) CH3 -CH 2 (b) CH3 -CH Answer the following questions:
I 1. Select most reactive compound for chlorination in presence
CH3 of light:
(b)
3. Which of the following free radicals will not show the phe-
nomena of hyperconjugation?
Mechanism of OrganiC Reactions
Passage 5
The electronic displacements in, covalent bonds may occur
either in the ground state Under the influence of an .atom. or a
(c) substituent group or in· presence .of .an· appropriate·· attacking
reagent. As .aresuIt of these electron diSplacements,· centres of
2. Chlorination of butane takes place as; different electron densities are created and these centres are
susceptible to attack by the reagents. These electron
3
CH 3-CHz -CHz -CH +Cl z L:~: displacements occur through inductive electromeric, resonance
and hyperconjugation effects. Whereas inductive effect involves
CI displacement of O'-electrons towards the substituent, resonance
I effect mvolves delocalization. of 1t-electrons transmitted through.
CH 3 -CH-CHz -CH3 + CH3 -CHz-CHz -CH z -Cl the chain and both are permanent effects. Electromeric effect is
2-Chlorobutane l-Chlorobutane the complete transfer of a shared pair of 1t-electrons to one ofthe
atoms joined by a multiple bond on the demand of an attacking
Percentage yield of 2-chlorobutane will be: reagent. Hyperconjugation effects on the other hand involve
(a) ~ x 100 (b) 21 x 100 delocalization of cr-electrons of C-H bond of an alkyl group
21 21 directly attached to an atom of unsaturated system (i.e.,
6 ·3' O'-1t-conjugation). Both inductive and hyperconjugation effects
(c) - x 100 (d) -x 100
21 21 can be used to explain the stability of carbocations and free
3. Which one of the following compounds will react with radicals which follow the stability order: 3° > 2° > 1°. The stability
NBS? of carbanions, however, follows the reverse order.
An organic reaction occurs through making and breaking of
bonds. The breaking of a covalent bond may occur either
homolytic leading to the formation of free radicals or heterolytic
forming positively (carbocations) or negatively (carbanions)
charged species. Most of the attacking reagents carry either a .
positive or a negative charge. The positively charged species
with electron deficient centre or neutral species (free radicals,
carbenes,nitrene) are collectively called electrophiles, while'
negatively charged species with electron rich centre or neutral
species (like· water, alcohol, .ammonia, etc.) are called
nucleophiles.
Answer the following questions:
1. Which of the following groups has highest inductive
effect?
4. Arrange decreasing order of reactivity of given compounds (a) CH 3 - (b) CH3 CH 2
with NBS (N.bromosuccinimide). (c) (CH 3 hCH- (d) (CH3hG-
I. C6HS-€H3 2. The decreasing order of basic strength in
II. C6HS -CHz -CHi ,-CH3 . C6H 5NH Z ' (C 6 H ShNH, CH3 NHZ ' NB3
III. C6HS -CH z -CH CHz (I) (II) (III) (IV)
IV. C 6 Hs -CH:-CH=CHz is:
. I (a) (IV)::> (III) > (II) > (I) (b) (I) > (II) > (III) > (IV)
CH3
(c) (III) > (IV) > (I) > (II) (d) (II) > (1) > (III) > (IV)
Select the correct answer from the codes given below: 3. Out of the following series, the one containing only
Codes: electrophiles is:
(a) IV, III, I, II (b) IV, III, II, I (a) H 20, CI+ ,NH3 (b) H 2 0,RNH 2 ,H3 0+
(c) I, II, III, IV (d) I, III, II, IV . (c) BF3 ,S03,NO; (d) AlCI 3 ,NH3 ,H2 0
5. Chlorinating agent for free radical chlorination may be
taken as: 4. Consider the following alkenes and what is correct decreas-
ing order of stability?
(a) Cl z (b) S02Clz
CH 3 CH2 CH . CHi, (CH 3 h C=C(CH3 h,
(c) (CH 3 hC-O-CI (d) PCls
But-l-ene 2,3-Dimethy~ but-2-ene
(I) (II)
G.R.B. Organic Chemistry fOr Competitions
,
(CH 3 )~ C CHCH3 , (CH3 )2 C=CH2 S. Which of the following is most stable cation?
2-Methyl but-2-ene 2-Methyl propene + +
(a) (CH3)2CH ;,;(b) CH3
1111) (IV)
(a) (I) > (n) > (III) > (IV) (b) (II) > (III) > (IV) > (I) + +"
(c) CF3 (d) F3 C-CH Z
(c) (N) > (Ill) > (n) > (I) (d) (ill) > (IV) > (I) > (II)
(CET (J&K) 2004]
. ,I"
"
H+H
H
(~) (~)
Neo-pentane
tetrahedron is an equilateral triangle and has three hydrogen (2,2-Dimethylpropane)
atoms. (3)
Fig. 6.1 (b) is the Wedge and Dasb representation (three
dimensional, 3-D) in which the solid wedge (....) or a thick
solid (or heavy) line is used to indicate a bond projecting
,above the, plane of the paper and projecting towards the
(+)
observer. The dashed wedge (""11111) or a dashed line is used to Greater the branching greater the stability; so increasing
represent a bond lying below the plane of the paper and , order of stability is: n-pentane < is0 pentane < neo-pentane.
8
projecting away from the observer. The bondS lyitig in the Hexanes:
plane of the paper are shown by a n9rmal (ordinary) line. As'
this representation describes the actual positions of various y
atoms present in the molecule in space, it is termed a spatial C--C-C--C-C--C; C-C-C-C-C;
fonnula. " " n-Hexane 2-Methylpentane
Fig. 6.1 (c) is the two-dimensional (2 D) representation of a'
8 (I) (2)
methane molecule. This is called II'8Pbie or displayed fonnula. C C C C
,This fonnula doesIiot reveal the true tetrahedral geometry of the .
molecule; however, this' is most commonly used (Fischer
I I I I
C-C-C--C--:C; C~C4-C ; C-C--C--C
Projeetlon Formuta). 3-Methylpentane 2,3-Dimethylbutane
(3) C (5)
6.3 STRUCTURAL ISOMERISM IN ALKANES 2,2-Dimethylbutane
Abes exhibit chain isomerism. The first three members, (4)
viz., methane, ethane and propane do not exhibit isomerism as
they can be represented by only one structural formula. 6.4 NATURAL SOURCES (OCCURRENCE).
H H H ' H 'H H OF ALKANES
H~C-H
I r I
H-C-C-H H-C-C-C-H
I I I Two main sources of alkanes are:
(a) Petroleum and (b) Natural gas.
II I I I I Petroleum contains ' large quantities of liquid
H H H H H H hydrocarbons along with little solid paraffin wax dissolved in
Methane Etbarie Propane
it. It is the main source of alkanes containing upto 40 carbon
Howev.er, propane consists of two types of carbon atoms; atoms.
primary and secondary. If hydrogen of primary carbon or Natural gas contains mainly lower alkanes. Ii cOntains
secondary carbon is replaced by a methyl group, two possible about ,80% methane, 10% ethane and the 'remaining 10%
structures result. being a mixture of higher members. It also consists 'of small
Replacement of r- Primary 1, Replacement of amounts of hydrogen, nitrogen, carbon' dioxide, etc.
primary hydrogen I secondary hydrogen
with meth.....--_y_Igro~up-,-~--,CH3-rH2-CH3 with methyl group "
',The natural wax, called ozokerite, found near petroleum
wells, is a mixture ofhigber ,solid hydrocarbons. Bee's wax"
Secondary, ~"---:--~---'I
which is mainly myricyl palmitate (an ester), also contains
(Propane) • small quantities of C 27H s6 and C 3l H 64 • Fuel gas obtained
CH 3 from coal contains about 32% methane. Methane (Marsb gas)
I is found at marshy places where it is formed by the
CI:I3CH2CH2CH3 CHj-CH~i decomposition of vegetable and animal waste with bacteria.
n-Butane , Isobutane
(2-Methylpropane) 6.5 GENERAL METHODS OF PREPARATION
preferred for the preparation of alkanes in pure fonn. It is one (a) Zinc' and dilute hydrochloric acid,
of the characteristics of a homologous series that various (b) .Zinc and acetic acid; Zn and NaOH, .
memhers can be prepared by similar methods. The similar' (c) Zinc-copper couple in ethanol, ..
methods are tenned as general methods of preparation of a (d) Red phosphorus and hydrogen iodide,
(e) AI-Hg in ethanol.
particular homologous series. The general methods of .
preparation of the alkanes are given below: Zn + HCI
CH 31 +2H . ) CH 4 +HI
1.. By hydrogenation of unsaturated hydrocarbons: Methyl iodide or Zn-Cu/C2H s OH Methane
Alkanes. are obtained by hydrogenation of unsafurated
.hydrocarbons (alkenes and alkynes) in presence of finely C 2H SI +2H. Zn + HCI .) C 2H 6 + HI
divided nickel *at 200-300°C. This is known as Sabatier and Ethyl iodide or Zn-Cu/~HSOH Ethane
Senderen's reaction. .' . + 2+ .
CH3CH 2CH 2Br + Zn + H . ~ CH3CH 2CH 3 + Zn + Br-
Ni or Raney Ni I-Bromopropane Propane
C n H 2n + H2 H ) C n H2n+2
Alkene eat Alkane . 150°C .
3C2HSI +3HI ) 3C 2H 6 +31 2
+2H NiorPtorP1
C n H 2n-2 2 Heat C nH2n+2 2P+31 2 .~ ~P13
Alkyne Alkane
3C 2HsI +3HI + 2P ~ 3C 2 H 6 +2P1 3
Ni Ethyl iodide . (lled) Ethane
H 2C=CH 2 + H2 ) H3C-CH 3
Ethene 200°C Ethane . . RedP ,
CH 3CH 2Br +2HI 1500C) CH3CH 3 + HBr +12
Ethyl bromide Ethane
The purpose of use Qf red phosphorus is to remove iodine.
Alkyl halides may. also be reduced catalytically by
HC==CH+2H 2 hydrogen using catalysts like nickel, palladium, platinum. etc.
Ethyne . . Pd
(Acetylene) . R-X+H2 ~ R-H+HX
When platinum, palladium. rhodium, ruthenium or B2H6 Primary and secondary alkyl halides may 't!e conveniently
in THF are used as catalysts, the hydrogenation takes place at reduced with lithium alUJ)liniUnl hydride in a dry organic
room temperature. Catalytic hydrogenation proceeds very solvent
smoothly and quantitatively. Organic
Transfer hydrogenation: The hydrogen is supplied by .. ~RX + LiAlH4 solvent) 4RH + LiA1X 4 (LiX + AlX 3)
a donor such as cyclohexene or hydrazine. LiAlH4 is not . useful for 3° alkyl halide which is
2~>C=C<~+ 0
Cyclohexene
Pd converted into alkenes. In such cases NaBH4 or TPH is used.
CH 3
H 3C-C-CH3
I
'
LiAlH
CH 3
4) H 3C-C=CH 2
I
I· 2-MethyJpropene
R>
2R CH-CH <RR+ 0:,...-1
-..;:,...
.+-cl
Cl
NaB14.. . >- .
Benzene 3° 2-Methylpropane
The driving force in the case of cyclohexene is the gain in Alkyl halides (10, 2°, 3°) can also be ~uced to alkanes
aromatic stabilization energy when benzene is fonned. With with TPH (Triphenyl tin hydride, Ph3SnH)."
hydrazine (H2 N-NH 2), the strongly bonded N 2 molecule is 3 •. By Wurtz reaction: This methOd was discovered
fonned. . by the French chemist Wurtz in 1855 and is very convenient
Limitation :.' No unsaturated hydrocarbon contains only for preparing paraffins of high molecular mass. .
one carbon atom, hence this method cannot be used for the An ether solution of an alkyl halide is treated with sodium
preparation of methane. which retnoves the halogen ofalkylhillide and the two alkyl
2. By the reduction of alkyl halides :. Alkyl halides radicals join' together to fomi an alkane.
undergo reduction with nascent hydrogen to form alkanes.
RiX +2H ~ R-H -+ HX R fX---+-2N;a-+-~--X:R .
l _____________________ I Dry ether) R-R +2NaX
Alkyl halide Alkane Alkyl halide Alkyl halide Alkane
The yields are generally good and. the hydrocarbons ----------------, Dry ether
obtained are pure. The nascent hydrogen for reduction may be
_
CH3l! __ .:!:11i~ _±"__ !JCH3 . ) CH r ---CH 3+2NaI
Methyl iodide Methyl iodide Ethane
obtained by using·any one of the following:
*Raneynickel is often used as an effective catalyst at room temperature and atmospberic pressure. It is obtained by boiling Ni-AJ al.loy with NaOH,
wbenaluminium dissolves leaving'nickelin finally divided state. It is filtered, washed, dried and stored under H 20 or <;HsOH.
. G.R.B. Organic Chemistry (Or Competitions
Note: Alkyl bromides :and iodides are preferred in this reaction. The c2H5i!-~-_-i..-~~_~_~-_Ilc2Hs ~. C 2H S-C 2Hs +ZnI2 .
net result in this reaction is the formation of symmetrical alkane Ethyl iodide Ethyl iodide Butane
(R-R) having an even number of carbon atoms.
Methane cannot be prepared by this method. When two
When a mixture of two different alkyl halides is used, a different alkyl halides are used, a mixture of three alkanes is
mixture of three alkanes is obtained. obtained as in Wurtz reaction.
Dry Ether S. By decarboxylation of carboxylic acid (Laboratory
CH3Br + 2Na + BrC 2H s ) CH 3-C2H s method): When the sodium salt of a fatty acid is heated at
Methyl bromide Ethyl bromide Propane 360°C with sodalime (mixture ofNaOH and CaO), a molecule
+2NaBr of carbon dioxide is eliminated as carbonate and an alkane is
Dry Ether formed.
CH3Br +2Na + BrCH 3 ) CH 3 -CH 3 +2NaBr ----------------, II t
Ethane R:COONa + NaO:H ~
----------------. CaO R-H
Alkane + Na2C03
Dry Ether
C2HSBr +2Na + BrC2HS ) C2HS-C2Hs +2NaBr CH 3COONa + NaOH Heat) CH 4 + Na2C03
Butane Sodium acetate CaO Methane
The separation of the mixture into individual members is
However, pure methane can be obtained if barium oxide is
not always easy. Thus, Wurtz reaction is not suitable for the
used in place of sodalime.
synthesis of alkanes containing odd number of carbon
atoms but the method is useful for the preparation of C 2H sCOONa +NaOH H~) C 2H 6 + Na2C03
symmetrical alkanes. . Sodium propionate Ca Ethane
Mechanism : The mechanism of Wurtz reaction is not The purpose of CaO in sodalime is to keep NaOH dry
fully understoOd. Two mechanisms are proposed for this since it is quite hygroscopic in nature.
reaction. , In this process, one molecule of carbon dioxide is
(a) Intermediate formation of an organometallic eliminated from a carboxylic acid and hence called
compound: decarboxyla1i:on. .
- +
RX +2Na ~ [RNa] +NaX A good yield of alkanes has also been obtained from the
/'\ /"), Intermediate photochemical decarboxylation of primary carboxylic acids
by lead tetraacetate in chloroform.
RNa+RIi+-1X~- ~R-R +NaX'
Alkane R,..-COOH Pb(OAc)4) R-H + CO
2
(b) Intermediate formation of free radicals : CIICl3Alkane
• Note: The alkane formed always contains one carbon atom less than
RX +Na ~ [R] +NaX the original acid. The yield is usually good in the case of lower
Free radical members but poor for higher members. The method is used for
• • reducing the carbon atoms in the carbon chain.
R+R~ R-R
Alkane 6. By electrolysis of sodium or potassium salts of fatty
. Other hydrocarbons are also obtained as a result of acids ,(Kolbe's method or Kolbe'S electrolysis):
disproporUonation, i.e., intermolecular hydrogenation of free Electrolysis of a concentrated aqueous solution of' either
radicals. .. sodium or potassium salts of saturated monocarboxylic acids .
e.g., C 2H; +C 2H; ~ C 2H 6 +C 2H 4 yiel~ higber alkanes at anode.
I Reduction j 2RCOOK + 2H 20
Electrolysis .
) R-R + 2C0 2 + 2KOH + H2
Oxidation 2CH 3COOK + 2H 20 ~ CH 3-CH3 + 2C0 2 + 2KOH
Wurtz r:eaction is useful in ascending the series of organic Potassium acetate . Ethane + H2
compounds, because it leads to the formation of carbon-
carbon bond. For example, methane can be converted jnto
ethane. Potassium
CH 4 +CI 2 ~ CH 3CI + HCI propionate
CH 3CI+2Na+CICH 3 ~ CH 3 -CH3 +2NaCl . In the electrolysis of potassium propionate, small amounts
Limitations: (i) Methane cannot be obtained by this of ethane, ethene and ethyl propionate are also formed.
method. Mechanism: The formation of alkane follows :free
(ii) The reaction fails with tert. alkyl halides. radical mechanism.
, (iii) The reaction is suitable for symmetrical alkanes CH 3COONa ~ CH 3COO- + Na +
(even, number of carbon atoms). J, J,
. 4. Jly Frankland's reaction: The method is similar to Anode Cathode
Wurtz reaction. The alkyl halide is heated with zinc in i~ert . At anode:
solvent, higher alkane is formed. •
2CH 3COO- 2CH 3COO + 2e-.
~
Ether Acetate free radical
RXi:Zn+XR ) R-R+ZnX2
AI.kaD.e 2CH3COO ~ 2CH3 + 2C0 2i
Methyl free radical
Saturated Aliphatic Hydrocarbons 263
<
NH 2
At cathode: RH +Mg
2Na + + 2e- ~ 2Na" Alkane X
2Na+2H 20 ~ 2NaOH+H 2
If mixture of two salts Rl COOK and R 2COOK are taken
then hydrocarbons R1-R 1, R2-R 2 are also obtained. Esters,
lower alkanes and alkenes are also obtained as side products.
C 2H sCOONa ~ C 2H sCOO- +Na+
C 2H sCOO- ~
•
C 2H sCOO + e-
•
C 2H sCOO+C 2H s
•
~ C 2H sCOOC 2H s
"Ester
• •
C 2 H S +C 2H S ~C2H6 +C 2 H 4 This method gives quantitative yield of alkane (pure).
"" I Reduction t "
. "<I
<
Oxidation
:~;B;:iH]C=C-CH3 ~ C 2 H6 + Mg .
Note: (i) This method is applicable for the preparation of only Mg . . Propyne Ethane ();:;eG-CH3
symmetrical alkanes of the type R"'-'-R I .
(ii) Methane cannot be prepared by this method. "
7. From Grignard reagents:" Alkyl magnesiUm
halides (RMgX") are called Grignard reagents. These undergo
double decomposition reactions with water or ammonia or
alcohol or amines having active H atom (attached to strongly
electronegative 0, N, S or F and triple bond "..., etc.) to give 8. By reduction of alcohols, aldehydes, ketones or
alkane corresponding to alkyl (R -) group of Grignard reagent. fatty acids and their derivatives: Alkanes are formed
Since, carbon is more electronegative (electronegativity = 2.5) when alcohols, aldehydes, ketones or fatty acids and their
than magnesium" (electronegativity 1.2), therefore, C-Mg derivatives are reduced with hot cone. hydroiodic acid and red
bond is quite polar. . " " phosphorus at 150-200°C. in a sealed tube. Phosphorus and
[ RX" + Mg Dry ether) R--:Mg-X] iodine react to form PI 3 which again produces" m.
Alkyl halide Alkyl mag. halide
RedP
+ "<OH CH 30H +2m 150"C) CH 4 + H 20 +12
RMgX" +HOH ~ R-H+Mg Methyl alcohol Methane
Grignard reagent Alkane X
RedP
CH 3CHO +4m 1500C) C 2H 6 + H 20 +212
<:
OH Acetaldehyde Ethane
H+
" C2HsMgBr +HOH ~ C2HSH+Mg RedP . "
Ethyl magnesium " Ethane r CH 3COCH 3 + 4m 150"C) CH 3CH 2CH 3 + H 20 + 212
bromide Acetone Propane
If heavy water, D 20 is used, then the product formed is RedP
RD, deutero alkane. " OD' " CH 3COOH + 6m 200"C) CH 3---CH 3 +2H 20 + 31 2
Acetic acid Ethane .
R-MgX+D 2 0 ~ R-D +Mg<
Deuteroalkane X
. ~ + DOD
~MgI •
. Br .
CH3MgBr . + HOC 2H s ~CH3H + Mg<
Methyl magnesium Ethanol Methane OC H
bromide 2 5 Higher fatty acids undergo reduction more readily as
I compared to the lower ones. This method is thus, useful for
C2HsMgI+HSCzHs ~ CzHsH+Mg<' the preparation of higher allqmes. However, the yield is
Ethanthiol Ethane SC 2 H S " usually poor.
G.R.B. Organic Chemistry (or Competitions
Aldehydes and ketones when reduced with amalgamated zinc and cone. HCI also yield alkanes. This process is known as
Clemmensen reduction. . .
> C--:-O
Zn-Hg
)
> .
CH z
Conc. HCI
Zn-Hg
CH 3CHQ + 2H z ) CH 3-CH 3 + HzO
Acetaldehyde Cone. HCI Ethane
Zn-Hg
CH 3COCH 3 +2H z ' ) CH 3CH zCH 3 + HzO
Acetone Cone. HCI Propane
. Aldehydes and ketones ()c=O) can be reduced to hydrocarbons in presence of excess ofhYdrazine and sodium alkoxide on
10. Corey-House alkane synthesis: An alkyl halide is first converted into lithium alkyl which reacts with cuprous iodide
to form lithium dialkyl cuprate, LiR 2Cu. It is then treated with an alkyl halide to give an alkane.
Dry ether
(i) CH3Br +2Li ) CH3Li + LiBr
Methyl lithium
(ii) 2CH 3Li + CuI ~ Li(CH3 hCu + LiI/
Lithium dimethyl .
cuprate
(iii) C 2H SBr + Li(CH3 hCu ~C2Hs-CH3 +CH 3Cu + LiBr
Ethyl bromide Propane
Saturated Aliphatic Hydrocarbons .265
For the third step to give a good yield of alkane, the alkyl Physical Constants of Some Alkanes
halide must be either CH 3 X, or a primary alkyl halide or a
secondary cycloalkyl halide. The alkyl group of the lithium
dialkyl cuprate (also called Gilman reagent) may be methyl
1°,2° or 3°. Moreover, the two alkyl groups being coupled Methane CH4 -161.5 -182.5 0.4240
need not to be different.
This method is particularly suitable for the preparation of Ethane CH3CH3 -88.6 -172.0 0.5462
unsymmetrical alkanes of the type, R -R' (via SN 2 mechanism). Propane CH3CH2CH3 '-42~1 -187.7 0.5824
n-Butane CH 3(CH 2)2 CH3 ~0.5 -138.4 0.5788
(CH3hCHBr ?~~) [(CH 3 hCHhLiCu
n-Pentane CH3(CH2)3 CH3 36.1 -129.7 0.6264
Isopropyl bromide \11 Lithium isopropyl cuprate
n-Hexane CH3 (CH2 )4 CH 3 68.7 -95.3 0.6594
CH3~H2Br) (CH 3 hCH-CH 2CH 3
2-Methylbutatie For example, the following boiling point values of
various isomers of butane and pentane justify the above
11. By tbe action of water (or dil. HCI) an aluminium statement.
and beryllium carbide: Both these carbides on treatment
with water or dilute HCI at room temperature yield methane. n-Butane > Isobutane
b.pt.
Al 4C 3 + 12H 20 ~ 3CH 4 + 4Al(OHh
n-Pentane > Isopentane > Neopentane
Be2C +4H20~ CH 4 +2Be(OHh
Beryllium carbide Methane b.pt. 36.1"C 28°C9.5"C
The trend in boiling points can be explained in terms of
12. Industrial preparation: Methane is formed by
intermolecular (dipole-dipole) forces of attraction. These
passing a mixture of hydrogen sulphide and carbon disulphide
forces 'act along the surface of the molecules and their
vapours through red hot copper tube.
magnitude increases with increase· in surface area. As the
CS +2H 2S +8Cu Hightemperatur\ CH +4Cu 2S molecular size increases in the series, ·the surface area
2 4 increases and with that the boiling points also increase. This
has been depicted in Fig. 6.2.
6.6 GENERAL CHARACTERISTICS OF The n-alkanes have most extended structure and larger
ALKANES . surface area in comparison to .branched chain isomers having
Physical: The physical properties (boiling point, melting compact structure (as the shape approaches that of a sphere in
point, solubility, density, etc.) of hydrocarbons depend upon the branched chain isomers). Thus, intermolecular forces are
the intermolecular forces of attraction. Since alkanes are weaker in branched chain isomers, therefore, they have lower
almost non-polar and therefore, their molecules are held only boiling points in comparison to straight chain isomers.
........-
by weak van der Waals 'forces which mainly depend upon the
size (surface area) and the structure of the molecule.
(i) State: Due to weak forces, the alkanes upto four
carbon atoms, i.e., methane, ethane, propane and butane are
P
c
300
reagents such as acids, alkalies, oXIdising and reducing CH 3 -C-H ~ CH 3\C+H·; AH==96kcalimol
agents, etc., at ordinary conditions because of their saturated I H7
character. The electronegativity difference between carbon H
(2.6) and hydrogen (2.1) is small and thus,C-H bond is
almost non-polar. The C--C bond' is completely non-polar. i H
CH 3
AH~93k<:a1/mol
3 •
Therefore, the polar reagents (electrophiles and nucleophiles)
do not find reaction sites (electron-rich or, electron-deficient CH'TH ---> CH,jc+H O
;
centres) on alkane molecules. The C--C and C-H bonds are CH ' CH 3
strong sigma bonds and cannot break under ordinary 3
conditions. At high temperature, energies of collisions are Bond energy for extraction of hydrogen lies in:following
sqfficient for breaking C-H and C--C bonds resulting the sequence.
formation of free radicals. CH~ > 1° > 2° > j 0; hence, the reactivity order will be
• • CH 4 <1°<2°<3°.
RCHz-H ~ RCH z +H
On the basis of relative reactivity of different types of
and stability of free radicals is in the order: hydrogen, the percentage of the products in mixture can be
•• • • • calculated, e.g., '
H zC"":"'CH<CH 3 <CH 3 CH z < (CH 3 h CH<(CH 3 hC (A) CH~Hr-CHz--2-CH2CI
, / Relative amoUnt'" No. of equivalent
« . ) CH2 - H2C=CH-CHz , hydrogen x reactivity
CH3--CH2-CHr-CH3 , 6x 1 6
Hdwever, alkanes do show some reactions under special (It has 6 primary hydrogen \ ' Cl
conditions. Some of the importan.t reactions of alkanes are and 4 secondary hydrogen) I
described below: ' (B) CH3--CH--CH2--CH3
1. Substitution reactions: These are most characteri- Relative amount"" No. of equivalent
stic reactions of the alkanes. hydrogen x reactivity
"'4x3.8 15.2
<a) Halogenation: When the alkanes are treated with
halogens (particularly chlorine or bromine) in presence of Total amount = 6+ 15.2= 21.2
light (sunlight or UV) or at elevated temperatures 250-400°C, . 6
the hydrogen atoms of alkanes are successively replaced by % of A = - x 100= 28.3'
. 21.2 '
halogen atoms. This process is known as halogenation. The 15.2
extent of halogenation depends on ,the amount of halogen %0f B =--x 100= 71.7
used. For example, methane undergoes chlori~ation in excess 21.2
of chlorine in presence of UV light giving the mixture of Note: The relative reactivity of 10 ,20 ,3° hydrogen to bromination is
methyl chloride, methylene chloride, chloroform and carbon 1 : 82 : 1600.
tetrachloride.. ,.- Ethane and higher alkanes react with chlorine in a similar
way and all possible substitution products are obtained.
However, propane and higher members contain hydrogen
Saturated Aliphatic Hydrocarbons ,.267
atoms of two or three types, i. e., primary, secondary or tertiary, (vi) Small amount of oxygen slow down the reaction for
which aiffer in reactivity. The order of reactivity is: a period of time, which depends upon the amount of oxygen.
Tert. hydrogen> Sec. hydrogen> Primary hydrogen Oxygen is believed to react with methyl free radical to form
Propane gives two monochloro substituted products on less reactive free radical.
chlorination. • •
CH 3 +0 2 ---7 CH 3-O-O
CH3CH2CH2CI
I-Chloropropane . Here, oxygen acts as inhibitor.
CH CH CH Ch (primary hydrogen is substituted) 45% (b) Nitration: Nitration is a substitution reaction in
3 2 3 which a hydrogen atom of alkane is replaced by nitro (-:-N0 2 )
Propane CI ' group.
{
I High
. CHr -CH-CH 3 R-H+HON0 2 ) R-N0 2 + H 20
2-Chloropropane Alkane (Fuming) temp. Nitroalkane
(secondary hydrogen is substituted) 55% Lower members do not react with concentrated nitric acid
The bromination proceeds in almost identical manner but at ordinary temperatures but long chain members on heating
the reaction is less vigorous than chlorination. Reaction with with fuming nitric acid yield nitroalkanes.
fluorine is very violent. Iodine does substitute as the reaction 400°C
is very slow and reversible but iodination can occur in C 6 H 13-:- H + HON0 2 ) C 6 H 13 N0 2 + H 20
n-Hexane (Fuming) Nitrohexane
presence of an oxidising agent such as iodic acid or nitric acid,
etc.; which decomposes HI into iodine. . However, when a mixture of vapours of an alkane and
nitric acid is heated at 400 500°C, nitroalkane is formed
CH 4 + 12 ~ CH3I + HI (reducing agent) readily..Jhis is known as vapour pbase nitration. By this
Heat process lower as well as higher alkanes can be converted into
5HI + HI0 3 ) 31 2 + 3H 20 nitroalkanes.
or 2HI+2lIN0 3 ~ 2N0 2 +2H 20+I 2 450°C
Halogenation of alkanes proceeds through free radical CH 3 H + HON0 2 ) CH 3 -N0 2 + H 20
~ Vi I Nitromethane
mechanism (See Chapter 5). Vapour state
Note: (i) Fluorination can be achieved without violence when alkane In alkanes having two or more carbon atoms, there is
is treated with fluorine diluted with an inert gas or by the always a possibility that the C-C bonds may break at high
action of inorganic· fluorides su~h as AsF), SbF) , AgF, HgF2 temperatures and a mixture of nitro alkanes is formed. For
or Hg2F2 etc. on bromo or iodo derivatives. example, in the nitration of propane, the following products
2C2HsI + HgF2 ~ 2C2HSF + Hgl2 are obtained: ' .
2CH)CH 2CI + Hg2F2 ~ 2CH)CH2F + Hg2CI 2 N0 2
Fluoroethane HN0 3 (f) I
4500C) CH 3CH 2CH 2N0 2 + CH 3 CHCH 3
This reaction is called Swarts reaction.
I-Nitropropane 2-Nitropropane
(ii) Iodo compounds are obtained by treating chIoro or bromo (25%) (40%)
derivatives with sodium iodide (concentrated. solution in .
+C 2H sN0 2 + CHiN02
acetone); It is a halide exchange reaction. (Finkelstein
Nitroetbane Nitromethane
~action). .
(10010)
Acetone . Similarly,
C2HSBr + Nal l ~HsI + NaBr
(Excess) . HN03
CH 3CH 2CH 2CH 3 ) CH3CH2CH2CH2N02
Points to remember: (i) Relative reactivities of n-Butane 450°C ..
halogens on alkanes follow the following order:
+CH 3 -CH-CH 2CH 3 +CH 3CH 2CH 2N0 2 +CH 3CHCH 3
F2 >C1 2 > Br2 > 12
The reactivity decreases with decrease· in the electro-
I . I
negativity of the halogens. . . N02 N02
(ii) The replacement of hydrogen atom by halogen +CH 3CH 2N0 2 +CH 3N0 2
follows the following order. • . Higher alkanes yield even more complex mixtures.
Tertiary hydrogen > Secondary hydrogen> Primary hydrogen Alkanes containing neo;.skeleton are easily oxidised with
> Methane H lIN0 3 to form carboxylic acids and no nitro compounds,
(iii) Halogenation takes place in presence of sunlight, UV
light or in dark at high temperatures (250- 400°.c). The CH3
I
3Y-· 3
reaction may be initiated by peroxide (dibenzoyl peroxide).
(iv) Laboratory chlorination of alkanes is often done with CH CH +40 2 -~2CH3COOH+C02 +2H 20
S02Cl2 (Sulphuryl chloride), instead of CJ.2 ana an organic
peroxide, ROOR is used as an initiator. CH 3
(v) Tetra-ethyl lead, Pb(C2Hs )4' initiates the Nco-pentane
chlorination of methane in the dark at 150°C..
•
268 G.R.B. Organic Chemistryfor Competitions
Nitration like halogenation also follows free radital (ii) Reaction with steam: Methane reacts with steam
mechanism. over nickel suspended on alumina at 1073 K, hydrogen gas is
formed with carbon monoxide.
Ni/Al 20 3
• • CH 4 + H 20 ) CO+3H 2
C 3H 7 -H+HO ~ C3H7 +H 20 Steam 1073K
Propane
• • (c) Catalytic oxidation: Lower alkanes undergo
C 3H7 + N0 2 ~ C 3 H 7N0 2 restricted oxidation in presence of metallic catalysts such as
. (c) Sulphonation: The replacement of hydrogen atom copper at high tempemture and pressure to form alcohols,
by sulphonic acid group (-SO 3H) is known as sulphonation. aldehydes, ketones and acids.
Lower alkanes do not undergo sulphonation but higher (i) When methane and oxygen mixed in the mtio of 9 : 1
members (from hexane onwards) are sulphonated slowly are compressed to 100 atmospheres and passed through
when treated with fuming sulphuric acid (oleum) at about copper tilbe at 200°C, methyl alcohol is formed,
400°C.
Cu-tube
so 2CH 4 + [Oh ) 2CH 30H
R-H+HOSO H 3, ) R-S03H +H 20 9 : 1 100 atm1200°C
Alkane 3 Prolonged heating Alkane
sulphonic acid (This is the industrial method for the manufacture of
S03 methyl alcohol.)
C 6HI3-H + HOS0 3 H ) C6H13S03H + H 20 (ii) When a mixture of methane and oxygen is passed over
Hexane . Hexane sulpbonic acid heated molybdenum oxide under pressure or in air at 543 K, it
However, lower members such as propane, butane, pentane, is oxidised to formaldehyde.
etc., react with S03 in vapour phase to form sulphonic acids.
Ease of replacement of H atoms is: Cf!:4 + O 2 MoO ) HCHO + H 20
3° >2° >1° Methane 543 K. 100 attn. Formaldehyde
Sulphonation also follows free mdical mechanism.
Higher alkanes are oxidised to carboxylic acids in
HOSO H
3
400°C)
HomolytlC
' f lSSlon
'
HO + SO 3 H presence of manganese steamte or silver oxide.
O2
• • IOo-160 0 C) CH3(CH2)nCOOH
C 6H!3-H + OH ~ C 6H l3 + H 20
H
C 6 13 + S03H ~ C 6HI3S03 H
AgzO
2. Oxidation: Oxidation of alkanes gives different 2R-CH3 +3[Oh ) 2R-COOH + 2H 20
products under different conditions. Heat
(a) Conibustion or. complete oxidation: Alkanes The controlled partial oxidation of m~thane at 1773 K·
readily bum with non-luminous flame in excess of air or yields acetylene.
oxygen to form carbon dioxide and water. The combustion of
alkanes is an exothermic reaction, i. e., large quantity of heat is 6CH 4 + 20 2. 1773 K) 2HC=::CH+
.2 + lOH i
2eO 2
evolved and heat of combustion increases with molecular Ethyne
weight. It forms the basis of the use of alkanes as fuel in the
(d) Chemical oxidation: Alkanes are usually not
internal combustion engines. The cooking gas, which is often
affected by oxidising agents like KMn0 4 or K2Cr207'
called LPG (Liquefied Petroleum Gas) is a mixture of However, alkanes having tertiary hydrogen are oxidised by
propane and butane .. these oxidising agents to the corresponding alcohols.
Cn H 2n +2 + (3n +1)02
2
~
nC0 2 +(n+l)H 20+Q
(CH3hCH + [0] KMn° 4
) (CH 3 hCOH
lsobutane (Alk.) Tertiary butyl alcohol
CH 4 (g)+20 2 (g) ~ CO 2 (g)+2H 20(l)+213kcallmol
2C 2H'; +70 2 ~ 4C0 2 +6H20+7~6kcallmol 3. Thermal decomposition or Fragmentation (pyrolysis
or cracking): The decomposition ofa compound by heat is
(b) Incomplete combustion or oxidation:
called pyrolysis (Greek: pyro = fire; lysis loosening). When
(i) When alkane is bumt in insufficient supply of oxygen,
pyrolysis occurs in alkanes, the process is termed cracking.
carbon monoxide or carbon black may be formed. The alkanes, on heating under high temperature in absence of
2CH4 + 30 2 Burn) 2CO + 4H 20
air, are broken down into a mixture of lower alkanes, alkenes
and hydrogen. During cracking of alkanes, either rupture of
(Lilnited)
carbon-hydrogen bonds or rupture of carbon-carbon bonds
CH 4 + O2 Burn) C +2H 20 (Occurs by a free mdical mechanism) takes place. Tbe rupture
(Lilnited) Carbon black
of C-H bonds is catalysed by the oxides of chromium,
vanadium, molybdenum, etc., and the rupture of C~ bonds
Carbon black is used for making printing ink, black is catalysed by silica, alumina, zinc oxide, etc. The following
paints, polishes and as a filler in rubber vulcanisation. are some of the examples of pyrolysis. .
Saturated Aliphatic Hydrocarbons 269'
" /CH 3
O+4H2
CH lOQO°C) C+2H
4 2 Hie; CH3
Methane I '~I Cr203/Al203 ,.
600°C/l5 atm
H2C'C .........CH2
Benzene
H2
n-Hexane
6
n-Heptane
600°C
6
Methyleyclo-
hexane
- -H2
6
Toluene
f
Hexene
insertion reagent because on photolysis they easily gjve
C 6.H14 ' C 4Hg +C 2H 6 carbene intermediate. So, due to introduction of methylene
Hexane Butene Ethane (-CH 2- ) group, the lower alkanes are converted into
C 3H 6 +C 2H 4 + CH 4 higher homologues. This process i~ known as methylation.
Propene Ethene Methane
CH 2N 2 ~ :CH2 +N 2
Diazomethane
C 4H IO +C 4Hg
hv
C6 H14 +C 2H 4 CH 2=C=O ---7 :CH2 +CO
Ketene
C 4H lO +CH 4 +C 2H 4 +C
CH 3CH 2 CH 3 + :CH2 ---7 CH 3 CHCH 3
C g H 16 + H2 Propane I
C 6H12 +C 2H 6 CH 3
C 7 H l4 +CH 4 lsobutane
+CH 3CH 2CH 2 CH 3
The pyrolysis or cracking of alkanes involves breaking of Butane
C---C and C-H bonds and occurs by a free radical 7. Reaction witb ketones: When isoalkane is heated
mechanism. It is of great importance to the petroleum with a ketone in the presence of conc. H 2S0 4, we get a tertiary
industry. alcohol (3°).
4. Isomerisation: The process of conversion of one
isomer into another isomer is called isomerisation. Alkanes
when heated in presence of anhydrous aluminium chloride
CH
I 3
°I COnc.H2S04
CH3-C-H+CH3-C-CH3 )
and concentrated hydrochloric acid or anhydrous aluminium
bromide and hydrobromic acid at about 200°C under a
I
Acetone ' (d)
pressure of 35 atmospheres are converted into one or more CH 3
other isomers. lsobutane
CH 3
CH CH CH CH I
A1C1 3 + HCI (Cone.) CH CHCH
3 2 2 3 200°C 35 atm 3 3
n-ltutoone ' Isobutane
. 2,3,3-Trimethyl butan-2-o1
~ A1CI3 +HC1(Cone.) ,. Uses of alkanes
2-Methylpentane Heat (i) Methane is used in the manufacture of compounds like
2,3-Dimethylbutane
, CH 3 0H, HCHO, CH3CI, CH 2 C1 2 , CHCl 3 and CCl 4 etc.
This isotnerisation involves 1,2 shift of hydride or methyl
(ii) Methane is used in the preparation of carbon black which is
group.
The branched chain alkanes have lower b.pts~ than, used for mak.ii:tg· printing ink, black paints and automobile
straight chain, hence isomerisation is important in petroleum tyres.
industry. (iii) Methane in the form of natural gas is used for running the
5. Aromatisation: The conversion of alipbatic cars, buses, etc. LPG (mixture of butane and isobutane) is
compounds into aromatic compounds is known as used as a fil,el.
aromatisation. Alkanes having 6 to 10 carbon atoms are (iv) Ethane is used for making hexachloroethane which is an
converted intO benzene or its homologous' at high artificial camphor. '
temperatures and in presence of a catalyst. (v) Higher alkanes in the form of gasoline, kerosene oil, diesel,
lubricating oils and paraffm waX are widely used.
2'lOll G.R.B. Organic Chemistryfor Competitions
Ascent and descent of series: When a higher homologue is prepared from a lower homologue, it is called ascent of series.
Similarly the preparation of lower homologue is called descent of series.
Ascent of alkane series: Use of wurtz reaction is made.
(i) Methane to ethane :
el 2 ) CH 3CI __
H_ea_t_w_ith_N_a_in_e_th_er--..+) CH -CH
. CH 4 3 3
UV Wurtz reaction Ethane
Methane
(ii) Butane from ethane:
el 2 Heat with Na in ether
C 2H 6 ) C 2H sCI -------~) C 2 H S-C 2 H S
UV
Ethane Ethy1 chlon·de Wurtz reaction Butane
(excess)
Descent of alkane series: Use of decarboxylation reaction is made. It is a multistep conversion.
Ethane to methane : o
CH3CH2CH2[!ii!:~~;i:!:~~CH<CH3 -c->
reason.
Solution: The liquid paraffin is lighter than water. It (e)
flows over water surface and continues burning. I-Bromopropane CH 3
2-Bromopropane
Problem S. How will you obtain? Give equations only:
(a) methane from acetone. CH 3
(b) ethane from acetic acid.
(c)· methane and ethane from sodium acetate.
I
CH 3CH 2CH 2-CH-CH 3
Solution: 2-Methylpentane
(a) (i) CH 3COCH 3 + 4[0] ~ CH 3COOH +C0 2 + H 20 The name of the reaction is Wurtz reaction.
. Acetone Acetic acid Problem 8. An alkane with molecular mass 72 formed
only one substitution product. Suggest a structure for the
(ii) CH 3COOH + NaOH ~ CH 3COONa + H 20 alkane. (BCECE 2006]
Sodium acetate
Solution: Let the molecular formula of the alkane be
C n H 2n +2 •
(iii) CH 3COONa + NaOH
Molecular mass of the alkane = nC + (2n + 2)H
(b) (i) CH 3COOH+NaOH ~ CH 3COONa +H 20 =nx12+(2n+2)xl
Aeetic acid Sodium acetate =14n +2
CH3:COONa
I I
Thus, 1412+2=72
I I
Electrolysis
(ii) +: I
:
,
) or 14n=72-2=70
cH 3icoqNa 70
So, n=-=5
I I
Cathode
14
2Na+ 2H 20 --72NaOH+H2 Thus, the molecular formula of the alkane isC 5 H 12 .It can
have three isomers.
(c) Apply a (iii) and b (ii) equations for obtaining methane
and ethane respectively. CH 3 CH 3
Problem 6. Why is the Wurtz synthesis not a good method I I
CH3CH2CH2CH2CH3 ; CH3 CHCH 2CH 3 ; CH 3-C-CH 3
for preparing propane? n-Pentane· 2-Methylbutane I
Solution: Two different alkyl halides (methyl chloride . (Isopentane) CH 3
and ethyl chloride) are to be used to prepare propane. Thus, 2,2-Dimethylpropane
three reactions may occur giving a mixture containing ethane, (Neopentane)
butane and propane. Since, the alkane forms only one mono substituted
Problem 7. Write the structural formulae and IUPAC product, it must have only one type of hydrogen atoms.
names of the different alkanes formed when a mixture of Therefore, the alkane is 2,2-dimethylpropane.
I-bromopropane and 2-bromopropane is reacted with sodium Problem 9. Give reason why chlorination of ethane to
in presence of ether. What is the name of the reaction? ethyl chloride is more practicable than the chlorination of
Solution: (a)CH3CH2CH2[~!~3:~~~~3:~!!CH2CH2CH3 n-pentane to l-chloropentane.
I-Bromopropane I-Bromopropane Solution: Ethane forms only one mono chloroderivative
~ CH 3(CH 2)4 CH 3 (ethyl chloride) on chlorination while n-pentane forms three
Hexane isomers on mono-chlorinati~n and the yield of l-cbloropentane
212: G.R.B. Organic Chemistry (or Competitions
is low as it is fonned by replacement of primary hydrogen (iv) Sulphur, nitrogen and oxygen compounds.: Besides
while other two isomers are fonned by replacement of hydr.ocarbons, there are also present certain .organic
secondary hydrogen atoms respectively. cDmpDunds containing oxygen, nitrDgen and sulphur. The
sulphur cDmpDunds are present tD the extent .of 6% and these
CH 3-CH 3 Gl2) CH 3-CHFI include mercaptans (R-SH) and sulphides (R-S-R). The
Ethane Ethyl chloride disagreeable smell of petroleum is due to these sulphur
Cl 2 cDmpDunds. Their remDval fr.om petr.oleum products is very
CH3CH2CH2CH2CH3 ~ CH3CH2CH2CH2CH2CI
necessary, DthelWise these will get Dxidised tD sulphurDuS and
n-Pentane l-Chloropentane
sulphuric acids during cDmbustiDn in internal cDmbustion
CI CI
engine and will cause cDrrDsiDn .of metal.
I I The chief nitrDgencDmpDunds are alkyl pyridines,
+ CH 3-CH-CH2-CH2CH 3 + CH3-CH2-CH-CH2CH 3
2-Chloropentane 3-Chloropentane quinDlines and pyrrDles. The .oxygen cDmpDunds present in
petrDleum include alcDhDls, phenDls and resins. CDmpounds
Problem 10. Prepare butane from chloroethane using like chlDrDphyll, haemin (green and red cDIDuring matter .of
the Corey-House synthesis. plants and animals, respectively) are alsD present in
Solution: Chloroethane is first converted into lithium petroleum.
diethylcuprate which then reacts with chloroethane tD fDnn (v) Natural gas: The gas found abDve the petrDleum
butane. deposits is referred tD as natural gas. It is a mixture of low
mDlecular weight alkanes, namely methane .(80%), ethane
(i) CH 3CH 2CI +2Li Ether) CH 3CH 2Li + LiCI (13%), prDpane (3%), butane (1%), the vapDurs ofl.oW b.oiling
pentanes and hexanes (0.5%) and nitrDgen (1.3%). The natural
. (ii) 2CH 3CH 2Li +Cuf ---; Li(CH3CH2hCu + Lil
gas in liquid fDnn under pressure mainly cDnsisting propane,
Lithium diethyl cuprate
and butanes is used as cDDking gas (LPG = liquefied
(iii) Li(CH3CH2hCu +CH 3CH 2Cl ---:-" petrDleum gas). It is highly inflammable. The gas burns with
CH 3CH 2CH 2CH 3 +CH 3CH 2Cu + LiCI blue flame prDducing IDt .of heat. The gas cDntaining methane,
Butane nitrogen and ethane is sDld as bDttled gas in compressed state
in steel cylinders.
6.7 PETROLEUM Theories of origin of petroleum: Many the.ories have
The tenn petrDleum (Latin: Petra =. rock; Oleum = .oil) is been prDpDsed t.o explain the .origin .of petr.oleum belDw the
applied tD the dark;coloured oily liquid with .offensive odour crust .of the earth but nDne is satisfactDry in itself. Any theDry
fDund at various depths in many regions below the surface .of prDP.osed must explain the f.ollowing characteristics
the earth. It is also called rock oil, mineral .oil or crude .oil. It is . associated wIth petroleum:
generally found under the rDcky strata of the earth's crust and (i) its associati.on with brine (s.odiUm chl.oride soluti.on),
.often floats over salted water.. It is covered by an atmosphere (ii) the presence .of nitr.ogen and sulphur compounds in it,
(iii) the presence .of chlDrDPhyll and haemin in it,
.of a gaseDus mixture known as natural gas.
(iv) its .optically active nature.
The chief oil producing centres in India are: Rudrasagar
Mining of petroleum: PetrDleum deposits .occur at
and Lakwa in Assam; Ankleshwar, Cambay and Kalol in
varying depths at different places ;ranging fr.om 500 to 15000
Gujarat and Mumbai high (offshore area). feet. This is brought to the surface by artificial drilling. The.oil
Composition: The cDmpDsitiDn of crude petroleum well is drilled till the .oil bearing regi.on is reached and pipes
varies with places of occurrence but essentially it is a mixture are fitted. SDmetimes, the .oil rushes .out thr.ough these pipes
.of hydrDcarbons. It contains mainly the fDllowing: due tD the pressure exerted by the natural gas. As the gas
(i) Alkanes: The percentage .of alkanes can vary from pressure subsides, air pressure is applied t.o raise the .oil fr.om
30 tD 70. Alkanes containing UptD 40 carbon atoms are. the well.
present. Alkanes are mainly straight chain but few are The crude .oil thus, .obtained is. either stored in big steel
branched chain isomers. tanks or sent to refineries by pipelines for processing.
(ii) Cycloalkanes: 'The perc~ntage of cycloalkanes Petroleum refining: The petr.oleum .obtained by
varies from 16 to 64. the cycloalkanes mainly present in mining contains impurities such as sand, brine .or sea water,
petroleum are: Methyl cyclopentane, cyclohexane and methyl sulphur comp.ounds and resins. It is technically called as
cyclDhexane. The .oil rich in cycloalkanes is knDwn as . crude on. The crude oil is mechanically freed fr.om sand and
asphaltic on.
brine and then subjected to fractional distillati.on in a refinery
(ill) Aromatic hydrocarbons: The percentage .of
because crude oil as such is not suitable f.or m.ost technical
. aromatic hydr.ocarbDnS varies frDm 8 tD 15. The chief arDmatic
cDmpDunds present in petrDleum are: Benzene, t.oluene, purposes.
xylenes and naphthalene.
Saturated Aliphatic Hydrocarbons 273
, .The process' of dividing crude oil into useful fractions Different fractions are furtherrefmed and subjected to
with, different boiling ranges a'nd free from undesirable refractionation to yield various useful products. '
.inipuritiesis termed refining. Purification: The fractions obtained above are called
The fractional distillation of crude oil is carried out sour fractions. These fractions are purified in order to impfC)ve
odour, stability to air oxidation, corrosiveness and, other
continuously in a specially designed tall fractionating tower or
properties. The actual process of purification differs from one
column, made of steel. The cnide oil is heated in a furnace to
fraction to the other depending upon,its commercial utility and
about 400°C and introduced in this tower. Higher boiling nature of unwanted substances· present.
fractions· condense fITSt whereas the low boiling fractions rise
(i) Treatment with concentrated su,phuric acid: The
upward and are collected as soon as they condense. The gases gasoline or kerosene fraction is shaken with sulphuric acid to
which do not condense at all (low boiling points such as remove ar.omatic compounds like thiophene and other sulphur
methane, ethane, propane and butane) are collected at the top compounds which impart offensive odour to gasoline and
of the column. Some portion of the crude oil does not vaporise kerosene and also make them corrosive. It is then allowed to
and i,s obtained as a residue or pitch. settle and the upper layer is withdrawn. It is treated with
The main fractions obtained are: sodium hydroxide to Fernove excess, of acid and finally
washed with water several times. It is then redistilled.
Boiling point
, Approximate
FractioD: , range upto room
1···.compositioD (ii) Doctor sweetening process: Sometimes sodium
temperature
plumbite is used in presence of alkali and calculated quantity
l. Uncondetised gases CI C4 of sulphur to remove mercaptans. Mercaptans are oxidised to
disulphides.
2. Crude naphtha (16%) C s CJO 30-1 50°C
2RSH + Na 2 Pb0 2 +S ~ RSSR +PbS+2NaOH
3. Kerosene (25-30%) CII C I6 I 50-250°C
Disulpbide
4. Heavy oiH25-30%) C 16 -C 18 250-400°C
(iii) Treatment with adsorbents: Various fractions are
5. Residual oil (about 30%) C I7 -C40 Above 400°C passed over adsorbents like alumina or silica or clay, etc.,
6. Non-volatile residue when the undesirable cumpounds get adsorbed.
A complete list of petroleum products, approximate
compositiOl~. boiling range and their uses is given below:
I. Uncondensed gases Upto room temperature Fuel gases; refrigerants; production of carbon
black; hydrogen; synthesis of organic
chemicals.
2. Crude naphtha on refractionation
yields:
(i) Petroleum ether 30-70° Solvent.
(ii) Petrol or gasoline 70-120° Motor fuel; dryclean~ng; petrol gas.
(iii) Benzene derivatives 120-150° Solvent; dryc1eaning.
"
LPG and CNG (Petroleum' Gases) low boiling points. The" proqess . of cracking involves the·
1. Liquefied petroleum. gas (LPG): The petroleum breaking of carbon-carbon, and carbon-hydrogen bend
gas liquefied under pressur~ is called liquefied petroleum gas resulting in the formation of smaller molecules of various .
(LPG). It is chiefly a mixture of butane and isobutane with a types depending on the conditions uSed.
small amount of propane and is easily compressed under For example, when Jong, chain alkanes are heated well
above their boiling points (400-800°C) with or without a
pressure as liquid and stored in iron cylinders. It is supplied in
liquid form, so that a cylinder of even ~mall volume may catalyst, they are broken (or cracked) to yield smaller alkanes,
aIkenes and hydrogen.
contain an appreciable amount of the gas. A domestic' gas
cylinder contains about 14 kg of LPG A strong foul smelling 800
substance called ethyl mercaptan (C 2 H sSH) is added to LPG
Long chain alkanes ".t()O- :C) Smaller. alkanes +
AIkenes + H . '. ..' .
cylinders to help in the detection of gas leakage. The gas used. 2
for domestic cookin~ is called Liquefied Petroleum G~s Thus; by crackin~of asmgle alkane (e.g.,decane), a lirge
(LPG). It is mainly used as a pollution free household neat number of hydrocarbons like heptane, 'hexane,pentane,.,
butane~ propene, butene, pentene, hexene, etc:, areprgduced~
and clean good fuel because the' combustion of butane and
isobut~e is, complete. When we turn the knob of the gas '\lf3 (CH 2)6 CH r +C ZH4
cylinder, the pressure' is released resulting decrease' of Octane Ethene
pressure inside the cylinder, so that highly volatile LPG CH 3 (CH 2 hCH3 + C3H6
changes into gas. When ignited, the gas burns with a blue ,Heptl,Ille 'PrQP~mi ,
flame producing a lot of heat. It hs a high calorific value CH 3 (CH2)4Gfh +C4H s .'
(about 50 kItg). The major sources of LPG are natural gas·and 'Hexane .Butene
from refining and cracking of petroleum. CH 3 (CH 2 hCH 3 +CSH10
2. Compressed natural gas (CNG): The natural gas Pentane Pentene
compressed at very high pressure is called compressed natural CH 3 (CH 2 hCH 3 +C 6:H 12
gas (CNG). It consists mainly of methane (95%) which is a Butane Hexene .
relatively unreactive hydrocarbon and makes it nearly. Similarly,
complete combustion possible. The other 5% is made up of Cracking
" various gases such as ethane, propane aud butane including G12 H 26 700°C )
C 7 H l6 + CSHIO
small amounts' of other gases nitrogen, helium, carbon , Dodecane Heptane Pentene
.dioxide, hydrogen sulphide and water vapours, etc. Because (b.pt. 489 K) (l:!.pt. 371 K) (b.pt. 309 K)
of the gaseous nature ofthis fuel, it must be stored in either a Cracking is carried ou~ in two differentways;
compressed natural gas (CNG) state or in a liquefied na1u!'a1 (a) Liquid-phase cracking and
gas (LNG) state. The CNG is now being used as a better fuel (b) Vapour-phase cracking. ,
than gasoline for running buses, cars and three-wheelers in (a) Liquid-phase cracking: In this process, the heavy·
metropolitan cities like Delhi, Mumbai, etc., because of its oil or residual oil is cracked at a high temperatUre
,complete combustion and no unburnt carbon is being released (475-530°C) under high pressure (7 to 70 atmpspheric,
into the atmosphere to cause air pollution. Recently a plant (or pressure). The high pressure keeps the reaction product in
LNG has been established in Gujarilt. 'CNG or LNG are vet)' liquid state. The conversion is app:roximately 70% and the
clean fuels which cause very little pollution and also have resulting petrol has the octane number in·the rang~,65to,70. '
very high. calorific value. Natural gas ,has octane rating 9f 130. The cracking can be done in presence of some catalysts'
like silica, zinc oxide, titanium oxide, ferric oxide and alumina
6.8 ARTIFICIAL METHODS FOR MANUFACTURE (catalytic cracking). The yields of petrQI are generally higher
OF. PE"rROL OR ·GASOLINE when catalyst is used at lower temperature.· '
Petrol or gasoline obtained from crude petroleum is not (b) Vapour-phase cr~cking: In this.pmcess,kerosene
sufficient and can meet only halfofworld's requirements. It is, or gas oil is cracked in vapbur-phase. The temperatureis:kept
therefore, necessary to fmd alternative methods of obtaining 60Q-800°C and the pressure is about 3.5 tg 10.5 atmospheres.
petrol. The deficiency is partly met these days by converting The cracking is facilitated by ,use of a suitable catalyst The
the other less valuable fractions such as heavy oil and yields are about 70%.
k~rosene fractions into petrol with the help of the cracking It is obServed that petrol obtained by cracking is" far
process. Synthetic methods have also been discovered for the superior, to petrol obtaioedby direct 6istillatioD ·ofcrode
manufacture of petrol. The methods generally eJ?1ployed for petroleum on account of its high octane number (due to
the artificial production of petrol can be studied under two presence of large quantities of unsaturated hydrocarbons).
main heads: . '. ' Petrol is also Qbtained by th,e pe.lymerisation and
, (i) Cracking, (ii) Synthesis. alkylation ,of' sWtPle llyQroca.Jibons o~tahled durlng.
0) Cracking: It is a process in which high boiling crackiQ.g~ Olefins underg0'P0lym~sation reactions in the
,fractions consisting of higher hydrpcarbons are heated presence of catalysts like 'HiS04 or H3PQ4.Simpie olefin,s
strongly to decompose theni into lower hydrocarbons with
Saturated Aliphatic Hydrocarbons .275
form molecules having 6 to 8 carbon atoms and can be (iii) Heavy oil 2o.0-3o.o. o C ,
converted into petrol by hydrogenation. (iv) Residue '.
H3 C '. Heavy oil and residue are again mixed with coal and the
)C=CH 2 + H-CH 2C=CH 2 70% H 2S04 > . above process is. repeated. Middle oil fraction can be
seParately hydrogenated in the vapour phase in· contact with a
He
3
I
CH 3 solid catalyst to form mo,:e of gasoline.
The yield of gasoline by this method may be as high ~s
2-Molecules of 2-methylpropene
60.%,'
C (b) Fischer-Tropsch process: In this method, stearn is
H3 ) H2 "
C-CH 2 -C=CH 2 ~ (CH3hC-CH2CH(CH3h fITst passed over hot coke to form water gas ..
H3 C 1 I 2,2,4-Trimethylpentane
C + H 20 1200°C ) CO H2 +
CH 3 CH 3 . (Iso-octane)
Coke Steam . '---v---'
2,4,4-Tri methylpentene Water gas
Water gas is mixed with half its volume of hydrogen and
The octane number of polYfl?er gasoline is generally high. then passed over a catalyst at 2o.o. o C under 5-10. atmosp!~.ric
Alkylation occurs under similar conditions. Isobuterie pressure. The product is synthetic petroleum.
reacts. with isobutane in presence of conc. H2S0 4 at about
C Co o r N i . :'
4o. oC to form iso-octane .. x 0 + y Hz Heat > MIxture of hydrocarbons + H 20
CH3
The best catalyst for this process is a mixture of cobalt
I
CH 3-C=CH z +CH 3-C-H
Cone. H2S0 4
---,--...--~)
(10.0. parts), thoria (5 parts), niagnesia (8 parts) and kieselguhr
I . . I 40°C (200. parts).
CH 3 CH 3 '. The artificial petroleum obtained is then fractionally
distilled. The various fractions separated are: petrol, kerosene,
Isobutene Isobutane
lubric;t1ing oil, diesel oil and paraffin wax. The high boiling
CH 3 fractions are cracked to get more gasoline. The overall yield in
I this process is slightly higher than Bergiu!> process.
CH3-C-CH2-CH-CH3
I I· 6.9 KNOCKING AND OCTA'NE NUMBER
CH 3 CH 3 ·
.Petrol is used asa fuel in the internal combustion engines of
Iso-octane cars, scooters, aerop la~es, etc. A mixture of petrol vapour and
CH 3 CH 3 . air is compressed by a piston within the cylinder of the engine
I I to its one-::.i,th or one-tenth volwne. The compressed mixture
CH3-C-H+ CH2 =CH z ---t- CH 3-C-CH 2-CH 3 , is ignited by a spark plug. The fuel burns apd energy produced
I '. Ethene . .I delivers a smooth thrust to the piston. This result in the
CH . CH movement of the piston and the' force is transmitted to the
3 3
Isobutane Neo-hexane wheel of the vehicle: The efficiency of the engine depends on
(ii) Synthesis Petrol can be" synthesised from coal the compression ratio. The increase in compression of the
(Synthetic petroleum) by the following two methods: fuel-air mixture beyond a certain point results in. irregular
(a) Bergius process and (b) Fi~cher-Tropsch process. burning of the fuel which causes jerks agairist the piston and
(a) Bergius process (Hydrogenation'of coal) : This gives rise to viole]).t mt:tallic sound. The metallic sound
method was invented by llergius in Germany during the first produced due to irregular burning of the fuel is termed as .
world war. Finely powdered coal and a catalyst (usually ferric . knocking. The knocking lowers the efficiency of the engine
oxide, Fe 20 3 or fin) is made into a paste withheaVy oil. The and results the loss of energy. A fu~l which has minimum
paste is then preheated ana pumped to the conyerter.Here-the knocking property is always preferred.
paste is heated to 450-500°C and hydrogenis passed at about It has been observed'that knocking property is related with
250. atmospheric pressure. The product of hydrogenation is the nature (composition) of fuel. The straight chain aliphatic
.subjected to fractional distillation. . hydJ::ocarbons have a higher tendency to knock while branched
chain or unsaturated hydrocarbons have less tendency to
~~ . . knock, i.e., the tendency to knock falls off hl the following
Coal + Hz ----==---:::.~.) MIX. of hydrocarbons or crude od
450-500°C . order: ' '
250atm
[synthetic petrolellm] Straight chain alkanes> branched chain alkanes> .
The following fractions are obtained: olefins > cyclo alkanes> aromati9, hydrocarbons
(i) Gasoline upto 15o.o C To indicate the quality of gasoline (petrol), a method of
(ii) Middle oil between 150-20o.o C 'gradation has been introducyd in 1929 which is ten;ned octane'
276 G.R.B. Organic Chemistry for Competitions
The cetane number of a diesel oil is the percentage of climate and Cl1ntrols the percentage of highly volatile
. , cetane (hexadecane) by volume in a mixture of cetane and hydrocarbons in l~e oil. The flash point is high fora hot
a-methyl naphthalene which has the same ignition country .and low f6r a cold country. The flash point in India is
property as the fuel oil in question under similar fixed at 44°C, in France it is fixed at 3,S°C, and in England at
experim~ntal conditions. Thus, the diesel oil having cetane 22.8°C. The flash point of an oil is usually aetermined by
number 75 \, 0uldhave same ignition property as a mixture of ' means of "Abel's apparatus'...· .
75% cetan~ and 25% a-methyl naphthalene.
6.12 PETROCHEMICALS
6.11 FLASH POINT Petroleum is the biggest and che.apest S,Ource of hydrocarbons.
Volatility of a liquid hydrocarbon determines its explosive These hydroca\bons can be converted into vari01,lS useful
nature. Kerosene used for illuminating purposes should not be organic compounds. All such chemicals which are derived
sufficiently volatile at ordinary temperatures so as to form from petroleum or natural gas are called petrochemicals.
explosive mixture with air. The lowest temperature at which The modem petrocherirical industry produces about half a
an oil gives sufficient vapours to form an explosive mixture million useful organic compounds. Petrochemicals provide
. with air is referred to as flash point of the oil. raw materials for the manufacture of dyes, drugs, plastics,
The flash point or ignition temperature fixed for a fabrics, . insecticides, detergents, food preservatives,
particular oil varies from country to country, depends on its disinfectants, etc. . '
The following list includes some of the chemicals which ar~obtained from petroleum:
Hydl'oearbons t~mp~"'ds derived
--------~~~~--~~.~.~.~.~.-'~~'~'--~~~--~~~------~-------
1. Methane Methyl chloride, chlorofornl: methanol, fonnald~hyde; fonnica<';I,', freon, hydrogen for synthesis of ammonia.
2. Ethane Ethyl chloride, ethyl bromide, acetic acid, acetaldehyde, ethylene,ethyl acetate, nitroethane, acetic anhydride.
. - • ! .
3. Ethylene Ethanol, ethylene oxide, glycol, vinyl chloride, glyoxal, polyetbene, styrene, butadiene, acetic acid.
4. Propane Propanol, propionic acid, isopropyl ether, acetone, nitrome~hane, nitroethane, nitropropane.·
5. Propylene Glycerol, allyl alcohol, isopropyl alcohol, acrolein, nitroglycerine, dodecylbenzene, cumene, bakelite~
6. Hexane Benzene, DDT, 'gammexane.
7. Heptane Toluene.
8. Cycloalkanes Benzene, toluene, xylenes, adipic acid.
9. Benzene Ethylbenzene, styrene, phenol, BHC (insecticide), adipic acid, nylon, ~yclohexane, ABS detergents.
10. Toluene Bertzoic acid, TNT, benZaldehyde, saccharin, chlo~amine-T; benzyl chloride, benzal chloride. '
cham alkanes have higher boiling points than branched o . Sulphonation also follows free radical mecbanism.
chain alkanes having same number of carbon atoms. . o Oxidation: Alkanes on' oxidation give different
products und~ different conditions.
n-alkane >- Isoalkane > N eoalkane '
'0 Combustion: Alkanes readily burn in excess of air or
Chemical properties oxygen to form CO 2, H 20 and heat. Combustion is ,an
o Both C-C and C-H bonds of alkanes are non-polar and exothermic reaction, hence it is used for the production of
strong sigma bO,nds cannot break under ordinary heat and energy. ,
conditions; hence; alkanes are quite inert towards common o Incomplete oxidation: When alkanes are burned in
reagents such as acids, alkalies, oxidising and reducing insufficient supply of oxygen, they give CO and carbon
agents. A few important reactions of, alkanes are as black.' '
follows: o Catalytic oxidation: Lower alkanes undergo restricted
o Halogenation:, Alkanes react with halogens in presence oxidation in presence of metallic catalysts at high
of UV or diffused sunlight at high temperature temperature and pressure to form alcohols, aldehydes and
(250-400°C), the hydrogen atoms' 'of alkane are acids, e t c . , '
successively replaced by halogen atoms. This process is o Chemical oxidation:' Alkanes containing tert. ~ydrogen '
known -as halogenation (substitution reaction). The atoms ~e oxidised to tert. alcohols by KMn0 4 •
extent of halogenation depends upon the, amount of
halogen ,used. (Reactivity order of' halogens ' is . (CH 3h CH
KMn°4 ) (CH h C-OH'
3
F2 ~C12 > Br2 >1 2 ) lsobutane ,[0] Tert. butyl alcohol
:.J Higher alkanes undergo halogenation in controlled
conditions and give a mixture of isomeric haloalkanes. 0, Thermal decomposition (or Pyrolysis or Crucking):
The order of reactivity is: , 'The thermal decomposition 'of organic compounds is
Tertiary hydfogen > Sec. hydrogen> Primary hydrogen known as pyrolysis and the, process of breaking C-C
o Chlorination and bromination proceed in almost identical bonds or C-H bonds of complex hydrocarbons into
manner. Reaction with fluorine is very violent but the simpler molef;;ules by heat is known as cracking.
reaction with iodine is very slow and reversible, so o Isomerisation: The process of conversion of Qne isomer
, iodination occurs in presence of an oxidising agent. into another. is called isomerisation. The straight chain
o Laboratory chlorination 'of alkane is often done with alkanes (n-alkanes) on treatment with Lewis acid catalysts,
S02Cl2 instead ofCl 2 arid an organic peroxide, ROPR is e.g., anhydrous AlCI 3,conc. HCI, etc., are converted into
used as an initiator. ' branched chain alkanes.
o Halogenation occurs by a ftee radical chain mechanism.
The important steps are: (i) Initiation (ii) Propagation n~Butane Anhy&AlCI 3/HC1) Isobutane
(iii) Termination. . 3QO°C
o Nitration: It is a substitution reaction in which a H-atom O\romatisation: The conversion of aliphatic compounds
of alkane is replaced by nitro (-N0 2 ) group. Alkanes can into aromatic compounds is known as aromatisation.
be nitrated with nitric acid in gas phase generally at a o Insertion reaction:..Ori reaction withdiazomethane
temperature 450-500°C. This is known as vapour phase (CH 2 N 2 ) or ketene (CH2=C=0), the lower alkanes are
nitration. '
Satit,ratedAliphatic Hydrocarbons 279 .
· - .
.- .. .
· . ' " <convened int() high~bo~ologUeS ~e to the introduction 3. Fischer-Tropsch process (Hydrogenation elf water
of methylene group (.,.....,cH2~). . gas):
·Petroleum .'. .• . ...• . . ..' . . .~. CoorNi
.The eomposition of crude pen-oleum varies with place Qf ,xCO+ yH~." ) Mixture of hydrocarbons
(Water gas) . 200 C~5-:l0 attn
.·ocCUtte~e but, essentially it isa mixture of alkanes, .
. cyeloalkanes, aromatic . hydtocarboris, S,Nand oxygen . + H 20 (Synthetic petroleum)
.' . compounds and :i1aturalgas~ etc" . Cl Knocking: The metallic sound produced due to irregular
(JMpdemtPeoryof origia of~oleilDl explains (i) the burning of the fuel is termed as knocking. A fuel with
· 'pf,esenceOfiililorophyll and w.emin(ii) p~seRce of coal miirimum knocking property is always preferred.
' .•. d~ositi~ea:r .oil .' 'fields., (iii)· .presence 'ofN and S to
Cl The tendency knock fall off is in the following order:
COInP~)\1D.ds along With optically aetive substances (iv) Straightchail) alkanes > branch.ed «hain alkanes .
presenc~of resins and heliumg,s. . . . '.' " '... > alkenes > cyc10alkanes > aromatic hydrocarbons.
piecmde Oil o~ed by mining of petroleum cootains Cl Octane num~er: . The octane nurilber of a given sample
. impurities: '. '. . .,: .' .' . ; ..•. '. may be defined as the percentage by volume of iso-octane
.•.1:;1. The Pl'ocess ofdividing ,?ruge..Oilintollseful ~tionSwith present in. a mixture of iso-octane and heptane. Heptane
..... .ditf~rentboiling.rangtls Ii. ~., 1UlCondensed ,gases (C1-C 4), which causes maxim'\lDl knocking is assigned the octane
'., cl'llde. n~phtha {C5~to;30'"'-1~0~C)>ckeT0sene {Ci i -016 ; number zero, while iso-octane (2,2,4-trimethyl pentane)
'. '·150--2~Qe C), 4~avy .oil (C1{j-"'Cis; 4'0-400~ C), residual which causes minimum knocking is given the octane .
oil;: (C17+(:40; above4~"'~)an49-on:':'volatile residueland number 100.' .
t\e¢ .natu \ltldesirabl~filnpwitie,s'is termed refining of Cl Antiknock compounds: To reduce knocking property
, ~e1irn •. .... ....•........ . . . . . . .<; .' •...
or to improve the octane number of a fuel. certain
...''. 1:1 A-udenapht~'on refh\ctionati<m yields: (i)' Petroleum chemicals are added to it. These ~e called antiknock
.. ·••e.ther ~.C. S.:..... c.~., at3~70~~.);(ii). Jle~1 or.,. gasoline (C 6:...o 8 compounds. Tetraethyl lead (TEL) is the best antiknock
at 70-120°c, and benzene .derivatives· (e 8-C 1O . at compound. y., .
. lZ~150OC).,< ..... .' ". '. . Cl Other methods for improving octane number of
'Cll;iqu~fiedpe~oleum gas '(LPG):Jt iscliiefly a mixture gasoline: The octane number of petrol (gasoline) can be
(tfbutane.and lsoh'tit$e (domestic gas) compressed under improved by (i) increasing the proportion of branched
·pressute·Qs liquid and stored;mll'on?eylinders .. chain· alkanes (by isomerisation or reforming) or
·0 Compressed natural gas \(CNG):The natural. gas alkylation (ii) the addition of aromatic hydrocarbons, BTX
·compres$ed at very <high ·pr~sQ.re· is called ~omp~ssed (by aromatisation) (iii) addition of TEL (CzHs)4Pb or
··~J.lathral ga$'.(CNG).Itmaittlycansists of methane (95%) methanol or ethanol. .
and other. 5% i~Hnade up of various gases sU9h as ethane, Cl Cetane number: The cetan,e number ora diesel oil is the
.;."ropimejID.d butaneia.eluding:$m.ll amount of other gases: percentage of cetane (hexadecane) by volume in a mixture
'. Atflncial"Methods for .Manufacture of Gasoline' of cetane anda-methyl naphthalene. It is used for grading
J.e Cracklng:Jt ·is. aproc:essin'whicb high boiling the diesel oils. Hexadecane has been assigned cetane
,fractiop~.cmlsisting..of higho.rhydr'ocarbons are heated number 100 while a-methyl naphthalene is assigned zero
'. strQllglyto decompose lliem, into lmver hydrocarbons with cetane number.
.lOw boiliftg points. . Cl Flash point: The lowest temperature at which an oil
. • ....;... ..•.... <,400-8()()"C gives sufficient vapours to form an explosive mixture with
·.LongCbain'alkanes .. ' '.' .' .'~) Snlaller alkanes air is referred to as flash point of the oil. The flash point in
. .. ".'. " ...... . + Alkenes + H2
at
India is ftxed 44°C. . '. .
Cl PetrochemicalS: All suoh chemicals which are derived
. . 2. Bergiu,s .proCess (Hydrogenation ..(coal):.
from pen-oleum Of natura1 gas 'ate called petrochemicals.
Fez03 catalyst. . ..... They provide raw materials fQT the manufacture of dyes,
Coal +' H2 ) Mixture ofhydrocitrboos drugs, plastics, fabrics. insecticides, .detergents; food
500"C, 250 attn . .
preservatives and disinfectants, etc. .
or crude rul (Synthetic petroleum)
280 a.R.B. Organic Chemistry for Competitions
.:. Very Short Answer Type (e) Sodalime is a mixture of -sodium hydroxide and
potassium hydroxide.
1. Fill in the blanks in the following:
(f) Methane can be obtained by wurtz reaction.
(a) The tenninal carbon in butane is ...... hybridized.
(g) Methane is also called as fire damp or marsh gas.
(b) Petroleum is the main source of ...... .
(h) Ethane on nitration at 400°C forms only nitroethane.
(c) Al 4C 3 evolves ...... when treated with water.
(i) The decreasing order of boiling points amongst the
- Ether H20
(d) CH3I+Mg ~ ...... ~ ...... isomeric pentanes is neo > iso > n.
(j) Petroleum is called liquid gold.
(e) Hydrogenation of unsaturated -aliphatic hydrocarbons (k) Petrol consists of hydrocarbons from C 12 H 26 to CIS H 32 •
using nickel as a catalyst is known as . . . . . . . ' (I) Straight chain hydrocarbons have high octane number
(f) n-Propyl bromide on reaction with sodium in presence values than branched-chain hydrocarbons.
of ether gives .. . . .. and the reaction is known as (m) TEL increases octane number of gasoline.
(n) Wurtz reaction is not suitable for the synthesis of
(g) Kolbe's electrolysis of ...... produces n-hexane at alkanes containing odd number of carbon atoms.
anode. (0) Kolbe's electrolysis method is applicable for the
(h) Paraffins mainly undergo ...... reactions. _ preparation of only symmetrical alkanes of the type
(i) The straight chain isomer of an alkane has a ..... . R-R. -
boiling point than the branched chain isomer. - (P) In Clemm~nsen reduction, LiAlH4 is used for _the
(j) Halogenation of alkanes does not occur in ...... . reduction of aldehydes and ketones to form- alkanes.
(k) The halogen which is most reactive in the halogenation (q) In alkanes, C-H bond is stronger than C-C bond.
of alkanes under the sunlight is ...... (cqlorine, (r) Photobromination of 2-methylpropane gives a mixture
bromine, iodine). of I-bromo-2-methylpropane and 2-bromo-2-methyl-
(I) Sodalime is NaOH arid ...... mixture. propane in the ratio of 9: 1.
(m)A sample of gasoline has same knocking properties as a (s) Fischer-Tropsch method is used for the preparation of
mixture containing40% n-heptane and 60% iso-octane. synthetic petrol.
The octane number of the sample is ...... . (t) Neopentane yields three different Inonochloro
(n) Breaking of higher hydrocarbons into lower hydro-
derivatives.
carbons is called . .. . .. . ' .
(u) The three carbon atoms in propane lie in straight line.
(0) Gasoline obtained' as a result of ...... has a higher
(v) Alkanes mainly undergo substitution reactions and
octane number than the straight run gasoline.
follow free radical mechanism.
(P) A lead compound known as ...... is used as antiknock
in petroleum industry to increase efficiency -of fuel (w) For grading diesel oil the term octane number is used.
consumption. (x) Higher -alkanes can be oxidised to fatty acids in
(q) Reduction of alkyl halides with ..... : yields alkane~. presence of manganese stearate.
(r) The gas supplied for cooking is ...... . (y) Methane when hC<-I'cd at lOOO°C in absence of air,
(s) Synthetic petrol is obtained by ...... . decomposes into carbon black and hydrogen.
-(t) Chlorination of propane give rise to ...... monochloro (z) Ethane is used for making hexachloro ethane which is
products. an artificial camphor.
(u) When ...... is strongly heated with sodalime C 2 H 6 is 3. Match the following:
_ obtained. _ [A]( 1) Decarboxylation (a) Lead tetraethyl
(v) CH3 JV1gBr + CH)OH ----7 ...... + .... : .. (2) Saturated hydrocarbons (b) Free radical
(w) The shape of methane molecule is ...... . substitution
(x) All alkanes are ...... than water. (3) Marsh gas (c) Alkyl halide +
(y) The conversion of n-hexane into benzene in presence of
a catalyst Cr203 at 600°C is termed ...... . Na Ether)
(z) ...... is obtained when methane is oxidised with (4) Antiknock compound (d) Isomerisation
ozonised oxygen at 450°C. (5) Wurtz reaction (e) Petroleum
2. State whether the following statement is True or False: Sunlight '
(6) CH4 + CI 2 ) CH 3 CI (f) Paraffins
(a) In alkanes all carbon atoms are sp3 -hybridized.
(b) Natural gas consists of lower hydrocarbons. (7) Conversion of n-butane into (g) Methane
(c) The general formula of alkanes is Cn H 2n +4 . 2-methylpropane
(d) The alkanes having four or more carbon atoms show (8) Liquid gold (h) RCOONa +
only chain isomerism. Sodalime
Saturated Aliphatic Hydrocarbons 281
6. (i) (A) CH 3CH zMgBr; (B) CHr -"CH3 (ii) (c) and (d).
(ii) (A) CH3 - CH 3; (D) CH 3CH 2Br; (e) CH3CH2CH2CH3 (iii) Br2Cf:[CH 2CH3 CH3CBr2CH3
(iii) (A) CH 3COONa; (B) CH4 ; (e) CH3Br 1,I·Dibromopropane 2,2-Dibromopropane
(iv) (A) CJ1SCH3 (Toluene) BrCH 2CH 2CH 2Br BrCH zCHBrCH3
(v) (A) CH4;(D) CH 30H 1,3·DibromOpropane 1,2-Dibromopropane
(vi) (A) [(CH3hCHhLiCu; (D) (CH3)2CHCH2CH(CH3)2 (iv) Cl 3CCH 2CH 3 CI 1CHCHCICH3
(vii) (A) [(CH 3hChLiCu; (D) (CH3)3CCH2CH2CH3 1,1, I· Trichloropropane 1, 1,2.Trichloropropane
(viii) (A) [CH 3CH2C(CH3hhLiCu; (B) CH3CH2C(CH3hCH2CH3 CI 2CHCH2CH zCl CICH2CCl2CH3 ;
(ix) (A) (CH3)3C- Br; (D) (CH3hCD 1, 1,3·Trichloropropane 1,2,2-Trichloropropane
(x) (A) CH 3CH(Br)CH3; (B) [(CH3)2CH]2LiCu; CICH 2CHCICH zCI
'(e) (CH3hCHI4CH3 1,2,3·Trichlor?propane
.(v) CH'.3CH2Br ~
roU (CH3CH2)2LiCu
. ~
~&
CH3CH2CH3
Br D Bromoethane (Il) Cui Uthiwn diethylcuprate Propane
(xi)(A) ~ ; (D) ~
further chlorinated to provide trichloro product" As the yield is 90, the actual ethane required
(C)H SCI 3 ). It was found that A providl.:o one trichloro 100
'" - x 66.93 = 74.37 g
product, B gave two and C and D 0:lch gil'vi: tl!r.:oc. \Vhat arc 90
the structural fommlae of A, B, e and m . 74.37
Volume of the ethane at NTP - - x 22.4= 55.5 L]
[Hint: Dichloro isomers, 30
7. An alkane, C 7 H 1u ' i~ produced by the reaction oflithium di-
11 (3-pentyl) cupratt .\ ith.etbyl bromide. What is the structu,re ..
(A) CH3- -CH 3
I
CI
of alkane?
[Hint: This is a Corey-House synthesis.
•
!
CI
Ci 2
[(CHJCH2)2CH]2CuLi + CH 3CH 2Br ~ (CH 3CH 2)3CH]
(3-Ethylpentane)
I ,. CI 2CHCH 2CH 2CI 8. The alkanes, (a) CsHli and (b) C g H I8 , on treatment with .
CH 2CI-C-CH 3 chlorine give only one monochloride. Give the structures of
2. CICH 2CICHCH 2CI
I (Two) each alkane and its chloride.
CI
(One) [Hint: (a) (CH3)4C ---'; (CH3)3C-CH2CI;
(C) CH 3CHCICHP (D) CH 3CH 2CHCI 2 (b) (CH3)3C"":'C(CH3)3 ---'; (CH3)3C-C(CH3hCH2Cl]
H3 C
C
CH 3
(iv)T
HC CH It has all equivalent hydrogens.
percentage of isomers formed during monochlorination of
2-methylbutane. [Hint: (iii) 3 > C< 3 hence, it gives single insertion
[Hint:
1°
CH3
I
CH3CHCH2CH 2CI + CH3CHCHCH3
CH3
I.
H,C I CR,
CH N
hv
P'~t.
2 2
H3C> C
HC
3
< CH z-CH31
CH
3
CH3 (a) I
CI
13. Give the major products of monobromination of following
1°· 301 2" 30 compounds.
CH:r=-cH-CH 2-CH 3 +Clz
2-Methylbutane
(bl
(i) 0 (ii)W
(iiif~ 0
(iv)
(a) (CH3hCHCH2CH2C1
reaction of)
1° H's
amount
3 equivalent
3x 1.0= 3 _3_ x 100= 13.9
21.6
(i) 0·-tBf2 --
(all carbons are identical)
(b) (CH),CHCHCH 3 2 equivalent
- I 2i. x 100= 35.2
CO cO
2° H'-s 2x 3.8;= 7.6
CI 21.6
-
CH 3
1
(d) CH 2-CH-CH 2CH)
6 equivalent
IOH's
6x 1.0=6.0 ~~ x 100= 27.8]
21.6
(iii)~ +Br2 ~
I (3 0 hydrogen is
CI more reactive)
11. The relative reactivity oflo : 2° : 3° hydrogen to bromination
is 1 : 82 : 1600. Calculate relative amount of each product
on monobromination of iso-butane.
(Ans. I-bromo 1-methylpropane 0.6%, 1-bromo-1-methyl-
propane 99.4"/,,1
(Allylic hydrogen is
iBint: Do like Q. No. 10] more reactive)
12. (a) What are the different products obtained on insertion of
\Hint: Allylic free radical is resonance stabilized.
n-pentane using diazomethane?
iB int : CHzN z ~ :CHz + N z
CH)-(CHz)3-CH3 + CHzN z
CH)
---7 CHy-(CH2k-CH)
II-Hexane -
I 14. Complete the following reactions:
+ CH3CHCH zCH 2CH 3 + CH3CH zCHCH 2CH 3]
2-Methylpentane I o
eH 3 ·11
3-Methylpentane C
(b) Which of the following alkanes will give single
insertion product?
(i)
0 HO/
CH2
"'-CH
I 2~_ (A) ZnlHg ~ (B)
Cone. HCI
286 G.R.B. Organic Chemistry {or Competitions
[Hint:
(iii) (A)alkene H2/Ni) (B)
300°C .
o COOH
II I
. [Hint: (i)(A)
("yC'l
~ ..'., (B) C)::J CH3-C- ell ,~-CH3;
I
CH}
-
(ii) (A) [(CH3)zCHhLiCu Four isomeric monoc,:arboxylic acids are possible.]
(B) (CH})zCHCH 2CH(CH3)2 p. How many monocarboxylic acids are possible, which on
CH} decarboxylation give neopentane?
I [Hint: Only one carboxylic acid is possible.
(iii) (A) CH 3-C-C=CH2
. I I CH 3
CH3 CH3 I
CH 3 -C-CHz-COOH]
(B) (CH3)3C CH(CH 3)2 .I .
(C) [(CH 3)3C]LiCu 1 CH 3
15. (a) An alkane, C6 H14 gives two monochloro derivative.
Give its structure. . 18. ~uggest a combination of organic halide and cuprate
(b) C6 HI2 (A)has chirall,'l1lre. When it is hydrogenated, reagent appropriate for the preparation of each of the
gives C6 H14 (B) in which there is no chiral centre. following compounds:
IdentifY (A) and (B). (a) 2-Methylbutane (b) I-Butylcyclohexene
(9) C sHll CI gives 2, 2, 5, 5-tetramethylhexane as main [Hint:
product on Wurtz reaction. Give the structure of (a) CH3I + LiCu[CH 2CH(CH3)2h ~ CH 3CHi.JI(CH 3h
. ' 2-Methylbutane
CsHIl Cl.
CH3 CH 3 (b) (CH3CH2CH2CH2hCuLi + Q - B r - -
CI
2
I . I
[Hint: (a) CH3-CH-'-CH~CH3 ~
2,3-Dimethylbutane Q - c H2CH2CH2CH3J
CH3 CH3 CH 3 CH3
I I I I 19. Complete the following reaction:
CICH 2 -CH-CH-CH3 + CH3-CH-C-CH3 CH2,
I H~
/
'C-H CH2
Cl
II \I + II -(A) ~~~~ I (B)
~
H· H-C C-H CH2 .
.
(b) (A) CH3-C-:-CH-:-CH 2
. I
C2HS
Chiral molecule
.
.I
r
CH 3-:- -CH2-CH3
C2H 5
.
Achiral molecule
[Hiot: (A) d:=::J ' d:=::J. (8) J-
(3-Methyl-I-pentene) Bicyc\o (2,2,1 )-2-heptene Bicyclo (2,2, I)-heptane
eH3 20. Indicate the reactivity of vinyiic, allylic and aliphatic
I Dry ether hydrogen in cyclohexene.
(c) CH3-C-CH2Cl + 2Na )
I
CH} . . ~ Allylic
HDH
l-Chloro-2,2- [Hmt: (
~
n
1"-..
Vmybc
dimethylpropane
Aliphatic .
. Reactivity sequence :
Allylic > Aliphatic > Vinylic J.
B.E. 87 kcalJmol 95 kcaVmol . 108. kcalJmol
Saturate4AliphaticHvdrocarbons . 287
.;
" .
SETI: TiIis. set contains questions with single correct answer. (a) CO 2 and H2 o (b) COand H2 o
1. The namefire~d3mp is given to: (c) CH30!Iand H2 o (d) none of these O.
(a) methane' '. o (b) ethane 0
14. Carbon black is obtained when methane is:
(c) proPane . D (d) butane 0 (a) heated in absence of air 0
Z., Marsh gasJ;llainly contains: '.' (b) heated in presence of nitrogen 0
:t(a)<;;iH~ . . . . '.0 (b) 9H4 0
(c) heated in presence of ammonia 0
'(crH~S' [J .(d) CO 0 (d) heated with steam 0
3. Botlnn.e~naethaneri:taybeobtained by asuitable one 15. What is the volume of oxygen required for the 'complete
step'reacti6p from: [BHU 2004; UGET (Med.) 2007) combustion of 4 litre of ethane?
(a).C831'; D (b) CH 3 CH 2I O (a) 4 litre 0 (b) 8 litre 0
(C)~H30H .' . o (d) C2 HsOH 0 (c) 12 litre 0 (d) 14 litre 0
. ;4. l';orn:mti~ of alkane, by IiCtionof zinc and alkyl halide is 16. Kerosene is a mixture of:
callea: .. . . (a) aromatic hydrocarbons 0
"(a)Wuttzreaction Cl '(h) Frankland reaction 0 (b) aliphatic hydrocarbons 0
. (c).Kolbe's.teaction . [] (d) Clemmensen reaction 0 (c) saturated hydrocarbons 0
5. The hi~stboilingp,?intis expected for: (d) alicyclic hydrocarbons 0
(a) jso-,()ctane . 0 17. Which of the following substances is used as antiknock
(b)h-o~e 0 compound?
(c) 2,2,3,3;.t¢tramethylbutane 0 (a) TEL 0 (b) Lead tetrachloride 0
(d) n'-butane 0 . (c) Lead acetate 0 (d) C2H s PbCI 0
6. When wawrvnpours are passed' over aluminium carbide, we 18. Most of hydi:ocarbons from petroleum are obtained by:
get: (a) fractional distillation 0
. (a) acetaldehyde . 0 (b) ethylene 0 (b) fractional crystallisation 0
(c) meth3ne 0 "<d) methyl alcohol 0 (c) vaporisation 0
7. When electrolysis of potassium acetate is carried out, we (d) isomerisation 0
get: 1~. The knocking will be minimum when the mixture of fuel is:
(a) methane' ·0 (b) ethylene 0 (a) straight chained 0 (b) iso-carboltation 0
(c) ethane 0 (d) acetylene 0 (c) neo-carbonation O. (d) none of these 0
·S. When Grignard reagent (CH 3 MgBr) is treated with water, we 20. Petroleum is a mixture of:
get: . (a) alkanes 0 (b) cyclo:llkanes 0
'(a) ethane 0 (b) ethyl alcohol 0 (c) aromatic hydrocarbons 0 (d) all of lh.:se 0
(c) qIcthyl alcohol .0 (d) methane 0 21. Iso-octane is added to petrol:
9~ Acti6nofheat on a mixture of sodium propionate and (a) to precipitate inorganic material 0
so~IUne produces: (b) to prevent freezing of petrol 0
'. (a}rriethane 0 (b) ethane. 0 (c) to increase the boiling point 0
, (c) propane . 0 (d)ethylene 0 (d) as an antiknocking agent 0
..to. Iithane canb"epreparedby: 22. The fraction obtained between tem(ft:ratures 150 -300°C
. {~l.betuingsodaliIneWithsQdium acetate 0 during fractional distillation of crude petroleum is:
(b)el~tl'olysis of sodiumsuccinafe 0 (a) paraffin wax 0 (b) heavy oil 0
(e) electrolysis of sOdii.U11 acetate 0
'(dj all of these 0
(c) kerosene 0 (d) naphtha 0
23. Hydrogenation of coal is done for the production of
11. wurtz reaction is used to prepare:
synthetic petrol in:
(a) ~ane only 0 (b) symmetrical alkanes 0
(c) Unsymmetrical alk:ahes 0 .(d) all of these 0 (a) Sabatier process 0 (b) Bergius process 0
12. For the conversion of CH 3 0H into methaIle, .the reagent
(c) cracking process 0 (d) none of these 0
24; Tfie number of chain isomers of alkane containing six
used is: carbon atoms is:
(a) s o d i m n ' O (b) P and HI 0 003 0 ~4 0
(c) hydrogen 0 (d) sodil\m hydroxide 0 (c) 5 0 (d) 6 0
13. Thepr04.uctsformed when the mixture of methane and
25. The compressed gas available in cooking gas cylinders is a
steam.: is paSsed over tmely divided nickel, at 1000°C are: mixture of: .
288 G.R.B. Organic Chemistry for Competitions
(a) C6H6 + C6HSCH3 D (b) C 2 H 4 + C 2 H 2 D 37. Which of the following compounds has been given an
(c) C 2 H 4 + CH4 D (d) C4 H IO + C3HS D octane number of 100?
26. By Wurtz reaction, a mixture of methyl iodide and ethyl (a) n-Hexane D (b) Iso-octane D
iodide gives: (c) Neo-pentane D (d) Neo-octane D
(a) propane D 38. The number of different substitution products possible
(b) ethane D when bromine and ethane are allowed to react, is:
(c) butane D (a) 6 D (b) 8 D
(d) a mixture of the above three D (c) 7 D (d) 9 D
[Hint: One mono-substituted, two di-substituted, two tri-substi-
27. Select the correct statement about alkanes:
tuted, two tetra-substituted, one penta-substituted and one
(a) they are polar in nature D bexa-substituted,]
(b) they are soluble in water D 39. The reagents and conditions to convert methyl iodide to
(c) they are non-combustible D methane are: .
(d) their dipole moment is zero D (a) action of dry Ag 2 0 D
28. Reaction of ROH with R'MgX produces:
(b) KCN followed by refluxing with diI. HCI D
(JEE (WD) 2009) (c) aqueous NaOH followed by boiling Al 20 3 at 640 K D
(a) RH . D (b) R'H D (d) Mg in'dry ether followed by boiling with water D
(c) R-R D (d) R'-R' D 40. A gaseous hydrocarbon 'X' on reaction with bromine in
29. It is necessary to use ...... in the iodination of alkane.
light forms a mixture of two monobromo alkanes and HBr.
(a) alcohol D (b) oxidising agent D
The hydrocarbon' X' is:
(c) benzene D (d) reducing agent D
(a) C2 H 6 D (b) C3H6 D
30. The reaction conditions leading to best yields of C 2 Hs Cl
(c) C3HS D (d) C4 H IO D
are:
41. Which of the following is notlinked with methane?
D (a) Marsh gas D (b) Natural gas D
Dark (c) Producer gas D (d) Coal gas D
room temp.
) D 42. The reaction,
Ni
(c) C 2 H6 + Cl 2 (excess)
UVlight
) D
H2C=CH2 + H2 250 -300o d CH3 -CH3
is called:
(d) C H + C1 UV light) D (a) Wurtz's reaction 0
2 6 2
31. A mixture ofCS 2 and H 2S on passing over heated copper (b) Kolbe's synthesis D
gives: (c) Sabatier and Senderen's reaction 0
(a) methane D (b) ethane D (d) Carbylamine reaction 0
(c) complex mixture D (d) propane D 43. Paraffin wax is:
32. For the preparation of alkanes, concentrated solution of (a) ester D
sodium or potassium salt of saturated acid is subjected. to: (b) alcohol 0
(a) hydrolysis D(b) oxidation D (c) unsaturated hydrocarbons 0
(c) hydrogenation D (d) electrolysis D (d) saturated hydrocarbons 0
33. The gas supplied in cylinders for cooking is: 44. Octane number of gasoline can be increased by addition of
BTX, BTX stands for:
(a) marsh gas o (a) butane, tetraethyllead and xylene 0
(b) LPG D
(c) mixture ofCH4 and C 2H6 o (b) butane, tetramethyllead and xylene 0
(d) mixture of ethane and propane . D (c) benzene, toluene and xylene 0
34. The thermal decomposition of alkanes is known as: (d) benzene, tetraethyllead and xylene 0
(a) cracking D (b) isomerisation D 45. The flash point in India is fixed at:
(c) dehydration D (d) reforming o (a) 44°C 0 (b) 35°C 0
35. Which of the following is not prepared by Kolbe's (c) 22.8°C 0 (d) 30°C 0
electrolytic process? 46. Photochemical chlorination of alkane is initiated by a
process of:
(a) C3 Hg D (b) C2 H6 o (a) pyrolysis 0 (b) substitution 0
D (d) C 6 HI4 o (c) homolysis 0 (d) peroxidation 0
36. When n-hexane is passed over Cr203 / Al 20 3 at 600°C, 47. Zinc~copper couple that can be used as a reducing ~gent is
...... is formed, obtamed by:
(a) hexane D (b) hexyne D (a) mixing zinc dust and copper gauze 0
(c) benzene D (d) none of these D (b) zinc coated with copper 0
Saturated Aliphatic Hydrocarbons
(c) copper coated with zinc 0 58. Grignard reagent gives alkane with:
(d) zinc and copper wires welded together d (a) H 2 0 0 (b) C2 H s OH . 0
48. 2.84 g of methyUodide was completely converted" into
methyl magnesium iodide and the product was decomposed
(c) C2HSNH2 0 (d) all of these 0
by excess of ethanol. The volume of the gaseous 59. The octane number of a fuel containing 90% of n-heptane
hydrocarbon produced at NTP will be: and 10% of 2,2,4-trimethylpentane is:
(a) 22.4 litre 0 (b) 22400 mL 0 (a) 10 0 (b)90 0
.(c) 0.448 litre 0 (d) 0.224 litre 0 (c) 100 0 (d) 50 0
49. Decarboxylation of isobutyric acid. gives n-alkane but 60. Kolbe's synthesis of sodium salt. of butanoic acid gives:
reduction of isobutyric acid with phosphorus and hydrogen (a) n-hexane 0 (b) iso-butane 0
iodide gives: (c) n-butane 0 (d) propane "0
(a) n-propane 0 (b) iso'-butane 0 61. The function of sodalime (a mixture of solid NaOH and
(c) n-butane 0 (d) none of these 0 solid CaO) ill the decarboxylation reaction is:
50. Correct IUPAC name of allGme obtained in the reaction of (a) to increase the rate of reaction" 0
2-chloropropane + sodium and dry ether is: (b) to decrease the rate of reaction 0
(a) 2,3-dimethylbutane' 0 (b) 2-isopropylpropane 0 (c) to change the rate of reaction 0
(c) n-hexane 0 (d) none of these 0 (d) none is correct 0
51. The IUPAC name o{neo-pentane is: [AIEEE 20091 62. Which of the following is the correct sequence ofSteps in
(a) 2-methyl butane 0 (b) 2,2-dimethyl butane 0 the halogenation of an alkane?
(c) 2-methyl propane 0 (d) 2,2-dimethyl propane 0 (a) Propagation, initiation, termination 0
52. In the complete combustion of Cn H 2n+2 , the number of (b) Initiation, termination, propagation 0
(e) Initiation, propagation,tt;!rmination 0 "
oxygen moles required is:
(a) 2~2 0 (b) ( n; 1)02 0 63.
(d) Propagation, termination, initiation
Reaction of alkanes with halogen is explosive in case of:
0
53. Which of the following isomers of the pentane gives four (a) ethane 0 (b) benzene 0 "
monochloropentane on chlorination?
(c) synthetic petrol 0 (d) LPG 0
(a) ~-Pentane 0 65. A hydrocarbon with formula C g H)8 gives one monochloro
(b) iso-Pentane 0 derivative. The hydrocarbon is:
(c) neo-Pentane 0 (a) n-octane 0
(d) 2,2-Dimethylpropane 0 (b) 2-methylheptane 0
54. Number of di-suestituted isomers of the product of the (c) 2,2,4-trimethylpentane 0
reaction, CH3 CH2 CH 3 + Br2' would be: (d) 2,2,3,3-tetramethylbutane 0
(a) 2 '. 0 (b) I 0 66. Which of the following alkanes can be synthesised in good
(c) 3 0 (d) 4 0 yield by the Wurtz reaction?
55. Aqueous solution of sodium acetate and sodium propionate (a) (CH 3 h CH-CH2-CH(CH3 )2 []
on electrolysis yields:
(b) (CH 3 h CH-CH 2CH 2-CH(CH 3 h 0
(a) ethane 0 (b) butane 0
(c) propane 0 (d) all of these 0 (c) CH 3 CH 2-C(CH3 )2-CH2CH3 0
56. What is the maximum number of carbon atomS in the (d) (CH 3 )3 C-CH2-CH2-CH 3 0
expected products of the Wurtz reaction? 67. The order of appearance of the following with iricreasing
CH3 - CH 2 Br andCH 3 -CH-CH;Br temperature during the refming of crude oil is:
(b) (CH3 )2.CH-CH2CH2CH3 and Mg(OH)Br 0 (c) miXing aluminium nitrate with mercuric oxide 0
(c) (CI:I3 hCH2 ,H2C=CH2 and Mg(OH)Br ' 0 (d) adding.mercury to aluminium chloride solution 0
(d) (CH3 h CHand CH3 CH20MgBr 0 82. Adam's catalyst is:
'70. Natural gas. is primarily composed of: . (a) platinum metal 0 (b) palladium 0
(a) methane o (b) n-butane 0 (c) nickel metal 0 (d) Pt0 2 0
(c) n-octane . 0 (d) a mixture of octanes 0 83. A gas oelieved to be the cause of explosion in coal mines is:
71. The ~ost important'method to prepare lower hydrocarbon (a) CH 4 0 (b) C2 H 6 . 0
is: (c) C3HS 0 (d) C4HlO 0
. (a) cracking 0 8 4 . When propanal is heated with Zn-,-Hg and conc. HCI, which
(b) 8abatier-8enderen's reaction 0 is formed?
(c) heating saltsoffatty acids witli sodalime 0 (a) C3H4 '. ·0 _(b) C3H6 o
(d) direct synthesis . '. 0 (c) C3 Hg 0 (d) C3 H7 CI o
72. Butane can be converted into 2-methylpropane,if heated 85. Catalyt'ic reduction of water gas gives:
with: /
(a) acetylene, 0 (b) ethylene 0
(a) Al 2Cl 6 0 (b) CrZO] 0 (c) ethane 0 (d) methane 0
(c) Cr02 Cl 2 0 ' (d) Nalether 0 • " . 86. The number of possible eQantiomeric pairs that can be
73. Percentage of hydrogen is maximum in: produced during monochlorination of 2-methylbutane is:
(a) C2H2 . 0 . (b) C 2 H4 0 (a) 2 .' 0 (b) 3 0
(c) C2 H6- 0 (d) CH4 0 (c) 4 0 (d) 1 0
74. Domestic cooking '~as consists of mostly: 87. (CH3 )3 C-MgCI on reaction with D 2 0 produCes:
(a) methane and ethane, ' 0 (a) (CH 3 )3 CD 0 (b) (CH 3 )3 OD 0
i(b)liquefied butane and iso-butane 0 , (c) (CD 3)3 CD 0 (d) (CD3hOD 0
(c) ethylene and carbon monoxide 0 88. The most stable conformation of n-butane is: .
(d) kydrogen and acetylene 0 (a) skew boat 0 (b) gauche 0
" 75. Paraffin dissolvesirJ: (c) staggered anti ,0 (d) eclipsed O'
(a) distilled wat~ 0 (b) methanol 0 89. Which of the following reactions is expected to readily give
(c) penzene' 0 (d) salt water 0 a hydrocarbon product in good yield?
76~ Uqui4 hydrocarb.ons is converted into a mixture of gaseous
ny~pcarbon by: [CBSE (PMT) Prelims 2010] (a) (CH3 h C-Cl C2H sOH) •0
(a) cracking 0 (b) hydrolysis 0
. (c) oxidation 0 (d) distillation 0 (b) RCOOK ElectrolysiS') o
77. The complete' combustion ofC~4 gives: [BHU.2004] Cl 2
(a) CO+ H 2 ' 0 (b) CO+N2 0
(c) CH3 -CH3 ~ o
0'
.
(C) CH3.~G-CH-CH3 o
(~): CH 3COCI CH 3MgX) ,
- HzO
o
, I I ' i02. Of the five isomeric hexanes, the isomer which can give two
D CH3
monochlorinated compounds is: (AIEEE 2005]
(d) CH3-CH-CH-CH3 o (a) n-hexane 0 (b) 2,3-dimethyl butane 0
. I (c) 2,2-dimethyl butane 0 (d) 2-methyl pentane 0
CH 3 103.% is heated with sodalime and gives ethane. Xis: ' ,
93. ' Which hydrocarbon is mainly present in gobar gas?
(A:FMC2005)
[AFMC 20031
(a) ethanoicacid 0 (b) methanoic acid 0
(a) Butane 0 (b) Propane 0 (c) propanoic acid 0 (d) either (li.) or (c) ' 0
(c) Methane 0 (d) Ethane 0 104. In order to .get propane gas, which of the following should
94. On mixing certain alkane with chlorine and irradiating it be subjected to sodalime decarboxylation? '(BVP 2006)
with ultraviolet light"it forms only one monochloro alkane. (a) Sodium formate ' D
The alkane could be: [AIEEE 2003; JEE (WB) 2010]
(b) Mixture of sodium aceta~e and sodium ethanoate' 0
(a) propane 0 (b) pentane' 0 (c) Sodium butyrate "0
(c) iso-pentane ,0 (d) neo-pentane 0
(d) Sodium p r o p i o n a t e : D
95. Which one of the following is reduced with zinc and
105. Methyl bromide is converted into ethane by, heating it in
hydrochloric acid to give the correspond1n.g hydrocarbon?
ether medium with:
[AIEEE 2004]
[CET (Karnataka) 2006; CET Engg. (Pb.) 2007)
(a) Ethyl acetate 0 (b) Acetic acid 0 (a) Al 0 (b) Zn '0
(c) Acetamide 0 (d) Butan-2-one 0 (c) Na 0 (d) Cu 0
96. A petrole~ fraction having boiling range 70-200°C and H3 C, " .'
containing~6-lOcarbon atoms per molecule is called: , P+ Brz Na .
106. /CH-OH--7~X; XIS: [DCE2006)
[UPSEAT 2004)
(a) natural gas 0 (b) gas oil 0 H3 C -
(c) gasoline 0 (d)' kerosene 0 CH3
97. The compound having only primary hydrogen atoms is: '\
o
,
~
o
.'
. ,
C12,hv, ( ; ' . : rod
) N Isomenc p
)
ucts,
,lOS• H3 e
o 'CH3
Fractional .'. d )
C SH l1 CI ) M (lsomenc proQ.Cts
, distillation . . ,,"
Give the number of Nand M: (lIT ,2006]
G.R.B. Organic Chemistry for Competitions
,
i
Saturated Aliphatic Hydrocarbons 293
II ANSWERS
. II
OBJECTIVE QUESTIONS
1. (a) 2. (b) 3. (a) 4. (b) 5. (b) 6. (c) 7. (c) S. (d) 9~. (b) , 10~ (c)
11. (b) 12. (b) 13. (b) 14. (a) 15. (d) 16. (b) 17. (a) 18. (a) , 19. (c) 20. (d) .
21. (d) 22. (c) 23. (b) 24. (c) 25. (d) 26. (d) 27. (d) . 2S. (b) 29. (b) , 30. (a) ,
31. (a) 32. (d) 33. (b) 34. (a) 35. (a) 36. (c) 37. (b) 38. (d) 39. (d) 40. (c)
41. (c) 42. (c) 43. (d) 44. (c) 45. (a) 46. (c) 47. (b) .' 48~ (c) 49. (b) 50. (a)
51. (d) 52. (c) 53. (b) 54. (d) 55. (d), 56. (a) 57. (c) 58. (d) 59. (a) 60. (a}
61. (b) 62. (c) 63. (b) .64. (c) 65. (d) 66,. (b) 67. (c) 6S. (a) 69. (d) 70. (a)
71. (c) 72. (a) 73. (d) 74. (b) 75. (c) 76. (a) 77. (d) 78. (d) 79. (a) SO. (c)
'Sl. (a) S2. (d) 83. (a) 84. (c) 85. (d) 86. (a) 87. (a) 88. (c) 89. (b) 90. (b)
91. (c) 92. (b) 93. (c) 94. (d) 95. (d) 96. (c) 97. (b) 98. (d) . 99. (a) 100. (b) .
101. (d) 102. (b) 103. (c) 104. (c) lOS. (c) 106. (c) 107. (a) 108. (b) 109. (b) 110. (c)
Ill. (a) 112. (b) 113. (c) 114. (d) 115. (d) 116. (a) 117. (a) 118. (b) 119. (a,b) 120. (a,c)
121. (a,b,c) Ill. (a,b) 123. (a,b,c,d) 124. (c,d) 125. (a,c)
x
.:.:Re;.:.:'
j' " ....
Reactivity of2° hydrogen
~-
2 J I I II III
=-x
6 3.8, 11.4 Decreasing order of their boiJjng points is:
% of 2-Chloropropane = 11.4 ~ 100 = 92% (a)I<II<IlI ,Q'(b)I>II>III 0
12.4
(c) II>I>III o
'(d) II1>I>II., 0
% of l-Chloropropane = 100 - 92 = 8%]
28. An unknown carboxylic acid salt on Kolbe's electrolysis
21. The highest boiling point is expected for:
form cyclobutane; the carQoxylic a9id can be: , '
(a) iso-octane o (a) adipic acid .' 0 (b) hexanoic acid 0 .
(b) n-octane o (c) succinic acid . [] .. (d) fumaric acid , " 0
(c,.2,2,3,3-tetramethyl butane o 29. A compound has molecular mass 42. It should be:"
(d) n-pentane '. 0 (a) propane O. (b) cyclopropane 0 '
22. Tetraethyllead (TEL) in petrol was used as antiknocking
(c) propene , , 0 .(d) butane , .D
agent, which creates lead pollution. In order to avoid lead,
30; Petrol is a mixture hydrocarbons from'C 6 to C g • The quality
pollution, the substitute of TEL is used in unleaded-petrol. .. ' ..." r •
The substitute is denoted as: ,of petrol is determined in terms of octane nUIJ:iber:, The .
(a) AK-33:-X 0 (b) BK-33-X o higher the octane number, better is the quality of.fUel. The
correct order of octane number is: ',
(c) CK-33-X 0 (d) DK-33-X o (a) cyclo~es < alkenes < alkanes < aromatic hydr~~ns '
[Hint: AK-33-X;' Its chemical name is cyc!opentadieny! (b) alkenes < alkanes <aromatic hydrocarbons .
manganese tricarbonyJ.]
, . '< cycloalkan~s
. 23. If an alkane has number of carbon atoms equal to n, then the (c), aJk;mes < aromatic llydrocarbons < cycloaikanes .
number of moles of oxygen required for its complete " , .' <fllkenes
combustion is: (d) alkanes < ,aJkenes :<:cycloalkanes
(a) 3n + I 0 (b) 2n 0 , < arowatic hydrocarbons
2
!,
3. Hexadecane is commonly called: s. Select the correct statement about the efficiency of gasoline:
(a) octane (b) cetane (a) branched alkanes are better fuel than straight chain
(c) gasohol (d) natalite alkane
4~ Octane number of regular gasoline is 87. It has same (b) lesser is the octane number, greater i~ the efficiency of
knocking property as: fuel
(a) a mixture containing 87% iso-octane and 13% heptane (c) high quality fuel has greater knocking property
(b) a mixture containing 13% iso-octane and 87% heptane (d) all of these
(c) 87 g iso-octane dissolved in 1 litre alcohol
(d) 13 g iso-octane dissolved in I litre water
7.1 INTRODUCTION n,~,y, etc., are written to indicate the carbon atoms having
The open chain hydrocarbons which ~ontain lesser number of double bond.
hydrogen atoms than the corresponding alkanes containing H 2C=CH 2 (Ethane - ane + ylene) Ethylene
same number of carbon atoms are called unsaturated CH 3-CH ,CH 2 (Propane - ane + ylene) Propylene
a
hydrocarbons. The members which contain two hydrogen CH 3-CH 2 -CH=CH 2 (Butane - ane + ylene) a~Butylene
atoms less than the corresponding saturated hydrocarbons are
~
known as olefins* and are represented by the general formula CH 3-CH=CH - CH 3 (Butane - ane + ylene) ~Butylene
C n H 2n • These are characterised by the presence of a double
bond between two adjacent carbon atoms,)C=C<' in the CH 3-C=CH 2 (lsobutane -:- ane + ylene) . ISo-butylene
* The tenn olefin has its origin from an old Dutch name of ethylene 'Olefiant gas' (oil fonning gas) which refers to the oily nature of the product
(ethylene chloride) fonned by the combination of ethylene and chlorine.
** Alkenes containing two carbon-carbon double bonds are called dienes or alkadienes.'
Unsaturated Hydrocarbons 299·
(iii) IUPAC system: The name is obtained by dropping Butene has two position isomers.
the suffix -ane from the name of the corresponding alkane and CH 3CH 2CH=CH 2 ; CH 3CH=CHCH 3
adding the suffix -ene. . '. But-I-ene But~2-ene
Alkane - ane +ene = Alkene (b) Chain isomerism :. This is. due to the difference in
The position of the double bond' is indicated by the the nature of carbon skeleton:
number of the first carbon atom (lowest numbered) involved CH 3CH2CH=CH 2 "
in the double bond. Alkyl groups are numbered, named and But-I..:ene
.. placed as prefixes in alphabetic order. When there are two or
three double bonds in the molecule, the ending -ane of the 2-Methylpropene
corresponding alkane is replaced by -adieneor -atriene.
H 2C=CH 2 CH 3CH=CH 2 Chain isomers
Etbene . Propene
CH 3CH2CH=CH 2 .., CH 3CH=CHCH 3
But-I-ene But-2-ene
CH34=CH2 CH 3CH 2CH 2CH=CH 2
CH 3
Pent-I-ene rIf3
2-Methylprop-l-ene
CH 3 -CH 2 -C-CH2
2-Methylbut-l-ene
CH 3CH 2CH=CHCH 3 ; . CH 3CH 2C=CH2
Pent-2-ene . I Chain isomers
CH 3 (c) Geometrical isomerism : Due to restricted rotation
2-Methylbut-l-ene about the double bond, the alkenes (with the exception of
ethene and propene) show geometrical isomerism. But-2-ene
H 2C. CH-CH-CH 2 shows geometrical. isomerism.
Buta-I,3-diene
3-Methylbut~l-ene .
Alkenyl groups: The monovalent groups obtained by .
. H3)C c~j\~;:ut:<~J
the removal of one hydrogen atom from alkenes are called H H H~ H
alkenyl groups. Cis-form Trans-fonn
H 2C=CH- H 2C=CH-CH 2- Pent-2-ene also shows geometrical isomerism.
H)C <~,~~;>ent:<~.
Etbenyl (Vinyl) 2-Propenyl (Allyl)
CH 3-CH=CH- . CH 3-CH=CH-CH 2-
I-Propenyl 2-Butenyl (Crotyl)
HC C- CH 3CH 2-C=CH-CH 2- C2HS . CH 3 . H CH 3
2 I .' I. Cis-form Trans-form
CH 3 CH 3 Besides. the above three types, alkenes show ring-chain
lsopropenyl 3-Methylp~nt-2-enyl . isomerism with cycloalkanes.
( I-MetJIylvinyl)
Alkylidene groups:
H3C- CH= ; CH 3-CH 2-CH=
Ethylidene Propylidene
CH 3 -C= H2C-CH2
I CH3CH2CH=CH2
But-l-ene
.I I
CH 3 H 2C-CH2
lsopropylidene Cyclobutane
In the dehydration of secondary and tertiary alcohols, result, the protonated ethanol breaks with the elimination of a
when there is a possibility of formation of two isomers, the water molecule to form ethyl carbocation. .
hydrogen atom is preferentially eliminated from the adjacent (1-+-H~
Slow +
carbon atom with the fewer number of hydrogen atoms. CH 3 CH 2 -O CH 3 CH z + H20
This is Saytzeff's rule. I Carbocation
H
CH -CH -CH-CH 60% H 2SO\ CH 3CH 2C. H=CH 2.
3 2 I . 3 100°C
But-l-ene (20%)
This step is slow and hence is the rate-determining step of
the reaction. .
OH 3rd step: Finally the carbocation being unstable and a
Butan-2-o1 (Sec. alcohol)
+CH 3CH=CHCH 3 reactive' chemical speCies, readily loses a hydrogen ion to
But-2-ene (80%) yield an alkene.
H H . • . . .
Dehydration of alcohols are stereoselective reactions in
which a single starting compound can yield two or more
(Main product)
I I
H-y-C-H~
.H) . H C=C<· + H+ .
stereoisomeric products and proceeds in the. direction that [J + H H Taken up by new
H alcohol molecule
produces the most highly substituted alkene and the more
stable one is formed in greater am.ounts. A carbocation As alkene is more volatile than alcohol, it is easily driven
intermediate is involved and sometimes' rearrangements take out from the reaction mixture and thus the reaction is
place during elimination. For example, butan-2-01 gives completed inspite of the reversible nature.
but-2-ene (80%) and more stable trans-stereoisomer [The formation of ethylene from ethyl alcohol c~m also be
predominates. Pentan-3-01 gives 75% trans-pent-2-ene and explained in the following manner.]
25% cis-pent-2-ene and so on. 1st step: When ethyl alcohol is reacted with H 2S0 4 at
Cone. H 2SO,,>
CH3CH2-iH-CH2CH3 Heat 170°C, it forms ethyl hydrogen sulphate.
C 2 H sOH + H-HS0 4 ---4 C 2H sHS0 4 + H 20
. OH 2nd step: Ethyl hydrogen sulphate decomposes to form
Pentan-3-ol alkene.
3 2 2 C 2H sHS0 4 ~ C 2H 4 + H 2S0 4
CH CH )C=c(CH 3 + CH 3CH )C=C<H
A controlling factor in the dehydration is the formation of
H H H CH 3 carbocation. The alcohol is dehydrated more easily which
Pent-2-ene (25%). Pent-2-ene (75%) foons a carbocation more easily. The more stable the
(Cis) (Trans) carbocation, the more easily it is formed. Thus, the ease of
H+ dehydration follows the same sequence as the ease of
R 2CHCR'2 ~ R 2C=CR '2 + H 20 formation of carbo cations, i.e., the stability· of the
I Alkene carbocations.
OH Tertiary (3°) > Secondary (20) > Primary (10)
Alcohol
OH (The detailed mechanism is given in chapter 5),
~.' '. The same sequence is observed when vapours of alcohols
~ are passed over alumina for dehydration.. Some . other
2-Methyl hexan-2-ol 2-Methyl hex-I-ene dehydrating agents are P20 S , BF3 , conc. H 3 P0 4 , dry ·HCI,
(20%) CaCl 2 and KHS0 4 , etc.
Al 20 3
+~ Primary alcohol --"":7)
350°C
Alkene +H 20
2-Methyl bex-2-ene Al 20 3 .
(80%) 3500C) H zC=CH 2 + H 20
Ethylene
Mechanism: The mechanism of acid catalysed
dehydration involves the formation of carbocation as an
intermediate. The reaction is believed to occur in three steps:
1st step: Due to the presence of two lone pairs of
electrons on oxygen, alcohols act as weak bases. Therefore,
they react with strong mineral acids (H 2S0 4 or HCI etc.) to
form a protonated alcohol (oxonium ion).
"..---"..
•• + +
CH 3CH 2 0H+H CH 3CH 2 0H CH 3 CH 3
•• ••
Ethyl alcohol H I I .
Protonated alcohol CH 3 -C-OH CH 3-C=CH 2
2nd step: The presence of positive charge' on highly
electronegative oxygen atom weakens the C-O bond. As a
I 2-Methylpropene
CH 3 (Isobutylene)
Tert. butyl alcohol
302 G.R.B. Organic ChemistrYjor Competitions
Cyclohexanol'
Conc.H3P04
100-130°C
.
o
Cycblhexene
In the case of secondary and tertiary alcohols, the
3 2
CH3
CH -6-CH OH- Conc. H2S0,\
I
CH
.6., -H20
3
CH 3-C=CHCH 3
fH 3
~ Ale.KOH
.6. ,,~-+~
2-Bromopentahe Pent-2~eDe Pent-l-ene
(Major) (Minor)
~
Alc.KOH
.. +
.6.
ar 2-Methyl but-2-ene 2-Methylbut-I-ene
2-Bromo-2-methyl-butane (70%)' - (30%)
CH3-b~-CH3
I X
S0 Alkyl halide
CH 3 -C--CH-CH3 COIl-c. H2 4) + H~B + X-
, I- I ' a,-H 2 0
2,3-Dimethyl but-2-ene
Conjugated . Halide
CH3 0H acid of base .
3,3-Dimethyl butan-2-ol
'~
ChlorocyeloheKane
o
Cyclohexene
The fQrmatiQn Qf less substituted alkene in an eliminatiQn
Mechanism: The functlQn Qf hydrQxide iQn is to, pull
reactiQn is called as Hofmann elimination.
the hydrQgen iQn away frQm carbQn atQm; simultaneQusly the
The increasing Qrder Qf dehydrQhalQgenatiQn is:
o-r-{;H,
halide iQn separates and the dQuble bQnd fQrms. .
. CH
OH-:-~
•• I
-C-C
·I~
----7 > <
C=C +X- +HzO
~2CH,Br < < OBr '
G.R.B. Organic Chemistry (Or Competitions
CH3CH2CHBr2 + Zn Methanol) [CH 3CH2CH(] + ZnB;~ CH2COO- -2e- CH2 2Na+ + 2e-- 2Na
l,l-Dibromopropane
(Propylidene bromide) .
1 I ; . - I I +2C02
CH2COO- CH2· 2Na + 2H 0 - 2NaOH + H
Ethene 2 2
CH 3CH=CH2
Propylene The method is an extension of Kolbe's method for the
preparation of alkanes.
If sodium metal is used in place of zinc (like wurtz S. Controlled partial hydrogenation (reduction) of
reaction), then higher alkenes can be obtained. alkynes :. Alkynes react with hydrogen when passed over
r-----------------~
/:Br Br heated catalyst (Lindlar's eatalyst)-Palladium poisoned
CH3CH~
I
Ether with CaC0 3 or BaS04 and partially poisoned by addition of
+4Na+ )cHCH3
.Br·------------~
I ______
I,l-Dibromoethane
Br I
In place of Zn dust, NaI in acetone can also be used by E 2 (a) Hydrogenation ofalkynes with Lindlar's catalyst or a
mechanism. nickel boride called P-l catalyst yields only cis-alkene.
t.~..;~::
_. .', .. _,,'~.' __ ,
~ .<:-.>,-.\'O:,:~_>-~_
R'--C==C-R+ H2
Li, NalLiq. NH3
)
I H 2C=CHC1 . ) H 2C=CH-CH3·
Propene
Alkyne H--C'-R
9. By GrigDardreageDts : . Alk:enes can be obtained by
Trans-rukene
,reacting Grignard
.
reagent with vinyl chloride.
.
.
So. R . . . . . "',
Lindlar's
.--..,.....--~
H 3) "
C=c
. ( "CH 3 Mg<. +X~CH=CH2'~ MgX2 +RCH'·~·-:-tH~
catalyst
, ,X Vinyl halide .' _ . AU<.ene .
H .' H
.Cis-but-2-ene " CH "',' .'
CHjO=CCH3 + 1I2
'+CI'--CH,-:-CH2'~ MgCI~ +CH 3CH
3
But-2-yne " Mg< 'CH 2
Na/Liq. NH3 CIVinyl chloride '. Propene
Birch reduction
10. By Wittig reactioD: ConverSion of aldehydes and
Trans-but-2-ene ketones to alkenes with the help of alkyUdene (methylene)
(c) Hydroboronation of alkynes (with B2Ho) followed by triphenyl phosphorus (Willig reagent) is .known as Wittig'
protolysis (with H+) gives almost pure cis-alkene. reaction, e.g. " . . .
. ." I ' . .' '. . '. , . ' . Heat'
CH 3C" , o + (C 6 H sh P =CH2 ~CH3CH=CH2
~ .
~~" .... H.j.·, ~.
'--C==C- ) (-CH=C-)3B -=-j'--CH CH- . Acetaldehyde " . Propene
'+(t.(jHshP . 0
6•. Pyrolysis or c:racking: Higher alkanes when heated ;Triphenyl
at high temperature (50o-700~C) decompose to produce a pho~hine Qxide
lower alkane and an alkene (C'--C fission).
C~)+~h)~2 Hw~8·+~h)3PO
Mo)~ h()wev~r, accelerates the C-H.linkagefission.
. . . . . Cracking . . . . . .
CH3'--Cl;I2-CH 3 . . .) .CH 3ClI-:-CH 2 + H2
. Propane' .. (Catalyst) . '. Propene ,
,'. .,. PyfoIysiS ofquatemary ammODiumeompoilnds:'
Many alkenes are conyeniently prepared by lieating quatetnary Now, ',carbonyl compound is ad~ed, din';~tly to ether
ammonium compounds.::..:.... . ' . . solution of Wittig reagent. " .'
+ -' Heat' 11. PetersoD reac:ti9D: . (3-Hydroxy alkyl silane gives
(C 2Hs )4NOH ) (C 2H s h N +C 2H 4 + H 20 elimination reaction in presence of acid as well as.base. It is
.Tetraethylammonium . Triethylamine Ethene
hydroxide (ten. amine) .
.stereosefective of E- and Z- iSOl;ners of alkene. .
(C 2 8 s )4 Heat) (C 2H ShN +C ZH 4 + ~
NX '.' H"c ' c/H ~. BF3,e~er Si(CH3~~c(~jf7
It is called HofmaDn eliJilinatioD with ,the fonnatioti of .' C3117/ "C3H7 (Anti-eliniination) C3H7 / ~iI
on
'an amine having smaller alkyl groups the x-bonded carbon. Z~alkene .
. This reaction is E2 elimination with an all}ine 'as leaving
/C==c,/~~7
.- group:. ,. ' .,. . Kil, THF
""
. 8. AdioD' of c:opper alkyl Oil' 'Vioyl-eblorides: ~lkyl
.J>. . .
(Syri-elimination) C3H?' .... . "-H
derivatives of ethylene can be conveniently prepared by the ....:{CH3hSi-DH· E-alkene
action of copper alkyls on vinyl chloride..
. .
-:Ail
--,,--.
306 G.R.B. Organic Chemistry tor Competitions
12. Cope reaction or cope elimination: When a The total bond dissociation energy of double bond
3°-amine oxide containing at least one j3-hydrogen is heated at (146 kcal) is greater than carbon-carbon single bond
150°C, it decomposes to fonn an alkene and a derivative of dissociation energy (83 kcal). Hence, the double bond is
hydroxylamine {Thennal elimination} " stronger than carbon-carbon single bond.
Chemical properties: ,The most important reactions of
alkenes are the addition readlons. Alkenes are reactive due to
the presence of double bond. The double bond consists of a
strong a-bond and, a weaker 1t-bond. The 1t-electrons are
loosely held, and are, therefore, easily polarisable. In addition
reactions, the 1t-bondis broken and ,two new a-bonds are
fonned. The fission of the bond may be heterolytic or
homolytic as shown below.
Transition state
C-C< .(Heter~lytic >C=C< 'HO~lytic) >c-c<
R-CH > fiSSlon fiSSlon. .
+ ' R2NOH Charged species Drradical
- II
CH Djalkyl In polar solvents, addition proceeds by ionic mechanism
2
Alkene hydroxylamine (i.e., at low temperature), whereas in the presence of light or
This reaction may also be carried out in dimethyl non-polar solvents, the addition occurs by free radical
sulphoxide or THF at room temperature. mechanism (i.e., at high temperature).
Ionic mechanism involves three steps:
7.6 GENERAL CHARACTERISTICS 1st step: The reagent E-Nu ionises to give an
Physical' properties: (i) The first three memb'ers are electrophile and nucleophile.
gases, the next fourteen members are liquids while' alkenes E-Nu ----7 E+ + :Nu-
with more than 17 carbon atoms in the molecule are solids at
room temperature. 2nd step: The electrophile attacks the carbon-carbon
(ii) Except ethene, all are odourless. Ethene has pleasant double bond and fonns a covalent bond with one ofthe carbon
odour. All are colourless. atoms by utilising the 1t-electrons. The other carbon atom
(iii) Like alkanes1 alkenes are insoluble in water but acquires positive charge, i. e., fonnation of carbocation occurs.
dissolve freely in organic solvents.
(iv) The boiling points, melting points and specific
E+ + >[\Alkene
C< SlOW) >C-c<
I
gravities show a gradual increase with the increase of E
molecular mass in the homologous, series. They are less Carbocation
volatile than alkanes, i. e., their boiling and melting points are 3rd step: The nuc1eophile now attacks the carbocation
higher than corresponding alkanes. Cis-isomer has a higher to fonn an addition product.
boiling point than trans-isomer due to higher polarity.
For example, cis-but-2-ene has boiling point 277 K and >C-e(+ :Nu- Fast) >C-C<
trans-but-2-ene has boiling point 274 K. I~ I I
However, trans-alkenes have higher melting points than E E Nu
their corresponding cis-isomers. For example, cis-but-2-ene Addition product
(m.pt. = 134 K) and trans-but-2'-ene (m.pt. = 167 K). This is
As the addition reaction is initiated by an electrophile,
due'to the fact that the trans-alkene molecules are symmetrical the reaction is termed as electropliilic addition. '
ap.d therefore, they can pac~ more closely in the crystal lattice The addition of electrophilic reagents relieves the strain
than the cis-alkene molecules. So, larger amount of energy is
required to break the crystal lattice 'of trans-a.lkene than the of >C=C< (bond angle 120°) by changing itto 7C-C~
corresponding lattice of cis-alkene, i.e., trans-isomers are (bond angle 109.5°). The r~ctivity order for alkenes hail been
more stable than the cis-isomers. given on the basis of heat of hydrogenation as,
(v) They are weakly polar. The values of dipole moment H 2C-CH 2 > R--CH=CH2 >R 2C=CH 2 ""
for alkenes are pretty close in the rang\.: of 0.35 to 0.40 D. , R-CH=CHR > R 2C=CHR > R 2C=CR 2
> However, trans-isomers have zero dipole moment and are
The reactivity of alkenes is, however, also related to the
non-polar.
following factors: '
(vi) The double bond in alkenes consists one sigma and
(i) Steric effect, ' (ii) Hyperconjugation and (iii) Heat
onepi-bon<J.
'of combustion.
, 'Carbon-carbon double bond (C=C) is shorter than the
Alkenes (except ethene) also contain' alkyl groups. Alkyl
, cali'on-carbon singlehond.
part is very stable. Like alkanes, this part can show
, , .
. .;.
Unsaturated Hvdrocarbons 307
1. Addition reactions: The important addition (b) AdditiOn of halogens: Halogens (chlorine and
reactions of alkenes are described below: bromine only) add at ordinary temperatures to alkenes in
(a) Addition of hydrogen (Hydrogenation): Alk~nes presence of an inert solvent, (e.g., CCI 4 ) to form vicinal
combine with hydrogen under pressure and in presence of a dihalides. Br2 water is decolourised by unsaturated hydro-
catalyst (Ni, Pt, Pd or Rh) to form corresponding alkanes carbons (hence the test of uusatoration).
(Sabatier-Senderen'sreaction). CCl 4 .
Catalyst Br2 + H 20=CH 2 ------~~) CH 2Br--CH2Br
Hp CH 2 +H 2 ---=~) CH 3 -CH 3 + Heat (Brown Ethylene (Inert solvent) Ethylene bromide
~ Ethene Ethane colour) (Colourless)
Catalyst Inert
CH 3 -CH=CH 2 + H2 ----=~) CH 3 CH 2CH 3 + Heat Br2 + CH 3CH=CH 2 --~)' CH 3CHBrCH2Br
Propene (Brown Propylene solvent .
Propane Propylene bronude
colour) (ColoUrless)
The reaction with fluorine is explosive whereas iodine
reacts very slowly. When alkene is bubbled through alcoholic
solution of iodine (12 solution in CCI 4 ), a mixed halide is
formed.
H 2C=CH 2 + I+Cr ~ CH 2I-CH 2CI
CH 3CH=CH 2 + I+Cr ~ CH 3 -CH-CH 2I
Cis-cyclododecene Cyclododecane (100%) Propene I
CI
When nickel is used as a catalyst, the reaction is carried
2-Chloro-l-iodopropane
out at 200-300°C and in presence of Pt or Pd, the
hydrogenation can occur even at room temperature. With trans-but-2-ene, the product ofBr2 addition is optically
Hydrogenation follows free radical mechanism. inactive due to the formation of symmetric meso compounds.
Hydrogenation is exothermic. The heat of hydrogenation CH 3 CH 3
of every alkene is fairly close to an approximate' value of
30 kcaVmol. The heat of hydrogenation of ~ alkene is an
H-C-CH 3
I +Br2
~H+Br + Br+H
index of its stability. The lower the heat of hydrogenation of H3 C--C-- H H+Br Br+H
an alkene, the more stable it is. Trans-but-2-ene Trans-but-2-ene CH 3 CH 3
(Meso)
(27.6 kcaVmol) is more stable than cis-btit-2-ene
(28.6 kcaVmol) and but-I-ene (30.3 kcaVmol). In general, for symmetrical alkenes and symmetrical
A terminal double bond may be reduced by sodium in reagents, the addition takes place as:
liquid ammonia in the presence of an alcohol (MeOH or cis-alkene + syn-addition ~ meso
EtOH). This is called Birch reduction.
trans-alkene +syn-addition.'~ racemic
RCH=CH 2 +2H Na/Liq. NH3 ) RCH CH cis-alkene + anti-addition ~ racemic
EtOH 2 3
trans-alkene + anti-addition ~ meso
Cyclohexene can also reduce olefinic bond, and itself is This re&ction provides a useful test for unsaturation, the
oxidised to benzene. .
0'1
brown colour of the bromine being rapidly discharged as the
O 2CH3~H3
colourless dibromoderivative is formed. The reaction is.
+ 2H2C=CH2 - + stereospecific, anti-addition is observed. A stereospecific
Ethene ::::,... , ,Ethane reaction . is that where stereoisomeric starting substrate
Cyclohexene Benzene produce products which are stereoisome~ of each other.
The double bond is also reduced in excellent yield by Mechanism
NaBH 4 -PtCI 2 • 1st step: . The Br2 molecule ionises on interactio~ with
q
Me Me
~.
H
Me Me
1t-bond.
Br2~· . Br+ +
Bromoniurn ion
(Electrophile)
.
:Br-
Bromide ion
(Nucleophile)
[Meso ()r syn addition product] 2nd step: Bromonium ion attacks the double bond to
form a carbocation.
The rate of hydrogenation of olefmic bonds at room
temperature is -CH=CH 2 > -CH=CH-' 'or a ring .. , Br
, I
double bond. . )c·rt< +Br+
Alkene .
Slow)
)C--C< '
Carbocation .
..
G.R.B.Orf!;.anic Chemistry for Competitions
. ,jrd step: Nucleophile (Br -) attacks the carb~ation to ' . Thus, ionjc . addition of
unsyminetrical reagents .to
. form addition product ' ,.,' unsymmetrical alkeQes is regioselective reaction. '
Br.,. Br Hi . ,. The order of reactivity of the hydrogen halides is:
," , + ,'I , . . I' ,I' '. ,. t.
HI> HBr :;> HCl >HF
, )c-e< + :Br- Fast) )C::-e( Mechanism
. ~., ,lststep : HXionis~s;' HX ~ 'H+ +:X-
'Mechanism-was proved by following addition reac~(m.
'.. ' ~ H"~;'H:.' . 'B ' NaCi (aq,) ~ . '. 2nd step :,' ElectroiJhile (H+)'attacks the double bond to'
:; " '. '.' ,2""'-"" 2 + r2 . - .) form carbocl!tion.
" CH z'-CH 2 ,+ CH 2-CH 2 +tH2~CHi
I ,t ·1,
Br OH Br
I" I
Br ' Br
. I '.
. CI
H+.+
,
C< ~ ,>c~~
)C,.
'.' R·
.~
Mechanism:
Step 1: HBr' -""-'-4 H+ + :Br-
, Attacking eleCtrophil~
Cyclopentene,
Br 'Br Step 2: The proton (H+) attacks the 1t-b()nd to give a
i
.l,2-Dibromocyclopenjane, stable carbo<;ation. .
-+
(Trans)' .
. .
. , ~CH3-CR-CH3
. (c), Additi~n of : halogen acids: . Alken:es react ,with 20 Carboeation
, halog~'acids (HCI~, H.Br or HI) to foi"Iri alkyl halides .. ' CH 3--r-C'H =nC~H
2 + H + Slow . ' . (More stable)
." '
Propene
., . r,.,.j.'
'+
CH 3 -CH 2,-CH2
. 10 Carbocation
(Less stable)
. .~ , Step 3: ' The nucleQphile bromide ion attacks the·,more
A protbn. 'ltnd 'a halogen add to the doubie ,bond of an stable 2~ carbocation togive2-bromopropane (major product).
alkene' ,to form an aU<yl Mlide 'in accordance With . , . + . . Fast '. . "
. ¥ar~o~ikoff's rule'undernonniil qoridition. ' ' . CH3-C.iI-CH:; +:Br~ ) CH 3--,-CH-CH 3
. " or
-
,RCH" CR z ' . '"
+ ,HX'; RCH2~C.R2 l' , I3r'
, Alkene:, " ,Hydrogen ',' , I, , 2-BrQmopropane ,
, ,halide,' X': '
. A.J.kylli.a1id«: , In another .example, an addItion' ofHBl' to isobutyl<:?ne
Uns~etrichlalkenes give ~o diff~rent products with forms tlirt., butyl bromide (2-bromo-2,-methyl propane) as .
unsymmetricalteagents; .These prOducts are constitu~ional major product It is a completely regioselective reaction, as
isot)1eis: the one ~duct y.rhichptedomi1ui:tes in the reaction, 'one ofthe possibl€: product'(1~bromo-2-methylprQPane)'is not
is ,called aregiosel~tive reaction, "" .' ) . . .' ., formed at alL '
;
(
,', \ :
.
~.
. . '. :
. "·.lsr-
CH .
I 3
CH 3...::.cc-CH 3
, . '!i . , .
'i-BroiOO~2-methyl propane
orTen: butyl bromide (Majorproduci)
Other examples are:
CH 3 · CH 3 Ca3
1 " . .
CH 3-CH-CH=CH2
+HBr I , I '
) CH 3 -,-CH 2CH 3 +CH 3-CH-'.
3-Methyl but-I-ene
Br
r-CH
Br .
3
2-Bromo-2-methyl 2-Bromo-3-methyl
. butane (Major) butane (Minor)
CH 3 CH 3 CH3
I ,+HBr I I',
CH 3 -C-CH=CH 2 ~ CH 3-C-'. CHCH 3 +CH 3-C-,.-CH-CH 3
I , ,l 1 . '. , 'I . I '",-
CH 3 . Br 'CH 3 'CH3 Br
3,3-Dimetbyl but~l~ene ..' 2-Bromo-2,3-dimethyl butane ,2-Btomo-5,3-<limethyl
(Major) butane '(Minor)
The addition of fIX to 2-i>entene V$'.notregioselective as both alkyl halides CZ-Bromopentane and 3~Bromopentane)'~ formed in
comparable amoun~s. . . . .
) CH3CHitH2'H~'. '
+
CH 3CH 2CH 2CHCH3
2° Carbo cation .
..:- '
, .
'. . ' Br
CH 3CH 2t:H==CHCH 3 H
, 2-Bromopentane
. Pent-2-ene + Br...·· .'."
CH3CH2CHCH2CH3 ." ) CH 3CH 2CHCll2CH 3
2°. Carbocation'
.. ',
I·
. Br
. ".
,J
3-Btomopentane
. Addition occurs rapidly ina variety ofsolvents~ mduding Peroxide effect :. Kharascb observed tbatthe addition
cblorofo~ benzene, acetic aCid and dicbloromethane; etc. of HBr totmsYnunetrical alkenes in the presence of organic "
CH3CH~'>'..... . <.'CH;CH3 . . . '. . peroxides [(C 6H sCOOh , Benzoyl peroxide] follows an .
.' -r::'
,. . C=C'. + HBr • Solvent )' . opposite course' to that. suggested by Markownikoff.This is
, . H·' . H~'
.
..
. termed anti-Markownikoff or peroxide effect.
. .
Peroxide . .
Hex-3-ene (cis)
. .', ." . CH3CH2CH2Br
I-Bromopi'opane'
';:;H3CHzCHCH2CH2CH3
· . I' . . . CH3~CH2 +HBr . . . ' .(l1-PrOPYlbrO~~e)
. Br .
opene . ' .No ~oxide CH CHBrCH
3-BromOhexane . ,3 ,3
(75%) . 2-Bromopl"9JJane
acc ~.'
. CH3 .r .... (Isopropylbromide)
. . .
~
+ HCl ~.~-CI
..
I-Methyl cyclopentene · .:~ I-Chloro-I-methyl-
, cyclopeptane (100%)
310·. G.R.B. Organic Chemistryfor Competitions
(termination). .
(More stable)
Step 4: More stable free radical attacks the RBr O CH
Methylene cyclohexane
2
O CH2Br
OH
I-Bromomethyl
.~ ~
CH 3CH-CH 2Br + H-Br
Fast
) CH 3CH 2CH 2Br + Br
• cyclohexanol (90%)
I-Bromopropane
Br2
• • (CH 3 hC=CH 2 H 0) (CH 3 h,-,H2 .
Step 5: Br + Br ----7 Br2 2
2 .. Methyl propene
Free radical chain reaction can also be initiated OHBr
photochemically either with or without adding peroxides. I-Bromo-2-methyl-
~CH2+ RBr ~
propan-2-ol(77%)
[)<H
~ CH2Br
Oxygen is more electronegative than bromine (or chlorine
Methylene
cyclopentane
Bromomethyl
cyclopentane (60%)
Note: Peroxide effect is effective only in the case ofHBr and not.effec-
tive in the case of HCI and HI. This is due to the following rea-
o
or iodine) and so the HO-Br bond is polarized.
+ el, H,o.
CycIopentene
H
et° CI
sons: 2-Chlorocyclo-
pentanol m'ans)
1. H-CI bond (103 kcal/mol) is stroIlger than H-Br bond
(87kcal/mol).H-Clisnotdecomposedbyperoxide-:fi:eeradical. In these halohydrin fonnation reactions, a halonium ion is
2. Iodine-free radical formed as H-I bond is weaker but fonned as .an intennediate which is attacked by water in
iodine-free radicals readily combine with each other to form aqueous solution. .
iodine molecules rather than to attack the double bond. The order of reactivity of different X 2/H 20 (H0-X) is:
3. InH-Br both the chain propagation steps 3 and 4 are exother- CI 21H20(HOCI) > Br 2/H 20 (HOBr) > I 2/H20(I-OH)
mic while in HCI step 3 is exothermic and step 4 is endother- Mechanism: The addition of halogens in presence of
mic. In HI, step 3 is endothermic. water occurs through the intennediate formation ofhal onium
ion as shown below:
The abnonnal addition ofHBr in presence of peroxide can
be ~revented by the addition of an inhibitor such as diphenyl 1st step: CH3CHVcH2 + 8~~~ ~ CHl:H-CH2CI + cr
anune or catechol, etc. .
An . M·
u- arkownik0 ff addItIon
..
is observed if the alkene
Propylene
~
bears a powerful electron withdrawing gl'llUp (-/ group) 1nd step: CH3-rn-CH2Cl + H--O: ~CH3-CH-CH2Cl
attached directly to the doubly bonded carbon. I I.
H H-o+
I
H
Unsatu.rated /fydrocarbQns .311
CH 3fHCH 3
2 S
CH )
HH
bond (Hydroboration oxidation).
C=C <C H
Hex-3-ene
2 s
,
2 s
B2 H6 '(ether») C H
H20 2 ,OH H
>
anti-Markownikoff's addition of water (hydration) to a double
C-C,<CzH
I I H
H OH
s
OH Hexan-3-QI
Propan-2-ol '+ Enantiomer
CH 3--C=CH z >CH 3-CH=CH 2 > H 2C=CH z Another convenient hydroborating agent is the
borane-tetrahydrofuran (BH3 - TIfF) complex. It is very reactive
I and the reaction is carried out in THF (tetrahydrofuran), ether or
CH 3
diglyme (diethylene glycol methyl eth~,
CH30CH2CH2OCH2CH2OCH3)'
G.R.B. Organic Chemistryfor ComBetitions
(CH3hCH-'-CH=CHzBH1-THF) (CH3)2CH-CHzCHzOH
• 3-Methyl but+ene .' H 20 2 ,OH '3.Methyl butan·l·ol
, ", __ ,'B2He (diglyme) , "
CH3(CH z)7 qr--CH z ' Hil2'0& ), ~H3(CHz)7 CHz:Hz()H,
, , Dec-l-~ " ,Pecan-l-ol(93Y..) , , " ,
The hydroboratiotl reaction was discoyetedby H.,C, Brown, ~ho was 'awarded Norn;IPrize in 1980 for the synthetic Uses of the reaction.
Trialkyl bOtaDe on decomposition,by aceti~ acidfomis alkane. '
~ 'Trialkyl borane reacts with organic acid, generally ~cetic acid, to give alkane corresponding-to alkanes.
(i) BD3/THF
CH 3- 'CH=CH 2 -----=---~) CH 3-CH-CH 2
~CH3COOHI I
D H
BD /THF
(i) 3 ) CH -CH-CH
(ii) CH3COOD 3 I I 2
D D
Tpalkyl b9raries undergo coupling reactiop. in presence of AgN03/NaOl:{.
(i) BH3/THF . ' '
CB3CB--:'CH 2 .. " ')CH3- ' (CH 2 )4-CH 3
Propene (u).AgN°3/NaOH ',' n-Hexane'·
, ' ~ "
(f) Addition of water (Hydration) : Alkenes add up water !ll0lecule in presence of aCids or catalyst BF3 or Mn phosphate,
etc.~ to yield alcQhQ\g., This' additi9n also follows Markownikoff's rule. A carbocation is an interme4iate and is captUred by a
molecule of water acting ,as, ~ npcleophile. For ~synthetic purposes, this reaction ordinarily' works well for the preparation of
secondary 'or tertiary alcohol. For example,
',.'
'
. * . .
" , ' .
Mechanism: ' 'The mechanism of acid catalysed addition of water (hydration) to alkenes involves the following three steps:
Step 1. Electrophilic attack by hydroniuin ion (H30+) on alkene gives an intermediate, carbocation. "
(H~S04 ,.....---72H+ +SO~-') ,
H
I
..O-':a +
• •• _<
H+ ~ H-O+-H(H30+)
H-,
'.. H~oni~ion '
,
1 '
H
," ~'I .+
0'
'
,'"
CH 3CH CH 2 +HT 8,-H Slow)" CH 3 - 'CH-,CH + H 2 ••
Propene V ,3
2° Carbocation
Step 2. Nucleophilic attack by water on carbocation to yieldprotonated alcohol.
Unsaturated Hydr.ocarbons
+~. Fast ..
CH 3-CH-CH 3 + :O-H --.....) CH 3-CH-CH 3
Isopropyl . . \ \
/ ..\
carbocation (2°) H 0 +
H a-··
Protonated alcohol
Step J. Deproronation (lossQf proton) to form an alcohol.
•• Fast' +
CH3-rH-CJH3+:Y-'H . ) CH3-rH-:-:-CH3+FhO:
19.\•. . . H P~~2~1
llrotonateda)cohol
Meehanism:
··CH 3 . . CH 3 · ~.. CH3
CH 3 .
. \ \~ !I-R-H\ \ -H+
CH 3-C-"::"'CH 2 + H+ --.....) CH 3--'-C-CH3 . ) CH 3-CH-CH j ~=-~) CH3-y~H3
2-Metliyl propene . . (Slow) .+ (Fast) I +.
Ten. butyl
car~cation 9\ OH·
2-Metbylpropan-2-o1
H .. H·
Oi
~ I. I-CH-CH
I .
3
'H OH
. 3-Phenylbutan-2-o1
(by Mark,ownikotf's rule)
(c)
CH3 .
I
3~Phenylbut-l-ene
~H~H3
VbH
2-Phenylbutan-2-o1
(by 1,2-hydride shift)
(Ii) Oxymercuration-demercura~on: With mercuric aCetate (in THF) followed by reduction with NaBHiNaOH is also
an example of hydration of alkene according to Markownikoff's rule. The ~gioselectivity of this reaction is identical with that
. of acid-catalysed hydration.
314~ G.R,B. Organic Chemistry for Competitions
3 H NaBH4
(CH3hC-CH. CH 2 0) (CH COO)2 g) (CH ) C-CH-CH HgOOCCH --~) (CH 3hC-CIH-CH 3
(ii) THF, H 0
3,3-Dimethyl but-I-ene
3 32 2 3 NaOH I.
OOCCH 3 OH
3,3-Dimethyl butan -2-01
Cyclopentene
(ii) NaB}4, mr
•
~OH
Cyclopentanol
Experimentally, it has been found that the product of the reaction is a result of the anti-addition reaction. For example,
CH3 (i) Hg(OCOCH3hIHO~ rY~Ifl
(XI D (ii) NaBH4 . ~g
Anti-addition can only be obtained if product formation takes place by the formation of cyclic intennediate.
Oxymercuration-<iemercuration is a better process of hydration of alkene than catalytic hydration by dil. H 2S0 4 , because it
avoids rearrangement (due to the absence of free carbocation involvement in this mechanism).
(i) Hg(OAch .
R-CH=CH2 ) R-CH-CH2-HgOAc
Alkene (ii) THF/H 20 I
OH .
If alcohol is used in place of water as nucle()phile, then this reaction is called alkoxy mercuration-demercuration and the
product of the reaction is ether. Addition of alcohol works better in the presence of mercuric trlfiuoroacetate.
OCH 3
(i) Hg(OCOCF3h/THF-CH30H . I
(ii) NaBH4, OH ) CH3CH-CH 3 + CF3COO
2-Methoxy propane
CH3 .
)c-1<H ~ )I~I=NOH
I
Cl Cl
Oxime
Unsaturated Hydrocarbons 3j5
(h) Addition of alkanes: Highly branched alkanes add to alkenes in the presence of cone. H 2S0 4 or HF (Alkylation of
alkenes).
CH 3 CH 3 CH 3 CH 3
I I Cone. H2S04 I I
CH3-C-H + H 2C=C-CH 3 0-5°C )
CH 3-C-,CH 2-CH-CH 3
I 2-~e~lpropene . I
CH 3 (Isobutene) CH 3
2-~ethylpropane Iso-octane (2,2,4-Trimethyl pentane)
(Isobutane)
.This reaction is used in the manufacture of iso-octane. .
CH 3
I
CH 3-C-H + H 2C=CH 2
I Ethylene
O-~d CH 3 -TH-1~H-CH3
CH 3 CH 3 CH 3
2-~ethyl propane 2,3-Dimethyl butane
(Isobutane)
(I) Alkenylation ofalkenes (Dimerisation): Two molecules ofisobutene (C 4 Hg) add together in the presence of H 2S04
or H 3 P0 4 at about 80°C to give an alkene, CgH16 in two isomeric forms, a dimer ofC 4 Hg and this is called dfmerisation.
CH 3 CH 3
I I
H 2C=C-CH 2-C-CH 3 +CH 3-C=CH-C-CH 3
I I I I
CH 3 CH 3 CH 3 CH 3
2-~ethylpropene (A) Major (B) ~inor
(Isobutene) (C SH I6 ) (C SHI6)
(C4Hs)
Products (A) and (B) are position isomers and on hydrogenation form the same alkane, 2,2,4-trimethyl pentane.
Similarly, styrene (Vinyl benzene) on dimerisation gives 1,3-diphenylbut-I-ene. .
!(5\-rH
~s~
CH2 + H2C=CH--fc:5\
V.nYlbe_~
~
Hou © ©. CH=CH-CH-CH3
.There are different types of dimerisation of alkenes in presence of sunlight forming cycloalkane.
H2C--CH2
2H2C=CH2 hv .. I I
Ethene H2C--CH2
Cyclobutane
(j) Diels-Alder reaction:. It is a diene-dienophile addition reaction. It forms cyclic compounds.
~CH2 ,../CH2........
CH CH2 CH CH2
I + II -II I
CH CH2 CH· CH2 ·
~CH Ethylene ........CH ,../
2 2
Buta-l,3-diene Cyclohel'ene
0 0-
~CH2 Il II
CH
CH
,.
~CH2
+
H-C-C-OH
II
H-C-C-OH
II·
0
- CH~-OH
II
CH II
0
-OH
~aleic acid
G,R.B. Organic Chemistry (or Competitions .
(k) Addition of oxygen:· Wherimixed with i:>xygen or oxidation with peroxy a~ids (CH3C03H~ C 6 H sC0 3 H or CF3C0 3 H)
or air and passed through a silver catalyst at high temperature (200':"400°C) and pressure, lo~er alkenes add atom of oxygen to an
. form epoxides, (i.e., cyclic ethers, jn which the ether oxygen atoin is a part of three membered ring). The·reaction is a stereo-
specific syn-addition.
·c
H 2C= H2 + 2 0 2 --~
I Ag
.~H2
Ethylene .
o
Ethylene oxi!1e (Oxirane)
(1,2-Epoxyet~) .
RCH=CHR
..
+1.0
2 .2
o o
I I
RtzC=CR 2 + R'-C-oOH ~R2C-CR2 +' R'-C-OH
Alkene Peroxy acid, ,V Carboxylic acid
o . '
Epoxide
CJ
CHj
I . +CH3-C~H
, .
o
'II·
. Peroxyacetic .
-
.O
..
.
.
..
CH
0
3 ..
+ CH3-C-OH
0
11
Acetic acid .
..
.I .I
. -C=C-+03
. CH2CI2
..
.
>c\I.:-01.fC<
: 1
ZnIH20 I..
-C=O+ 'O=C-
I
..
Alkene· 196-200 K 0HO· ,...ZnO Products
(Reductive cleavage) (Aldehydes or ketones o.r mixture)
Ozonide
Zinc dust is' added. to Ilreveht the formation ofH 20 2 produced by the reaction ofH 2Q and 0 (Reductive ozonolysis); .
-0 1
H
'- -0r-C
CH~Y,
1
<H ZrtIH20 .
H
I .
. H
. I
3 1 \I :I 1 H . -----...... CH~=O + O=C-H
Of--!;-O ... -ZnO . Acetaldehyde. Formaldehyde
(Reductive cleavage)
Unsaturated Hydrocarbons
196-200K
Knowing the number and arrangement of carb~n atoms in these aldehydes and ketones, the structure of the original alkene
can be worked out. . .
Note: (a) All a1kene9!typeRCH .. CHR'gives aDnxtllre of two aldehydes..
(b) ~ alkerie'6ftype R2C CHR'givesllmiXtute of aldehyde and ketone." ' . .' ..... .
.' (c) .~alkene ofth.e· type R2(;--:-Clf.2. gives a. mi?tt].lre of two ,ketones.,~ lind R'cntaY. be·.sanie;nr;difrerept,
(d)EtP¢n~(H2Cc,CI:l2)giVeson1Y.fomia1aehYde;'i; '. i ., . , ; .... ' . .
. (1l)ZnlCH3COOH .;;,·elf2~HO
Butane-l,4-dial
". ":;;'~.~.·.;8
. '.'~.·'.'.' ~ "',:(i:~'~k~d~ ..OHC~Hr-CH~~~IIO' ..' .
;.i. '.:· •". .•
. '. " .
Cyclopeniene :
".':'.:' >
. . .·.•.•..•
. ; ;Pen~e-l ;5.,dial .;
So, ozonolysis of cycloalkene gives one molecule of dialdehyde. Cycloalkfidiene on ozonolysis gives two molecules (,)f ,
dialdehyde. .
HC~H2--:-CH2--:-CH (I') 203 CH~--:-CHO
'\I" II " 2 I" ,
HC-CH~H~H. (ii) 2ZnlH20 CHz---CHO
Cyclo-octa-l ,5~diene But;me-l,4-dial
CHO
(i) 203 .2H2 C<·
" I'
(ii),2ZrilCH3COOH . . CHO
Cyclohe:xa-I,4-diene Prop,ane-l,3-dial
While conjugated diene and.triene gives mainly glyoxal (dialdehyde) ~i1d formaldehyde.
. (01) .Addition "f HN03 ':, Nitric acid (funung) .adds to a~arbbn:caibon doubl~ bond to yield nitro alcohol.
+
, Fl 2C ,CH 2 HO~N02 .~ CH20HCH2NO~
, . Bthene .)' . ,. .' 2·Nitroethatiol ". ' . ' . •• .
(n) Addition 'of aietyl ~hloride: 'A molec~le of ace~l chloride adds ,to a carbon-carbon double bond in prest;nc.e of AlCI 3.
to form chiaro substituted ketone,' ., ',\ . ,'.. .' ..' .
J
G.R.B. Organic Chemistry tor Competitions
nCH 3 -CH=CH 2
Propene
.
Peroxides, a
or Zlegler-Natta catalyst
,
)
f CH 2 -CH
I
CHt.
. Polypropene
Polythene. polypropene and polybutene are "plastics" of industrial importance and squeeze plastic bottles
n
ate moulded from high density polyethylene. Polypropene is a harder and stronger polymer than polythene and its fibres are used
in carpets and automoblIe tyres. Polystyrene -( C 6 H sCH=CH 2 + n is used in television cabinets, housewares luggage and
packaging, etc., cis~polyisoprene fH2 =f-CH=CH! is a natural rubber.
CH 3
n. ,
[Polymer and the original alkene have the same empirical mass but different molecular masses. The molecular mass of the
polymer is generally very high. The derivatives of alkenes of the type H 2C=CHX (X may be Cl, Br, I~ CN, COOR, C 6 H s , etc.)
are also used as monomers and undergo polymerisation to fonn useful plastics.]
,
nH 2C=CH I
CI
Polymerisation
in presence of
benzoyl peroxides
) t CH 2 -CH
I
CI
tn
Vinyl chloride Polyvinyl chloride (PVC)
PVC is used for making plastic bottles, sheets, pipes, raincoats, hand bags, table mats, records, etc.
Polymerisation
I
nH 2C=CH in presence
.) of tCH2-C~Ht
CN (FeS04 + H:P2)
Acrylonitrile Polyacrylonitrile (PAN)
Polyacrylonitrile is used for making Orion and Acrilan fibres used for making clothes, carpets and blankets, etc.
(N~nS:P8
nF2C CF2
High pressure
+CF2-::-CFftn
Tetra fluoroethene Polytetra fluoroethene (PTFE)
(Teflon)
Teflon is chemically inert and a heat resistant polymer. It is very tough, electrical resistant and is used for making non-stick
surfac,e coating particularly for cooking utensils. It is also used in the manufacture of pipes and surgical tubes.
2. Substitution reactions (Halogenation): The alkyl group of the alkenes undergo substitution at high temperature.
Chlorine or bromine replace hydrogen of the alpha carbon atom with respect to the double bond of alkyl group at about 500°C
wit~out breaking the double bond (allylic substitution). The substitution proceeds by free radical mechanism. If the alkyl group
contains more than one carbon atom, then the substitution occurs at the a-carbon to the double bond.
Unsaturated Hydrocarbons
Allyl (H 2C=CH-CH:r-H) H 88
J------,
H2C=CH~T-_-HJ
,
H
Primary (0) (CH 3-CH 2-H) H 97.9
J------.
CH "'-:f-- Ji:
3
H
1--"
[(CH3)2 CH-H1 1H,:
·'I'..
Secondary (2°) 95
'
e,;;.,
CH3-i l-CH
r
H
3
I
CH3
On the basis of bond dissociation energy data, abstraction reactivity for different types of hydrogen may be given as:
Allylic > 3° > 2° > 1° > methyl> vinyl
3. Oxidation reactions: Alkenes are readily oxidised. The oxidation products depend on the nature of the oxidising agent
used. ,
(i) Oxidation with cold dilute alkaline potassium permanganate (Hydroxylation): Alkaline potassium perrnanganate
(Mn0 4 +OH-) is known as Baeyer's reagent. When alkenes are treated with dilute alkaline KMn0 4 (1%) solution at low
temperature, dihydroxy (glycol) compounds are fonned. The pink colour of KMn0 4 solution disappears during the reaction.
Thus, this reaction is used as a test of unsaturation. '
. CH 2 CH 0H
I + H20+O Alk. KMn04 ) I 2
CH ' ' (Cold) CHzOH
2
Ethene Etbane-l,2-diol
(Glycol)
G.R.B. Organic Chemistry {Or Competitions
CH
\
I 3 ,
CH 3-C-H H-C-OH
Alk.KMn04
, II ,
(Cold)
) I
CH 3 -C-H H-C-;--OH
~But-2-ene (cis)
I'
CH 3
(Mesofonn)
CH3 CH 3
CH 3 -C..:....-H '
I HQ..:....-C-H
I ,
H-C-OH
I Alk. I04nO4
.I + I,
H-C-CH3 HO-C-H ,H~C..:....-QH
But-2-ene (trans) 'I' ' I,
CH 3 CH 3
(dl) mixture
Hydroxylation by KMn0 4 is always syn-addition.
P ~H' H'o/.
Alk:. KMn04
..
(Syn-addition)
,, ,
,.
CH3 , CH3 OH OH
1,2-Dimethyl cyclohexene 1,2-0imethyl cyclohexanediol (cis-)
[Glycols are Iillso fanned when alkenes are treated with osmium tetraoxide (OsO 4) and the product is ret1uxe~ with NaHSO 3
(ate.) or Na2S03 or H20 2. ' ' " ,
o
Cyclopentene
H~~H" A
.
,
)--{
OH 'OH"
C2~>~ C<~2~S, ~:~: ..
C2Hs~
H7 c-c"H
HO ",
LC2Hs '
"OH
(Meso)
'l ~2-Cyclopentanediol (trans-)
(Anti-addition)
can also be used for diols fonna~on. ,
, '
(ii) Oxidation with aei~le potassium pennanganate or p«!tassium dichromate: When alkenes are treated with acidic or .
hot KMn0 4 0r acidic K2Cr207' glycols are fU'St formed which are further oxidised to aldehyde~, ketones or acids. Terminal
fon;nic ,acid isoxidised to CO 2 and H 20 ; . . .
CH 3CH' .' CH CHOH' '.' .
3
(a) I (H20 + 0),) I [0]) CH CHO +HCHO [0]) HCOOIl
3
CH2 · . CH20H ~[O]" Formic acid
Propene CH C O O H t [0]
3
Acetic acid CO 2. + H 20
(HzO+ 0)
)
But-3~en-2-o1
If perbenzoic acidi(C 6 H sC0 3H) or peroxyacetic acid, (CH 3C0 3H) is used then ftrstly glycols are fo~ed and ftmdly yields
oxirane (epoxide). Peroxy. formic /ilcid forms only glycol, ids strong to decompose epoxy link.
OH OH o
Epoxide
. .
·
O
Cis-meso
-I
Cyclohexene ,---=.H=-=C-=.O-=.O-=.O.;;;.:.H~
Anti-addition
..... ~OH + Bnan.tiomer
It!g)-H
Racemic mixture·
Reactivity of alkenes for peroxy acids: More is. in the substitution at double bond, gteateris the reactivity.
Me Me Me Me
I :I. I I ,
Me-,-C ,. C-CH2-CH=CH2 . Me-C-C-CH2-CH CH2 ·
'---..--' '--:-----' V -
More reactive site . Less reactive ·0
(Highly substituted) . . .site
(iv) Combustion: .. · When: bumt in air, alkenes are oxidised to carbon dioxide and water. The ~action is exothermic because
heat is evolved;
Burn
C 2H 4 + 30 2 . ) 2CO z + 2H 20 + Heat
They bum irith luminoiIs flame and fonn explosive mixture ~th air or oxygen.
4. InsertioD,'of methylene (Carbene): Photolysis of diazomethane and ketene gives methylene. Alkenes react with
methylene in presence of light to fonn cyc1oalkanes.
CH 2N 2 .l!:4 :CH z +N 2
.Diazomethane
H 20=C=0 ~:CH2 + CO
Ketene •
". ,~. ...
Qnly si11~let carbene (CH ) is involved in alkene addition reaction.
..
.,
2
. . " .
.. <•.... /. . . . . CH
..' " ' ':. I 3
.... . . (eH) C--'-OK: '. ............... '..' . . . '., ' . . ' . . .." .
CH3~_2.;~~CH~+CHC13 , 3 3 ..••. ·..~.C:{I3~II~H3 + CH3-?~H +KCl:
.. ~:. ':A . '.' .CH 3 .: .
.CI .Ct . ':Tert.buty1alcohol~
7.7 ALKYNES
Alkynescontain four hydrogen atonis less thim the coirespondingallolriegand ~echar~cteri~.edby.fu~presence of airiplebond in.
the molecule. The first and the most important member of this .seiies~s acetylene; He. CH, He,nce,;tn<? alkynes (C';H2~"':2) are '
also called acetylenes.. . .' ." _. _ . . . . . ... ! . . .'
. Nomenclature: There are, three systems for naming. alkyrtes.':·.: . ' ." .' ". . •. .' ,
(i) The common name system: '. The c9DllllonnamesofalkYtt--e$dQilot bear any relationshfp and are based onthe names-
.ofrelatedoorupounds. . .. ' .... . . ....... .-"i" ":""'. ';,', '" .,....... -'.' '. . '. .'
Formula (C H - ) _ . . . . • C(nn~onntin.e .... - . .
II 2n Z
C2 H 2 (gC-CH)' ,-A¢,ctyHlne'-
C3H 4 (CH 3C .. GH) ··-AUylene •
. C4 H6 (CH 3C==CCH 3 r croionylen~ .
.Except acetylene, other names ar~.nci 10ngeruSed~
,.;" ·'·3
..201014_·_..;......;.;...~~_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _~G~.R'-l...""B~.J..Qa.r~gp.wnwi~c,..!.Cd.hloSOe:.u.mu.i,.uS'tu'£.t.fi.LIoQ~r,..!.C..sQaJmW1J;ae<!Jtlw·tii.!.:Qwns
(ii) Derlyed system: In this' system, the higher alkynes CH 3" " , .
are'regarde~ as allryl derivatives of acetylene; CH 3CH 2CH 2C==CH /CH-C=CH
.... forinula Derived name Pent-I-yne CH 3
3-Methyl 'but-I-yne
\. 'HC==CH Acetylene
(U) Position isomerism: . It is due to 1he difference in
CH 3C==CH Methyl acetylene
the position of triple bond in the carbon chain.
CH 3CH 2C-CH Ethyl acetylene
CH sCH 2C-CH ; . CH 3 -C==C-CH 3
CH;C-CCH 3 Dimethyl acetylene But-I-yne But-2-yne
o
.Alkynyl groups :
Sodamide (NaNH 2 ) in liquid NH3 can be used instead of 2PH 3 +3CuS04 ---7 CU3P2' + 3H 2S0 4
alcoholic KOH. ' Cupric phosphide '
H Bi.- (Black ppt:) ,
I I Li uid NH
q 3) R-C==CH +2NaBr
'
(vi) Manufacture: (a) Laboratory method of prepara-
R-C-C-H +2NaNH 2
, I I 196K Alkyne tion of acetylene is also used 'on a large scale ·for its
Br H manufacture. The start is made with limestone (CaCOi). It is
heated at IOOO°C to fonn.quick lime, (C'hO). A mixtUre of
quick lime and coke is then heated in an electric furnace when
Note: By this method, ethene can be ~onverted mto acetylene.
calcium carbide is fonned.
Br2/CCI4' Ale. KOH ' . Heat
H2C=CH 2 ) CH2Br-CH2Br ----,-7) H2C=CHBr ~=.-4) CaO + CO 2
Ethene 1,2-Dibromoetharie Vinyl bromide
lNaNH 2
CaO + 3C 2000-3000°C) CaC + CO
2
HC=CH (b) Acetylene is manufactured by heating methane' or
Acetylene natural gas at I SOO°C in an electric arc. .
(ii) By heating 1,1,2,2-tetrachloroethane with zinc in
2CH Electric arc) HC ' CH + 3H
methanol (Dehalogenation of tetrahaJides): 4 2
CHCl 2 ' CH (c) A recent method for the manufacture of acetylene is
I +2Zn Alcohol) III +2ZnC1 2 the controlled partial oxidation. of methane at high
CHCl 2 Heat CH temperature.
.Note: This method can be used for the punhcatlOIi of ethyne and 6CH4 + 02 1500°C) 2HC=CH + 2CO + IOH 2
higher alkynes can also be prepared.
X X (d) Propyne can be prepared by the hydrolysis of
I I ,gnesium carbide. ,_; , . - \
aY~Orbital'J'e;cei>la:~~~~i;i; ~C+!l+~N~f~J4~~~~~
s p 2 ; ' : ' } } ; : . " ' ; 'Ethyne .' Sod.$JIide'··. Pisodiwut:tbyDide ... '
,.
,./
HC=C-CH 2 -CH=CH2"
Br2 (1 mole)
, )
IIICH
Acetylene
+ HOCI ~ II,
. CHCl
HOCl) I , OH
CHCl 2
""
, Unstable
HOCI)
I
CH -C-CHCI
acrylonitrile or PAN) and Buna-N rubber.
3
1,I-Dichloroacetone
2
flH + I Ba(CNh) ~H2
(e) Addition of sulphuric acid: Acetylene gas when CH CN CHCN
passed through conc. H 2S0 4, it gets absorbed fonning Acetylene Vinyl cyanide,
(Acrylonitrile)
ethylidene hydrogen sulphate.
CH' ,CH 2 H SO ' CH 3 (h) Addition of acetic acid: Acetylene combines with
II +H2S0~~ II, 2 4} I acetic acid in presence of mercuric sulphate or zinc acetate or
CH (Conc.) CHHS0 4 Conc. CH(HS0 4h , BF3 (as catalyst) at 160°C. It first forms vinyl acetate and then
, Acetylene Vinyl hydrogen Ethylidene ethylidene acetate.
sulphate hydrogen sulphate H
CH
E~} :.idene hydrogen sulphate on boiling with water
produces acetaldehyde.
III +100CCH 3
CH
>~jCH3 ao CH3 CH 3 Acetylene Vinyl acetate
I 2)I<OH~ I, (Vinyl ethaooate)
CH(HS0 4 h CH CHO
OHAcetaldehyde
Unstable
H()()CCH 3 ) TH 3
CH(00CCH 3 h'
(f) Addition of water (Hydration): Alkynes cannot
Ethylidene acetate
be hydrated more easily than alkenes because of their low
reactivity tc:>wards electrophilic addition reactions. Further Vinyl acetate on polymerisation fomis polyvinyl acetate
when acetylene is passed through 40% H 2SO 4 containing 1% (PVA), used in' plastic industry and ethylidene acetate on
HgSO 4 at 80°C, a water molecule adds upto give heating at 300-400°C yields acetaldehyde and acetic'
acetaldehyde. anhydride.
fiR
,CH
+'HOH 40%H 2S04 )
1% HgS04
[112) 1
CHOH
TautOmerises)
H
CHO
T3 /
CH3CH"" '
00CCH 3
Heat
) CH 3CHO'
"OOCCH 3 300-400"C Acetaldehyde
, Acetylene Vinyl alcohol Acetaldehyde
(Unstable) Ethylidene acetate
R~Cli + HOH H':~~L) [R1~ ),] (i) Addition of alcohol : In presence ofNaOH or KOR
+ (CH 3COhO
Acetic anhydride
! Tautomerises
of alkynes) to form ethyl vinyl ether.
R-C-CH 3 CH 3
I ',' I
o CHO
, Ketone' Ace,tyiene Ethyl vinyl ether Acetaldehyde
This is called keto-enol tautomerism. '
+CzHsOH
However, if the unsymmetrical alkyne is non-tern;rinal, a
mixture of two isomeric ketones is obtained in which methyl BF3
HC===CH ,+ CH 30H HgO) H 2C=CH-0-CH 3
ketone predomina~es. For example, Acetylene 'Methanol Methyl vinyl' ether
H 2 S04 (dil.)
CH 3CH 2 --C=C-CH 3 + HOH-----~ e a!'
Pent-2-yne HgS04, 70" C CH10H
)
, (Non-terminal alkyne)
~ ~
CH 3CH 2CH 2 -C-'CH 3 +CH 3CH 2-C--CH 2CH 3 Such a reaction is termed vinylation.
Pentan -2-one Pentan-3-one (i) Addition of ozone (Ozonolysis): Acetylene
(Major product) (Minor product) combines with ozone in presence of some inert solvents such
(g) Addition of hydrogen cyan~de: The addition of a asCC1 4, CHCl 3 orCH2Cl 2 at low temperature (196--200 K) to
form an ozonide which on decomposition with zinc dust and
molecule ofHCN occurs in the presence of barium cyanide or
CuClIHCI (catalyst). Vinyl cyanide is formed. This is an water or H2IPd (reductive cleavage) yields glyoxal.
330· G.R.B. Organic Chemistry for Competitions
CH CCl4' " /' CH~O, ,CHO' (iii) Linear polymerisation: When acetylene" is
II '+0 3 ~ ,/ ,"I I, Zn!lI2q, I" + H 2,0' 2
0,' passed into cuprous chloride solution containing NH 4 Cl,
CH 'CH-O -Zno CHO linear polymerisation occurs forming monovinyl acetylene
Acetylene Ozonide Glyoxal and divinyl acetylene.
~ 2HCOOH CU2Cl2
HC===CH + HC===CH --~~ H 2C=CH-C==CH
Glyoxal is further converted into formic acid. Formic acid Acetylene NH4CI Monovinyl acetylene
0, (Two molecules)
1\ Zn/H20 HC-CH 1300. molecule
CH 3 - .~-:-CIH )
I (-znO) H 2C=CH-C==C - C;fI=CHi
0-0 Divinyl acety16iie' .
Propyne ozonide
Vinyl acetylene on reduction with H 2 /Pt in:presence of
CH3-C-C-H BaSO 4 forms buta:-l,3-diene.
! A
Methyl glyoxal
H 2C=CH-C==CH
H2 /Pt
) H 2C=CH-CH...:-CH 2
Vinyl acetylene (Ba804) , Buta-I,3-diene
(2-Oxopropanal)
[Higher alkynes form diketones which are further Butadiene and vinyl cyanide form polymer Buna
oxidisedto carboxylic acids. N-syntbetic rubber:
o Butadiene adds to acetylene (Diels-Alderreaction)to
CCl 4 /, form addition product.
R-C===C-R' +0 3 ~'R-H-R'
Alk:yne Reductive ~CH2 /CH2"
" cleavage
-'
·0-0 CH CH HC CH
Ozonide
I + III II II
CH CH HC CH'
~CH2 Ethyne "CHr'
R-C~C-R' + H 20 2 ~ R-COOH + HOOC-R']
Buta-l ,3~diene Cyclohexa-I,4-diene
II I A~ids' ' ' ,
o 0 But if 1~alkynes react with Cu 2Cl2 con~ining NH 4CI and
. Dia1ky1 glyoxal air, oxidative coupling takes place and dimerised products are
formed.
(k) Self addition or polymerisation: Acetylene .
Cu 2Cl 2
undergoes polymerisation yielding different types of HC==CH + HC==CH . ) HC=C-C==CH + H2
polymeric compounds under different conditions : ' NH4CI,air
,(i) ,Cyclic polymerisation: When, acetyle~e is passed, CU 20 2
2R~=CH, ) ,R-C==C-C===C-R +H2
through a red-hot metallic tube at 600°C, cyclic polymeri- ~CI,air
'0
sationtakes place with the formation of benzene.'
When monovinyl acetylene is treated with HCI. it forms .
3HC==CH
Acetylene
Red hot
(~g!~)
I
~.
chloroprene which is used for making synthetic rubber like
substance; neoprene.
. , Benzene, Cl '
Propyne on heating trimerises under similar, conditions
and formsmesitylene (1 ,3,S-trimethyl benZene). H 2C-:-CH-C==CH
HCI
) H 2C-.:-CH-C=CH 2
I
HC
3
0'"
~ CH3
Vinyl acetylene 2-Chlorobuta-l,3-dJ.ene
H
,8$ I 0._ RONa. .... . ' .'. .' . • . . .CH2 --:C ""
(1) HC==C-H + H-C . 0 ........,-4. HC==CCH20H (:Hr-C==CH+ I. .' /NBr
Propyne" . CH 2-C/.
., '. Ethyne" Formaldehyde . Prop~2~yn~1-ol
. .'. . I
H o
. ··1.··· ....... '.. ' ."; N-Bromosuccinilllide .
HC==C-CH 20H+H--,-CO ~ HOCH 2C==CCH 20H o
. ." But-2-yn-l,4-di'ol .'
.' '. '.' ..... '....... CH 2 -C
I
(ii) CH 3--"C=CH+ H-'-C~Hj CH 30Na)
Propyne '. . .' I .. ' .
. BrCH2-c~H+1
, '. Propargyhc..
.'
CH 2-C
)NH
.. ' O' . . . . .' . bromide'· .' I .'. .
Acetaldehyde '...... ; . " ...... O. .
(3) ~ea~don$with$illphur, 'ilitrogenand ammonia:
. . '. . .
. CH r ":C=C-.-:.CH 2-CH 3 ·· '. ..'. •'(a)Wben acetyleoeispassed .oVerheated iron pyrites at
.. . r . ,.' .
. . OIl .. 300°C. ifoornbines with stllphur to form,tbiQpb~Jie.
.
.
. .... \,'
..
V CH 3 .
. ".' .
. ·······~2+s'S·~!L~~-
'·'(iii)CH3~~-~i +O==='C( .•.. ' ...~~
'., CI:I 3 . rhloPhette '
'. Acetone·
(tl)'Wb~~ari:el¢ctric SP~ki$"pas~ed througpa.rmxmte 'of .
.' .. ' ..... '.. .... . ' '. ···ac~tYletiemld!Ilittqgen,hydtQcyanieaciid is form~.
·CH r -.C' C , ' / .. ,.CH3>.· .... :.:, ....:... '. '.. ". ...
.'. '. . )c«.> ' + LtCl .. ' II1'+,Ni E~:~c)2HCN .' . 'ci
. ',' ..•... ' .... .'/... ..... . . { HO
3
CH . . ..... (c)~cetyletie:~ombine!?Witharrimonia
at high
. '...• (iv)Terrilin:~ralkyne(R~C-H) on reaction with temperatnreto· fol1l1Pyrrolew
certainhydroxy compounds can also undergo, ethiny1ation . . ~Ii ". '. .' p <. CH~H
. "2111' +NH3 ... e-Pyrite) 'II '11 +lIi··
. 'witbtheremoval ofHiO
, . CH '... ,Heat CH CH
H--C==C-JI +H.oCH t l\JR 2~ H-C-C~CH2N~2
+lIo···
Acetylene
. ....
" ¥ .H
.
. (nJ CarbonylatiQn :Acetyl~ereactswit1i(CO +I-I~~) .•. . .' .... '.. ' . .. .....':. . pyrroie
'or (CO R0H)~n~esence of
+ nickel<:atalyst~ndfo:rins(4)OXidati6n'::DifferentoXidation' pn>ductsare.
. a.~Wlsaturatedacid o:r estet.. '.. ' . obtained with differentreagents:. ....
. . '.. . .... . . (a).BunJing (CQm~ust,oQ):A(:etylene burps'. with
.. a~===CH+CO+Hi) .'. Ni\. lItC 'CHCOOH .. slJ1okyflameirlexCessofaitUndercontrolledstipplyofair, it
..... ..' '. .'. .• '. •..... Prop-2-erioic acid ; ·bwns;WitIia brig)lt lighfwhi~h:is;ilijuriQuS· to eyes> The
. . ..... '.' . . burning'isrughlY.· exothenmc'ait& al&ieaniount heat is . of
. 'HC==CH +CO+HOCH 3 Ni·).· H 2C=CHC()OCH3 ptoduced;TheoxY~aeetylene;flanie(blue.flatne)is used for
. Ester
G.R.B. Organic' Chemistry for Competitions
welding and cutting purposes and gives a temperature of about (e) With SeOz (Selenium .dioxide) : Acetylene is
3500°C.. oxidised to glyoxal (ethane-I,2-dial) with se0 2.
2C2H 2 +50 2 ~ 4C0 2 +2H 20; AH=-1300k) CH CHO
(b) With alk. KMn04 solution: Acetylene is finally III + 2[0] se02 ) I
CH CHO
converted into oxalic acid with cold, dilute alk: KMnO 4 Ethyne Glyoxal
is
solution and pink colour of the soluti9n dischargoo.
Se02
CH Alk. KMn04 COOH CH3 -C==CH +2[0] -~)CH3COCHO
1\1 + 4[0] ) I Propyne 2-Ketopropanal
CH COOH
. Ethyne Oxalic acid (I) With chromic acid (K ZCrZ0 7 + HzSO 4): Acetylene
Alk.KMn04
is converted into acetic acid and orange colour of the dilute
CH 3C==CH +[0] . ) CH3-C-C---OH acidified dichromate changes to light green.
Propyne 25-30"C . AA
CI1IH
+ H 20+[0] ~
cI H 3
. 2-0xopropanoic acid .
(Pyruvic acid) CH COOH
Acetylene Acetic acid
Alk. KMn04
CH 3 -C==C-CH 3 + 2[0] 30"C) CH 3-C-C-CH 3 Oxidation of alkyne is slower than that of alkene. Thus,
But-2-yne 11 11 only double bond can be oxidised leaving behind triple bond.
o 0
B\ltan -2.3-dione
(7) Oxidative-Hydroboratio.. : Alkynes react with BH3 (in THF) and fmally converted into carbonyl compounds.
3C~3-C==CH BH3 , THF ) . (CFi3~H'-:""CH-hBHP2' OH; 3CH 3-CH ~ Tautomerise\· 3CH CH CHO
3 2
Propyne Propanal
Thus, this method is useful for preparin,g aldehyde from terminal alkyne, which is otherwise not possible by hydration.
o
H 2S04
.------.....::....-.:...--+
Ie
CH -C-CH
3 3
HgS04 Propanone
CH 3-C==CH
. Propyne (i) BH3> TIIF .
' - - - - - - + CH 3CH 2CHO
(ii) H20 2, OH- Propanal
Higher ketones can also be prepared by this method.
rHO
~. I ·
Tautomenses) ?!
R-CH=C-CH 3 R-CH2--':"C-CH 3
(enol) . Ketone
o o
CH 3-C==C-CH 2CH 3
(i) B2H6, THF
------''--'--~)
I
CH3-C-.CH 2CH 2CH 3 +CH 3CH 2-C-CH 2CH 3
I
.. Pent-2-yne (ii) H20 2• OH- . Pentan-2-one . Pentan-3-one
(Major) (Minor) .
Aldehydes can likewise be prepared from terminal alkynes, but to avoid complications due to double addition.of diborane,
bulky sterically hindered boranes such as (1,2-dimethylpropyl) borane commonly known as disiamylborane (R2BH) is used in
place of ~H6'
(i)R2BH
CH 3C==CH ----=----"7) CH 3CH 2CHO
Propyne (ii) H20 2 , mr Propanal
[:> <:1
Note: . (a) This test is also given by aldehydes qr primary and secondary alcohols which are readily ox!.dised. . .
. (b) AJk_ wiiliohy hydroge. atom on ... =tOn £0.-"" double bo.d c do 001 ,oow ""..,,'
2~ Bromin~arbon tetracbloride test: The compound is dissolved in carbon tetrachloride or chloroform and then a few .
drops of5% bromine solution in carbon tetrachloride are added to it. If the colour of the bromine is discharged, i.e., disappears, it
indicates the presence of unsaturation in the compound.
334' G.R Ii. Organic ChemistQ?for CO'Ppeiitious
Note : This test also fails in the case of alkenes of f!!e type
Besides the above two tests, l~al.k)'nesgive a white precipitate when passed through allllri6niacal silver nitrate solution
(Tollens' reagent). . ., ..
The double and triple bonds are located by the identification of the products of ozonolysis .
. Degree 01 Unsaturation
The number of pairs of hydrogen atoms that a-molecular formula lacks to be an alkane (CnHZn+Z) is called degree of
unsaturation and this value is also called the index of hydrogen deficiency.
For example, amolecularformula, C 4 H 6 has 2° ofunsaturation, because a molecule with four carbon atom needs IOH atoms
to be an alkane. It has 4Hatoms (or two pairs of hydrogen atoms) less than alkane.
. (C~H6 +2H z ~C4HIO)
So, C 4H6 with 2° of unsaturation can· have the following possible isomers:
(i) H 2C=CH-,CH=CH 2, or :H 2C=C=CH-CH 3 ;
(ii) HC-C-CH 2-CH 3 , or H 3C-C==C-CH 3 ;
(iij) 1: l or or 1
The number of degree ofunsaturation in a hydrocarbon is given by:
or D; (iv) LSJ
2nl +2-n2
= 2
where, nl is the number of carbon atoms; n; is the number of hydrogen atoms.
F·or exampIe, m
. C H h d f . ' . 2 x6+2-12
6 12' t e egree 0 unsaturatlon IS =, 2 =1
(ii)~. or '
(iii) >=< or or
(iv) 0 or or
2. The molecule that will have dipole moment is; (a) cis-l,2-dichlorobutane
(a) trans-3-hexene (b) trans~2,3-dichloro-2-nexene
(b) trans-2-pentene (C) cis:l,2-dichloro-l-hexene
(c) 2,2-dimethyl propane (d) trans: r,2-dichloro-I-hexene
(d) 2,2,3,3-tetramethyl butane t\ns. .(d)] .
~ns; (bH 5. I-Pbenyl-2-chloropropane on treatment with alcoholic
3. Which of the following cannot be obtained by oxidation of KOH /sives.mainly:
alkenes with potassium pennanganate followed by acid (a) l-phenylpropan-l-ol . (b) I-phenyl prop~-2-o1
hydrolysis? . (c) I-phenyl propene (d) 2-phenyl propene. '
(a) Carboxylic acid (b) Aldehyde~ t:\ns. (c)l
(c) Ketones (d)C0 2 ' 6. Allene' (C 3 H4 ) contains:
~DS. (b)] , (a) one triple' and two double bonds
4. Find the identity of compound [B] in the following reaction (b) two double and four single bonds
sequence; (c) two triple and one double bond
(d) . one double bond and one triple bond
HC-C-r--:Na + CH3CH2CH2CH2Br ----? [AJ,
t:\ns. (b)]
[A] + C1 2. ----? [BJ
11l1Ole 11l1Ole
7.12 INTEACONVEASIONS
(i) Conversion of ethane into ethene : (Alkane into alkene)
CH 3-CH 3
,Ethane
PBr3
. Ale.
CH 3CH==CH 2 (KOH CH 3CH 2CH 2 Br
Propene l-sromopropane
Or H 2= HI CH CH I CH 3I1Na' CH CH CH
C CH 2~ 3 2' ) 3.23
Propane
CH~CH
~~)
.Lindlar's catalyst C OJ/H 20 PCls ) CH CHCl
CH 3C=CH ) H3 - 2 ---7) CH 3CHO 3 2 HC=CH
Propyne Propylene Acetaldehyde Ethylidene Acetylene
chloride
(ix) I-Butyne into 2-pentyne : (Ascent)
1.
C"H2n + H2'~
.. 300°C
CIIH 2n+£
Alkane' .
CJ.f . +H .~ CH
U
IT 2n-2 . 2 .. 3.00°C Aike~
C2H.i + H2 ~ C2H6- .
C,jH2n + H2 ~ C"H2n+2
300°C Alkane
Decolourises. . Decolourises.
Dibromo derivatives,. Tetrabromoderivatives,
, ~H4 + Br2 . ~ C2H4Br2 ~H2Br4:
7: Baeyer's reagent Decolourises. Decolourises..
(Alk. KMn0 4 ) Glycol is formed. Oxalic acid is fonned. -
C~. . CH 20H CH COOH
~. +H20+0~. I .... III +40·~·1··
CH 2 ' . . ···CH20H CH· COOH'
+ 2NH4N0 3 + 2H20
,338,' . G.R.B. Organic Chemistry (or Competitions,
hOME-SOLVED PROBLEMS (b) Ethyneand its derivatives will give white precipitate
with ammoniacal silver nitrate solution. ldention the-
Problem 1. Write the structures of all the isomers of condition under which this statement is true. '
dichloroethene. which one of them will have zero dipole Solution : (a) 2~Methylpropene . reacts with HBr in
moment? presence of peroxide as' the addition '. occurs . through
Solution: There are three isomers of dichloroetherie. anti-Markownikoff's rule.
CI-C-Cl H-C-CI H-C-CI CH 3 CI:I3
· I , I , I . I Peroxide' '. I '.
H-C--'-H H-C-CI CI-C-H CH 3-C=CH 2 + HBr ) CH 3-:-CHCH 2Br
I,I-Dichloroethene' Cis-f,2-Dichloroethene Trans-! ,2-Dichloroethene 2-Methy!propene . Isobutyl bromide
',.(i)·' '(ii) (iii)
(b) Only those derivatives of ethyne will give white
The'structure (iii); i.e., trans,;,isomer has zero dipole precipitate with ammoniacal sHyer nitrate which possess
moment. . . acidic hydrogen atom, i.e., R-C!:1!5!!CH. The derivatives
'f'roblem2.Propene reacts with HBr to give isopropyl ,R tC==C-R 2 do not give precipitate with ainmoniacal silver
bromid~ Qut does not give n-propyi bromide.. nitrate. "
.. ' Solution: The addition of HBr on propene takes place Pro~lem 7. 36.4 g of 1,1,2,2-tetrachloropropane was'
in accordance to Markownikoff's rule, i. e., negative p.art ofthe . heated with zinc dust- and the product was bubbled through
additive goes to that carbon atom which is linked with lesser ammoniacal AgN03' What is th~, mass. of. preCipitate
nJ.1ll1ber of hydrog~n atQms. The addition of an electrophile obtained? Give equations for the reactions involved. .
involves the intermediate' formation of a more stable Solution:
· ,',. +.'. . +.
carbonium ion. (CH 3hCH is mo~e stable, than CH 3CH 2CH 2. CI Cl
. carbonium ion; , I I
CH 3-C-C-H
Problem 3. Acetylene is acidic but it does not react with , I I Propyne
NaOH or KOH. Give reason. CICI (Mol; mass 40)' .
Solution :~cetylene.is very weak acid. The value of Ka is 1,1,2,2-Tetrachloropropane
. near about 10:-25 . Thus, it does notreact with NaOH or KOH but (Mol. mass 182)
·.reacts with very strong base such as NaNH2' . " . Mass of propyne obtained from 36,4 g of
. '. Problem 4;Ethene'01z:treating with Br2 in presence of , " 40 '
.$odium "chloride forms i:l mixture' of CH 2CICH 2Br and 1,1,2,2-tetrachloropropane == 182 x 36.4= 8 g
CH 2BrCH 2Br. Give reason.
Solution: The . ,addition . of Br2 follows ionic CH 3C==CH + AgN0J + NH 40H ~ ~H3C=C-Ag
,mechanism.. 'The intermediate carbonium ion formed is Ag-salt
, (Mol. mass 147)
attacked by Br- as well as byCl- given by NaCl: .
+ NH 4 N0 3 -+ H 20
+.
H 2C=CH 2 · - '---'-"::"::---'-"'-:"'~ HiC-CH:i Mass· of precipitate obtained from 8 g of propyne
. (NaCI ~ + cn '. . . 147
=-x8=29,4g
40 ..
· +.' -c:+
H 2C-CH 2Br . .
.
Br
- BrH 2G-CH2Br
1,2-DibromOethane
Problem 8. Compound .
(A) contains only carbon and
'.
HBr
-:---7 CH3CH2CH2THCH2CH3
,
R2 R4
,
Rj-C=Q '. 0= C-R3'
Br (A) . (B)
Ni:tOH . , 4. The '-:".0 of both the compounds is removed and linked,
, ,
CH3CH2CH2CHCH2CH3 - - '~) CH 3CH 2CH 2C,HCH 2CH 3 through a double bond. This is the structure of unknown'
alkene.
Br OH
CH · CH CH Oxidation CH CH CH CCH CH
, 3 CH 2CH 2\
CH 2 3 ) . 3 2: '21\' i, 3
OH 0 R j , Ri, R 3 , R4 are either hydrogen atoms or alkyl groups
Problem 9. Anorganic compound (A), having carbon or both.
and hydrogen, adds one mole of hydrogen in the presence of Problem 11. An olefin was treated with ozone and the
platinum catalyst to form normal hexane. On vigorous resulting ozonide' on . hydrolysis gave 2..pentanone and
oxidation with KMpO 4' it gives a single carboxylic acid acetaldehyde. What is the structure of the original olefin?
containing three carbon atoms. Assign structure· to the Write equations for the reactions involved, .
compound (A). Solution : 'The products of ozonolysis are .2-poo.tanone ,
Solution: The compound.combines with hydrogen to and acetaldehyde. Writing the structure of both the carbonyl
form· normal hexane by conswning one mole of hydrogen, compounds.
hence the hydrocarbon is n-hexene. . H
C 3 H7"'- _
C 6 H!2 + H2 -:---7 C 6 H14 /C-O. Q=C/
n-Hexene n-Hexane CH 3 ,'. "'-CH '
3
. The position of double bond is indicated by its oxidation Pentan-2-one Acetaldehyde
to propanoic acid. Thus, the double bond is_ pr.~sent in the .
middle of the chain (a symmetrical alkene). Removing =.0 of the compoUnds· and linKing both
,through double bond, we get the alkene.,
CH 3CH 2CH=CHCiI 2CH3
Hex-3-ene C3H7,~, /H
.~~. C=C
CH3/~CH3
2CH 3CH 2COOH CH3CH2CH2CH2CH:zCH3 Thus, the alkene is3-methyl hex-2~ene.
Propanoic acid n·Hexane . . Reaction :,
P~obJem 10. How is the structure. of an. at/rene C H7 -H,
' '. CR' C I
determined? .. ' 3 ". ". ../
. ", 2 Z
·Solution: Ozonolysis is the best method for locating " . /C=G"" CH3+ .03 -
CH3' ,.
the double, bond position in 'unknoWn alkene. An alkene is
treated with ozone in an inert solvent to form an ozonide. The
ozonide is treated with Zn/H 20 to obtain the carbonyl
compounds., The structure of' the carbonyl compounds
depends upon the structure of the alkene. The following points' , Acetaldehyde, ,Pentan-2-one
Pr~blem 12.. Writfi! the strUcture and give ·the ]UPAC 'name of the alkene which gives only pent'dn-2-one onreductive
ozonolysJs:'Give equations, '
· :Solll~iori: As the alkene gives only pentan-2-one, it is symmetrical. Writing the structure of pentan-2-one,
C3H 7 " , ' "
'. /C=O.
CH 3 '
, ,".
,C 3H 7 "", . / C 3H 7
Hence, the alkene is, /C=C",
CH 3 "CH 3
Problem i3. Write the structure oj the isomeric butenes and name them. Give the products obtained on reductive
ozonolysis. ,
Solution : Butene exists in three isomeric fonns:
CH 3
I
CH 3-CH 2-CH=CH 2 CH3-CH=CH-CH3 CH 3-C=CH 2
But-I-ene But-2-ene , 2-Methylprop-I-ene
But-I-ene on reductive .ozonolysis gives propionaldehyde and formaldehyde.
'.- ',. :.
.....;.,u._ns_a..;.,tu;.;..r...;.,a..;.,te_d_H""'y_d_ro..;.,c_a_rb_o_n_s-=-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _.3.;...,41 ... ·.
•
(b) According to Saytzeff's rule, stability of alkenes
depeflds upon the substitution in CC bond. More of
. substitution by R, the more stable is the alkene. Hence, the BH3!TIlF
.. order of stability is: (H) CH 3CH 2CH 2CH=CH 2 . ')
R 2C---':CR 2 > R 2C=CHR > RCH=CHR >
(CH3CH2CH2CH2CH2hB DOAc). (B)'
RCH= H 2C > H 2G-CH2
Problem 16. .Write the structural and steredisomers of BD~!TIlF
(iii) )
pentene, CSHIO and compare their stabilities. ,
Solution : .Pentene exist in the following isomeric forms:
CH3~H2CH2-CH=CH2;· CH r .......CH 2-C-H ..
Pent-l-ene II Problem 19. Write the expected products formedfraw'
H3C- C:........H hot KMn0 4 oxidation o/{i) alkenes"C 4 H s',(ii)cyclobutene"
(iii) l-methylt:yclobutene, (iv) l,2~dimethylcyclobutene.. ,
Pent-2-ene (cis)
Solution:
CH 3 -CH 24-H ; CH 37'-CH 2-C=CH 2 0'
.
I
CH3'
.11 '
H-C~H3 (i) . But-I-ene ~ CH 3CH i C-OH +C0 2
Pent-2-ene (trans) 2~Methylbut-l-ene
, . o 0
CH 3-C . CHCH 3 ' CH 3 -CH-CH-:-CH2 ~ ~
, I' I . But-2-ene ~ CH 3-C-:-OH + HO'-G-.:cH3
CH 3 ,CH~
2-Methylprop-'1-ene ~ CHr~1 . 0 + CO2
2-Methylbut-2-ene 3-Methylbutc l-ene
and the stability order is: CH 3
Pent-l-ene < pent-2-ene (cis) <' pent-2-ene (trans)
< 2-methylbut-2-ene (ii) _ ICHr-COOH. J
D. -
t/ecreasing yield, obtained from the reaction of3-bromo-2,3- CH 2-C· O'
dimethylpentane with alc. KOH? ' (Hi) ·1.
Solution: CH~dH
1. -Methykyclobutene
CH 3-C=C-CH 2CH 3 >CH 3-CH-C=CHCH 3 CH3
,I I I I ' 1.
CH 3 CH 3
> CH 3CH-C-:-CH 2
CH 3 CH 3
(RzC=CHR, trisubstituted) (iv)
DC"' - CH3 ·
1,2-!?imethylcyclobiitene .
CH2-C=0
I
CH2-C-0
t
I I ' CH3
CH3 CH 2-CH 3
(RzC=CH z disubstitnted) Problem 20. Predict the product of the reaction,
Problem 18. Prepare the following from I-pentene : Ph>'.C=c<H . . HBr ) produci
H . CH 3
(i) CH 3CH 2CH2,CHDCH 3 (A), . .
[AIPMT (Mains) 2008]
(ii) CH3CH2CH2CH2CH2D (B), Solution:
(iii) CH 3CH 2CH 2CHDCH 2D (C). In the first step of electrophilic addition reac;tion: H+ idd~'
to that carbon atom of the· double bond whicbcarriesCH1 "'.
Solution:
group since, it produces carboc~tion (I} which is stabilized by
+R-effect of the Ph group. In the second step, the micleophile.;
Br- attacks the carbocation (I) to give l-bromo-l-phenyl~
propane (II). .
G.R.JJ.. Organic Chemistry fo~ Competiti(Jn8
"~<H
Ph)C=C "
H+
)
Ph)C-CH2CH3
+
CH2
:Diethyl adipate
geometrical figures: a triangle (D.) represents
cyclopropane; a square ( ) cyclobutane, a.pentagon
0
"~
" "I OH
+3H2
",
Ni,200°C
Under pressure
•
not undergo addition reactions under ordinary conditions.
However, it can be hydrogenated to n-butane at 120°C.
CH2-CH2
I I +H2
Phenol , Cyclohexanol CH 2-CH2 n-Butatie"
Cyclobutane
Physical properties: (a) First two members are gases, (3) Oxidation : Cyc10alkanes are oxidised by alkaline
next three members are liquids and higher ones are solids. potassium" permanganate to dicarboxylic acids with ring
(b) They are insoluble in water but soluble in alcohol and fission.
ether. '
H2
(c) Their boiling points show a gradual increase with C
increase of molecular mass. Their boiling points are higher H 2C"""""" '"'cH2 CHz-CH2COOH
Alk.
than those of isomeric alkenes or corresponding alkanes. I I + 5[0] I"" '
(d) Their density increase gradually with increase of H 2C""C........-CH2 CHz-CH2COOH
molecular mass. " Adipic acid
, Chemical properties: Cycloalkanes resemble alkanes H2
in their chemical properties. However, the first two members, "Cyclohexane
i. e., cyclopropane and cyc10butane are exceptions which are
comparatively less stable and tend to break open like a double 7.16 BAEYER'S STRAIN THEORY
bond and give addition reactions. The similarity of
cyc10alkanes with alkanes can be attributed to the fact that all In 1885, Adolf Baeyer proposed his famoustheQry in order "to
the carbon atoms in cycloalkanes are sp3 -hybridized forming explain the relative stability of cycloalkanes. The theory is
sigma bonds with two neighbouring carbons and, two based,ona purely mechanical concept of bonding._Th~ main
hydrogens. It has been observed that cycloalkanes from assumptions of the theory are:
cyclopentane onwards show hi!$ degree of stability and are (i) Since carbon atom is "tetrahedral in nature with aIr the
not affected by acids, alkalies and corinnon oxidising agents four valencies directed towards four comers of a regular
under usual conditions. tetrahedron, the angle between any two bonds should be
(1) Free radical substitution with C1 2 , and Dr;!: 109°28', Any deviation from'thisi,mgle would result in internal
"Cyc10alkanes undergo halogenation in presence of sunlight or strain in the molecule.
ultraviolet light. (ii) All cydoalkanes are planar, i. e., cyclopropane ring is'
equilateral" triangle; "cyclobutane ring is a square and other
CH 2-CHCl + HCl
~/ cyc16alkane rings are polygons. In the formation of these
CH 2 rings, there is deviation from the normal bond angle causin~ a
Chlorocyclopropane
lot of strain in the molecule. This stiain"commonly referred to' '
H2 as angle strain, would depend up~n the, extent. of sU9h
____C'---
H 2c CHC1" . deviation, "
I"" I ' .. (iii) The deviations from normal tetrahedral angle can be
H2C"" C ....."CH2 calculated as follows: _.
H2 D~viation =~ [109°28' bond angle in the planar ring]'.
Chlorocyclohexane 2
34A G.R.B. Organic Chemistry (or Competitions
"
y-Br
reactiQns Qnly under drastic conditiQns ,;18 expected. The angle tetrachloride.
strairi is minimum in cyclQpentane and thus, it is 'mQststable and
dQes not undergo. ring opening reactiQns.
From cyclQhexane Qnwards the angle strain CQntinuously . CJ:clopentene
increases. AccQrding to" Baeyer's ,strain theQry, higher, Br
cyclQalkanes ,shOuld' become incFeasinglyunstable and hence' 1,2-Dibromo-cyclopentane .
mQre reactiv'e,But, cyclQhexane 'and higher members are
0+
fQund to be quite stable. Thus, it is concluded that the'theo,ry is '
valid fQr first three members Qnly, "
In Qrder to. aCCQunt fQr the stability Qfcyclohexane and
higher members, Sachse and Mohr (1918) prQPosed that such'
' .
Cyclopent-l-ene
0 + H 20 KMn04 (aq.),.
OH
YaH
Cycfopentane-l,2-diol
rings can becQme free from strain if all the ring carbQns are nQt
forced into' Qne plane but assume a, strain-free' puckered
cQnfiguration in which each carbQn atQm retains its nQrmal
7.1ffOIENES
valency angle. Onthis basis Sachse proPQsed two. models fQr These are hydrQcarbQns with two. carbon-carbQn dQuble
cyclQhexane-called the bQat and chair forms. MQhr bonds. Dienes ,are of three types:
, supported .this prQPQsal and'the theQry."became knQwn as, (i) Conjugated dienes : Double bonds are separated by
Sachse-Mohr theQryQf strafuless rings. ' , , one single bQnd. FQrexampie,
~.
Buta-l,3-diene H 2C==:!CH----CH =CH 2
, (H) Cumu'ative dienes: Double bonds are adjacent to.
, Boat form' . Chair form 'each other. FQr example,
The reactivity. of unsaturated hydrocarbQns (alkenes and Allene (PrQpadiene). H 2C=C=CH2 .
alkynes) is explained with the help QfBaeyer's strain theory. Buta-l,2-diene CH 3 ----CH=C=CH 2
When carbon atQms are linked by dQuble bQnd, the valen~y
bQnds undergo bendirig and are distQrted from their nQrmal (iii) Isolated or Non--conjugated dienes: DQuble bonds
directiQns. This bending produces strain in the molecule with are separated by mQ~ than Qne single bond. FQr example,
the result that it becQmes unstable and hence mQre reactive. In - Penta-I,4-diene H 2C=CH-CH 2 ----CH=CH2
, acetylene, there is greater strain and hence is reactive. The . The general fQrmula of dienes is Cn H 2n - 2 • Dienes are
strain disappears when addition QCcurs. .
iSQmeric -with alkynes. The most impQrtant class of dienes is
7.17 CYCLOALKENES that Qf conjugated dienes. Their chemical properties are
Carbocyclic cQmpQundswith dQuble bonds in the ring are , different frQm those of Qrdinary alkenes. Thepredominent
called cyclQalkenes. SQme,Qf the CQmmQn cyclQalkenes are> . ,member Qf this class is Buta-l,3-diene.
'.
Unsaturated Hydrocarbons
,
Parti.81 double
bond character (ii) From 1,4·dichlorobutane: 1,4-Dichlorobutane is
heated with alcoholic KOH when dehydrohalogenation occurs
H>VV-fJfJ<H with formation of buta-! ,3-diene.
C-C-C-C
or H M.61J H
CI
I
CHzCHzCHzCH2
CI
I Ale. KOH ) HzC=CH-CH=CH z
Delocalisation of 1t-electrons
1,4-Dichlorobutane Buta-I,3-diene
or
H>VVVV<H
C-C-C-C C> <J (iii) From 1,4-butanediol: Acid-catalysed dehydration
H 8--(J 8--(J H HzG-CH-C.H-CHz is done by heating 1,4-butanediol with cone. H ZS04 •
Overlap ofp-QrbitaIs in a C> <J OH' OH
conjugated diene to fonn ,I I H S04
2
two double bonds " . CHzCHzCHzCH z heat) H zC=CH-CH=CH2
The central carbon atoms in this molecule are close to 1,4-Butanediol Buta~I,3·diene
each other and there is a possibility of overlapping between (iv) From butane: Buta-l,3-diene is obtained by
p-orbitals of C2 and C 3 • Tliis gives the partial double bond passing the butane vapours overheated catalyst (CrZ03 on an
character to the central bond. Rotation of the molecule about alumina support) at 600°C., '
atoms C 2 and C3 requires only about 5kcaVmoi whereas that
about the double bond in ethylene, the barrier is 60 kcaVmol.. CH 3CH zCH zCH,3 Catalyst ) HC=CH-CH=CH
~
2
The stability of conjugated dienes are supported by bond n-Butane 600°C· Buta-I,3-diene
length measurement and study of heat of hydrogenation and (v) From cyclohexene: Buta-l,3-diene may be
heat of combustion, etc. prepared by passing cyclohexene over a heated nicbrOme wire.
The heat of hydrogenation of monosubstituted alkenes
(R -CH=CH2) is 30.3 kcaVmol (or 126 kJ/mol); The heat of,
hydrogenation of butadiene, having two double bonds, should
,.'0'I ~ HzC=CH-CH, . CH2 +HzC ,', CHz
." Buta-l,3·diene Ethene '
be 2 x 30.3= 60.6 kcaV mol (or 252 kJ/mol). The experimental Cyclohexene
(observed) value is 57.1 kcaVmol (or 236 kJ/mol). Thus
butadiene is more stable by about 3.5 kcal (15 kJ/mol). This is Properties : Buta-I,3-diene is a gas. It shows the
foUowing reactions:
reSOnance energy of butadiene. These values support that
(I) Addition of ,halogens: Buta-l,3-diene reacts with
conjugateddienes are !Dore stable.
halogens (Brz or Clz) in ~e presence of an inert solvent (CCI 4 )
• The CZ-C 3 bond length in butadiene, is 1.48 A and for to yield a mixture of 1,2- and 1,4-addition products.
Cj"-"":'C 2 andC 3-C4 bond length is 1.37 A. TheC 2-C 3 bond
, , { CH2BrCHBrCH=CHz
length is i shorter than the C-C :bond ~ength in ethane (1.54 , 3,4-Dibromobut-l-ene (l,2-Addition)
A). ' , H 2C=CH-CH= CHz + Br predominates (62%) in non-i9nising
The resonance struotures ofbuta-I ,3-diene are;as follows: Buta-l,3.dien~ i solvent (hexane) ,
H>'
H
C=C,'
H
C=C
5' H> +
<H - -
H
5H
C-C,-
C-C
_<' H,
CHzBrCH=CHCH2Br
1,4-Dibromobut-2-ene (1,4Add~tion)
predominates (70".4) in an ionising
; H 'H' H H solvent (acetic acid)
, HH The mechanism of the above reaction involves the
--
c
H>c- 5c_c<H
following steps: "
lststep: The halogen molecule (Br2) undergoes
H H
heterolytic fission.
G.R.B. Organic Chemistry for Competitions
Br2 ~ Br+ + :Br-' , The presence of electron attracting groups such as ---{;N,
BromoniUIll 'Bromide ---{;HO, ~OR. ---{;OOH, ---{;OOR, etc., oil., dienophile
, ion 'ion
facilitates the reaction. This reaction is widely used in the,
, 2nd step: ,The bromonium ionattacks the double bond ' synthesis of six membered ring compounds. ' "'
to give' a resonance stabilized carbocation.'
(vii) Ozonolysis: Dienes undergo ozonolysis to give
, ' BrCHr-CH~CH2{A) three molecules. Buta-I,3-diene yields formaldehyde and
glyoxal on ozonolysis.
Br++ H2C=CH---{;H= CHz{ 't ,+'
.' Zn/H 20 .
Buta-l,3-diene BrCHz-CH= CH-CH2(B) HzC=CHCH=CH z +20 3 ) 2HCHO+OHCCHO
Buta-1 ,3-diene
, 3rd step: The bromide ion combines with (A) to form,
3,4-dibromobut-I-ene (l,2-addition). It combines with (B) to Problem 20. How will you distinguish between:
form I,4-dibromobut-2-ene (l,4-addition). (i) Cyclop~pane and propene,
(ii) Cyclopentane and pent-2-ene,
(il) Addition of halogen acids: A mixture ,of two
(iii) Buta-I,3-diene and but-I-yne,
compounds is formed when buta-l,3-diene reacts with
(iv) Buta-I, 3-diene and butane?
halogen acids (HX). Solution: (i) Propene decolourises dilute KMnO 4
CH 3 CHBrCH=CHz
(1,2~Addition)
solution whiie cy~lopropane does not give this test.
3-Bromobut-l-ene KMn° 4(aq·) )
(Major yield at low temp.) CH 3CH=CH z +[0]+ H;>O
HzC=CH-CH=CH2 + HBr
Buta-l,3-diene 'Propene
H3C-CH=CH-:-CH2Br
(l,4-Addition) , 1,2-Propanediol
I-Bromobut-2-ene
(Major yield at high temp.) (ii) Pent-2-ene decolourises the purple colour ofKM:it0 4
solution. It also decolourises red colour of bromine in CC1 4 •
, (iii) Addition of water: ' Buta-I ,3-diene reacts with These tests are not given by cyclopentane.
water in the presence of H 2SO 4 to give a mixture of 1,2- and
l,4-addition products. CzH sCH==CHCH 3 +[0] + HzO
KMn° 4(aq·) )
' CH3CHOHCH= CHz
OH OH
H2C "-:'CH-CH=CH2+ H20 ' But-3-en~2-ol
. Buta~Ii3-diene,
{
CH3CH CHCH20H
I I
CzH s CH-CHCH 3
But~2-en-l-ol 2,3-Pentanediol
. 3-Chloropropene is treated witn sOQlUm in presence of (a) ClCH 2CH-:-CH z, (b) (CHjhC=CH2,
ether, i. e., undergoes Wurtz's reaction to form hexa-l ,5-diene .. (c)CH 3CH=CH2 , (d) H 2C=CHCI
Ether· (iv) . Stereochemical struc(ure ofthe reaction product of
)
Br2 with (a) cis-2-butene and (/J)trtlns-2':'butene.
H 2C=CHCH 2 CH 2CH=CH 2 (v) Why alkynes are generally less reactive than alkenes
Hexa-I,5-diene towards el~ctrophilic reagents such as H+ ? ',
(vi) The central carbon-carbon bond in buta-I,3 -diene is
(ii) Propene is first treated with bromine at 500--600°C shorter than that of n-butane.
whim 3-broinoprop-I-ene is fonned which on treatment with (vii) Arrange following alkenes in decreasing order of
alcoholic KOH yields allene (propadiene). stability towards acid-catalysed hydration.
Brz (a)' l-phenyl-l-butene; l-phenyl-2-butene; 2-phenyl-2-butene
CH 3 -CI-!--=CH2 ) CH 2BrCH=CH 2
:'r,'ene 500-600°C 3-Bromoprop-I-ene (b) 2-methylpropene; cis-2-butene; trans-2-butene
(c) l-hexene, 2-methyl-I-pentene, 2-hexene.
Ale. KOH) H C=C=CH Solution: (i) See mechanism on Page 345-346.
2 2
Allene (ii) The addition occurs at double bond because isolated
(iii) 1,3-Dibromopropane on heating with zinc forms double bond is more reactive than an isolated triple bond in
cyclopropane which is reacted with conc. HBr to yield electrophilic additions.
l-hrorilopropane. (iii) Electron releasing alkyl groups make the pi-bond
more electron rich and more reactive. While electron with-
/CH 2Br /CH 2 drawing halogen atoms make the pi-bond more electron poor
H 2C"" + Zn ~ H 2C "",I and less reactive. The order is:
CH 2Br CH2 (b) Two R>(c) oneR > (a) one R and a CI > (d) CIon a
1,3-Dibromopropane Cyclopropane double bonded carbon.
Cone. HBr (iv) 2,3:-Dibromobutane (a) racemic (b) meso.
----'--~) CH 3CH 2CH 2Br (v)-The reaction of alkyne or alkene with electrophiIic
I-Brom6propane reagent proceeds through the formation of carbocation. Since
/CH2\ CH2 the alkyl carbocation from the alkene group is more stable
H2C CH2 Cl z H2C~ "CHCI than the vinyl carbocation from alkyne group, the MI for its
(iv) I I ~
hv I I formation is less in case of alkene and hence alkene reacts
H2C",-C /CH2 H2C.......... C~CH2 . faster than alkyne ..
(vi) Buta-I,3-diene (H2C=CH-CH=CHi) has
H2 H2
Sp2 _Sp2 C--C bond length, while n-butane has sp3 _sp 3 C--C
Cyclohexane Chloroeyclohexane
bond length. More is 'i character in' hybridization, lesser is
CH2 bond length. '
Ale.KOH ·HC.,..,... -""':::CH (vii) (a) 2-phenyl-2-butene> l-phenyi-2-butene
Heat
2 I I > l-phenyl-I-butene . .
H2C.......... C~CH·· (b) ,2':methylpropene > trans~2-butene > cis-2-butene
H2 '(c) , 2-methyl-I-pentene > 2-hexene > J -hexene.
Cyclohexen.e Problem Z3. A , hydrocarbon; C 4 Hg, neither
deco(ourised bromine in carbon tetrachloride nor reacted with·
(v) CH 3CH 2CH=CH 2 HBr. When heated to 200°C 'with hydrogen in presence of a
ijut-I-ene nickel catalyst, a new hydrocarbon, C4 B 10 ' was formeq,. What
Ale.KOH
was the original hydrocarbon?
Heat) H 2C=CH-CH=CH 2 S(dution : The hydrocarbon can have the following
Buta-I;3-diene isomers:
H 0 Hz C1 · CH 3CH 2CH . CH 2, CH 3CH=ciIcH 3 ,
z C Ii
(VI.) CaC 2 ~ )C H .2) C Cl But~2-ene
2 2 Ni, 3000C 2 6 4000C 2 6 But-I-ene
(A) (B) Cyelobutane
Pro~lem 22.Explain the following: (C)
(i)' Buta-l ,3-diene gives 1,2- and 1,4-addition products. (A) and (B) are ruled,out as the compound does not react
(ii) Addition of HBr to H 2C=CHCH 2C=CH gives with Br2 and HBr~ Thus, the compound is cyclobutane.
CH 3CHBrCH 2C==CH . ' , Cyclobutane on reduction opens up the ring and forms
(iii) Alkenes in decreasing order of reactivity towards n-butane.
electrophilic addition:
D
Cyclobutane
+H2
Ni
n-Butane
...;;,348,.;;,'
:~_ _~_ _ _ _ _~_ _ _--.,_~_____________..;:;G:.:.:.R:..::.:.::B:.:..;.!?rganic Chemistry fOr Competitions
Pro"lem 24.' (i) Anorganic compound" C4 H 6 " on (b) !JP . .' ':j:rtV\:"'~ structures ofthe stereoisomersformed
ozonolysis gives formaldehyde, and glyoxal. What" is this when cis-.. <>u~~e is reacted with bromine. '
compound?' ' , . Solution: (a) Only cis-fonn of the alkene is fonned.
. '(ii) C 4 H 6 cqnrepresent various structures; identifY:
(a) Which reacts with ammoniacal AgN03" H)C=C<H
(b) Which does not react with ammoniacal AgN03 but R R
by hot alkaline KMn04 gives CH 3COOH, Cis-form
(c) Which decolourises Br2 water and by catalytic
hydrogenation (using I mol) and subsequent reaction H3C) <CH 3
with alkaline KMn04 givesCH 3 COOH and (b) C=C + Br2 ----7
(d) Which by ozonolysis using 03/H20 gives succinic H H
acid. CiS-but-2-ene
Solution: (i) The fonnula suggests that either the
compound is an. aJ.kYne or an alkadiene. The products of
ozonolysis suggest that the compound is alkadiene. It may
have the following structures~ , ,
H 2C . CH-CH=CH2 CH 3-CH=C=CH2
Buta-l,3-diene Buta-l,2-diene
(A) . (B) It exists in two optical isomers.
CH 3
Formaldehyde and glyoxal can be obtained from (A).
Hence"the compound is buta-I,3-diene. H + B ,r and
(ii) (a) C 4H 6 reacts With ammoniacal AgN03'SO it is a Br-t-H
terminal aJ.kYne (-C ' C-H). For example, CH 3 .
, CH 3CH 2-C==C!I (But-l-yne)
Problem 26. Give the structureS of the major products
'(b) C 4H 6 AIkalin: KMn0 4 ) CH 3COOH from , 3-ethylpent-2'-ene under each' of tke, following
conditions.
, Hence, it is CH3-Ci!!!!!!!C-CH3 (But-2-yne) (a) HBr in presence ofPeroXide,
(b) Bt:2/H2Q
CH3~==C-CH3 +3[O]+H 20 A1k.KMn04 ) (c) Hg(OAch/H20; NaBH 4 •
'Bu,t-2-yne ' . A Solution:
HBr
(C)C4H6 + H2 ----7 C4Hg
}>eroiU'de ) ..
(H2C=CH-CH--:-CH2 ) (CH 3CH=CHCH3 )
Buta-I,3-diene' But-2-ene
A1k,KMn04,
. 8.
) CH 3COOH
Ethanoic acid
Explanation: Buta-I,3-diene is converted into B~ ,
,but-2-ene by lA-addition. (b) CH 3CH2C=CHCH 3 ----7 CH3CH 2CBrCHBrCH 3
" () (\ + -
, I' 1
H2C=CH-cH~CH2 ----7 H 2C-GH=CH-CH2
C2 HS C2 Hs
Buta-I,3-diene H 20
. )CH3CH2r(OH)CHBrCH3
H2 .
----'~~) H 3C-CH=CH-CH 3
1,4-addition ,But-2-ene, ' C2 HS
03/H20 CH2COOH Hg(OAc)z
------"~~) I ' (c) CH 3CH 2-C=CH":"-CH 3
I H 20
)
CH 2COOH
Succinic acid C2 H S
CH 3-CH i-y.<HgOAC)-CH2-CH;l
Problem 2S. (a) Draw the stereochemical structure of
the product in the following rea,ction, ' C2 H; ,
Hz
'R-C==C-R )
Lindlar's catalyst
Unsaturated Hydrocarbons
Problem 27Jndicate.allylic, vinyl,IO, 2°,3° hydrogens. ·Only (B) gives.Camiizzaro's reaction. "
in· theJollowingcompound. Give the sequence ofreactivityfor Alkene (A) exist in following two geometrical isomers
free radical substitution. (A-l) and (A-2), ofwruch (A-2) is more stable. ' .
. . /C~3
CH3-CH. CH-:-CH 2-CHr -CH "'-CH (CH,hC)=c(CH, (CH,hC)cc/H
3 . H . H H ' "eH 3 .
. (A-1) CIs- . (A-2) Trans-
OT~H'; ~{)-{o""'CH;
. CH) , CH3 H H
.I , . '(i) ~I\ ." I I I • (c)[I'] [WJ
CH3-C-C-C-CH3' ' ) CH3-C-C=C-CH3
I .. (ii) CH3COOH•.W I . .' Br Br
CH3 CH3
r\Jlo
'
.
(X)
4,4-Dimethylpent-2-yne .
(A)
"1--; " " [X] = "---I- -CH v 3;
Ozonolysis (1) 0 3
NNHCONH2
H
,
H CH 3
(ii) Zn/IIOH
[11= (Y...:...cH3; .
1 I. 1 .
CH3-C====O+ O=C-C-:-CH 3
(C)· I '
Acetaldejlyde CH 3
(Bt
2.2-Dimetbylpropanal
350, G.R.B. Organic Chemistry (or Competitions
", HBr only to unsynnnetrical alkenes in the presence of a Addi~on of oxygen: When mixed with air or oxidation
organic peroxides, i.e., benzoyl peroxide (C 6H sCOOh with peroxy acids (CH 3COOOH, C 6 H sC0 3H
follows anti-MarkowDikoWs addition and called as orCF3C0 3 lI) or air passed through silver catalyst at high
peroxide effect (free radical mechanism). temperature' (200-4000C), the lower alken,es form
Peroxide .
epoxides (cyclic ethers) which on hydrolysis give diols.
CH 3CH=CH 2 +HBr . ~CH3CH2CH2Br a Addition of ozon~: When. 0 3 or ozonised oxygen' is
. Propene' 'l-Bromopropane
passed through a solution of alkene in an inert solvent,
a Addition of hypohalous acid (H~X): A1k~mes form addition takes place across the double bond to form an
halohydrin with .. hypohalous acid (i.e., Cl 2 orBr2 in ozonide. Ozonides are easily decomposed on warming
presence of water). In H---O-CI or H-:-O--Br, the . with ZnlH 20 or reduction with HilPdcatalyst breaks
---O-Cl or --:...o-Br: (rather than -:-O--H bond) is )c= C( to produce two carbonyl compounds.
,broken and the molecule is polarised' in the manner a An alkene of the type RCH=CHR' gives two aldehydes'
8- 8+3- 8+' '.
Ho---Clor HO--- Br.·· , . (same or different).
a An alkene of the type R 2C=CHR' gives one aldehyde
a In these halohydrin formation reactions, a halonium ion is' and one ketone.
formed as an intermediate which' is attacked by water
a An alkene of the type R 2C=CR 2gives two keto~es (same
(nucleophile) in aqueous solution. .
or different).
a Addition of sulphuric acid:. Cold and concentrated
a The two step process of forming the ozonide,and then
HzSO 4 readily adds to alkenes and forms alkyl hydrogen
decomposing it to give a mixture' of two carbonyl
G.R.B. Organic Chemistry for Competitions
D
(i) 0 3
(ii) H2IPd
~
I · ·' R-CHOH
1 +H20s04
CH2-CHO
Cyclobutene Butane-I,4-dial R-CHOH
Glycol
CHO CHO
D
Cyclobuta-I,3-diene
(i) 203
(ii) 2ZnlH20
~
1
CHO
+1
CHO
Ethane-I,2-dial
I:lHydroxylation can also be done with 12 /CH 3COOAg,
peroxy acids (HC0 3H or a mixture of H 20 2 and
HCOOH).
I:lCyc1odienes on· ozonolysis give two. products each I:l Oxidation with addk KMn0 4 or addk· K2Cr207
containing two carbonyl compounds.
(Strong oxidising agent): They break the double bond
[JCyclotrienes on ozonolysis give three products each
and give ketones and carboxylic acids (because aldehydes
containing two carbonyl compounds.
formed cannot be isolated from KMnO 4 solution as they
0
CHO are easily oxidised to carboxylic acids).
1· ~
31
~ (ii) 3H2IPd CHO R 2C=CHR' KMn04, ~ R 2C=0 + RCHO ~.RCOOH
Cyclohexa-I,3,5-triene Ethane-I,2-dial Alkene [0] Ketone Acid
I:lPeriodk add (HI0 4) or lead tetra-a£etate
I:lConjugated dienes on ozonolysis yield three products, i.e., [(CH3COO)4Pb] oxidises alkene int!l glycols and finally
two monocarbonyl· compounds and one dicarbonyl gives aldehydes or ketones depending upon the nature of
compound. alkene.
. ... (i) 203
H2C~C-CH=CH2
. I . )
(ii) 2H2/Pd >r----r< .~ )=o·+o=<
CH3 Alkene OH OH Ketone
2-Methyl buta-I,3-diene Pinacol
(Isoprene)
oI 1:l0xidation of alkenes by Se0 2 affects the allylic position
CHiO +CH3-C-CHO+OH 2C and not the double bond. .
Methanal 2~Ketopropanal Se02
I:lA cumulated diene gives two monocarbonyl compounds H 2C=CHCH 2CH 3 ) H 2C=CH?HCH 3
But-I-ene
and.one mole of CO 2, . ·OH
. . (i) 203 . But-3-en-2-o1
H 2C=C--.:....CH-CH 3 .. ). CH 20 + CO 2
Buta-I,2-diene (11) 2H2/Pd· Methanal I:l Combustion: When burnt in air, alkenes are oxidised to
+OHCCH 3 CO 2 and H 20. The reaction is exothermic, because heat is
Ethanal evolved:
Oxidationreadions: Alkenes are readily oxidised. The I:l Insertion of methylene (£arbene): Phptolysis of diazo-
oxidation products depend on the nature of oxidising agent methane (CH 2N 2) and ketene (CH 2=C=0) gives·
. used: - . methylene (carbene). This adds to alkene ·to yield
I:l Oxidation or Hydroxylation with £old, dilute, alkaline cyc1oalkanes.
_KMnO 4 (Baeyer's reagent): Glycols are formed.
.......,/ Alk. KMn04....... rV
CH3-CH=CH2 + CH2N 2
,/C=C ....... +[0]+H20---~) ,/C-\...., Propene Diazomethane
Dil., cold .I I
UVLight
OHOH ~.
~'.£'':'':'ot=
This reaction is used for the detection ofunsaturation and is Methyl cyclopropane-
called Baeyer's test.
. I:lHydroxylation by KMnO 4 is always syn~additi.on. I:l Polymerisation: Two or mote molecules of an alkene
unite together to form a bigger molecule of higher
molecular mass called polyalkenes.
Unsaturated Hydrocarbons 353
Polyethene, polypropene and polybutene are "plastics" of a By rea4!ting l-alkynes with Grignard reagen"t followed
industrial importance. by treatment witb R-X : .
[J Substitution .rea4!don (Halogenadon): NBS (N-bromo CH3MgI . .
HC==C-H ) HC==C-MgI
. succinimide).is a reagent used for the'specific purpose of Ethyne ('---:CH4) . .
CH3I
brominating alkenes at the allylic position (i.e., ---7) HC==C-CH 3
replacement of H atom of the alpha carbon atom with Propyne . (-MgI2)
respect to double bond of alkyl group by th~ atom at about CH3MgI
500°C without breaking the double bond). This type of CH 3 -CFCH (-cT-f .) CH 3 -C=C-MgI
Propyne ''4
substitution is kpown as aUylk substitution. It takes place
RI
in gas phase by free radical mechanism. . --~) CH 3 -C==C-R
(-MgI2) Higher a1kyne
ALKYNES [J By oxidation of bis-bydrazone of an a-diketone :
[J Unsaturafed hydrocarbons with one triple bond are known
2NH2NH2
as alkynes or acetylenes and represented by the general . R-C-C-R' R-C--C-R'
fonnula C lI H 211 - 2 • Their functional group is -C=C-. I I I I
Alkadienes (H 2C=CH-CH=CH 2 ), cycloalkenes o 0 NNH2 NNH2
(C 4 H 6 ) D and bicycloalkanes. LSJ are isomeric with (lft-Diketone Vic-dihydrazone.
alkynes containing same number of carbon atoms in their --~) R-C C-R +2N 2 +2H 20+2Hg
molecules. Heat Higher a1kyne
a The triple bond in alkynes consists of one sigma and two
Pbysi4!al properties
pi- bonds. Each C-atom of the triple bond is sp-hybridised
and -C==C- bond length (1.20 A) is shorter as a Acetylene IS a colourless gas with ether-like odour, b.pt. is
, compared with )C=c( (1.34 A) and 7C-CE (1.54 -84°C Acetylene (liquefied or when compressed) .is
explosive, burns with a luminous smoky flame, hence used
A). for lighting purpose. Oxy-acetylene flame is used for
a Monosubstituted acetyleI)es or l-alkynes. are called cutting and welding of metals. Alkynes have linear
terminal alkynes, and the H atom attached to C=C is structure and' therefore, their molecules are rather more
called acetylenic (acidic) hydrogen (R-C==C-H). closely packed in space as compared to alkanes and.
alkenes. .
General metbods of preparation
[J By debydrobalogenation (-HX) of dihalldes: On Cbemi4!alproperties
heating dihalides (vic- and gem-) with alcoholic KOH'or
[J A4!idi4! nature: The H-atoms of ethyne are more acidic
sodamide, NaNH 2 (in liquid NH 3 ) or solid KOH or KNH2 than those of ethene or ethane. The decreasing order of
etc. acidity is: H-;C==C-H> H 2C=CH2 >CH 3 -CH 3 .
[J By debalogenation (-X) of tetrabaUdes: On heating , The group -C=CH (l-alkynes) is acidic in nature due to
wi.th Zn dust in alcohol. more s-character (50%) of C==C which is sp-hybridised.
a By heating iodofonn with silver powder. Hence, proton release in -C. CH .takes place more
a By the electrolysis of Na/K salts of unsaturated readily. On account of acidic nature, ethyne and all other
dicarboxylic acids (Kolbe's method). tenninaL alkynes fomi salts with metal derivatives which
[J By the action of water on calcium carbide (Lab method). are called acetylides or. al~nides.
[J By heating methane or natural gas at I 500°C in an electric [J Formation ofsodium a4!etylides: Acetylene reacts with
arc (Manufacture method). NaNH 2 or Na/liq. NH3 fonDS sodium alkynides which is
[J By the controlled partial oxidation of methane at high utilized for the preparation'ofhigher alkynes with 10 alkyl
temperature (Manufacture method). halide (because 2° and 3° R-X give mainly alkenes).
[J By the hydrolysis of magnesium carbide, propyne is a Formation of ~oppera4!etylides: Acetylene when
fonned. passed through an ammoniacal cuprous chloride solution,
a By passing an electric arc between carbon electrodes in an a red precipitate of cuprous acetylide is formed.
atmosphere of hydrogen at 2500°C (Berthelot's [J Formation of sliver acetylides: Acetylene when passed
synthesis). through an ammoniacal solution of silver ilitrate(Tollens'
[J By reading sodium alkynides with alkyl halides : reagent), a white'precipitate of silver acetylide is fonned.
Higher alkynes are fonned. , [J Addition of bydrOg~n (Hydrogenation): Alkynes oil
treatment wjth hydrogen in presence of a catalyst (Ni, Pt or
Na/liq.NH3
HC==CH. )HC==C-Na HC==C-R Pd) fonnalkenes and finally alkanes. .
or NaNH2 Sod. alkynide . l-Alkyne
.'
•• , • • ~F
[J Alkenes (cis-) can be obtained 'from aIkyne~ by partial give ethylidene acetate which on heating gives
hydrogenation with PdlCaC0 3 poisoned by quinoline or acetaldehyde and acetic anhydride.
lead acetate (Lindlar's catalyst). . [J Addition of alcobol: In presence of NaOH'Or KOH or
[J LiAlH4 or Na/liq. NH3 converts alkynes to trans' (E) mercUry salt, acetylene reacts with alcohol to form alkyl
alkenes. ' vinyl ether (vinylation) which on hydrolysis gives
[J Addition of halogens: Alkynes add two molecules of acetaldehyde and alkanol.
halogens and decolourise Br2 water (test of , o Addition of 0 3 and subsequent hydrolysis: Acetylene
unsaturation). The reactivity order of halogens is as
follows: F> CI > Br > I. Liquid bromine yields tetrabromo
°
and its homologues form ozonides with 3 and these
comp'-"lnds are decomposed by water to form diketones
derivative while BrzlH 20' or Br2ICCl4 forms dibromo which are then oxidised by H 20 2 (formed in the reaction)
derivative. Iodine reacts slowly in alcohol to fonn di-iodo to carboxylic acids.
derivative (predominantly trans- isomer). o Polymerisation: Acetylene undergoes both cyclic and
o Alkynes are less reactive than, alkenes towards addition of linear polymerisation.
halogens, because alkynes form less stable intermediate. o Cyclic polymerisation: When acetylene is passed
,0 Acetylene reacts with Cl 2 in the presence of catalyst SbCI s through a red hot metallic tube at 600°C, it is polymerised
. _to give westrOn which'on heating with BaCl 2 or lime or to benzene. Propyne on heating' trimerises to form
alc. KOH gives westrosoi; mesitylene (l,3,S-trimethyl benzene).
o Addition· of halogen acid (HX): The decreasing order . 0 Linear polymerisation: When acetylene is passed into
of reactivity is : HI> HBr > HCI > HF. Addition of one cuprous chloride solution dissolved in NH4 CI, linear
molecule of halogen acid gives vinyl halide which then ,polymerisation occurs forming monovinyl acetylene and
adds another molecule of HX to form; gem-dihalide~ The divinyl acetylene. Vinyl acetylene onreduction with H21Pt
addition follows Markownikoff's .rule. In presence of in presence of BaS04 forms buta-I,3-diene. Butadiene
peroxides, anti-Markownikoffproduct is,obtained. . and 'vinyl cyanide form polymer buna-N-synthetic
o When acetylene is passed into dilute HCI at 6O-6s o C in rubber. . Vinyl acetylene reacts with HCI to give
presence of mercuric ion (catalyst) only one molecule is chloroprene (2-chloro-buta-I,3 -diene) which polymerises
added to give vinyl chloride (vinylation). Vinyl chloride to neoprene (synthetic rubber).
(CH 2=CH-CI) is ,the monomer of PVC. IJ Addition of arsenic trichloride (AsCI 3): Acetylene
o Addition of HBr to an alkyne can be facilitated by using combines with Asa 3 in presence of anhydrous AICl 3 or
acetyl bromide (,CH 3COBr) and alUmina (Al 20 3) instead Cu 2Cl 2 or HgCl2 to form Lewisite (a poisonous gas).
of aqueous HBi. t '
o Addition of carbonyl compouncts (Alkynylation of
, . CH3COBr/Al203 '"
CsHIl-C==CH + HBr ) , )C=O compounds) : Terminal alkynes can add to
Hept-I-yne. ' I n CH2Ch solvent
)C=O group in presence ofC 2H sONa orCu2C2 to form
CSH 11 -C=CH 2 alkyndiol which is called ethinylation.
I
Br o Carbonylation: Acetylene adds to (CO + H 20) or
"i 2-Bromoh~-I-ene (CO + R-OH) in presence of catalyst nickel carbonyl,
o Addition ofhypochlo~us acid,(HO--cI): It is chloro- Ni(CO)4' and forms a,j3-unsaturated acid or ester.
hydroxylation. by chloririe water. Alkynes when passed o Formation o~ heterocyclic compounds: When acety- ,
into H{}-cl form dichloroaldehydes or ketones. lene is pass~d with sulphur over a heated tube at 300°C, it
o Addition of IhSO 4 (conc~): Acetylene gas, when forms thiophene. Acetylene combines with NH3 in red
passed through concentrated H 2S0 4, gets absorbed hot tube and forms pyrrole: With HCN in a red hot tube,
forming ethylidene hydrogen sulphate which on boiling acetylene produces pyridine.
with water gives'acetaldehyde.
o Addition of water (Hydration): \ Alkynes add on one
molecule of water when passed into dilute H 2S0 4 at 60°C
2HC=CH + H-C N
Red hot
. • ..
O·I
Acetylene ~N
in presence of HgS04 catalyst to form aldehydes or Pyridine
ketones through ketO-enol tautomerism.
o Addi~on of HCN:Ethyne adds HCN in preseJ;lceaf IJ Oxidation reactions: Different oxidation products are
, ,Ba(CN)2 or'NaCN or CuClIHClorCuCl 21NH3 cat<.):nl to obtained with different reagents.
formvinyl cyarude (acrylonitrile) which is a mon . 'ner for o Burning (combustion): Acetylene bums with ~moky
the polymer polyacrylonitrile (PAN). fla!lle in excess of air to give CO 2 and H 20 and large
• 0 Addition' of CH 3COQH: Ethyne adds tw~ moles of amount of heat is produced.
. acetic acid in presen~ of Hg 2+, or Bf.3catalyst at 80°C to o Oxidation with alkaline KMnO 4 solution: Acetylene
.- •• j'
is finally converted into oxalic acid with cold, dilute
,
" ;
Unsaturated Hydrocarbons .
alkaline KMnO 4 (Baeyer's reagent) and pink colour oftbe. [J Oxldative-hydroboratio~: Alkynes react with BH3 (in
solution is discharged. Higher alkynes under similar THF) at O°C to give an intennediate trivinyl boratie which
conditions give diketones. At higher temperature (110°C) on oxidation with alkaline H 20 2 gives an unsymmetrical
the final products are carboxylic acids, CO 2 and ketones. alcohol that tautomerises to an aldehyde or ketone.
Cl Oxidation with acidlfted KMnO .. : Acetylene is Cl Degree of unsaturatioD: The number of pairs of
converted into formic acid with acidic KMnO 4 on heating, hydrogen atoms that. a molecular ~onnula lacks to be an
while higher alkynes give R-COOH. Symmetrical . alkane (C n H2n + 2) ~ called degree of unsaturation and this
alkynes give a single product while unsymmetrical value is called the index of hydrogeli: deficiency. The
alkynes give a mixture of two products. number of degree of unsaturation'~ a hydrocarbon is
CJ Oxidation with chromic acid (K2Cr207 + H 2SO.. ): given by:
Acetylene is converted into acetic acid and the orange = --!.---=-.
colour changes to light green.
Cl Oxidation with selenium dioxide (se0 2): Acetylene is where, nl is the number of carbon atoms andn2 is the .
oxidised to glyoxal with Se02 while propyne gives keto- number of hydrogen atoms. ' •
propanal. [J Tests of UDsaturatioD: ,The tests of unsaturation
CJ Substitution reactions: When acetylene is passed (detection of double or triple bonds) are generally per-
through sodium hypochlorite (NaOCI) solution at O°C in fonned by:
absence of light, hydrogen atoms are replaced by chlorine 1. Baeyer's reagent: To an aqueous ,solution of the
atoms with the formation of 1,2-dichloroethyne. With 12 compound, a few'drops of Baeyer's'reagent (cold, dilute,
and NH3 at low temperature, acetylene formS 1,2-di-iodo . alkaline KMnO 4 soluti0'fl) is added. The decolourisation of
ethyne. pink colour indicates the presence of unsatnration.
CH. CI 2. Br2 water in CCI .. or CHCI 3 : The compound is
Low temperature
III +212 +2NH3 ) III dissolved in an inert solvent like CC1 4 or CHcl, and then a
CH CI few drops of 5% bromine. so lutiotl iIi CCl 4 are added to· it.
Ethyne 1,2-Di-iodo
ethyne If the colour of bromine disappears, it indicates the
presence of unsaturation. .
Cl lsomerisation: On heating with alcoholic KOH or [J The presence of double arid triple bonds are located by the
NaNH 2 in inert solvent, the triple bond of l-alkyne is .identification of the products of ozonolysis.
shifted towards the centre to fonn an' isomer 2-alkyne. [J l-Alkynes give a white precipitate when passed through
Similarly, on heating with sodamide (Na in liquid NH 3 ) ammoniacal AgN03 solution and also red precipitate
the triple bond (2-butyne) shifts towarqs the end when treated with ammoniacal cuprous chloride solution.
(l-butyne).
•
(];R.B. Organic Chemistry tor Competitions
)e=c<H
(I) The carbon atoms of ethene are ...... hybridized. forms ...... .
(m) The carbon atoms of ethyne are ...... hybridized.
'(n) A white precipitate is obtained by passing ac~tylehe
through ammoniacal ... . . . . sol"\ltion.
(0)
Ph
H" CH3
~ ..... .
(0) Buta-I,3-diene with bromine in molar ratio generates
predominately . . . . . . .
(P) The electrolysis of potassiwn fumarate gives . .. . . . .
(q) The position isomer of butene" 1 is ...... .
NaNH 2 CH3Br
(r)The ozonolysis product of CH3 CH=CHCH3 is (q) HC==CH ) ...... ~ ..... ".
HBr KOH(aq.)
(s) Lewisite and mustard gas are ...... in nature. (r) CH 3 -CH=CH2 .) )
, PerOXIde
(1) Alkyl halides undergo ...... reactions with alcoholic
KOH and form ...... .
Br2
(u) A compound of carbon and hydrogen used for welding (s) H 2 C=CH2 '---"-f
purposes is . .. .. . . CCl 4
(v) Carbon atoms in Ag 2C2 (silver acetylide) are ..... .
hybridized. ,
(t) HO=CH~ ~
Zn
.. ....
,
CCl 4
(w) Hydration of ethylene in presence of an,acid produces
Ph~H
(u) ~ +KNH2
(x) ...... is formed whell cthvlene is treated,with alkaline
··KMn°4 • • ,
Ph/' "'-Br
, ' (y) S2Cl2 reacts with ...... to form mustard gas.
(v) HO=CH
, (z) The' kind of delocalization involving' sigma bond
orbitals is called . . . . . . .
2. Fill in the blanks :
(a) 'The structura1 formula of the compound which yields
(x) CH 3-C==CH B2~ ) . . . . .• NaOH)
H 20 2
'ethylene upon reaction with zinc is ...... .
, AlCI)
(b) The intermediate product in the preparation of (y) HC==CH + CH3 0CH 2 CI ~
ethylene from ethanol and sulphuric acid is .. : ....
Unsaturated Hydrocarbons 357
(c) Ozonolysis (3) Alkaline potassium
(z) (CH 3 h C=CH2 + CHCl 3 (CH 3)3 C- OK; per-manganate
(d)" Mustard gas (4) But-2-ene
3. Sta~ whether the following statements are True or False:
(e) Acetylene tetrachloride (5) 2-Chlorovinyldichloro-
(a) Moist ethylene can be dried by passing it through conc.
arsenic
H 2 S04 ,
(f) Baeyer's reagent (6) Alcoholic kOH
(b) 2-Methylpropene gives isobutyl bromide with RBr.
(g) Geometrical is;)merism (7) Structure of alkene
(c) Ethyne and its derivatives' will give white precipitate
(h) Lewisite (8) Polymerisation
with ammoniacal silver nitrate solution.
[B] (a) Cn H2n ' (I) Formaldehyde
(d) The acidic nature of three types of hydrocarbons
(b) C n H 2n - 2 (2) Plastic'
follO\·'s the order,
(c) Alkyl halide + Ale. KOH (3) Allene
Alkanes < Alkenes < Alkynes. (d)Polythene (4) Thiophene
(e) Peroxide effect is effective only in the addition of HBr (e) C 2 H 4 + 03/H20 (5) Alkene
and not HCI and HI. (f) H 2C=C=CH2 (6) Pyrrole
(f) Acetylene is colourless, odourless gas. (g) C2 H 2 + S (7) Alkyne
(g) Vinyl acetate used. in plastic industry can be prepared (h) C2H2 + NH3 (8) Dehydrohalogenation
by the action of acetic acid on ethyne. 5. Complete the following equations:
(h) Bromine water can be used to distinguish ethyne and (a) H 2C=CH-CH3 + HCI ~ (A)
ethene.
(i) Decolourisation ofBaeyer's reagent is sure test ofa1kenes. (b)
G) The process of conversion of acetylene into benzene is
polymerisation. (c) H 2C=CH2 +0 H20) (A) NaOH(aq.~ (B)+(C)
(k) The reaction of ethyl alcohol with acetylene is 3
0..,. "
Unsaturated Hydrocarbons 359
lr
Hint: HC.=CH CH 3CHCl 2
(Ale.) KOH
) H2C=CHCI
1
J or
(b) But-l-yne from acetylene:
r .NaNH 2
. . CH 3CH2 Br
l Hint: HC==CH ) HC==CNa' )
~)
Hint: HC=CH
.
Chloroprene from acetylene:
HC CNa
CH]CH2Br 2 H S0 ,H 0 '
4 2
) HC=CCH2CH 3 -=--.:........::---+).
But-I-yne HgS04
?i J
CH3~C~CH2CH3
.
r.
Hint: 2HC==CH
Cu 2Ci 2
NH4 Cl
) H2C=CH~C
Vinyl acetylene
. CH
CH CH CH Br '
3 2, 2
Na I ether ) CH
Wurtz reaction 3
(~H2 )4 CH3]
(i) Cyclohexene from cyclohexane:
rHint: Ci'
Cyclobexane ~ Chlorocyclobexane ~.
c. . CyclohexeneJ
Al 1
hv, KOH
l
. (j) Vinyl ac~tate from ~thyl alcohol:
rlHint: <;H5 0H
(Cone.) H2S04 ' Br2
1700C') H2C=CH2'~ CH2Br~CH2Br
[Hint:
.
0.
NBS, • r'l, ~C~~H O~
~Br .' ~
]
14. How will you obtain the following from propene?
(a) n-Propyl bromide,
[Hint: Reaction of HBr in presence of peroxide]
, (b) n-Propyl alcohol,
[Hint: First convert into n-propyl bromide and then do hydrolysis with aq. NaOH or AgOR.]
(c) Isopropyl alcohol,
[Hint: First react with HBr to form isopropyl bromide and then do hydrolysis.]
(d) 1,2-0icbloropropane,' .
[Hint: Treat with Cl 2 in CCI 4 ]
360 G.R.B. Organic Chemistry [or Competitions
(e) Acetylene; . 0
[Hint: By ozonolysis propene is converted into acetaldehyde, ~ II
(k) HC CH2 CH2-CH and OHC-CHO
, 1 II .
CH3CHO CH 3CHCl 2 HC==CH J o
o
(t) Allene (propadiene). ~ II
rI Hint: CH CH =CH (1) HC CH CHr-CH
2 only
3 2 II
L o
, CH
3
C2 HS (1) (»
(h) OHC-- CH2 CH 2 CH 2 CHO only
(i), OHC-CH 2-CHO (two moles)
2)4) (m) [>-cH-CH--<:j
(,)00
. «CH
mO=C C=O only
. (CH 2 )4
Unsaturated Hydrocarbons
&~,
(0) CH3-f=CHCH2 CH3 ]
CH 3
2-Methyl pent-2-ene
(Major)
(ii) &
(Minor)
CH
2 ....
(e) Dehydrohalogenation
(1) Saytzeff's rule
(g) Baeyer's strain theory
ZOo Explain the following:
[ill) aCH3]
(a) Why alkenes are more reactive than alkanes? (Minor)
[Ans. it-bond is weaker than a sigma-bond and is easily broken. (j) Which of the following reactions would provide a
The :rt-electrons are less firmly bound to carbon nuclei.] better synthesis of 2-pentene?
(b) Acetylene reacts with ammoniacal silver nitrate solution
. or ammoniacal cuprous chloride solution or sodamide to (i)~
form an acetylide while ethylene does not. Br
[Ans. Acetylene reacts to fonn· acetylide because it contains acidic Br
(ii)~
hydrogens.]
(c) But-2-ene shows geometrical isomerism but but-l-ene
does not show. .
[Ans. (i) is better because it gives only one product ...
[Ans. ill but-l-ene, the carbon atom linl<;ed by double bond is
~,
. attached with two hydrogen atoms (similar groups) and
thus does not show geometrical isomerism. while(ii) gives a mixture of
~and~.]
H~ /H (k) Write the major products of dehydration of:
/C=C"", OH OH
H S C2 H
But-I-ene (i) ~ (ii) + O H (iii)~
[Ans. (i) ~ (ii) ~ (iii) ~ ]
Trans-but-2-ene 2-Methyl pent-2-ene
2-Metbyl but-2-ene
.
But-2-ene ANSWERS
(d) Why has but-l-yne a larger dipole moment (0.80 D) than 1. (a) Ethyne; (b) propadiene; (c) but-2-yne
but-l-ene (0.30 D)?
[Ans. A C-C sp bond is more polarized than C-Csp 2 bond [Hint: (i) CH!!!5CH 2Na .. NaC!!!5CNa,
NH3 (liq.)
because carbon with more s-character is more (ii) NaC==CNa 2CH3I) CHP==CCH~ + 2Nal]; (d) acetylene
electronegative.] .
[Hint: C2H 2 + HCI CH 2=CHCI]; (e) vinyl chloride;
--7
(e) Why alkynes are slightly more soluble in water than
(1) Markownikoff's; (g) CICH 2CH=CH 2; (h) ethene; (i) HgS04,
alkenes and alkanes?
[Ans. Alkynes are somewhat more polar in nature and thus, their H 2S0 4; (j) Baeyer's; (k) acetylene; (I) sp2; (m) sp; (n) silver nitrate;
solubility is slightly more in water.} (0) 3,4-dibromobut-l-ene (at low temperature) or 1,4-dibromobut-
(f) Cyclopropane is more reactive than cyclobutane. 2-ene (at high temperature); (P) acetylene; (q) but-2-ene;
(g) Cyclopentane is inert like alkanes. . (r) acetaldehyde; (s) poisonous; (t) elimination;
(h) Which isomer of C4H9Br yields only a single alkene on (dehydrohalogenation), alkenes; (u) acetylene; (v) sp; (w) ethyl
alcohol; (x) ethylene glycol; (y) CH 2=CH 2 (ethene);
dehydrobromination?
(Alc.)KOH (z) hyperconjugation.
[Ans. (CH3)3C-Br ) CH 3-C CHz) 2. (a) CH2BrCH2Br; (b) C2H sHS04; (c) 2-methylpropene;
Tert. butyl bromide A I (d) acetone; (e) Baeyer's reagent; (t) ethylene chlorohydrin;
CH 3
(g) HOH 2CC==CCH20H (But-2-yn-l,4-diol); (h) 120°; (i) oxalic
2-Methyl propene
acid; (j) ethyne; (k) alkadiene; (I) HOCI; (m) :rt;(n) alIame;
(i) Write the products of dehydrochlorination of the
following: y
(0) Ph- H-CH 2CH 3 ;" (P) CH3CH2HSO~ 0I3CH 20H;
Br
G.R.B. Organic Chemistry for Competitions
(q) CH==CNa, CH 3-C==CH; (r) CH3CH 2CH 2Br, (e) CH 3CH 2CH-CH3;
CH3CH2CH20H; (s) CI:I2Br-CH2Br, CH==CH; I
(t) CHBr2 - CHBr2' CH==CH; (u) Ph-C==C-Ph; COOH
(v) HC==C-Na, HC==C-D; (w) Na-C==C-Na, (w)(A) CJlrCH-CH-CH3 (Major);
D-C==C-D; (x) (CH 3-C=CH-hB, CH3CH2CHO; I I .
(y) CH30CH zCH=CHz; (z) (CH 3)2 \/CH 2 OH Br
/~ (x) UCI
CI Cl
3. (a) False-Ethylene combines with H 2S04; (b) False-Tert. butyl
bromide is formed; (c) False-Only R-OaCH derivatives give
white ppt. but derivatives of the type R-C=C-R' do not give
(y) VOH
white ppt. with ammoniacal silver nitrate; (d) True; (e) True; (z) CCliperoxide
(t) False-Acetylene is colourless with garlic odour gas; (g) True; 6. (a) Lewisite; (b) CHz=CHOOCCH 3, vinyl acetate;
(h) False-Both decolourise bromine water; (i) False-.-Reducing (c) C 2HsO-CH=CH2 , ethyl vinyl ether;
compounds can also decolourise Baeyer's reagent; G) True; . CH=CH"",.
(k) True; (I) False-Propyne is less acidic than acetylene; (m) False- (d) I /NfI, pyrrole;
The torch oontains CaCz and Ca3PZ; (n) True; (0) True; (P) False-
gives propene; (q) True; (r) True; (s) False-Baeyer's reagent is
alkaline KMn0 4 solution; (t) True; (u) True; (v) True; (w) True;
CH=CHr
(e) HCN, hydrogencyanlde;
. .
CH=CH"",
(x) False-It does not react with Tollens' reagent as it has no acidic (t) I /S, thiophene.
hydrogen; (y) False-forms only acetic acid; (z) True. CH=CH
4. [A] (a-{j); (b-8); (c-7); (d-I); (e-2); (f-3); (g-4); (h-5). ,
[B] (a-5); (b-7); (c-8); (d-2); (e-J); (f-3); (g-4); (h-{j).
7. See properties of ethylene and acetylene.
8. (a) Bond length decreases and bond energy increases;
5. (a) (A) CH3CHCICH3 ; (b) (A) CH 3CHO, (B) CH3COCH 3; (c) (A)
(b) Electrophilic addition reactions; (c) Geometrical or cis-trans
HCHO, (B) HCOONa, (C) CH 30H. Formaldehyde undllrgoes
isomerism; (d) Cumulated; (e) Ionic mechanism; (t) Free radical
Cannizzaro's reaction; (d) (A) 2-chloro-2,3-dimethyl butane;
mechanism; (g) Alcoholic potassium hydroxide; (h) Bromine and
(e) (A) Me-CHz-C==CNa, (B) MeCH 2C=C· Et; (t) (A)
. Baeyer's reagent.
CH==CH, (B) CH 3CH CHCOOH; (g) (A) CZH4, (B)
9. (a) The decreasing order of acidic strength is:
CH2BrCH2Br, (C) C2H 2; (il) (A) CH3CHO, (B) CH3CH 20H, (c)
C2H4; (i) (A) CH 3-CH=CH2• (B) CHzCLCH=CHz; (j) (A)' Ethyne > Benzene > n-Hexane
CH 2BrCH=CHz, (B) H 2C=C=CH 2; (k) (A) cyclopropane;
(I) (A)methylcyclopropane; (m) (A) cyclohexene, (B) eyclohexane;
(n) (A) C~7CH(OH)CH2 - HgOAc, (B) ~H7CH(OH)CH3;
(0) (A) (CH 3CH 2CHz)3B, (B) CH 3CH 2CH3;
H--C=C-H
sp 0sp2
CH3(CH2)4CH3
sl
(P) (A) CJlsCHBr-CH2Br, (B) C1;HsC==CCH3; S-character 50% 33% 25%
(q) (A)CJlsCH=CHC1;Hs (cis- and trans-);
The acidic character is linked with the percentage of S-character.
Greater the S-character, more is the electronegativity of the carbon
(r) (A) C1;HsC03H ( D)I°'c(D] , atom and more will be the acidic character.
(CH3 h C " ' - H (b) CH3CH2CH2CH=CH 2 (Pent-l-ene), CH3CH2CH=CHCH3
(Pent-2-ene), (CH3)2CHCH=CH2 (3-Methylbut-l-ene),
CH 3
I
CH)CH2-C=CHz (2-Methyl-l-butene)
(CH3)2C=CHCH3 (2-Methyl-2-butene)
(c) Position isomerism-Example: but-I-ene and but-2-ene
Chain isomerism-Example: but-l-ene and 2-methylPropene
Geometrical isomerism~Example : cis- or trans-but-2-ene
Ring chain isomerism-Example: propene and cyclopropane.
10. (iii) and (iv) will show cis-trans isomerism.
CH 3"" /CH2C~2CH3 CH 3"" /H • .
11. /C=C" /C=C,
H "H H "cH 2CH2CH 3
Cis Traru
The cis form will have higher boiling point due to more polar nature
leading to stronger intermolecular dipole-dipole· interaction, thus
requiring more heat energy to separate them.
',.
Unsaturated Hydrocarbons
!H 2 [Hint: (A)
+ Hz(Pt)
) CH3CH2CH2CH2CH2CH3
CH3CH 2CH 2CH=CHCH3 CH3CH2CH2CH2CH2CH3 [0] ~04) 2CH CH COOH
(B) (Hex-2-ene) (C) (Hexane) 3 2
!
Acidified KMn04 So (A) is CH3CH2CH CHCH l CH3 (Hex-3-ene)]
S. A hydrocarbon (A) of the formula C 7 H l2 on ozonolysis
CH3CH l CHl COOH] gives a compound (B) which undergo aldol condensation
[F] Butanoic acid
giving l-acetylcyclopentene. Identify (A) and (B).
2. (A), (B) and (C) are isomeric heptenes. (A) on ozonolysis [liint: Since, the ozonolysis of the hydrocarbon (A) gives only one
gives ethanal and pentanal, (B) on ozonolysis gives ethanal
compound (B), the compound (A) must be a cyclic alkene.
and pentan-3-one, while ,(C) on like treatment yields Moreover since the number ofC-atoms in the product obtained
propanone and butanone. Give the structural formulae and from the aldol condensation of (B) is the same as that of (A),
IUPAC names of (A), (B) and (C). the compound (B) must have gone intra aldol condensation.
[Hint! Compound (A) gives: So, (A) and (B) are as follows:
CH3CH =f:.9~fQ+=CHCHlCH2CH2CH3
Ethanal Pentanal CH3
c5 ~~.&;
.So, (A) is CH3CH -'-CHCH2CHl CH2CH 3
(A)
f1ept-2-ene
, _______ , /CH2CH 3
Compound (B) gives: CH3CH~.Q_·LQ_TC"'-.. (A) (B)
1
&'H
Ethanal CH 2CH3
Pentan-3-one
/CH l CH3 Intra-aldol
So, (B) is . CH3CH=C"", i.,. condensation
CH 2CHj
(B) 6. Hydrocarbon (A) C6 H 10 ' on treatment with H2 /Ni,
3-Ethylpent-2-ene H2/Lindlar's catalyst and Na/liquid NH3 forms three
different reduction products (B), (C) and (D) respectively.
Compound (C ) gives: (A) does not form any salt with ammoniacal AgN03
solution, but forms a salt (E) on heating with NaNH 2 in an
inert solvent. Compound (E) reacts with CH31 to give (F).
Compound (D) on oxidative ozonolysis gives n-butanoic
acid along with other product.
So, (C) is Give structures of (A ) to (F) with proper reasoning.
[Hint:
(C)
2,3-Dimethylpent-2-ene
3. An organic compound (E) (CsHs ) on hydrogenation gives
compound (F) (C S H12} Compound (E) on ozonolysis
gilles formaldehyde and 2-keto-propanal. Deduce the CH3CH2CH2C=:::C-CH3
(A)
structure of compound (E).
[Hint: CSHg consists two double bonds as on hydrogenation, it
NalLiq.NH3
is converted into CSH I2.
Heat NaNH2
G.R.B. Organic Chemistryfor Competitions
H3:O H3:>()]
C,Ji16 ~ CgHgO .) (1;H sCOONa
, (A) (B) Sodium benzoate
[Hint: or Alkene Only product
I. KOHlNH NH
2 2 ,
('r(CH , CsHIO
9. C 7HI2 ~
HOH
V OH
3 (C)
Since, (A) on ozonolysis gives only one product (D), the alkene
must be a symmetrical one. This reaction may be written as,
What are
the possible isomers of fonnula C 7 HI2 which give
above product?
'· D
[Hmt: f .
egree 0 unsaturation =
14 - 12 + 2 . 2
=
~IH,O > [:>c~o1
2
2
Thus, the compound should have a ring and a double bond. (A) (D)
.. Possible isomers will be . (where a + b = C7 Hg)
c5 c5
Further, (D) on treatment with 12 /NaOH (iodoiOrm test) gives
sodium benzoate, one of the group (a) and (b) may be identified
with C1;Hs and hence the other one may be CH 3 group. The given
J reactions are as follows:
9. Identify (X), (Y)and (Z) in the following synthetic scheme C1;Hs\ /{1;Hs 0 IH 0 (1;H 5\ I IN OH
and write their structures. /C=C'",- ~2 /C=O 2 a ) C6H sCOONa
CH 3 CH 3 CH 3 Sodium benzoate
CH CH C==CH (i)NaNH2 ) (X) H 2 /Pd-BaS04 ) (A) (D)
3 2 (li) CH 3CH 2Br . Acetophenone
+CHI3
(Y) AlkalineKMn04 ) (Z)
Is the compound (Z)optically active? JustifY your answer.
(liT 2002)
b
.. KOHlNH2NH 2
Wolff _Kishner
reduction
{1;HsCH2CH 3
Ethyl benzene
(C)
The alkene (A) will have two isomers, cis- and trans. The catalytic
hydrogenation (H2 /Pd-C) involves syn-addition of hydrogen.
The trans-isomer gives racemic mixture while cis-isomer gives a
meso compound.
Alkaline KMn04
Trans-isomer .
C~s
I
H-C-OH
I
H-C-OH
I
C2H S
Hexane-3,4-diot'
(Meso or inactive form)
(Z)
10. An alkene (A)C'6HI6' on ozonolysis gives one product (B)
CsHsO. Compound (B) on reaction with NaOWI2 yields
sodium benzoate; Compound (B). reacts with
KOWNH2 NH2 yielding a hydrocarbon (C)CSHIO' Write
the structure of compounds (B) and (C). Based on this
Unsaturated Hydrocarbons 365
OBJECTIVE OUESTIONS
SET I: This set contains the questions with single correct answer. (a) Me2CO+CH3CHO o
1. When ethyl iodide is treated with a!coholic potash, we get: (b) CH3CHO+CH3COOH o
(a) ethyl alcohol 0 (b) ethane 0
(c) acetylene 0 (d) ethylene D. (c) MeiCO+CH3COOH o
2. Ethylene is produced by: " (d) 2Me2CO o
(a) dehydration of acetic acid 0 12. Ethyl alcohol is heated with conc. H 2 S04 at 170°C. The
(b) electrolysis of methyl alcohol 0 product formed is: [VITEEE 2008]
(c) mixing acetic acid and c~lcium formate 0 (a) CH3 COOCH3 0 (b) C2H 6 0
(d) passing C 2 H 5 0H vapourS over hot Al 2 0 3 0
(c) C2 H 4 0 (d) C 2 H 2 0
3. A gas decolourises alkaline KMn0 4 solution but does not
13. The maximum number of isomers for an alkene with
give precipitate with silver nitrate. It is:
molecular formula C4 Hg is:
(a) CH4 0 (b) C2 H 6 0 (a) 2 0 (b) 3 o
(c) C 2 H 4 0 (d) C 2 H 2 0 (c) 4 0 (d) 5 o
4. Acetylene on treatment with dil. H 2 S04 having HgS0 4 LlIint: CH 3CH2CH =CH2 , CH 3CH =CHCH 3 (cis- and Irans-)
gives: CH 3
(a) acetaldehyde 0 (b) acetic acid 0 I
(c) ethanol 0 (d) ethylene 0 and CHr-C=CH2]
5. Which of the following reagents distinguish ethylene from 14. When ethylene is passed through alkaline KMn04 solution,
acetylene? [BHU 2006] we get:
(a) Ammoniacal cuprous chloride 0 (a) ethanol 0 (b) glycol 0
(b) Br2 water 0 (c) oxalic acid 0 (d) acetaldehyde 0
(c) Alkaline KMn0.i solution 0 15. But-2-ene can be obtained by reacting: '
(d) ChlOime dissolved in CCl 4 0 (a) 1,2-dibromopropane with zinc 0
6. Which of the following not only decolourises alkaline (b) ethyl bromide with sodium 0
potassium pennanganate but also gives red precipitate with (c) ethylidene bromide with zinc 0
ammoniacal cuprous chloride solution? (d) n-butyl alcohol with alcoholic KOH 0
[EAMCET (Med.) 2006] 16. On electrolysis of potassium succinate solution, the
(a) Ethane 0 (b) Methane 0 hydrocarbon obtained is: [JIPMER 2004)
(c) Ethene 0 "(d) Acetylene 0 (a) ethene 0 (b) ethane 0
, 7. The most reactive hydrocarbon is: [JIPMER 2003] (c) ethyne 0 (d) aU of these 0
(a) ethene [J (b) ethyne 0 17. Ethylene reacts with sulphur monochloride to form:
(c) ethane 0 (d) methane 0 (a) ethyl chloride 0 ' (b) ethylene chloride 0
8. Aqueous solution of an organic compound 'A' on (c) mustard gas 0 (d) ethylidene chloride 0
electrolysis liberates acetylene and CO 2 at anode. 'A' is: 18. Ethylene reacts with air under pressure in presence of silver
[EAMCET (Engg.) 2007) catalyst at 250°C to form:
(a) potassium citrate o(b) potassium acetate 0 (a) ethylene glycol 0 (b) formaldehyde 0
(c) potassium succinate o (d) potassium maleate 0 (c) acetaldehyde 0 (d) epoxide 0
9. Baeyer's reagent is: 19. 1,2-dibromopropane on reaction with ale. KOH yields:
(a) alkaline KMn04 solution 0 (a) acetylene 0 (b) propylene 0
(b) acidic KMnO4 solutioQ, 0 (c) propyne 0 ' (d) none 0
(c) neutral KMnO4 solution 0 20. ...... is obtained when iodoform is heated with Ag
(d) aqueous bromine solution 0 powder.
10. The negative part of the addendum adds on to the unsaturated (a) CH 4 0 (b) C2 H 4 0
carbon atom joined to the least number, of hydrogen atoms. (cl C2 H 6 0 (d) C2 H 2 0
This statement is called: [AFMC 2004)
21. Benzene is a polymer of:
(a) Saytzeffrule o (b) Kharasch effect 0 (a) methane [J (b) acetylene o
(c) Markownikoff's rule [] (d) Anti-Saytzeffrule 0
11. Products of the following reaction,
(c) ethane 0 (d) ethylene o
22. Acetylene on ozonolysis gives:
Me2C=CHCH3
(i) 0 3
' ) ? are: (a) glycol o
(ii) (CH 3 h S [AMU (PMT) 2009) (b) glyoxal and formic acid o
366 G.R.B. Organic Chemistry (or Competitions
~
CH . CHOH HOCI CH< CHO ] precipitate with ammoniacal silver nitrate solution. The gas
Hint: III +HOCI-/l ~I OH-I evolved is:
CH CHCl CHCh CHCl2 (a) CH4 - 0 (b) C 2H 6 0
26. Whenacetylene is reacted with HCI in presence of HgC12, . (c) C 2 H4 0 (d) C2 H 2 0
the product obtained is: 38. Which one has of the red colour?
(a) methyl chloride 0 (b) vinyl chloride 0 (a) C2Na2 0 (b) C 2Ag 2 0
(c) formaldehyde 0 (d) acetaldehyde 0 (c) Cu 2 C 2 O. (d) CH 3C==CNa . 0
21. When propyne is treated with aqueous H 2S04 in presence 39. The gas, which is used for artificial ripening of fruits, is:
of HgS04 , the major product is: [PMT (Kerala) 2010] (a) CH4 0 (b).C 2 H4 . 0
(a) propanone 0 (b) 2-propanol 0 (c) C 2 H 6 0 (d) none 0
(c) ethanal 0 (d) ~thyne 0 40. The gas, which is used for welding purposes is:
(e) propane 0 . (a) CH4 o
(b) C2 H 6 0
28. The bond between carbon atom (1) and carbon atom (2) in (c) C2 H4 0 (d) C2 H 2 0
the compound, . 41. Propane can be distinguished from propylene with:
I 2
N==C-CH CH2 (a) sodium 0 (b) bromine water 0
involves the hybrids as: (c) ammoniacal AgN03 0 (d) NaHS0 3 0
(a) s p a n d s p 2 . · p (b) sp2 and sp2 0 42. Reaction of HBr with propene in the presence of peroxide
(c)spand sp. -0 (d) sp3 and sp 0 gives: [CBSE .(Med.) 2004)
(a) isopropyl bromide 0 (b) ally~ bromide 0
29. Which of the following displaces hydrogen on reaction with
(c) n-propyl bromide 0 (d) 3-bromopropane 0
sodium in liquid ammonia?
43. The compound which is insoluble in cold H2 S04 is:
. (a) C2H 2 '0 (b) CH4 0
(c) C2 H 6 . 0 (d) C 2 H4 0 (a) n-butane 0 (b) I-butene 0
(c) 2-tmtene 0 (d) ethyl acetate 0
30. When I,I,2,2-tetrabromoalkane is heated with zinc powder 4-1. Which one of the following molecules is linear?
in alcohol, which is formed? (a) HC==CH 0 (b) H 2C=CH 2 0
(a)Alkyne o
(b)Alkene 0
(c) CH 3 -CH3 • 0 (d) H-O--H 0
(c) Alkane 0 (d) None of these 0
31. The end product of the following seqQence of operations is: 45. In the laboratory by dehydration of ethyl alcohol, ethylene
was obtained in 50% yield. The ethylene so obtained reacted
Cac2 H20) (A) H2S0 4 ) (B) . H ) (C) with bromine to give ethylene dibromide in 80% yield. If the
HgS04 LiAlH4
amount of ethyl alcohol was 0.5 mole then ethylene dibromide
(a) methyl alcohol 0 (b) ethyl alcohol 0 produced would be:
(c) acetaldehyde 0 (d) ethylene 0 (a) 0.8 mole 0 (b) 0.4 mole o
32. The name of the poisonous gas formed by the interaction of (c) 0.2 mole 0 (d) 0.1 mole o
acetylene and arsenic trichloride is: 46. Conjugated double bond is present in:
(a) phosgene 0 (b) lewisite 0 (a) propylt.;,ne 0 (b) isobutylene
(c) mustard gas 0 (d) westron 0 (c) butylene 0 (d) butadiene
Unsaturated Hydrocarbons 367
47. When alcoh~lic solution of ethylene dibromide is heated (a) zinc 0 (b) sodarni~¥ 0
with granulated zinc, the compound formed is: (c) alc. KOH 0 (d) aq. KOH 0
(a) ethylene 0 (b) ethyne 0 59. Indicate the organic structure for the product expected when
(c) cyclobutane 0 (d) butane 0 2-methylpropene is heated with acetyl chloride in presence of
48. In the reaction given belo,w, X is: anhydrous zinc chloride:
H SO (a) (CH 3 )2 CCICH 2OCCH3 0
Neo-pentylalc?hol 2 4) X (DPMT 2009]
(b) (CH 3 h CHCH 2 OCCH 3 0
(a) 2-methylpentane 0 (b) Neo-pentane 0
(c) 2-methylpent-2-ene 0 (d) 2-methylbut-2-ene 0 (c) CH 3 COCH(CH3 h 0
. 49. Which of the following will have least hindered rotation (d) none of the above 0
about carbon-carbon bond? 60. Reactions of alkenes with ...... are explosive in nature:
(a) Ethylene 0 (b) Acetylene 0 (a) Cl 2 0 (b) 12 0
(c) Ethane 0 (d) 'Hexachloroethane 0 . (c) F2 o(d) Br2 0
[Hint: Hexachloroethane has less rotation than ethane because
61. Catalyst used in dimerisation of acetylene to prepare
of greater size·of chlorine than hydrogen.~
chloroprene is:
50. The olefin which on ozonolysis gives CH3CH2CHO and
(a) HgS04 + H 2S04 o0) Cu 2 Cl 2 o·
CH3 CHOis:
(a) I-butene 0 (b) 2-butene 0
(c) Cu 2Cl 2 +NH4 0H o (d) Cu 2 C1 2 + NH4 CI o
(c) l-pentene 0 .(d) 2-pentene 0 62. Ammoniacal silver nitrate forms a white precipitate easily
51. Dilute aqueous KMn04 at room temperature reacts with with: IUPSEE (Engg.) 2008]
(a) CH3 CH=CH2 0 (b) CH3 --C=:CH 0
R-CH=CHR to give:
(a) R-CHO 0 (b) RCOOH 0 (c) CH 3 -C=C-CH 3 0 (d) H 2C=CH2 0
(c) R-CHOHCHOHR 0 (d) CO2 + H 2 0 0 63. Structural formula for lewisite is:
52. Lindlar's catalyst is: CHCI CHCI
(a) Pt in ethanol o (b) Pd + BaS04 . o (a) II 0 (b) II 0
CHAsel 3 CHAsCI
(c) Ni in. ethanol o (d) Na in liquid NH3 o CHCI CH2
53. Which of the following molecules is not linear? (c) II 0 (d) II 0
(a) H2C' CH2 0 (b) CO2 0 CHAsel 2 CHAsCl 2
(c) BeCl 2 0 (d) HC==CH 0 64. An olefm may be converted into alcohol by:
54. Butyne on reaction with hot alkaline KMn04 gives: , (a) B2H6 and H 20 2 0 (b) LiAlH4 0
(a) CH 3CH2CH 2COOH 0 (c) alkaline KMnO4 0 (d) HOCI 0
(b) CH3CH 2COOH 0 65. Propene is- more reactive than ethene towards HBr because:
(c) CH3 CH2COOH+C02 0 (a) propene can more readily undergo a free radical chain
reaction 0
(d) CH 3 CH2COOH + HCOOH 0
(b) propene gives rise to more stable carbonium ion 0
55. When C 2 H 2, CH4 and C 2H4 passes through a test tt,tbe (c) the double bond incase of propene is unstable 0
which have ammo~iacal Cu 2 C1 2, find out which gas comes (d) the' methyl group attached to double bond withdraws
out unaffected from test tube? (BCECE (Med.) 2008] electrons and facilitates the attack 0 '
(a) C 2H 2 and CH4 0 (b) C2H 2 and C2H 4 0 66. Acetylene when passed through cuprous chloride in
(c) C 2H 2 q (d) C 2H 4 and CH4 0 presence of ammonium chloride forms:
56. When propene is treated with chlorine at 500°C, allyl (a) benzene 0 (b) vinyl acetylene 0
chloride is formed as the main product. The mechanism of (c) allyl chloride 0 (d) allene 0
the reaction is: 67. Which of the following alkynes is most acidic?
(a) free radical addition 0 (a) CH3-C==CH 0 (b) CH3-C==C-CH3 0
(b) free radical substitution 0 (c) CH3-CH2-C==CHO (d) HC==CH 0
(c) electrophilic addition 0 68. Acetylenic hydroge~s are acidic because:
(d) electrophilic substitution 0 (a) sigma electron density of C-H bond in acetylene is
57. The general formula of the product formed when nearer to carbon which has 50% s-character 0
1,1, I-trichloroethane is heated with metallic silver is: (b) acetylene has only one hydrogen on each carbon 0
(a) Cn H2n+2 0 (b}Cn H2n 0 (c) acetylene contains least number of hydrogens among
(c) Cn H 2n - 2 0 (d)C n H2n+1 0 the possible hydrocarbons having two carbons 0
(d) acetylene resembles acetic acid 0
58. To prepare 2-butyne from 2,2,3,3-tetrachlorobutane, use is
69. Sample of2,3-dibromo-3-methylpentane is heated with zinc
made of: dust. The resulting product is isolated and heated with HI in
368 G.R.B. Organic Chemistry tor Competitions
the presence of phosphorus. Indicate which is the structure 78. To which class cyclopentane does belong?
that represents the fmal product in the reaction: (a) Aromatic 0 (b) Heterocyclic 0
(a) H 2 C CH-fH-CH2-CH3 0 (c) Alicyclic 0 (d) Unsaturated aliphatic 0
79. The compound 1,2-butadiene has:
CH3
(a) only sp-hybridized carbon atoms 0
(b) CH3-CH2~H-CH2-CH3 0 (b) only sp2-hybridized carbon atoms 0
CH3 . (c) both sp- and sp2-hybridized carbon atoms 0
(d) Sp_sp2_ and Sp3 -hybridized carbon atoms 0
(c) CH3-CHI--fH-CH2-CH3 o 80. A compound with molecular formula C4 H 6 may contain:
CH3 (a) a double bond 0
(d) none of the above 0 (b) two double bonds or a triple bond 0
70. Which of the following reactions will yield 2,2-dibromo- (c) a triple bond 0
propane? [CPMT 2004; AIEEE 2007] (d) all single bonds 0
(a) H 2 C=CHBr + HBr 0 81. Cyclopentene on treatment with alkaline KMn04 gives:
88. Alkene RCH=CHz reacts readily with B z H6 . and the 97. All alkyne combines with a conjugated diene to give an
product on oxidation with alkaline HZ02 produces: unconjugatedcycloalkadiene. The most likely title of this
(a) R-CH-CHz n (b) R-:-CHz-CHO 0 reaction is: ..
(a) Schotten-BaUmann reaction
(JEE (Orissa) 2008]
0
I I (b) Hofmann-bromamide reaction 0
OH OH
(c) Diels-Alder reaction. 0
o (d) R-C-CH3 o (d)Pinacol-Pinacolone rearrangement 0
I 98. When cyclohexane is poured on water, it floats because
°
89. The intenitediateduring' the addition of HCI to propene in
cyclohexane is:
. (a) in boat form . 0 (b) in chair form 0
the presence of peroxide is: (c) in croWn form 0 (d)' less dense than water 0
o 99. The cylindrical shape of an alkyne is due·to the fact that it
. • . + has:
(c) CH3 CH zCHz 0 (d) CH 3 CH zCH z 0 (a) three sigma C-:-C bonds 0
90. The compound which reacts' with . HBr obeying (b) two sigma and one pi C-:-C bond' 0
Markownikoff's rule is: (c) three pi C-:-C bonds 0
(d) one sigma and two pi C-:-C bonds 0
H3e) <CH3
O (b) C=C 0 100. During debromination' of meso-2,3-dibromobutane, the
. H· . H major product formed is:
(a) n-butane 0 (b) I-butene 0
(c) H,C)CFC<H 0 (d/,C)C==e<H 0 (c) cis-2-butene 0 (d) trans-2-butene
101. Addition of bromine to buta-I,3-diene gives:
0
H· CH 3 . H3 C. . H (a) 1,2-addition product only 0
91. The number and type of bonds between two carbon atoms in (b) l,4-addition product only 0
CaC z are: (c) both 1,2 and 1,4-addition products 0
(a) one sigma and one pi (1t) bond 0 (d) no reaction . 0
(b) one sigma and two pi (1t) bonds'
(c) one sigma and one and a half pi (1t) bonds
0
0 102. The reaction 6f CH3CH=cIi-(. )-?H with ~r
(drone sigma bond 0 gives:
92. Cyclohexadiene contains how many degrees ofunsaturation?
(a) 1 -0 (b) 2 0 (a) CH3CHBrCHZ-(. )-OH 0
. (c) 3 0 (d) 6 0
93. Acetylene contains same degrees of unsaturation as: .
CH CH,CHBr-( }-OH
(aJ 0 D(bJO o
(b) 3 0
(c) 0 o (d) 0 o
(C)CH3CHBrCI:Iz-(
.~
0
Q
. 94. Four degrees of unsaturati9Jl are present in which of the
compounds given below? . ~. 103. The product(s) obtained via oxymercuration (HgS04 + .
(a) But-I-yne 0 . (b) But-2-yneD H 2S04 ) of l-butyne would be:
(c) Buta-l,3-diene 0 (d) Toluene 0 ° .
95. Which one of the following alkenes will react faster with Hz II
(a) CH 3CH2-C-CH3 0
under catalytic hydrogenation condition?
(b) CH 3 CH 2 CHzCHO 0
(lIT 2000; eBSE (Med.) 2005]
(c) CH3CHzCHO+ HCHO 0
R,,---/R R,,---/H
o o (d) CH 3 CHzCOOH+HCOOH 0
(a)~H (b).
R/
r-....
"H 10-:'. The reaction of propene with HOCl proceeds via the
R,,---/R .R,,---/R addition of: [lIT (S) 2001]
(c)r-.... o (d) r-..... o (a) H+ in the first step 0
R/ . "H R/"R
(b) Cl + in the first step Q
96. Propyne and propene can be distinguished by:
(c) OH- in the first step . 0
[ItT 2000; DCE 2005)
(d) CI + and - OH in the single step D.
(a) conc. HZ S04 . 0 (b) Br2 in CCl 4 0
(c) AgN03 in ammonia 0 (d) dil. KMn0 4 0
370 G.R.B. Organic Chemistry (or Competitions
105. Which ofthese will not react with acetylene? (AIEEE 2002] (c) forms polymers 0
(a) NaOH Cl (b) Ammoniacal AgN03 0 (d) all of the above 0
(c) Nil. D. (d) HCI 0 113. Acetylene reacts with HeN in the presence of Ba(CN)2 to
106. Identify the set of reagents/reaction conditions' X' and 'Y' in yield: (UPSEAT 2004]
the following set of trans,formations: (lIT (S) 2002] (a) I,I-dicyanoethane 0 (b) 1,2-dicyaooethane 0
(c) vinyl cyanide 0 (d) none of these 0
r
. 'X' 'Y'
CH3CH2CHiBr --7 Product .---7 CH3- H-CH 3 114. Which one of the following has the minimum boiling point?
(AIEEE 2004]
Br (a) n-Butane 0 .(b) I-Butyne 0
(a) X = dilute aqueous NaOH, 20°C' (c) I-Butene 0 . (d) Isobutene 0
Y = HBr/ac;:etic acid, 20°C o 115. Which of the following alkenes will give an optically active
(b) X conc. alcoholic NaOH, 80°C alcohol when treated with H 20/H2S04? [CPMT 2004]
y' HBr/acetic acid, 20°C o (a) I-Butene 0 (b) Ethene 0
(c) X == dilute aqueous NaOH, 20°C (c) Propene 0 (d) 2-Methyl propene 0
y= Br2/CHC13,O°C o 116. CH 3COOH is reacted with HC==CH in presence of Hg2+ ,
(d) X = conc. alcoholic NaOH, 80°C the product is: (DPMT 2004; BHU'2005]
y = Bt2 /CHCI 3 ,O°C o CH2 (OOCCH 3 )
107. In presence of perOXide, hydrogen chloride and hydrogen 001 0
iodide do not give anti-MarkownikotI's addition to alkenes CH 2 (00CCH3 )
because: (lIT (S) 2001] (b) CH 3CH 2 (00C-CH3 ) o
(a) both are highly ionic 0
(b) one is oxidising and other is.reducing 0 (c) CH3CH(OOC-CH3 )2 o
(c) one of the steps is endothermic in both the cases 0 (d) none of the above 0
(d) all the steps are exothermic in both the cases 0 117. The product of acid catalysed hydration of 2-phenyl
propene is: [lIT 2004]
108. In the preparation of alkene from alcohol using AI 20 3,
(a) 3-phenyl-2-propanol 0 (b) l-phenyl-2-propanol 0
which is etIective factor? (CBSE (Med.) 2001] (c) 2-phenyl-2-propanol 0 (d) 2-phenyl-I-propanol 0
(a) Porosity of AI 20 3 0 118. Which of the following used for the conversion of2-hexyne
(b) Temperature 0 into trans-2-hexene? ' [lIT 2004]
(c) Concentration 0 (a) H2/Pd/BaS04 0 (b) H 2,Pt02 0
(d) Surface area of AI 2 0 3 0 (c) NaBH4 0 (d) Li-NH3/C2HsOH 0
109. Consider the following statements; a hydr~)Carbon of . 119. Which of the following givespropyne on hydrolysis? .
molecular fOrmula CSHIO is a; . (AIIMS 2005]
(I) mono substituted alk€me (a) AI 4C 3 0 (b) Mg 2C3 0
(Ii) disubstituted alkene (c) B4 C D' (d) La 4 C3 0
(III) trisubstituted alkene 120. When Z-butyne is treated with Pd-BaS04; the product
Which of the following statements are correct? formed wilLbe:' (DCE 2005; JEE (Orissa) 2006]
(SCRA 2001] (a) cis-2-butene 0 (b) trans-2-butene 0
(a) I, II and III 0 (b) I and II 0 (c) I-butene • 0 (d) 2-hydroxy butane 0
'(c) II and III 0 (d) I and I!I 0 12L In the reaction,
110. Identify a reagent from the following list, which can easily (i) X
. CH3C==C-CH~ . ). CH -C-C-CH3
distinguish between I-butyne and 2-butyne: (lIT (S) 2002] • ~ (ii) ZnIH20 . 3
11 II
(a) bromine, CCl 4 0
o 0
(b) H 2, Lindlar's catalyst o X is : [DCE 2005]
(c) dii. H 2 S04, HgS04 o (a) RN0 3 0 (b) O2 0
(d) ammoniacal Cu 2Cl 2 solu!ion , 0 (c) 0 3 '0 (d) KMn04 0
111. But.;.l-ene may be converted to butane bya reaction with:~ 122. Reaction of 'one molecide of JIBr with one molecule .of
• [AIEEE 2003] 1,3-butadiene at 40°C gives predominantly:
(a) Zn-HCI o (b) Sn-HCI 0 , (AIEEE 2005]
(c) Zn-Hg [J (d) PdlH 2 0 (a) 3-bromobutene under kinetically controlled conditions
112. Correct sta~emeritabout 1,3-dibutene: [UPSEAT 2003]
o
(b) I-bromo-2-butene under thermodynamically controlled
, (a) conjugated double bonds are present' 0 ,,' conditions 0
. . (b) reacts with HBr 0 (c) 3-bromobutene under thermodynamically controlled
conditions 0
.'
Unsaturated Hydrocarbons
(d) I-bromo-2-butene under kinetically controlled 131. The Markownikoff's rule is best applicable to the reaction
conditions 0 between: ' [ P E T (Kerala) 2006]
123. Which of the reagents on reaction'with cyclohexanol gives (a) C2H 4+ HCI 0 (b) C3H6 + Br2 0
best yield of cyclohexene? [lIT 2005]
(a) Conc. H 3P0 4 0 (c) C3H6 + HBr 0 «i) C3Hg + Cl 2 ~ 0
(b) Conc. HCI 0 (e) C2 H4 + 12 ' 0
(c) Cone. HBr n 132. An alkene on reductive ozonolysis giv(!s two molecules of
(d) Conc. HCl with ZnCl 2 0 CH 2(CHOh. The alkene is:' [PET (Kerala) 2006]
124. Acid catalysed hydration of alkenes except ethene leads to (a) 2,4-hexadiene ' Q
the formation of: [AIEEE 2005; JCECE (Med.) 2008] (b) 1,3-cycloliexadiene 0
(a) primary a l c o h o l [ ] (c) 1,4-cyclohexadiene ' 0
(b) secondary or tertiary alcohol 0 (d) I-methyl-l,3-cyclopentadiene 0' ,
(c) mixture of primary aDd secondary alcohols [] (e) 1,2-dimethyl cyclopropene, 0
(d) mixture of secondary and tertiary alcohols 0 133. Identify the product (Y) in the following reaction sequence:
125., Elimination of bromine from 2-bromobutane results in the [CET (Karnataka) 2006]'
formation of: [AIEEE 2005]
(a) equimolar mixture of 1- and 2-butene 0 , CH 2-CH2-C00) Heat " Zn-Hg,
(b) predominantly-2-butene [J I Ca --HX) , , ) (Y)
, CH2-CH2~00 " " HCI,Heat
,(c) predominantly-I-butene 0
(d) predominantly-2-~utyne 0 (a) cyclobutane 0 ' (b) cyclopentane 0
126. The only alcohol, that can be prepared by the indirect
hydration of alkene is: [AFMC 2005]
(c) pentane 0 (d) cyclopentanon~ 0
134. Which cycloalkane has the lowest heat of combustion per
(a) ethyl alcohol 0 (b) propyl alcohol 0
-CH2 group? [CET(Karriataka) 2006]
(c) isobutyl alcohol 0 (d) methyl alcohol 0
(a) Cyclopropane ,0 (b) Cyclobutane []
127. 3-phenyl propene on reaction with HBr gives (as a major
(c) Cyclopentane 0 (d) Cyclohexane 0
product): [AIIMS 2005]
135. HBr reacts with H 2C=CH-OCH3 under anhydrous
(a) C6Hs CH 2CH(Br)CH3 []
conditions at room temperature to give: [AIEEE' 2006]
(b) C6Hs CH(Br)CH2CH3 []
(a) CH 3CHOand CH3Br 0
(c) C6HsCH2CH2CH2Br []
(b) BrCH2CHOand CH30H . 0
(d) C6H s CH(Br)CH=CH2 []
(c) BrCH 2-CH 2-OCH 3 o
128. HO=CH HgS04 ) ,(A) CH3MgB~ (B) P/Br2 ) (C) (d) H 3C-CHBr-OCH3 []
H2S04 HOH
136. Reaction of trans-2-phenyl-l-bromocyclopentaneon
, In this reaction, the final prodl1;ct (C) is: [DPMT 2005] reaction with alcoholic KOHproduces: [AIEEE 2006]
(a) CH3CH(Br)CH3 0 (b) CH3CH 2CH2Br 0 (a) A-phenyl cyclopentene []
(c) CH 2=CHBr 0 (d) BrHC=CH-CH 3 0 (b) 2-phenyl cyclopentene o
129. One mole of an unsaturated hydrocarbon on ozonolysis (c) I-phenyl'cyclopentene 0'
gives one mole each of CH3CHO, HCHO and OHC-CHO. . (d) 3-phenylcyc1opentene o
The hydrocarbon is: , [PMT (Kerala) 2006] 137. Trans-2-butene + Br2 gives: [CET (Gujarat) 2006]
(a) CH3CH 2-C==C-CH3 0 3
CH ' "Br=t=CH3 H' .
(b) HC===C-CH 2CH 2CH3 0
(a) HH BBrr 0 (b) ,'0
(c) CH3CH ' CHCH-CH2 o =t= H . Br
(d) H2C=CH-CH2-CH CH 2 [] CH3 CH3
(e) H2C C=CHCH2CH3 [] CH3 " CH 3 '
130. Addition ofBr2 to Z-but-2-ene gives:
(c) : = t = : .0 (d) : , = t = : . .D
[PMT (Kerala) 2006]
(a)(R, R)-2,3-dibtomobutane only 0 CH 3 CH3
(bt (S, S)-2,3-dibromobutane only 0 138. Reaction of acetylen'e and propyl~Qe with HgS04 in'
(c) (R, S)-2,3-dibromobutane only ,0 presence of H2 SO 4 produces' respectively: [BHU 2006]
(d) (R,SH,2-dibromobutane 0 (a) acetone and acetaldehyde []
(e) a mixture of (R,R) and (S,S)-2,3-dibromo butanes (b) , acetaldehyde and acetone 0
,. (50% : 50%) , [] (c) propanaldehyde, and acefone. 0
(d) acetone and propailaldehyde £]
372 G.R.B. Organic Chemistry {or Competitions
(·;0 o (b) 0 o o
(e)O o (d) D o
(d) CH3 CH 2 CH 2-C-H
I
I
o
141. What is fOrnied when calcium c~bide reacts with heavy . I
water? [DCE 2006] CI
(a) C 2D 2 0 (b)CaD 2 0 ' 147. CaC 2 + H 20 ~ (X) 03/ 20) HCOOH, (X) is:
H
(c) CaD 2 0 0 (d) CD2 0
[DeE (Engg.) 2007]
142; A molecule (X) has (i) four sigma bonds fonned by the (a) C 2 H 4 0 (b) C 2 H 2 0
overlap of Sp2 and s orbitals; (ii)one sigma bond fonned by
(c) C 2 H 6 0 (d) Ca(OHh 0
, sp2, and Sp2 -orbitals and (iii) one x-bond fonned by p z and
148. In the reactions
p z orbitals. Which of the following is X?
(EAMCET (Engg.) 20061 (B) (Lindlarcatalyst R--C==C-R Na/ NH 3) (A)
o (b) C2 H 3 CI 0 , H2
(c) C2 H 2Cl 2 o(d) C 2H 4 0 (A) and (B) are geometrical isomers. Then.:
[EAl\:1CET (Med.) 2007; DeE 2008]
. Na/NH3(l)
143. RCH CH2 . ) RCH 2 CH3 (a) A is cis and B is buns 0 (b) A is trans and B is cis [J
C2HSOH (e) A and B are cis 0 (d) A and B are trans 0
This reaction is called as: [BVP 2006] 149. The reagent(s) for the following conversion,
(a) Fischer-Siper reaction o is/are: . . [lIT 2007]
(b) Clemmensen reduction o Br~ ..1.- H H
(c) Birch reduction _0 Br
(d) Arndt-Eistert synthesis o (a) alcoholic KOH , 0
144. CH3 CH==;CH2 + NOCI ~ P (b) alcoholic KOH followed by NaNH2. 0
" . Identify the adduct: [lIT 2006] (c) aqueous KOH followed by NaNH2 0
~. '. (a) CH3-r~2. 0 (b) CH 3 -CH-CH 2 0 (d) ZiIlCH3 0H 0
II 150. The compound
CI NO NO. CI
CH .
H 2 C=CH-CH 2 - N < .3, is an:
CH3
(DPMT (Med.) 2007J
145. Identify 'B' in the·following reaction: . (a) alkyne, 3° amine 0 (b) alkene, 2° amine 0
(c) alkene, 3° amine 0 (d) alkyne, 2° amine 0
. H 2 C=CH2 + HCI Anhy.d. Alel )3
~---=....---=..~- (A)+ 2H Zn-Cu j,
7
151. Identify the produJ::t/(s) in the following reaction:
~HsOH
. BH3 H 20 2I OH- .
(B) + HCI • 3CH3CH=CH 2 ~ (X) . ) Product(s)+H3B03
.. , ,[EAMCET (Engg.) 2007) [PET (KeraJa) 2007J
(a) CH4 . 0 .(b) C2 H6 0 (a) CH3 CH 2 CH 2 0H 0 (b) CH3CHOHCH3 0
(c) C2 Hs CI o
(d) CiHsOH 0 (c) CH 3 CH 2 CHO 0 (d) CH 3CH20H+CH30H 0
146. Predict the product' C'obtained in the following reaction of . (e) CH3 CHO+CH3 0H 0
. I-butyne: '. (CBSE (Med.) 20071 152. A hydrocarbon of molecular fonnula, C6HlO re~ts, with
sodamide and the same on ozonolysis followed by hydrogen
Unsaturated Hydrocarbons 373·
185. The reagent used for the following reaction is/are: (c) In the second step NaB~ reduces--Hg (OAch group
CH3-CH=CH-C2 H s ~ CH 3CHO+C 2 Hs CHO to hydrogen 0
(d) Th~ net reaction is addition, of water. according to
(a) 0 3 and Zn/steam 0 (b) Baeyer's reagent 0 Markowniko:tI's rule q
(c) KMn0 4/H 2 S04 0 (d) Lemieux reagent 0 191. Hexa~2,4-diene on ozonolysis by using 03/CC14 followed
186. Which of the following on reductive ozonolysis give only by ZnlHz 0 gives :
glyoxal? (a) acetaldehyde 0 (b) glyoxal 0
(a) Ethylene 0 (b) Benzene 0 (c) formaldehyde 0 (d) propanaldehyde 0
(c) Toluene 0 (d) Acetylene 0 192. Alkenes can be prepared by:
187. Aqueous solution of which ofthe following compounds is (a) dehydrohalogenation of alkyl halide D
electro lysed, when acetylene gas is obtained? (b) Sabatier-Sanderen's reduction of alkynes 0
(a) Sodium fumerate 0 (b) Sodium maleate 0 (c) dehydration of alcohols with conc. H 2 S0 4 at 443K 0
(c) Sodium acetate 0 (d) Calcium carbide 0 (d) treatment 0:f3° alkyl halide at 573K '0
188. Anti-Markowniko:tI's addition of HBr is/are observed in : 193. The compound(s) which will give propylene on
(a) propene 0 (b) but-I-ene 0 dehydration with conc. Hz SO4 at 440 K is/are. :
(c) but-2-ene 0 (d) pent-3-ene 0 (a) isobutyl alcohol 0 (b) n-propyl alcohol 0
189. What product(s) results when two moles of hydrogen (c) isopropyl alcohol 0 (d) n-butyl alcohol. 0
chloride react with 4-methyl-2-pentyrie? 194. Which of the following alkynes show acidic charact~r?
(a) 3,3-Dichloro-4-methyl pentane 0 (a) 0 (b) CH3-Cs=C-H; 0
(b) 2-Chloro-4-methyl pentene 0
(c) 2,2-Dichloro-4~methyl pentane
(d) 3-Chloro-4-methyl pentene
0
0
(c) 0
~C .C-H .
.0 (d) CH3 -C==C-CH3 0
190. Which is/are' correct statements about oxymercuration
demercuration? 195. Presence of unsaturation in organic compounds can be
(a) The rearrangement takes place 0 tested with: .
(b) In the fIrst step (OAc)zHg and H 2 0 are added to the . (a) Brz water 0 (b). Baeyer's reagent, O'
double bond 0 (c) Tollens'reagent 0 (d) Grignard reagent 0
12. (A) Addition of HBr on 2-butene gives two isomeric 13. (A) C-H bond in ethyne is shorter than C-H bonds in
products. ethene.
(R) Addition of HBr on 2-butene follows Markownikoff's (R) Carbon atom in eth,ene is sp hybridised while it is Sp2 in
rule. [AIIMS 2006] ethyne. [AIIMS 2007)
'ANSWERS'
..
OBJECTIVE QUESTIONS c
1. (d) 2. (d) 3. (c) 4. (a) 5. (a) 6. (d) 7. (a) 8. (d) . 9. (a) 10. (c)
11. (a) 12. (c) 13. (c) }'\t (b) 15. (c) 16. (a) 17. (c) 18. (d) 19. (c) 20. (d)
21. (b) 22. (b) 23. (b) 24. (e) 25. (c) 26. (b) 27. (a) 28. (a) 29. (a) 30. (a)
31. (b) 32. (b) 33. (d) 34. (d) 35. (b) 36. (c) 37. (d) 38. (e) 39. (b) 40. (d)
41. (b) 42. (e) 43. (a) 44. (a) 45. (c) 46. (d) 47. (a) . 48. (d) 49. (c) : 50. (d)
51. (c) 52. (b) 53. (a) 54. (d) 55. (d) 56•. (b) 57. (c) 58. (a) 59. (a) 60. (c)
61. (d) 62. (b) 63. (c) . 64. (a) 65. (b) 66. (b) 67. (d) 68. (a) 69. (b) 70. (c)
71. (d) 72. (e) 73. (e) 74. (b) 75. (d) 76. (a) 77. (d) 78. (e) 79. (d) 80•. (b)
81. (e) 82. (a) 83. (d) 84. (d) ·85. (b) 86. (a) ~7. (c) 88. (e) 89. (b) 90. (d)
91. (1) 92. (e) 93. (b) 94. (d) 95. (a) 96. (c) 97. (c) 98. (d) .99. (d)' 100. (d)
101. (c) 102. (b) 103. (a) 104. (b) 105. (a) . 106. (b) 107. (c) 108. (d) 109. (a) 110. (d)
111. (d) 112. (d) 113. (c) 114. (d) 115. (a) 116. (c) 117. (c) 118. (d) . 119. (b) 120. (a)
121. (c) 122. (b) 123. (a) 124. (b) 125. (b)- 126. (a) 127. (b) 128. (a) 129. (c) 130. (e)
131. (c) 132. (c) 133. (b) 134. (d) 135. (d) 136. (d) 137. (a) 138. (b) 139. (c) 140. (e)
141. (a) 142. (d) 143. (c) 144. (a) 145•. (b) 146. (b) 147•. (b) 148. (b) 149. (b) 150. (c)
151. (a) 152. (d). 153. (a) 154. (a) 155. (a) 156. (b) 157. (d) 158. (c) 159. (a) 160~ (d)
161. (c) 162. (b) 163. (b) .164. (a)' 165. (d) 166. (a) 167. (b) 168. (c) 169. (a) 170. (a)
171. (e) 172. (d) 173. (b) 174. (d) 175. (c) 176. (a) 177. (c) 178. (c) 179. (d) 180. (b)
181." (b) 182. (d) 183. (c;d) 184. (c,d) 185. (a,d) 186. (b,d) 187. (a,d) 188. (a,b,d) 189. (a,c) 190. (b,c,d)
191. (a,b) 192. (a,c,d) 193. (b,c) 194. (a,b,c) 195. (a,b)
.
1: Write down the products when following compounds are dehydrated:
CH3
. (a)A
CHzOH
~.H3OR H 3C-C
I
X H
Q-LO Cyclohexene .
~OH
(b) ~
"""" ",so,
--H~-4-(~~H-2-m·~
0+0+6
Major Minor
H3C'-.,/CH3
Rare amount
CH
(c)
Major
+
6
Minor
(These products are according
to Saytzeff's rule)
[Hint:
-H+·
~~~'.
6
CH
,rn, +
..]
H
"'6CH-C 3
3° Oubocation
(More stable)
G.R.B. Organic Chemistry for Competitions
[Ans.
H Br
(i) 0
4. Complete the following reactions:
')-
(1
~ (iii)
_
cr
0
-
CH2
•
CoHsCOOOH I> ?
CHCl3 at 25"C _
C6H sCOOOH
CHCl3 at 25"CI> ?
•
U CH
'
C6HsCOOOH"
CHCll at 25°C
C
C=O
(iii) I
OH
- ?=O
OH
(iv) Since, C;:-":'C bond in ring is more substituted than that in open chain, epoxide will be fonned at the unsaturation of ring.
~H=CH2
~]
5. Give the structures of (A) and (B) in the following reaction:
~
.. - CH3 ,. ~CH'-.CH / CH2'-.CH /CH3
(i) (n) ~ 2 2 (iii)
0-·· H
- o-
[Hint: (i) _ .
CH
3 (ii)
7. An unsaturated compound C6 H12 (A) decolourises Br2 water and on oxidation by -acidified KMn04 gives optically active
carboxylic acid C 4 H9 COOH (B). Give the structure of (A) and (B),
[Hint: Compound is unsaturated because it is decolourising Br2 water. On oxidation it gives a carboxylic acid with one carbon atom less than
alkene; it shows that compound is tenninal alkene. Thus, structure of terminal alkene with chiral carbon can be given as:
Unsaturated Hydrocarbons
H H
I [0] I
CH2 =CH-Y--CH3 • HOOC.-:..c-CH3]
CH2-CH3
I
CH CH 2 3
(A) Optically active
(B) .
8. A compound CSH9Br (A) does not decolourise Baeyer's reagent or Br2 water. (A) on treatment with alcoholic KOH forms
(B)CsHs which reacts with Baeyer's reagent and Br2 water. Ozonolysis of (B) forms (C) C SH S 0 2. Identify (A), (B), (e) and
explain reactions. .
(Hint: CsH9Br is not deoolourising Baeyer's reagent or Br2 water hence. it should be cyclic compound. Possible structure for (A) can be given as:
(i)~
r-v Br
(U)
Bru
.
CH3
(iii) A
CH3
Br
CH3
'>,
. CH ·
3
(A)
Ozonolysis
(iii) Alc.KOH
.. d'>. "'- ..
/'
CH3 CH 3
(B)
9. Give the structnre of polyisoprene (natural rubber). Write down the ozonolysis of polyisoprene.
-. CH
3
I
[Ans. Monomer of natural rubber is isoprene CHz-C-CH=CH2• General structure of polyisoprene will be:
10. Limonene (C IO HI6 ) is a naturally occurring hydrocarbon. It absorbs·2 molecules of hydrogen for each molecule during
hydrogenation. On ozonolysis followed by zinc dust and steam hydrolysis, it gives one mole of fon;naldehyde and one mole of
tricarbonyl compound of following structure. . . .
o °
CH3 +HCHO
. r 2
-' C
H3 - C D -
#
(Probable sttucture of
CH3]
limonene)
11. Hydrocarbon (A) (C =87.2%) on hydrogenation forms (B) (C =84.1 %). Ozonolysis of (A) fonns acetic acid, acetone and pyruvic
•
" 'II0 1
acid [ CH3-C-COOH' What are (A) and (B)?
{Hint: Percentage composition shows that (A) and (B) has empirical fOIDlula (A) C4H7 and (B) C4Hg.
Compound (A),
Ozonol~s ) W
CH 3-C-OH + CH3-C-CH3 + CH 3-C-C-OH
~'. ~ ~
Thus, compound (A) should have eight carbons.
:.Molecular fOIDlula of (A) will be CSHI4 and that of (B) will be CsH ls .
Degr~ ofunsaturation in compound (A) = + 2 = 2 x 8 -14 + 2= 2
-
2 2
Thus, compound (A) should have two double bonds. On the basis of ozonolysis products structure of (A) can be guessed as,
CH~-.:oH CH3
\I CH3 CH3-C-H C<
+0 + C< - 1\ II CH3
WW II CH3 CH~--C-H
CH~-C-OH 0 Probable sttucture of
(A)
. CH3 <CH3
CH3-C-H C< 82 CH:r-CH2 CH
Reactions may be summarized as: II II CH3 - I, I CH)
CH3-C--C-H CH~H--CH2
(A) (B)
,' 1 Ozonolysis ,
H
[CH3 A'j[O] ] + [CHjJJ-H) + CHLH3
j[O] 0 0
" II II
CH3-COOH CH3-C-C-OH]
Acetic acid Pyruvic acid
f~ 12. CII Hl6 (A) reacts with two equivalent ofH2 and on reductive OoZOnolysis gives two equivalents fonnaldebyde and (B) offollowing
structure:
It
(i) Ozonolysis
(ii) ZnlSteam •
(Xc,- c,/CH2 ,+ lHC.HO]
·f
W
~CCH~Ha
(B) ~
(c) Deduce the structural fonnula of a compound, ClOH10 (A) that gives (~) on oxidation:
HOOC-CH~H-Car-COOH
(B) I .
CHr,:'-eOOH
y=OONa
C=C-CH)
(A) - HC=C-CH:r-CH-CH:r-C=C-H]
, I
. CH:r-C=C-H
16. Explain why the addition of ill to 3,3-dimethylbut-I-ene gives 2-iodo:-2,3-dimethylbiltane as the major product and not the
l-iodo-3,3-dimethyl-butane. . [Roorkee 2001]
CH) CH) CH) CH3
. I r... (HI) I + 1,2 M~':yl sht'ft I +1- I
[Htnt: CH)-C-CH:::bCH2 ----to- CH)-C-CH-CH) - CUI • CH~H-CH) ___ CH,-<:-CH-CH3]
I +H+ I j I. I t
CH) CH) CH3 I eH3
3,3-Dimethylbut-I-ene 2° Cll!bocatiOD 3°Cll!bocation 2-Iodo-2.3-di-
(More stable) methylbutane
17. In which case the product fonned is in accordance of anti
Markownikoff's rule? 20. ( ) • on reaction wub HBr and peroxide gives:
o
or
(a) CH -CH=CH HCI Peroxide)
3 z
CXCH2~ D~)
HBr
(b) CH3-CH=CH-CH 3 ..) .
PeroXlde
o
(a)
o
o .CH2Br
(d) (CH3 h C=CH2 0
cb
HBr/Peroxide)
n-<Br
. 18. In which of the following cases, the correct product is not
written? (C)W o (d) o
. CI Br
. '.
(a) CH3-CH=CH2'~ CHr :-CH-CH2
BrCI I· I 0 . 21. A hydrocarbon has the formula C 3H 4 • To find out whether it
contains two double bond or a triple ~()fid, the following test
(b) (CH 3 )2 CH' CH! ~~~)' (OI3 )2 CH(OH)CH 2CI 0 is preferred:
(a) passed ~ough anunoniacal AgN03 0
Hydroboration (b) treated witl;t Fehling's solution 0
(c) (CH 3 )3 C-CH=CH2 )
(c) treated with Baeyer's reagent . 0
(CH~ h e--;CH 2CH20H 0 (d) treated with Br2 water 0
. HCl .
(d) CCl 3CH CH2 ~ CCI 3-CH2-CH 2-Cl 0 22. Which among the following alkenes will be, oxidised .by
se02 ? .
19. Cis-2-butene. on reaction }Vith Baeyer's reagent gives:
(a) CH 2=CH 2 . 0
(a) meso-geminal diol 0 (b) racemjc-viCiIial diol 0
(c) meso-vicinal diol . 0 (d) none of these 0 0
,(b) CH3-CH-CH=CH
I . 2
CH)
.~
CH 3
I
.(c) CH3-C-CH=CH2
. I o
CH3
CH 3 CH 3
I . I
(d) CH3 -C-CH=CH-C-CH3 o
I, I
CH3 CH)
[Hint: Only CH 3-CH-CH=CH2 has bydrogen ata-carbon.]
I o
CH 3
23. Match List-I with List-IT and select the correct answer from
the codes given below the lists:
List-l List-II o
Reaction Product
A. CH3CH=CH2 (i)BH 3-THF) '1. n-propylamine
(ii) HCOOH
2. n-propylbromide
27. Alkyne (A) on catalytic hydration gives only one ketone
while alkyne (B) gives only aldehyde. (A ) and (B ) may be:
(a) pent-2-yne, acetylene 0 (b) oct-3-yne, propyne 0
4. n-propane (c) pent-2-yne, 'but-I-yneO (d) but-l-yne, propyne 0
28. The catalyst used in the manufacture of polythene by
Codes: Zeigler-Natta method is:
ABC D (a) TiCI 4 ,(C6Hs )3Al 0 (b) TiCl4,(CH3)3Al 0
(a) I 2 3 .4 ' (c) Ti0 2 0 (d) Titanium metal 0
(b) 2 I 4 3 29. Intermediate in hydration of alkene is:
(c) 3 4 2 I
(d) 4 3 1 ,2'
(a)fJ:ee radical 0 .(b) carbene 0
(c) carbonium ion 0 (d) carbanion 0
24. A hydrocarbon of formula C6HIO absorbs only one
'30. Order of reactivity of given four alkenes for hydrogenation
molecule of H2 upon catalytic hydrogenation. Upon , reaction will be:
ozonolysis, the hydrocarbon yields a compound of the , I. CH2=CH2
following structure,
CH3)
H 0 III. . C=CH2
I , I CH)
O-:-C-CH2-CH 2-CH 2-CH 2--:-C-:-H
(a) III> IV> II > I 0 (b) I> U > IV > ill 0
The hyilrocarbon is: (c) I> II > III > IV 0 (d) II> I > III > IV 0
(a)cyclohexane 0 (b) cyclohexyne 0 31. In the given reaction,
(c) cyc1oh~xene 0 (d) cyclobutane P
25. Match List-I with List-II and select the correct answer using ' C==£"' CH NaINH3(liq~ X
CH 3 - ~-) . )
the codes' given below the lists:
List-] , List-II 'Compound (X) will be:
Reaction Reagent , (a) ,butane 0 (b) trans~2-butene '0
,A. CH3-CH=CH2 ~ (c) cis-2-butene 0 (d) I-butene 0
CH3-CHBr-CH3 ' 1. HBr 32. 3,S-dimethyl cyc1opentene, on ozonolysis, yields: .
B. CH) -CH-CH 2 ~ (a) onlyan aldehyde 0
CH3-CH2-CH2Br 2. NBS (b) only a ketone 0
C. CH 3-CH==CH2 ~ (c) an aldehyde and a ketone 0
BrCH2-CH==CH2 3. Br2/CCl4 (d) a dialdehyde 0
D. CH3-CH=CH2 .~
. CH3 "":"'CHBr.:..-CH2Br 4 .. HBr (peroxide)
I'
384 G.R.B. Organic Chemistry for Competitions
33. A compound C4HS decolourizes a KMn0 4 solution. How Compounds [X] and [Y] are respectively:
many structures are possible for this compound?
(a) 3
(c) 2
0 (b) 4
0 (0)5
0
0
(a) ~-CH
I I 2
D-e' CH 0
o
(d) CH3 -C=CH2
I .
CH3
(d) ~=CH2
;' I
D-e H3 0
<Ii
(I) (II)
2-pentyne respectively are:
. (a) 4 and 3 0 (b) 2 and 4 0
H
3
) ..
c=C ; (c) 4 and2 o
(d) 2 and 7 0
40. H2 C=CH-C==CHon reaction with one mole DBr gives:
. CH3
(III) (a) CH z . CH-CBr=CHD 0
I (b) CHz (Br}-CHDC==CH 0
(c) DCH 2-CHBrC==CH o
. is of the order:
(a) I>II>III>IV>V>VI 0
(d) CH 2=CH-CD=CHBi o
41. Which of the following reactions are expected to give
(b) VI> V> IV> III> II> I 0
(c) I>III>V>II>IV>VI 0 CH)
(d) II> 1;> IV> III> V> VI . O. I
CH 3-C-CH=CH2
36. Alkenes can be converted to carbo.nyl cOmpound in one step
by:
I
CH .
3
(a) Wacker process 0
(b) Oxylnercuration;'demercuration .0 in yields of more tha.J;l50%?
(c) Hydroboration oxidation 0 . CH3
(d) Wittig reaction 0 c . I
,(a) CH1-C- CH-CH3
. o
37. Unknown COl'QP9und (A) on oxidation with hot basic .
KMnb 4 'gives only one'compound whose structure is given I I
below, CH3 0H
CH
. I 3 ..
(b) CH3 -C-CH-CH3
.
I
CH3 Br
I
Compound (A) will be:.
(a) CH3-C C-(CHz k-=-C=:C-CH3, o CH3
(b) CH3-:-CH=CH~(CHz )4-CH . CHz o I
(c) CHJ-C-CH-CHj Zn) .. o
(c) CH3-CH-CH-(CHz )4-CH=CH-CH3 o I I· Acetone
(d) 0 o
CH3 Br
43. Which of the following contains acidic hydrogen? 47. Which of the following ~ll reach with sodium metal?
(a) Ethene 0 (b) Ethane 0 (a) Ethyne D (b) 'But':'l-yne ' 0
(c) Ethyne 0 (d) But-I-yne 0 (c) But-2-yne 0 (d) Ethane 0
44. Which are the possible intennediate8 in the' following 48. Which of the following will give cis,-di(lls'!
reaction?
(a) )C=C< ' LKMn04 ) 0
CH CH CH=CH 1. Br2/CCI4 ) CH CH C==CH , 2. H 20
3 2 2 2. NaNH 2 (1l0-1600 C) 3 2
0
(d)O 35%,H~2
. o
45. Which of the following statements are not correct. for 49. Ionic addition of bromine to clS-2-butene yields:
alkanes? (il) meso-:2,3-dibromobutane 0
(a) All C~H and C-:-C bonds have a length of 1.112 A and (b) racemic-2,3-dibromobutane 0
1.54 A respectively ,0 (c) d-2,3~bromobutane 0
(b) All bond angles are tetrahedral, having a value of, (d) 1-2i3-dibromobutane 0
109.5° 0 SO. The exacts representation(s) of molecular formula C6HS
(c) The C-C chain is linear and not zig-zag 0 containing sp, Sp2 ,and sp3 -hybrid-states of carbon atoms
(d) All alkanes exhibit isomerism 0
is/are:
46. What are the products obtained by the ozonolysis of
RCH-CR 1R 2 ? ' (a) H2 C=CH-CH=CH-CH=CH2 ' o
(a) RCHO 0 (b) R 1R 2 CO 0 (b) H 2 C=CH-O==C--':CH2-CH3 o
o (c) CH3-CH-:-C=CH-CH CH2 o
(d) H();;;;;;C-CH2 -CHr ':-CH=CH2 o
I II III IV
(a) II>III>IV>I (b) I>fV>I1I>II or
A~O
(c) I1I>IV>I>II (d) II>IV>I>I1I
Pd/CaC0 3 . Presence of unsafuration· -in alkenes is detected by using
2. H3C-G-C-CH3 + H2 ----"'--7) (A) Baeyer's reagent. Alkenes decolourise pink colour of Baeyer's
Boiling Quinoline .r
. reagent.· In presence of Baeyer's reagent, 'syn' addition of-OH
groups takes place on bOth carbons· of double· bond. The net
reaction <;an be given as,
OH OH
KMn04
I . I
R-CH=CH-R OW ) R-'---CH-CH-R
H
C=C·..·
. CH3
.,
Ozonolysis of· alkenes gives ozonide, which on further
hydrolysis gives aJdehyde and/or ketone.
H H
(d) CH3-CH 2-CH=CH2 Rl) I (CH Cl) . RI
)c·\P, I
\ "C-
I 3. In which of the following cases, the;:.r~action is most C=C- R3 + 0 3 . 2 i. R3
. exothermicf ... . ( . ... . Rz . .. R2 a+o'
(a)()~ o 0
Znduststeam. RI-1-R3 +'R3-1-H
cY
2. Ort~o' xylene on reductive ozonolysis will give:
I ,./ +H2
PdtCaC03
... o
'v" Boiling Quinoline
(a) CHO-,-CHO and CH3-C-CHO
I
Unsaturated Hydrocarbons '387
o 0 0 . / C I I3
I I . I +O=C~ .
(b) CH3-C-C-CH3 and CH 3-C-CHO
. , .. , CH
o 0 .
Propanone
3
I I .
(c) CH3- C - C-CH3 and CHO-CHO Oxidation ofalkenes with 080 4 followed by alcoholic
000 NaHS0 3 or Na2S0J yields glyCols.
. I I I .' '.CH 2 - · ° . 0
(d) CH3-C-C-CH3' CH3-C-CHOand
CHO-CHO
3. Which of the following will give only formaldehyde on
CH 2 +080 4
II·
---1 I. /"'0<'
CH 2 - 0 ' ~O
CHz
ozonolysis? '
Ethylene
V
CH3
(a)
0-:7'
"'"
I'
.
'(b) ,
~.'
2.
gives only butanoic acid?
(a) Oct-3-ene
(c) Oct-2-ene
(b)Oct-4-ene
(d) 3-Methyl-hept-3-ene
Which of these compounds. on treatment with 0s0 4.'
followed by Na2 S03 will give cis-2-methylbutan-2,3-diol?
(d) All of these (a) 2-Methyl-2-pentene (b) 4-Methyl-2-pentene
(c) 2,3-Dimethyl-2-butene . Cd) '2,2-Dimettiyl.. 2~butene
3. An alkene I-methyl cyclohexene on oxidation ,with hot
5. Product of ozonolysis gives information about: basic KMnO4 gives:
(a) configuration (b) conformation (a) heptanoic acid
(c) both of these, (d) none of these (b) 2-methyl hexanoic acid
(c) 6-keto heptanoic acid
Passage 3 (d) butanoic acid and acetone
Oxidation of alkenes by cleavage with acidic or alkaline 4. Which of the following alkenes on oxidation with hot .
KMn04 or acidic K2Cr207 at higher temperature yields products KMn0 4 gives .cyclopentanone? . '.
depending upon the nature ofaIkene. A hot solution ofKMn04 is (a) 2-Methyl cyclopentene (b) Cyclopentene
a strong oxidising agent which gives only ketones and carboxylic . (c) Methylene cyclobutane (d) Methylerie cyclQpentane
acids and not aldehydes (as they cannot be isolated). 5~ An alkene 1,2-dimethyl cyclobutene on oxidation With. hot
KMn0 4 gives: . ,
o
. H 3 C, ~. /. CH3 [0] I (a) 4-ketopentanoic acid
",-,-c(\
.
----4) CH3'~C-OH (b) 2,3-diketo cyclohexane
(c) hexane-2,5-dione .' . .
H/ CH3 Hot KMn04 Ethan' 'd
OlcaCl
2-h{ethylbut-2-ene
(d) ethanoic acid and butanoi(; .acid
[~4J
fonnula C n H 2n - 1X 3' The tri-halogen derivatives of first
alkane (methane) are:
CHC1 3 ; CHBr3 ; CHI 3
, Chloroform Bromoform Iodoform
~2 ~
These compounds are tenned as halo forms. '
C1
4. Tetra-halogen derivatives: The tetra-halogen ,deriva- .. CH-ffi2
,
tives are derived by the replacement of four hydrogen atoms
from alkanes by four halogen atoms. All the four halogen
atoms are attached to the same carbon atom in derivatives of
SUI 6 ,
,
CHi:H
•
< CI
. CI
Ethylidene chloride I,I-Dichloroethane
]UPAC names:
(a) Sec-butyl chloride
(c) Tert.-butyl chloride
(e) Tert-amyl iodide
(b) Iso-butyl chloride,
(d) Iso-propyl bromide
(j) Iso-pentyl bromide
CH1CI-CH;CI Ethylene chloride 1,2-Dichloroethane (g) Neo-pentyl chloride (h) Neo-hexyl bromide
CHCl 3 Chloroform Trichloromethane W !so-propylidene bromide (j) Allyl iodide
CHl3 Iodoform Triiodomethane (k) Crotyl bromide (1) Propargyl bromide
(m) 4-Chloro-2-pentene
:.:R=a:::::lo.o.ge::::.n.:;:::a:.::.:te.:;:::d;.:,;A:.:.:b:t::.·p:..:::ha::::t.:::::ic;...:.H~y:.:::d.:....:ro:::::c;::::ar:..:::b:..:::.o:..:::ns::...- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _..,.-_.-.:3I\;1,9~~F. ' '
Solution:
(a) CH 3 -CH-CH 2CH 3 2.Chlorobutap.e f2 H 5 f2 H S
, I (d) CH3 -'C-, CH 2 - C - CH3
Cl I 'I
Cl ' Br '
(b) CH) -CH-CH 2Cl l-Chloro-2-methylpropane
, .' I (e) (CH3hC-.CH 2-CH 2Cl
CH 3 '(f) (CH3hC-CH~CH-CH2CH3 .
CH 3
. I I
. CH)' I,
I
(c) CH 3 -?-CH 3 2-Chloro-2-methylpropane C2H 5 C 2H S
I' I
Cl (g) CH 3 -,C-CH2 -,'C-' CH 3
, . '. ,. ' . 1
(d) CH 3 -CH-CH 3 2-Bromopropane . p' Cl
I ' . " .
Br (~) HC==C-CH 2-CH=CHCl
(i) BrCH 2-CH 2 - ,CH 2 - 'GH 2Cl
(j) CH 3 - .C==C-CH-'CH J
" I .
2-Iodo~2-methylbutane . Cl .'
I-Bromo-:3-methylbutane
CH 3
CH 3
CH 3
I C
(h) CH 3 -G-CH2CH 2 Br ( P ) 'ryCH,.3
H3 ' . H
I , . H Br
C1h
H .
I-Bromo-3,3-dimethylbutane,
fr H~'CH 3 ·
(i) CH 3 ---'C-CH3 2,2-Dibromopropane (r) , . , ' H;
. I .
H .
Br '.
Br
CH 3
(j) H 2C=CH-CH 21 3-Iodoprop-l-ene
(k) CH 3CH=CHCH2Br I-Bromo-but-2-ene Solution: (a) 2-Chloro..2-methylpropane
(I) HC=C-CH 2Br 3-Bromoprop-I-yne (b) l-Chl(:)ro:'2-methylbutane ? '
(m) CH 3CH-':""CH-CH-CH 3 4-Chloropent-2-ene (c) 2-Chloro-3-ethylpenta-l,4-diene
, 1
(d) 3-Bromo-5-chloro-3 ,5-dimethylheptane
Cl (e) l-Chloro-3,3-dimethylbutane
(f) 4.Iodo-2,2,3-triniethYlhexane
Example 2. Give the IUPAC names of the following
(g) 3-Chloro-5-fluoro-3,5-dimethylheptane
compo~nds: .
(4) (CH 3hC-Cl
(bY l-Chloropent-l-en-4-yne
(i) I-Bromo-4-chlorobutane .
(b) CH 3 -?H-.CH 2Cl (j) 4-Chloro-pent-2-yne. '
(k) 3~Chloro-3-ethylpentane
C H
. 2 5 "
(I) 2,3-Dibrorho-l-chloro-3-methylpentane
(c) H 2C=CH-CH-'C=CH 2 (m) 3-Bromoprop-I-yne .' .
, I I (n) I-Bromobut-2-ene
C ZH 5 CI
392' G.R.B. Organic Chemistry (or Competitions
x
C 2H sCI +HCl I
Ethyl chloride R-CH=CH-R + HX --7 R-CH2-CH-R
(Major product) Symmetrical alkene Alkyl halide
CH 3 CH 3
.
Racemic
1
CH 3-C-CH 2CH3 ~ CH 3-C-CH 2CH 3
B-1 +
Alkane can react with sulphuryl chloride only in presence 1 (30 Carbocation)
Br More stable than 2°
of light and .traces of organic peroxide.
2-Bromo-2-methyl butane
by
RH + S02Cl2 ) R-Cl + HCl + S02
Alkane Sulphuryl or Peroxide Cbloroalkime • CH 3-CH=CH2 + HBr Peroxide) CH 3-CH 2-CH 2Br
chloride Propene (Anti-MR I-BrOioopropane
1. From alkenes: Halogen acids (HCl, HBr, HI) react addition) (n-Propyl bromide)
readily with alkenes to form alkyl halides. The order of CH 3 CH 3
reactivity of haiogen acids is: . I, (";u CO) 0
U
I
HI> HBr> Rct> HF CH -C=CH
3 2 :t- HBr "'6 S 2, 2) CH 3-C-CH 2Br
I .
2-Methylpropene
·H2C==CH2 +HBr - - 7 CH 3CH2Br
H
The urisymmetrical alkenes follow Markownikoff's rule I-Bromo-2-methyl propane .
during addition forming secondary or tertiary alkyl halides
It may be noted that the peroxide effect applies to the
predominantly through the formation of most stable carbo-
addition of HBr only and not to the addition of HCI or HI. .
cation. Addition occurs through electrophilic attack.
However, in· presence of peroxide (R~R), such as A1lylie substitution
benzoyl peroxide (C 6 H sCO-O-O--COC6 H s ), the HBr
When alkenes are heated with Cl 2 or Br2 at a high
addition follows anti-Matkownikoff's rule (peroxide effect
temperature of about 500°C, the hydrogen atom of the allylic
or Kharaseb effect) and form primary or normal alkyl
carbon (i.e., carbon atom next to the double bonds) is
bromides. Such an addition follows free radical mechanism.
substituted with the halogen atom without breaking the double
This method is well suited for the industrial preparation of bond (allylic substitution) and forms allyl halide. For
alkyl halides as the lower alkenes are obtained during example,
cracking of petroleum products.
394 G.R.B. Organic Chemistry (or Competitions
Pyridine) RCI + S0 2i + HCIi 3CH 3CCl 2CH 3 +2SbF3 ----7 3CH 3CF2CH 3 +2SbC1 3
ROH+SOCI 2
Retlux 6. By Rydons method: An alcohol on heating with
halogen in presence of triphenyl phosphate (PhOh PO
C 2H sOH + SOCl 2 Pyridine) C 2 H 5CI + S02i + HCli produces alkyl halides.
Ethanol Thionyl Chloroethane Heat
chloride R-CH 20H + Br2 + (C6HsOh PO----7
This method is widely used for the preparation of alkyl R-CH2Br +C 6H sOH + (C6HsOhPOBr
chlorides only as it has advantage over phosphorus chloride
because the bypro ducts sulphur dioxide and hydrogen 8.4 PROPERTIES OF ALKYL HALIDES
chloride are gases which can be easily removed from the Physical properties: (i) CH3F, CH 3CI, CH3Br and
reaction mixture. Bromides and iodides are not prepared by
C 2 H sCI are gases at room temperature, while CH31 is Ii liquid
this method, because thionyl bromide is unstable and thionyl
at room temperature. The alkyl halides upto C I8 are colourless
iodide does not exist.
liquids while higher members are colourless solids. -
4. From silver salts of fatty acids: Alkyl chlorides or (li) Alkyl halides are insoluble in water but soluble in
alkyl bromides are prepared by the action of chlorine or organic solvents.
bromine in CCl 4 on silver salt of the fatty acids. This reaction (iii) They bum on copper wire with green edged flame
is called Borodine-Hunsdiecker reaction or Hunsdiecker (Beilstein test for halogens).
reaction.
'396 G.R.B. Organic Chemistry for Competitions
(iv) Alkyl bromides and iodides are he,avier than water. inductive effect. When approached by a strongest base (B), it
Alkyl chlorides and fluorides are lighter than water. tends to lose a proton usually from the j)-carbon atom. Such
(v) Alkyl iodides become violet or brown in colour on " reactions are termed elimination reactions. They are also EI
exposure as they decompose in light. and E2 reactions.
Light E 1 reaction :
2RI ) R-R +1 2 , B-
(vi) For a given alkyl group, the boiling, points of alkyl ••
H H H H H
halides are in the order RI > RBr> RCI > RF and for a given
halogen, the boiling points of alkyl halides increase with the
I I
R-C-C-H---tR-C-C-H
Slow t1 I ~
Fast
R-C=C-H
I
increase of the size ofthe alkyl group. fn a group of isomeric I I -X- I + I
alkyl halides, the order of boiling point is: H X H H
Primary> Secondary> Tertiary +B-H'
(vii) Alkyl halides are in general toxic compounds and
bring unconsciousness when inhaled in large amounts.
E'Z reaction :
'
B-:H Ii
.
B---H H
.. 'H,
Cbemical properties : The alkyl halides are highly
reactive, the order of reactivity is: ' R~-1_HSID~~R~~-H~R~=h-H
Iodide> Bromide> Chloride (nature of the halogen atom)
Tertiary> Secondary> Primary (type of halogen atom) Al A'i
Transition state
A
+ B~H + X-
Amongst the primary alkyl halides the order of reactivity
is: As the above reactions involve leaving of X -, the
CH3X>C2HSX>C3H7X, etc. reactivity of alkyl halides (same alkyl group, different
'halogens) should be limited with C-Xbond strength.
The high reactivity of alkyl halides can be explained in
tenns of the nature of C-X bond which is highly polarised Type of bond C-I C-:- Br G-CI
Bond strength (kcal/mol) 45.5 54 66.5
covalent bond due to large difference in the electronegativities
of carbon and' halogen atoms. The halogen is far more
-----------------
Bond strength increases
electronegative than 'carbon ,and tends to pull the electrons The breaking of the bond becomes more and more
away from carbon; i. e., halogen acquires a small negative difficult and thus, the reactivity decreases:
charge and carbon a small positive charge. The order of reactivity (tertiary> secondary> primary) is
0+ 0- due to + I effect of the, alkyl groups which increases the
-C-X polarity of C-X bond.
This polarity gives rise to two types of reactions.
(i) Nucleophilic substitution : The Co+ site is
susceptible to attack by nucleophiles (an electron rich
;jc~x. :> CH-+-+-X , R-+-CH,-+-X
species). ~ + _
The primary alkyl haiides undergo reactions either by
:Nu- + R°Fx° ---t Nu-R + X-:
SN 2 or' E2 mechanisms which involve the forrrmtion of
Nucleophile Halide ion
transition state. The bulky groups cause steric hindrance in the
R-X
-x-
~:--~) R+
N
U- ), R-Nu (SN I reaction) ".
formation of transition state. Therefore, higher honi~logues
Slow Fast ~, are less reactive than lower homologties.
Slow Fast,' - CH 3X >C2HSX >C 3H 7 X,etc. '
.
Nu- +R-X--~) Nu ... R ... X ---t Nu-R+X
Transition state Alkyl halides are extremely'nnportant reagents in organic
synthesis as they Undergo a large variety' of reactions' which
(SN2 reaction)
are listed below. '
In SN I reaction', there can be racemization and inversion '
and order of reac~ivity is: , ' " 1. Nucleophilic Substitution Reactions
SN1 order: Benzyl> allyl> 3° > 2° > 1°> CH 3-:X of
(i) Hydrolysis (Formation aJeobols): Alkyl halides
SN 2 reactions are concerted reactions and configuration 'are hydr()lysed to corresponding alcohols by moist silver
oxide (AgOH) or by boiling with aqueous alkali so~ution
of carbon is changed (Walden Inversion).
(NaOH or KOH). The attacking nudeophile is ofi-.
SN2 order :Meth~l > 1° > 2° > 3° > allyl> benzyl ,halides.
Heat
So, tertiary ~lkyl halides are practically inert to RX ,+ AgOH ~ ROH, +AgX
Alkyl halide Moist Alcohol
substitution by SN2 mechanism because of sterie hindrance. , silver oxide '"
(ii) ,Elimination reactions: The positive charge' on , + - Heat' ,
carbon is propagated to the neighbouring carbon atoms by 'RX + KOH(aq.) - - - t ROH+ KX
\
Halogenated Aliphatic Hydrocarbons ·397
Nitroethane
CH 3-N-> C +4H Na/C2HsOH ) CH 3-NH-CH 3 (vi)Reaction with ammonia (Formation of
Methyl isocyanide Dimethylarnine amines): On heating with aqueous or alcoholic solution of
Explanation: The fonnation of cyanides· or ammonia in a sealed tube at lOO°C, alkyl halides yield a
isocyanides from. alkyl halides involves nucleopbilic mixture of amines and quaternary ammonium salt.· The
nucleophile is NH2" in the first reaction.
substitution reaction. The cyanide ion ( :CN) is a resonance
Heat
hybrid of the following structures: ' C2Hs~r + H-NH2 ~ C2HSNH2 + HBr
_ •• _ 1)- 1)- (Alc.) Ethylarnine (10)
[:C=N: ~ :C=N: ] C==N·
Resonating structure Hybrid structure
As is evident from the hybrid structure in the cyanide ion,
both the carbon and the nitrogen atoms have a pair of
electrons. Therefore, either the carbon or the nitrogen atom (C 2H 5 h NH +BrC 2HS
N-Ethyl
can act as the electron donor to the alkyl halide. Such a
ethanamine (2° )
nucleophilic species which is capable of attacking the
molecule through two sites is called ambident nucleophiles. (C 2H 5 hN + Br C 2H S CzHsOH) [(C2Hs)4N+]Br-
Thus, CN ion is an ambident nucleophile. N;N-Diethyl Heat Tetraethylammonium
Now alkali metal cyanides (KCN or NaCN) are ethanamine (3°) bromide (Quaternary salt)
predominantly ionic. Therefore, both carbon and nitrogen This reaction is called Hofmann ammonolysis of alkyl
atoms are free to donate electron pair. Since C-C bond is halides.
relatively stronger than C-N bond, therefore, in this case (vii) Reaction with silver salts of carboxylic acids
attack mostly occurs through the carbon atom of the cyanide (Formation of esters): On heating with silver salts of
group and alkyl cyanides are the major product. carboxylic acids in alcoholic solution, alkyl halides yield
On the other hand, silver cyanide is predominantly esters. The nucleophile is R'COO-.
covalent. Consequently only nitrogen electron pair is R'COOAg + XR C2BsOH) R'COOR + AgX
available for bond fonnation, and the attack mostly occurs A Ester.
thrQugh the nitrogen atom of cyanide group giving alkyl
isocyanides as the major product. CH 3COOAg + Br C 2H S CzHsOH) CH 3COOC 2H s + AgBr
(v) Reaction with potassium nitrite or silver nitrite Silver acetate A Ethyl acetate
(Formation of alkyl nitrite· and nitro alkanes): On (viii) Reaction with sodium acetylide (Formation of
heating an alkyl halide with potassium nitrite in an aqueous higher alkynes): Alkyl halides react with sodium aJkYnide
ethanolic solution, alkyl nitrite is obtained as the main product (R-C=C-Na) to fonn higher alkynes. The nucleophile is
though some nitroalkane is also fonned. It is because the bond CH=C-.
between K-O is ionic in nature, therefore, negative charge + -
on oxygen serves as attacking site.The nucleophile is RX + Na-C=CH ~ R-C==CH + NaX
Sod. acetylide Higher alkyne
. -ONO-.
Heat CH 3CH 2Br + NaC=CH ~ CH 3CH 2C==CH + NaBr
RX +K+-O-N=O- ~ R-O-N=O+KX Brornoethane But-l-yne
Haloalkane. Alkyl nitrite
Halogenated Aliphatic Hydrocarbons 399
Note: Sodium alkyirides are prepared when terminal alkynes react H H H H
withsodamide (or sodium in liquid NHi) at 197 K. I I +- . . I I
Liq. NH3 . . H-:-C~-C(X-H + K-OH(alc.) Heat) H-C=C-H
R-C. CH + NaNH2
Terminal alkyne . 197 K
) R-C===C-Na + NH3
Sod. alkynide
. _L ___1-. Ethene
iH Br:
__________ J
k cl-/
Haloalkane
k
Alkene
The ease of dehydrohalogenation is in the order:
Tertiary alkyl halide> Secondary alkyl halide
> Primary alkyl halide
and the ease of formation of alkenes is:
R 2C=CR 2 >R 2C=CHR >R 2C=CH 2 > RCH=CHR
. > RCH=CH 2 > H 2C=CH2
400 ' G.R.B. Organic Chemistryjor Competitions
~. O'(~~ili' cb
TEL
(c) Alkyl halides form dialkyl mercury compounds when
treated with sodium amalgam. .
. 2C zH sBr +Na-Hg ~ (CzHs}zHg + NaBr
Bromoethane Diethyl mercury
Br
(d) Reaction with Lithium: Alkyl halides'react with
NO z lithium in. dry ether to form alkyl lithiums.
I, BU3SnH, ,
RX +2Li Ether) R-Li + LiX
[CH 3CH 2CHCOOC zH s . ) CH3CHzCHzCOOCzHs]
ReductIon ' .. ,,
(xiv) Wurtz reaction: An ether solution of an alkyl C2HSBr +2Li ~ CzHs-Li + LiBr
balide (preferably bromide or iodide) forms s~etrical Ethyl bromide Ethyl lithium
alkanes when heated with metallic sodium. 2R-Li +CuI ~ LiRzCu
Alkyl lithium Lithium dialkyl copper
2RX +2Na Dry ether,. R-R +2NaX Alkyl lithiums are similar in properties with Grignard
Alkyl halide Alkane
reagents. These are reactive reagents also and serve as strong
bases.
CH 3EC~~~a=~H-CH3 Dry ether) CH r -eH 3 + 2NaI Alkyl halide reacts with lithium dialkyl cuprate (RzCuLi)
Methyl iodide Ethane to form unsymmetrical alkanes (Corey-House synthesis).
RzCuLi + R' X ~ R-R' +R---Cu + LiX
Alkane
Halogenated Aliphatic Hydrocarbons ·40~
(CH3 hCuLi + Br CH 2CH 3 ~ CH 3CH2 CH 3 CH 3CH zCH 2CH 2Br 300"C or ) CH -CH-'CH -CH
Lithium dimethyl Ethyl bromide Propane. , l-Bromobutane
Anhyd. AlCl 3 ",3 I' 2 , 3
cuprate "Sr ".,
. + CH 3Cu + LiBr BrOIoobutane
(xvii) Friedel-Crafts reaction Alkyl halides react
with benzene in presence of anhydrous ~luminium halides to Uses: (i) Lower members are used as anaesthetic agent,
fonn a homologue of benzene. refrigerant and solvents. '
(ii) Alkyl halides are used as alkylating agents, i.e., to
C H 6 + RCI AlCI 3(anhyd.) ) C6HSR + HCI introduce the alkyl group in a molecule.
6
Benzene Alkyl benzene (iii) Alkyl halides are starting materials for the
preparation of many organic compounds. Ethyl chloride is,
AlBr3(anhyd.) employed for the manufacture of tetr~thyllead, Pb(CzH s )4'
C 6 H 6 + CzHsBr, ) C 6 H sC zH s + HBr
Benzene Bromoethane Ethyl benzene used as antiknock in gasoline for nirining automobiles, ',' "
(xviii) Substitution (Halogenation): Alkyl halides 8.5 DI-HALOGEN DERIVATIVES'
undergo further halogenation in presence of sunlight, heat
energy or peroxide. General Methods of Preparation
Br2 C 'H Br
C zH sBr ~ Br2 C ' (i) Alkylidene halides or gem-dihalidesor 1,1~dihalo
z 4 Z ~ 2H 3Br3'"
alkanes : The given general methods are used for, the
(xix) Oxidation reaction: Only primary and· preparation of gem-dihalides:
secondary alkyl halides undergo oxidation while tertiary alkyl (a) By the action of 'phosphorus pentahalides' oil
halide does not. aldehydes and ketones: Two halogen atoms can be added to
Primary (10) alkyl halides on oxidation with dimethyl same carbon atom when aldehydes or ketones are treated with
sulphoxide, (CH3)2S0(DMSO) give aldehydes (Swern phosphorus pentahalide.
oxidation). CH 3CHO + PCIs ~ CH 3CHC1 2 ,+POCI 3 ·
o Acetaldehyde l,l-Dichloroethane
R-CH 2 X ,
DMSO
>R-C-H
11- (Ethylidene chloride)
CH
1° Halide ( 3hSO Aldehyde CH 3COCH + PCIs ~ ,SH 3CCI 2Cl:I 3 + POCl 3
Acetone ~', ,L-Dichlor ,opane
Oxidation can also be done with hexamethylene
(Isopropyl idefl~ 'chloride)
tetramine, (CH2)6N 4 followed by hydrolysis.
Secondary (2°) alkyl halides give ketone in this reaction. (b) Fromalkynes:, Additivu of halogen 'acids to alkynes
o fonn getp-dihalides. For each molecule of an alkyne, two
molecules of halogen acid are required, i.e., triple bond is first
II
DMSOor converted into dbubie bond and then double bond into single.
R-CH-R ---~)R-C-R
(i) ( CH2)6N 4 bond. . .
X1
Ketone'
(ii) H20/H +
HC==CH + HCI ~ H 2C=CH-Cl + HCI) H3C-'CHCl 2
, 20 Halide
o Acetylene 'Vinyl chloride 'l,l-DichlorOelhane
DMSOor II HC==CH +2HBr ~ CH3CHBr2
C6 H sCH 2 - X ) C6 H S-C-H Acetylene 1,1-Dibromoethane
Benzyl halid.e (i) (CH 2)6N 4 Benzaldehyde
(ii) H20/H+ (Ethylidenebromide)
Oxidation of benzyl halides with (CH2)6N 4 is known as CH 3C , CH+2HCI ~ CH 3CCl zCH 3
Sommelet aldehyde synthesis. Propyne 2,2-Dichloropropane
(a) Reactivity for oxidation reaction depends on the (Isopropyliderie chloride)
number of hydrogen atoms on alpha (a.-) carbon of alkyl :; ,Ie halides, or vic-dihalides or 1,2-dihalo-
halides: These may be obtained by following methods:
Reactivity oe number of a.-hydrogen 'y the addition of halogens to alkenes :, Addition
(b) Reactivity of different halides in decreasing order is as occurs on the two carbon atoms linked by a double bond.
, follows: H;C CfIz +Cl z ~ CH 2CICH 2C\ '
Benzyl halides> Allyl'halides > Alkyl halides' Ethylene 1,2-Dichloroethane
(xx) Isomerisation: Haloalkanes on heating at 300°C or (Ethylene chloride)
"
in presence of anhydrous AlCl 3 at low temperature undergo CH 3CH=CH 2 + B:r2 CHjCHBrCHi'Br
molecular rearrangement to fonn an isomeric haloalkane. For 1,2-Dibromopropane
example, (propylene bromide)
CH3CH 2CH 2CI 300"Cor ) CH -CH-CH (b) By the action of phosphorus halides on
3 3
l-Chloropropane Anhyd. AlCl 3 1 glytols : Glycols or dihydric alcohols react with phosphorus
CI halides or halogen acids or SOCl 2 to fonn vic-dihalides.
2-Chloropropane
402: G.R.B. Organic Chemistry (or Competitions
Chemical properties: Chemically, alkylidene halides proposed by Dumas as it gave formic acid on hydrolysis. In
are less reactive while alkylene halides have nearly the same the past, it was extensively used as anaesthetic for surgery but
reactivitY as alkyl halides. The important chemical properties now it is rarely used as it causes liver damage.
are given aheaIJ. in comparative form. . Preparation : 1. Chloroform is prepared both in the
laboratory and on large scale .by distilling ethyl alcohol or
·8:6 TRI-HALOGEN DERIVATIVES acetone with bleaching powder and water. 'the yield is about
Chloroform or Trichloromethane (CHCI 3) 40%: The available chlorine of bleaching powder serves both
It is an iniportant trihalogen delivative of methany. It was as oxidising as well as chlorinating agent.
'. discovered by Liebig in 1831 and its name chloroform was
Halogenated Aliphatic Hydrocarbons 403
CaOCl 2 + H 20 ---7 Ca(OHh +C1 2 ;t';" Physical properties: (i) It is a sweet smelling
Bleaching powder colourless liquld.
From alcohol : (i) Alcohol is first oxidised to (ii) It is heavy liquid. Its density is 1.485. It boils at 61°C.
acetaldehyde by chlorine. (iii) It is practically insoluble in water but dissolves in
[C1 2 + Hp ---7 '2HCI+0] organic solvents such as alcohol; ether, etc.
(iv) It is non-inflammable but its vapours may burn with
CH 3CH 20H+CI 2 Oxidation) CH 3CHO +2HCI green flame.
Ethyl alcohol Acetaldehyde (v) It brings temporary unconsciousness when vapours
(ii) Acetaldehyde then reacts with chlorine to form are inhaled for sufficient time.
chloral (trichloro acetaldehyde). Chemicallroperties: (i)Oxidatlon: When exposed
to sunlight an air, it slowly decomposesjnto phosgene and
CH CHO +3Cl 2 Chlorination) CCl 3CHO ' + 3HCl hydrogen, chloride. '
l
3
Acetaldehyde ' Trichloroacetaldehyde
(Chloral) CI) <CI Light CI) <CI
[So, Cl 2 acts both as an oxidising (i) and chlorinating,agent C +[0] ) C
(ii)]
(iii) Chloral thus fonned, is hydrolysed by calcium hydroxide. a ChloroformH ~. a, ,'COIH ,
or
Calcium fonnate
or Light
d .) COCl 2 + HCl
an au
. 1
[2CCI 3CHO+Ca(OHh Hydrolysis) 2CHCl 3 + (HCOOhCa]
From acetone: (i) Acetone first reacts with chlorine to
or
form trichloroacetone.
Chlorination Phosgene is extremely poisonous gas: To use chloroform
CH 3COCH 3 + 3Cl 2 ) CCl 3COCH 3 + 3HCI as an anaesthetic agent, it is necessary to prevent the abdve
Acetone Trichloroacetone reaction. The following two precautions are taken when
:(ii) Trichloroacetone is then hydrolysed by calcium hydroxide. chloroform is stored. '
(a) It is stored in dark blue or brown coloured bottles
.CCI3 : COCH3 H3CCOl CCl3 ',
: + : Hydrolysis which are filled upto the brim. ,
I I ~ 2CHCl3 (b) '1% ethyl alcohol is added. This retards the, oxidation
H! --O-----Ca-O----j H
, . Chlorofonn
. and converts the phosgene formed into hannless ethyl carbonate.
+ (CH3COOhCa
Calcium acetate ", <OC 2 H$ . '
2. From carbon tetrachloride: Now-a-days, chloro- COCl 2 +2C 2 H 50H ---7 O=C . +2HCI
form is obtained on a large scale by the reduction of carbon OC 2 H 5
tetrachloride with iron fillings and water. This method is used (Di) Ethyl carboIUlte
in countries like USA.
(ii) Reduction: When reduced with zinc and
CCl 4 +2H Fe/H20) CHCI + HCI hydrochloric acid in presence of ethyl alcohol, it forms
Heat 3 methylene chloride.
This chloroform is not pure and used mainly as a solvent. CHCI + 2H Zn/HCI) CH CI' + HCI
3. Pure chloroform: It is obtained by distilling chloral Chlorof;nn (Ale.) Met~yle;e'
hydrate with concentrated sodium hydroxide solution. chloride
CCI 3CH(OHh + NaOH ---7 CHCl 3 + HCOONa+ H 20 When reduced with zinc dust and water, methane is the
Chloral hydrate main product. '
Note: Chloral hydrate IS a stable compound , CHCl 3 +6H Zn/H 20) CH 4 +3HCl '
inspite of the fact that two -OH groups
are linked to the same carbon atom. This
is due to the fact that intramolecular
hydrogen bonding exists in the
molecule between chlorine and
q"Cl7
C
I __ --~H~
C-C
---- H
0
H
0 presenc~
, , Methane
(iii) Chl~rinatio.. : Chloroform reacts with chlorine in
of diffused sunlight or UV light to form carbon
tetrachloride.
hydrogen atom of -OH group.
404 G R B Organic Chemistr)! (or Competitions
H~:
phenol when heated in presence of sodium hydroxide or
H-C~§:t~~?H(aq.) -3NaC\
OH]
potassium hydroxide. The product formed is salicylaldehyde.
[
<
0
I:I_C<O NaOH) H-Cf',
-H20 Phenol a-Hydroxy benzaldehyde
OH . ONa (Salicylaldehyde)
Fomnc acid Sodium formate
+ 3NaCI + 2H20
. Hydrolysis
[So, CHCl 3+ 4KOH(aq.) ' ) HCOOK + 3KCI + 2H 20] (x) C~rbylamine reaction (isocyanide test): This
(v) Nitration': The hydrogen of the chioroforrrl is reaction is actually a test of primaryamines. Chloroform,
replaced by nitro gr~up when it is trea~ed with concentrated \\h~n . heated with primary amine in presence of alcoholic
nitric acid. The product formed is chloropicrin or trichloro potassium hydroxide forms a derivative called isocyanide
nitro methane or nitro chloroform. It is a liquid, poisonous and (carbylamine) which has a very offensive smell.
used as an insecticide and a war gas (tear gas).
C 6H SNH2 +CHC1 3 +3KOH (Warm) C 6 H s NC+3KCI
CHC1 3 + HON0 2 ~ CN0 2Cl 3 + H 20 Aniline Phenyl
Nitric acid Chloropicrin isocyanide
(vi) Heating with silver powder: Acetylene is formed
when chloroform is heated at high temperature;with silver
RNH2 +CHCI 3" +3KOH(alc.) RNC +3KCI
powder. . 1° Amine Carbylaminoalkane
, r--------------~-------: d (Alkyl isonitrile)
H-C~h-·:I::Ji.~g_tJl~+C-H ~ HC=CH + 6AgCI +3H 20
Chloroform ACetylene
. This reaction is also used for the test of chloroform.
(vii) Condensation with acetone: Chloroform (xi) a-Elimination reaction: Chloroform undergoes
condenses with acetone on heating in presence of caustic a-elimination reaction to give dichlorocarbene (singlet) which
alkalies. The prqduct formed is a colourless crystalline solid is a reaction intermediate;
called chloretone and is used as a hypnotic (drug) in
medicine ... CHCl Ale. KOH) :CCl +CI
2
+ HOH
3
"~ Dichloro-
HO>~/CH3
C1 3CH +O=C
.. <
Acetone '
'CH 3
CH 3
(NaOH$
. Cl 3C
L~
CH 3 .
1,1 , I-Trichloro-2-methyl propan-2-o1
(Chloretone)
carbene
Uses: (i) It is used as a solvent for fats~ waxes, rubber,
resins, iodine, etc.
(ii) It is used for the preparation of chloretone (a drug)
and chloropicrin (insecticide).
Mechanism: (iii). It is used in laboratory for the test of primary amines,
iodides and broIT).ides.
(i) CHC1 3 +OH- ~ :CCl3" + H 20
(iv) . It can be used as anaesthetic but due to harmful
(:CCI3" ~ :CCl 2 +CI-) effects it is not used these days for this purpose. It causes liver
damage when inhaled in excess (SO is CC1 4 ).
CH3) A . (v) It may be used to prevent putrefaction of organic
(ii) C . LO materials, i.e., in the preservation of anatomical species.
CH 3 "Tests of chloroform : (i) It gives isocyanide test
, (carbylamihe test).
(ii) It forms silver mirror with Tollens' reagent.
(iii) Pure chloroform does not give white precipitate with
silver nitrate.
Halogenated Aliphatic Hydrocarbons 405
3. Iodoform reactio~: With I~;and NaOH or 12 and Physical properties: (i) It is a colourless liquid having
Na 2C0 3 , the iodoform test is mainly given by ethyl alcohol, characteristic· smell.
(ii) It is non-inflammable and poisonous, It has boiling
°II point 77°C,
(CH 3CH 20H), acetaldehyde (CH3-C-H), a-methyl (iii) It is insoluble in water but soluble in organic
solvents.
°I
ketone or 2:-one (-C-CH 3), secondary alcohols or 2-01
(iv) It is an excellent solvent for oils, fats, waxes and greases.
Chemioal properties: Carbon tetrachloride is less
OH reactive and inert to most organic reagents. However, the
I 'I'
following reactions are observed,
(- CH-CH 3 ) arid secondary alkyl halide at C2 (i) Reaction with steam (oxidation): Carbon
CI tetrachloride vapOurs react with steam above 500°C to form
I phosgene, a poisonous ,gas,
(-CH-CH 3 ). Also lactic acid (CH 3-CHOH-COOH),. Superheated'
CCl 4 + H 20 .) COCl 2 + 2HCI
°I Steam, 500°C Phosgene
pyruvic acid (CH 3'-:""C-COOH), methyl phenyl ketone • (il) Reduction: It is reduced by moist iron filling into
chloroform.
°II
(C6HS-C-CH3) and 2-amino alkanes (R-CH-R) give CCl 4 +2H Fe/H 20) CHCl 3 + HCI
I ,(iii) Hydrolysis: On heating with aqueous potassium
NH2
hydroxide it forms carbon dioxide which combines with
this test. potassium hydroxide to give KCI and potassiulll carbonate
8.8 CARBON TETRACHLORIDE OR (inorganic salts),
TETRACHLOROMETHANE, (CCI 4 ) CCl 4 +4KOH -4KCI) [C(OH)4] -2H20) CO 2
It is the most important tetrahalogen derivative of methane. Unstable
Manufacture: (i) From methane: Chlorination of
2KOH) K C0 + H 0
methane. with excess of chlorine at 400°C yields impure' 2 3 2
carbon tetrachloride, (iv) Reaction with phenol . (Reimer-Tiemann
reaction): It combfues with phenol in presence of sodium
CH 4 + 4Cl 2 400°C) CCl 4 +4HCI
hydroxide .to form salicylic acid,
(Excess)
Metliane used in this process is obtained from natural gas, OH OH
@,COOH
©
(il) From carbon disulphide: Chlorine reacts with
carbon disulphide in presence of catalysts like iron, iodine, +4NaOH
+CC4 )
aluminium chloride or antimony pentachloride.
AlClj or SbCIs Phenol o-Hydroxy benzoic acid
CS 2 + 3Cl 2 ) CCl 4 + S2C12' (Salicylic acid)
(Catalyst) Sulphur
monochloride + 4NaCI + 2H20
S2Cl2 further reacts with CS 2 to form more of carbon (v) Friedel-Crafts reaction: Benzene on treatment
tetrachloride, .
with CCl 4 in presence of anhydrous AICl 3 gives dichloro-
AlCl3 diphenyl methane which on hydrolysis forms diphenyl
. . ) CCl 4 +6S
ketone (benzophenone),
Carbon tetrachloride is obtained by fractional distillation. Anhyd. AlCb 2HOH
It is washed with sodium hydroxide and then distilled to get a 2C 6H 6 +CCI 4 ) (C6HshCCI2 )
Benzene ~,(-2HCl) Dichloro- (-2HCl)
pure sample,
diphenyl methane
(ill) From propane: Propane is reacted with chlorine
at about 400°C and at a pressure of 70 -100 atmosphere,
Heat
C 3Hg +9C1 2 -Pr-es-~ur-e~) CCl 4 + C2Cl 6 +8HCI
Propane Carbon Hexachloro-
tetrachloride ethane Unstable
(Liquid) (Solid)
." ··~/:f~:':;'
Halogenated Aliphatic Hydrocarbons '40('
Uses: (i). It is used as a fire extinguisher under the name (i) Carbon-chlorine bond in vinyl chloride -has some
pyrene. The dense vapours form a protective layer on the double bond character and is, therefore, strongerthallacpure-
burning objects and prevent the oxygen or air to come in single bond... _. ,_ -
contact with the burning objects, hence the room or windows (ii) Carbon atom is sJl-hybridized an<;l ,C-.:.-.clbono
should be well ventilated. . length is shorter ( 1.69 A) and stronger than in alkyl halides,_
(ii) It is used as a solvent for fats, oils, waxes and greases, 0.80 A) due to sp3 -hybridization of the carbon atom. -
resins, iodine, etc. and also in drycleaning.
(iii) It finds use in medicine as helminthicide for Addition Reactions
elimination of hook worms.
CH2Br-CHBrCl
CC4
8.9 UNSATURATED HALIDES 1,2-Dibromo-l-chloroethane
HEr
·
The most common and important members of alkenyl halides CHr--CHBrCl ,
are vinyl chloride and allyl iodide. -l-Bromo-l :chlo~oetliane
CI: . CF
t
1. Vinyl chloride or chloroethene (H 2C=CHCI) H 2C=CHCl- .
Vinyl chloride can be synthesised by a number of methods
described below:
(i) From ethylene chloride: It is easily prepared in the
laboratory by the action of dilute alcoholic solution of
(Vinyl cbloride) Polymerisation
peroxide
NaOI;I
.-
. f . ". I
H 2--CH-CH2-CH
..... ,.
Polyvinyl chloride (PVC)
No reaction .
n
..
. . .
potassium hydroxide on ethylene chloride. .
The main use of vinyl chloride is in the manufacture of
CH 2CI CHCI polyvinyl chloride plastic which is employed these days for
I + (Alc. ) KOH --:--7 II +KCI+H 20 making synthetic leather goods, rain coats, pipes" floor tiles,_
CH 2CI CH 2 gramophone records, packaging materials, etc.
Ethylene chloride Vinyl chloride
2. Allyl Iodide or 3-Iodoprop-l-ene (lCH 2CH=CH 2)
Vinyl chloride can also be obtained from ethylene It is obtained:
chloride by thermal decomposition at 600-650°C. (i) by heating allyl chloride with sodium· iodide :in
CH 2CI CHCI acetone. Allyl chloride required in, the reaction is' prepared
I ~ I +HCI . either by chlorination of propene at 500°C or by action of
CH 2CI CH 2 PCl 3 on allyl alcohol.
(ii) From ethylene: Free radical chlorination of CH 3C:ij=CH 2 +C1 2
--ethylene at 500°C yields vinyl chloride. Propene
(\ n· - +
CHOH + 3- HI
I
CH20H
-3H20
CHI
CHiI
I -Heat·
-12
Problem 3.· (a) Give simple test to distinguish among (d) A leaving group must be a weak base: The leaving
hexane andCH 3-CH=CHC1. -OH group of alcohols in neutral or alkaline solution would
(b) Give simple test to distinguish among be stronger base, hence cannot be.removed by weaker bas~s
CH 3-CH=CHCI, CH 3CH 2CH 2CI and CH 2=CH-CH 2Cl. like cr, Br- ,r.
Solution: (a) Hexane and methyl vinyl chloride are Problem 5. A halide, CsHu X, on treating with ale.
distinguished by adding bromine in CC1 4 to each. The red
KOH gives only pent-2-ene. What is halide? .
brown bromine colour persists in alkane but disappears in
Solution: Two possible halides which on elimination
methyl vinyl chloride.
ofHX can form pent-2-ene are:
(b) H 2C=CH---:CH 2Cl is an allylic chloride (The Cl is
very reactive). This reacts rapidly with AgN03 in the cold to CH 3CH 2CH 2CHXCH 3; CH 3CH 2CHXCH 2CH 3
(I) (II)
give a white ppt. of AgCl. CH 3CH 2CH 2CI gives white ppt.
when warmed with AgN03 as it is comparatively less The (II) structure being symmetrical gives only
reactive. CH 3-CH=CHCI is inert and does not form wp.ite pent-2-ene on elimination of HX
ppt. with AgN03' . CH3CH2CHXCH2CH3 Ale. KOH) CH 3CH=CHCH 2CH 3
Problem 4. Give reasons for the following: Pent-2-ene
(a) Potassium cyanide reacts with R-X to give alkyl Thus, the halide is 3-halopentane.
cyanide, while silver cyanide forms an isocyanide as a major
Note: Tbe structure (I) forms a mixture,
product.
CH3CH2CH=CHCH3 and CH3CHiCH2CH=CH2'
(b) Silver nftrite reacts with R-X to give a mixture of (Major product) (Minor product)
nitroalkane and alkyl nitrite.
(c) :ROH does not react with NaQr but on adding H 2 S0 4, Problem 6. A ·white preCipitate was formed slowly when
it forms RBr. AgN03 is added to a compound (A) with molecular formula
(d) Alcohols do not undergo substitution in neutral Dr C 6 H 13C1. Compound (A) on treatment with hot alcoholic KOH
alkaline s o l u t i o n . ' gave a mixture of two isomeric alkenes (B) and (C) having
Solution: (a) Potassium cyanide is an lomc formula,C 6 H 12 • The mixture of (B) and (C) on ozonolysis
compound, K+[:C==N:r and provide cyanide ions in fornished four compounds.
solution, in which each of carbon and nitrogen carry a lone (i) CH 3CHO, . (ii)C 2 H sCHO,
pair of electrons [CN is an ambident nucleophile (ligand)]. (iii) CH 3COCH 3• (iv) (CH3hCHCHo.
As lone pair on carbon is more reactive, the carbocation, What are (A), (B) and (C)?
R +, preferentially attacks the carbon atom and thereby forms
an alkyl cyanide predominantly. Solution: Alc.KOH) (B) + (C)
HCl
R+ +[:C==N:r ---t R-CN:
Alkyl cyanide The molecular formula of (B) and (C) isC 6 H 12 • Thus, on
ozonolysis of each alkene, the tWo products must have six
On the other hand, AgCN (being insoluble) is a covalent
carbon atoms.
compound and only nitrogen has the lone pair of electrons.
One alkene gives CH 3CHO and (CH3 hCHCHO. Thus,
Thus, carbocation attacks through nitrogen and thereby forms
the hydrocarbon should have the structure,
an alkyl isocyanide as a major product.
CH 3CH=CHCH(CH 3h ... (B) ,
Ag-C==N: +RX ---t RNC: +AgX·
r
Other alkene gives C 2H sCHOand CH 3COCH 3 • Thus, the
hydrocarbon should have the
structure,
..
C 2H sCH=C(CH 3h ... (C)
(b) The rutrite ion [:N<: has two nucleophilic Since (B) and (C) are formed from (A) by dehydro-
halogenation, the structure of (A) is:
sites, i.e., N and either of the oxygen atoms. The carbocation CH 3CH HCH(CH 3 )2
2T
can attack either N or 0, thereby forming a mixture of
nitroalkane, R-N0 2 and alkyl nitrite, R-ONO. CI
3-Chloro-2-metbyl pentane
(c) Br - ion is a very weak Bronsted base and thus, it can
not· displace the strong base -OH-. When H 2S0 4 acid is Alc.KOH
CH 3CH 2CHCH(CH 3 h ) CH 3CH=CHCH(CH 3 h
+
added, H+ are available which form ROH 2 • Under this I (B)
CI
condition, Br - displaces H 20 which is a very weak base.
+CH 3CH2CH=C(CH 3 h
+ (C)
ROH 2 +Br- ---t R+ +H 20+Br- ---t RBr+H 20
As it is 2° halide, it slowly reacts with the AgN03 to form
white ppt. .
Halogenated Aliphatic Hydrocarbons 411
Problem 7. How many isomers are possible forC 4 H g F2 . reagents are very reactive and used as synthetic reagents for the
and give their IUPAC names?· synthesis of alkanes, alcohols, aldehydes, ketones, acids, etc.
Solution: n-Butane can have· two possible gem- Organometallic compounds are prepared from the
difluoro isomers: respective alkyl or aryl halides in solvents like ether. These
F2 CHCH2CH 2 CH3 CH3 CF2 CH2CH 3· compounds are mostly colourless, mobile liquids having low
l,l-Difluorobutane 2,2-Difluorobutane
boiling points and are generally very unstable. A number of
these compounds bum violently in air and are readily
There are four isomers with two fluorine on different
decomposed by water and alcohol.
carbon atoms:
Grignard reagents are prepared by. the action of alkyl
FCH2 CHFCH 2 CH3 CH 3 CHFCHFCH 3 halides on dry magnesium turnings in presence of dry
1,2-Difluorobutane (vic) 2,3-Difluorobutane (vic)
alcohol-free diethyl ether. The ether solution of the Grignard
F'"':H 2 CH 2CHFCH 3 FCH2 CH2 CH 2CH2F reagent is used immediately in the apparatus in which it has been
1,3-Difluorobutane 1,4-Difluorobutane prepared. Dry ether dissolves the Grignard reagent through
The; ~obutane can have three possible difluoro isomers: solvolysis.
FCH2-CF-CH 3 F2CH-CH-CH 3 FCHz-CH-CH2F C2HS R C2H 5
I . 1 I 1 1 I
CH3 CH3 CH3 :0: ' ~Mg ~ :0:
1,2-Difluoro-2-methyl l,l-Difluoro-2-methyl 1,3-Difluoro-2-methyl 1
C2H 5
I 1
C2H 5
propane (vic) propane (gem) propane X
Problem 8. Give the structures of two different alkyl Grignard reagents are. never isolated in free state on
bromides both of which yield the indicated alkene as the account of their explosive nature.
exclusive product of E2 elimination: Note: (i) For a given alkyl radical, the ease offonnation of a Grignard
(a) CH 3CH=CH 2 (b) (CH3hC=CH2 .reagent is,
(c) BrCH=CBr2 . Iodide >' Bromide > Chloride
Br Usually alkyl bromides are used.
(ii) Addition reactions with compounds con,taining the CH3 - Li + HOH --+ CH 4 + LiOH
following groups. .
CH3-Li + CH2"':""CH 2 --+ CH 3CH 2 CH 2 0Li
)C=O, -C N, )C=S
In each case, alkyl group attaches to carbon atom and
"'cI·
MgX part to the oxygen, nitrogen or sulphur atom.
'HLOH'
> c=o+ RMgX --+)f-oj MgX --+ >f~OH o
R R CH3-Li+ CO 2 --+
II H 20
CH3-C-O-Li ---=-t CH3 COOH
OH +LiOH
+Mg< CH3-Li+H-f=O --+ CH3CH2 -O-Li
X
H
Hi OH 1
RMgX --+ -C=: Ni MgX --+ -c=o H 20) CH3CH 2 0H + LiOH
I O:H:2' . I
R .
I
. R Unlike Grignard reagents, alkyl lithium can add to an
alkenic double bond.
OH
R-Li + CH 2=CH 2 --+ R-CH 2 -CH 2-Li
+NH3 +Mg<
X Dialkyl zincs: These were the first organometallic
compounds discovered by Frankland.
The addition products decompose with water or dilute These can be prepared by heating alkyl iodide with zinc in
acid. These type of reactions are given by molecules such as an atmosphere of CO 2 ,
02' CO 2 , etc.
Alkyl Iithiums: Organo-lithium compounds are lIeat lIeat·
2RI+2Zn ~ 2R-Zn-I ~ R 2 Zn +ZnI2
prepared by the action of alkyl halides with lithium metal in CO 2 Alkyl zinc iodide CO2 Dialkyl zinc
dry ether at low temperature in the presence of an inert·
atmosphere of nitrogen. Owing to the difficulty in handling and better synthetic
reagents are known, their use is restricted to the following
CH3I + 2Li Et~er) CH3Li + Lil preparations:
Methyl iodide -10 C Methyl lithium (i) Prepamtion of quaternary hydrocarbon such ~s .
neopentane.
Alkyl iodides and alkyl bromides usually undergo Wurtz
reaction. Alkyl chlorides are usually used and they give good (CH3 h Cel + (CH 3 )2 Zn --+ (CH 3 )4 C + CH3 ZnCI . ..
Tert. butyl Neopentane
yields. . chloride
The high reactivity of organo-lithillm compounds over
Grignafd reagent is due to the greater polar character of C-Li (ii) Preparation of ketones: Acid chlorides reacts
bond in comparison to C-Mg bond. with dialkyl.zinc to fonn ketones;
Genemlly, alkyl lithiums behave like Grignard reagents
R'COCI + R 2Zn --+ R'COR + R-Zn-CI
but are more reactive. They react with compounds containing Acid chloride . Ketone
active hydrogens, aldehydes, ketones, carbon dioxide,
ethylene oxide, etc. .
•
Halogenated Aliphatic lfydrQcarbQns 413
Cl Physical properties: Lower members (CH 3F,CH 3CI, Cl Action of alcoholic Na2S or K 2S or NaSR: Formation
CH 3Br,C 2H sCI) are gases at room temperature while of thioethers (alkyl thioalkane).
CH3I and others are pleasant liquids and higher members Cl Action of NaI in acetone or methanol: Formation of
are solid. R-ar and R-I are heavier than water while alkyl iodides.
R-F and R-CI are lighter than water. Cl Action of alcoholic Na 2S0 3: Formation of sodium
Cl These are slightly soluble in water but completely soluble alkyl sulphonate (R-S03Na).
in organic solvents. Cl Action of sodium diethyl malonate
Cl They burn on copper wire with green edged flame NaCH(COOC2H sh: Formation of alkyl malonic ester
(Beilstein test for halogens). RCH(COOC 2 H sh· .
Cl Boiling points are in the order RI > RBr > RCI > RF, while Cl Action of sodium ethyl acetoacetate,
in a group of isomeric. halides, the order is 10 > 2° > 3° . + _ /COCH 3
Cl ' Boiling points. of organo halogen compounds are Formation of alkyl
NaCH~
comparatively higher than the corresponding
hydrocarbons because of strong dipole-dipole and van der COOC 2 H s
Waals' forces of attraction. acetoacetic
Cl Chemical properties: The high reactivity of R-X can /COCH3
be explained in terms of the nature ofC-:-Xbond which is ester,RCH~
highly polarised because the halogen is more electro- COOC 2 H S
negative than carbon and the dipole moment decreases as
the electronegativity decreases from F to I. Cl Action of sodium azide NaN3: Formation of alkyl
azide, RN 3'
Cl The polarity ofC-Xbond in alkyl halides is responsible
for their nucleophilic substitution reactions, elimination Elimination reactions
reactions and the reaction with metal atoms to form
organo metallic compounds. Cl Dehydrohalogenation of alkyl halides: On heating
with alcoholic KOH, alkenes are formed. This elimination
Cl Chirality has a profound role in understanding the
proceeds by E 1 or E 2 process.
reaction mechanisms of S N I and S N 2 reactions. SN 1
. reactions of chiral alkyl halides are characterised by the. Cl Unimolecular elimination (E 1): The R-X dissociates
first to form carbocation and halide ion.
inversion of configuration while S Nt reactions by
Slow + .:..
racemisation. CH 3-CH-CH3 ~ CH 3-CH-CH3 + CI
,Cl Nucleophilic substitution (S N) reactions of R-X Cb EI Carbocation
R-X + :Nu ----t R-Nu + X-
The 'strong nucleophile (which is also a strong base)
Cl Hydrolysis [action of moist silver oxide (AgOH), or attacks the carbocation to give alkene.
. 'boiling with aqueous alkali (NaOH or KOH) solution]:
+ Fast .
Formation of alcohols. CH3 -CH + yH2 ) CH 3 -CH CH 2 + H-OH
Cl Action with sodium alkoxide (R-ONa) or dry Ag20 : " '-1 OH- (Base) Alkene
Formation of ethers with RONa is known as Williamson's H-.J
synthesis. Cl El involves the formation of most stable carbocation
Cl Action with aqueous alcoholic NaSH or KSH: intermediate due to 1,2-hydride or methyl or phenyl shift
Formation ofthioa1cohols (alkane thiol). . giving unexpected products.
Cl Action with aqueous alcoholic KCN: Formation of o The order of reactivity of alkyl group is 30 > 2° > 10 and the
alkyl cyanides (alkane nitrile) as the major product. most substituted alkene is the Saytzeffproduct and the less
Cl Action with aqueous alcoholic AgCN: Formation of substituted alkene is the Hornann product.
, alkyl isocyanides (carbylamines or isonitriles) as the major I:] Bimolecular elimination (E 2): It involves the
l
product. formation of intermediate TS.
Cl Action of aqueous alcoholic KN0 2 : Formation of
alkyl nitrite as the major product. ~H H B---H H .
Cl Action of aqueous alcoholic AgN0 2 : Formation of ~ I I S- I
Base (OH) + H-C"1.-c-H ~
Slow :
nitroalkanes as the major product. H-C-«-H
Cl Action of aqueous alcoholic NH3: Formation of a I rl [ I :~-
u
mixture of pri-. sec-, tert- amines along with quaternary H "':CI: H :CI:
•• ••
ammonium salts. TS
Cl Action with silver salt of carboxylic acids: Formation Fast .
of esters. ~ BH + H 2C=CH 2+ CI
Cl Action with sodium alkynide (Na-C=C-H): For-
mation of higher alkynes. CI E2 elimination is stereospecific and follows trans-
elimination.
Halogenated Aliphatic Hydrocarbons 415.
o Action oCheat: Alkyl halides ori heating above 300°C carbocation). Anhydrous AlCl 3 (a Lewis acid) generates.
loses a molecule of HX tofonn an alkene. The electrophile.from the reactant. It is thus SE reactio~.
decomposition follows the order: I> Br >CL o Halogenation (Substitution) : Alkyl halides undergo
further substitution (halogenation) in presence of sUnlight,
Miscellaneous (some other) Reactions heat, etc.
o Reduction: R-X on reduction with nascent [H] Bf2 Br2
obtained by ZnlHCI or Nalalcohol or ZnCwCiH50H or C2 HSBr ~h C2H 4Br2 ~ C2H 3 Br3 .••
v hv
LiAlH4 etc. gives alkanes.
CJ Wurtz reaction: An etheral solution of RX (preferably o Oxidation reaction: Primary alkyl halides (1°) on oxid-
bromides and iodides) fonns symmetrical alkanes when ation with dimethyl sulphoxide, (CH3 h SO (DMSO) gives
heated,.with metallic sodium. ' an aldehyde (Swern oxidation) while 2° halides give
o 'Tertiary halides do not undergo this reaction. ketone.
0'
R-~-H,
, Reaction with metals
R-CH2 X DMSO) R2 CHX DMSO) R2 CO
o Alkyl halides fonn Grignard reagents when treated with 00) (CH3hSO Aldehyde (2°) (CH3hSO Ketone
Mg powder in dry ether.
Dry ether Oxidation can also be done with (CH2)6N41H0H, H+
RX + Mg powder ) R-Mg-X
~xidising agent. Benzyl halide on oxidation with
(Reactivity order is RI > RBr > RCI} (CH2)6N41H0H, H+· gives benzaldehyde (Sommelet
o The C-Mg bond is considered to be covaltlll:t but highly aldehyde synthesis).
+ -
polar, the Mg-X bond is ionic (R-Mg-X). The Methods of preparation'of gem-dihalides (Alkylidene
. Mg-metal is bonded in between X and carbon, hence' halides)
nature of~arbon chain does not alter. o From aldehydes and ketones: By the action of PC Is.
o Grignard· reagents find wide applications as the starting o From alkynes: By addition of two moles ofHX (HBr or
material for the preparation of a very large number of HCI).
organic compounds. ,'
o R-X on heating with zinc powder in ether fonns dialkyl Methods of preparation of vic-dihalides (Alkylene
zinc. These are called Frankland reagents. halides) ,
Eth . o From alkenes:· ay the addition of halogens (C1 2 or Br2)'
2C2HsBr+2Zn~ (C 2HS )2Zn + ZnBr2 o From glycols: By the action of PCIs or HCI or SOCI 2.
o Ethyl bromide when heated with sodium-lead alloy gives
tetraethyl lead (TEL) which is used as anti-knock Chemical properties of gem- and vic-dihalides
compound in petroleum products. o Chemically alkylidene (gem-) dihalides are less reactive
Ether while alkylene (vic-) dihalides have nearly the same
4C2HSBr + 4Na(Pb)~ (C2HS )4Pb + 4NaBr+ 3Pb reactivity as alkyl halides.
o R-X forms dialkyl mercury compounds when treated o Hydrolysis with aqueous KOH:· Gem-dihalides give
with Na-Hg. aldehyde or ketones while vic-dihalides give glycols.
o R-X forms alkyl lithiums when treated with lithium in o Action of ale. KCN followed by hydrolysis and
dry ether. ' heat: Gem-dihalicies give monocarboxylic acid while,
o R-Xreacts with lithium dialkyl cuprate (R 2 CuLi) to fonn vic-dihalides give cyclic anhydride.
alkanes (Corey-House synthesis). . These reactions are distinction tests between gem- and
o R-X and aryl halide can react with sodium in presence of vic-dihalides.
ether to fonn substituted (alkylated) benzene o Reaction with Zn dust in methanol: Both gem- and
(Wum-Fittig reaction). vic-dihalides give alkenes.
o Friedel-Crafts reaction: R-X reacts with benzene in o Reaction with ale. KOH (Dehydrohalogenation): Both
prese~ce of anhydrous AICl 3 to fonn alkyl benzenes. .. give alkynes.
R 0' Reaction with sodamide (NaNH2) on heating: Both
give alkynes. •
~o
© 1
' " n hYd.. AIC13
I< ..\ .,. - - - lS::dJ + HX
aldehyde by chlorine. The aldehyde then reacts with D Tests of chloroform: It gives isocyanide test (pungent
chlorine to formtrichloro acetaldehyde (chloral) which on smell). Pure CHCl 3 does not give white precipitate with
hydrolysis with Ca(OHh yields chloroform. AgN03' but with Tollens' reagent, it gives a grey
D From acetone: Acetone first reacts with chlorine to precipitate of silver. On heating with Fehling's solution, it
form trichloro acetone which is then hydrolysed by gives brown precipitate.
Ca(OHh to give chloroform.
D From carbon tetrachloride: By the partial reduction Tri-iodomethane, CHI 3 (Iodoform)
with FeIH 2 0. D Iodoform resembles chloroform in methods of preparation
D From chloral hydrate: Pure CHCl 3 is obtained by and properties.
distilling chloral hydrate with concentrated NaOH D It is prepared by heating compounds like ethanol,
solution. . 2-alkanols and methyl ketones with iodine and alkali
D Properties: Chloroform is a sweet smelling liquid, b.pt. solution or Na 2C0 3.
61°C, non-inflammable but its vapour causes Heat
unconsciousness. CH 3 CH 20H + 412 + 6NaOH~ CHl3 + 5NaI + HCOONa
D Oxidation: When exposed to sunlight and air, it slowly +5H 20
decomposes into phosgene (COCI 2), a poisonous gas.
Such chloroform cannot be used for anaesthetic purpose, Heat
CH3COCH3 + 31 2 + 2Na2C03 ~ CHI 3 + 3NaI
so it is stored in dark blue or brown coloured bottles filled
up to the neck. + CH 3COONa + 2C02
.D It is mixed with 1% C2H sOH which retards the oxidation The reactions producing iodoform are called Iodoform
and converts the phosgene into harmless ethyl carbonate. reactions.
D Properties: It is a yellow crystalline solid, pungent
COC1 2 +2C2HsOH~ (C2HsO)2CO +2HCl characteristic odour, m.pt. 119°C and is steam volatile. It is
Phosgene Diethyl carbonate
used as an antiseptic for dressing wounds.
D Reduction: On reduction with ZnlHCl in presence of D Hydrolysis with KOH: Iodoform gives HCOOK.
alcohol, chloroform forms methylene chloride (dichloro- D Reduction with red PIHI: It gives methylene iodide,
methane). CH 212 ·
But on reduction with Zn dustiH 2 0, methane is the main D Heating with Ag powder: Acetylene is formed.
product. D Carbylamine reaction: With aniline and KOH gives phenyl
D Chlorination: Chloroform reacts with Cl 2 in presence isocyanide, C6HSNC (an offensive smell).
of diffused sunlight or UV light to form CCI 4 • D Heating alone: It gives 12 vapours.
D Hydrolysis with aqueous alkali: It gives NaIK salt of D With AgN03: It gives a yellow precipitate of AgI
formic acid. (difference from CHCI 3).
DNitration: With concentrated HN0 3, chloroform forms D Tests of CHI ~: Iodoform reaction is mainly given by
chloropicrin (nitro chloroform) :which is a liquid, poison-
ous and used as an insecticide and a war gas (tear gas).
o
D Heating with silver powder: Acetylene is formed when II
CH 3CH 20H, CH 3CHO, -C-CH3 group (methyl
chloroform is heated at high temperature. with silver
powder.
D Condensation with acetone: Chloroform condenses ketones), -2-01s (-b:CH3)' secondary alkyl halides
with acetone on heating in presence of alkali to form
chloretone (1,1, I-trichloro-2-methyl propan-2-01) which is
used as a hypnotic (drug).
(-b~-CH3 )'
etc. Lactic acid
o Reaction with sodium ~thoxide: On heating
chloroform with C 2H sONa, it gives ethyl ortho-formate,
HC(OC 2 H s h· [(CH 3CH(OH)COOH)] and pyruvic acid
D Reimer-Tiemann reaction: Chloroform reacts with
. phenol when heated at 65°C in presence of alkali gives
salicylaldehyde (o-hydroxy benzaldehyde) as major
product.
( CH 3 -[-COOHl also gives iodoform reaction.
. D Carbylamine reaction (isocyanide test): Chloroform
on heating with primary (10) amine in presence of Tet~achloromethane, CCl 4 (Carbon tetrachloride):
alcoholic KOH forms isocyanide (carbylamine) having D Preparations-From methane: By chlorination
very offensive odour (a test ofCHCl 3 and also of primary (excess ofCl 2 ) at 400°C. Methane used in this method is
amine). obtained from natural gas.
Halogenated Aliphatic Hydrocarbons ,417
[J From CS z: Chlorine reacts witbCS 2 in presence of [J Preparation: Action ofHF on CC1 4 forms freon-12.'
catalyst AlCl 3 or SbCl s to form sulphur monochloride
CC1 + 2HF SbCIs or SbF3' )CCI F +'2HCL
(S2CI2) and then CCI 4 • 4 22
or SbFs, Catalyst Freon-12
[J From propane: By reacting excess of Cl 2 at 400°C
under atmospheric pressure forms liquid CCI 4 • [J Freon-12 is widely used as refrigerant and propellant in
[J froperties: It is a liquid, b.pt. 77°C, non-inflammable, aerosol sprays of all kinds. Halothane (CF3 CHBrCI) is
hence used as a solvent for fats, oils, waxes and resins, etc. used as inhalation anaesthetic.
It is used as a fire extinguisher under the name pyrene. [J Action ofSbF3 0n CCI 4 :
Reaction with steam (oxidation): CCl 4 reacts with SbCIs "
3CC1 4 + 2SbF3 ~ 3CCl 2F2 + 2SbCl 3
superheated steam at 500°C to form pliosgene, a poisonous
gas.
Reduction: It is reduced by iron filling into chloroform. 6HF+ 2SbCl 3 Heat) 2SbF3 + 6HCl
Hydrolysis with aqueous KOH: It gives CO 2 and then
[J Freon is a gas under ordinary condition. Its b.pt is -29.8°C
KCI and K 2C0 3 • and can easily be liquefied. It is chemically inert.
Reimer-Tiemann reaction: Phenol combines with [J Westron (CHCI 2-CHCI 2) or acetylene tetrachloride:
CCl 4 in presence of alkali to form o-hydroxy benzoic acid
(salicylic acid). , FeCh or
HC== CH + 2Cl 2 ) CHCl 2-CHCI 2
Friedel-Crafts reaction: Benzene on treatment with Acetylene AlCI3,Catalyst' 1,1,2,2-Tetrachloroethane
CCl 4 in presence of anhydrous AlCl 3 gives dichloro-
It is non-:inflammable liquid, b.pt. 'is 146°C and highly
diphenyl methane which on hydrolysis forms diphenyl
toxic in nature.
ketone (benzophenone).
[J Westrosol (CHCl ' CCl 2 ) or Trichloroethene:
Some important halogen derivatives , Heat . ,
CHCl 2-CHCI 2 + Ca(OH)2 ~ 2CHCI=CCI 2 + CaCl 2
[J Chlorofluoro carbons: Freons (CFC's) Westron Westrosol
Freons are small organic molecules containing C, q andF. +2H zO
The most common freons are CF2CI 2, dichlorodifluoro-
methane (freon-12) and CF3 CI, chlorotrifluoromethane [J Both westron and westrosol are used as solvents for oils,
(freon-Il). fats, waxes, resins, paints and varnishes, etc ..
418 G.R.B. Organic Chemistry (Or Competitions
L O'lESTlONS _.
VetY?Short,Jthswer Type (x) Gem dihalides on hydrolysis yield ...... .
(y) Vinyl chloride on reaction with dimethyl copper
1. Fill.in the blanks:
gives ...... .
(a). The compound prepared by the action of magnesium on
(z) Both westron and westrosol are used as ...... for oils,
dry ethyl bromide in ether is known as ...... .
fats and varnishes. .
(b) The interaction of elemental sulphur with Grignard
reagent gives ...... . 2. State, whether the following statements are True or False:
H' t ' , . "H20 ,
m : S + RMgX~ RSMgX ~ .RSH
1
+ Mg(OH)XJ
(a) Alkyl halides follow the reactivity sequence,
[ . Tnoalcohol
" R-I > R-:-Br > R-CI > R-F
(c) Pure chloroform is obtained by heating ...... with
(b) Alkyl halides when treated with dry silver oxide form
aqueous solution of sodium hydroxide ..
alcohols. "
(d) Grignard's reagent has.the general formula: .. , .. .
(c) Carbon tetrachloride is inflammable.
(e) When acetone is heated with bleaching powder ..... .
(d) Alkyl halides are soluble in water.
is oI;otained. " '.
(e) Chloroform gives carbylarnine reaction with primary
(f) A sensitive test of chloroform is based on the formation
arnines.
of ...... .
(t) Westrosol is a very good solvent for fats, oils, waxes,
(g) The yellow precipitate in the r~action of acetone with
resins, etc.
iodine in the presence of alkali is ...... .
(g)' Ethy~ bromide when heated with silver acetate forms
(h) An alkyl halide may be .converted into alcohol
ethyl alcohol.
by. .. . . . reaction:
(h) Polytetrafluoroethylene is commercially known as
(i) The most reactive alkyl halides are ...... .
teflon. .
(j) Another name ofl,I,2,2-tetrachloroethane is ...... .
(i~ Iodoform is a yellow coloured antiseptic compound.
(k) The well known refrigerant freon has the
(J) Pure chloroform gives precipitate with silver nitrate.
structure ...... .
(k) Iodoform when heated with silver nitrate gives yellow
(9 Chloropicrin is formed by . the action of...... on precipitate.
chloroform.
(1) Gem-dihalides on hydrolysis yield aldehydes or ketones.
(m) Carbon tetrachloride is used as fire extinguisher under
(m) The reaction of methyl magnesium iodide with acetone
the name....... .
followed by hydrolysis, gives secondary alcohol.
(n) ~ie~hyl ether is obtained from ethy}.bromide by treating
(n) Chloroform is stored in dark colopred bottles.
1t WIth ...... and the name ofthe reaction is . ~ .... .
(0) Vinyl chloride reacts with dihi~'~NaOH to form vinyl
(0) Chloroform when exposed to light and air forms a
alcohol.
poisonous·.gas known as ...... .
(p) Allyl chloride is more reactive than vinyl chloride.
(p) , Chloroform forms ahypnotic when reacts with ...... .
(q) CCl 4 is more reactive than CHCI 3.
(q) Allyl chloride is a .•.... compound while vinyl
(r) Alcohol is added to chloroform to prevent its oxidation.
chloride is inert towards nucleophilic substitution.
(s) Alkyl iodides are less stable and thus, 'darken on
(r) The dihalides in which halogen atoms are attached to
standing.
adjacent carbon atoms are termed ~s . . . . . . . .
(t) -Acetaldehyde and all methyl ketones undergo \laloform
(s) Alkyl halides are formed when thionyl chloride
test.
and , : .... are refluxed in presence of pyridine.
(u) Alkyl halides react with benzene in presence of
(t) !he order of reactivity (tertiary> secondary> primary)
. anhydrous aluminium chloride to form homologues
1S due to + I effectofthe alkyl groups which ... , .. the
of benzene. This reaction is called, Wurtz-Fittig
. polarity of C~X bond. '
reaction.
(u) The hydrolysis of trialkyl chlorosilane, R3 SiC!, yields
J
(v) (CH3 h CCI is a 3° halide.
(w) Alkyl halides being polar compounds are soluble in
(v) Ethylene chloride on hydrolysis with aq. KOH
water.
forms....... . ,.
(x) Tertiary butyl bromide undergoes S 1 reactions.
(w) When chloroform is heated with primary amine and
(y) Bo~ vic- and gem-dihalides on hea~ng with zinc dust
alcoholic KOB, it forms a. very offensive smelling
in presence of alcohol form same alkene.
compound, the name ofthe compound is ...... and
(z) Pyruvic acid and lactic acid do not give i~doform test.
the reaction is known as ',~ ., . '. reaction.
Halogenated Aliphatic l{vdrocarbons
~CH2-CH=CH2
3. Match the following:
(i) (A) Carbon tetrachloride 1. Antiseptic
(B) Chloretone 2. Refrigerant
(ix) 0 ' +HBr-?
' .
I ,
a
(E) CH 2 CI-CH 2 CL 5. ,Orignard reagent
(F) RMgX 6. CHC1 3 + HN0 3 ' CH3 , lIlT 1000]
4. What is the final product in each reaction? CH3
(xxiiD + HBr i
C2~50H Na~H)
P"""",,.
(i) ?
, Ag IRoorkee 1000]
(ii) CHCl 3 ----; ?
O><
Heat CI
(xxiv) II
?. '
(iii) CHC13 HN0 3)? Br
7. Describe the acti.on of KOH(aq.) on: (b) NaOH(aq.), (c) NH 3 , (d) H 2 S, (e) C6H6 + AlCI 3 ,
(a) CH 3 CI, (b) CH 2 CI 2 , (c) CHCI 3 , (d) CCl 4 (f) C 2 H sONa.
8. How will you synthesise? 11. How will you distinguish between the following?
(a) Isopropyl bromide from n-propyl bromide. (a) Chloroform and carbon tetrachloride.
(b) n-Propyl bromide from isopropyl bromide. [lIi~t : ChlQroform gives carbylamine reaction, i. e., when
(c) Propionic acid from ethyl bromide. heated with aniline and alcoholic KOH, offensive smell
(d) 1-Bromopropane from l-chloropropane. . of isocyanide is produced. CCl 4 does not give this test.]
(e) Ethylene glycol from ethyl chloride. (b) Ethyl.ch·loride and vinyl chloride.
(f) Chloroform from ethyl alcohol. [lIint: Ethyl chloride reacts with alcoholic silver nitrate to give
(g) Iodoform from acetylene. a white precipitate of AgCl. Vinyl chloride does not give
this test.]
. (h) Vinyl bromide from ethyl alcohol.
(c) Alkyl halIde and an alkane.
(i) Allyl chloride from propane.
[Hint: Alkyl halide gives a positive Beilstein test. Alkane does
(j) Methyl iodide from methane. not give this test. Alkyl halide gives a ppt. of AgXwhen
9. Complete the following by providing (A), (B), (C) and (D): warmed with alcoholic silver nitrate solution. Alkane
does not give this test.]
(d) Ethylene bromide and ethylidene bromide.
(e) Chloroform and iodoform.
(B) ~ (e) (D) [lIint : Chloroform is a sweet smelling colourless liquid while
iodoform is a yellow crystalline solid having a pungent
..) CH3 CH 2CH2I
(n Ale. KOH ) (A) H* IH 20 ) characteristic smelL Iodoform gives yellow ppt. with
AgN03 solution. This reaction is not shown by
(B) SOCI 2 ) (e) --~ (D) chloroform.]
12.' (a) Identify the product (A), (B) and (C).
(c) 6 or
N0 2
(ii) In the following pairs of halogen compounds, which
compound undergoes faster S N 1 reaction?
Halogenated Aliphatic Hydrocarbons .' 421
CI CI [Solution: When exposed to sunlight and air, chloroform
(d)~ ~
slowly decomposes into ,phosgene and hydrogen chloride.
and Phosgene is extremely poisonous gas. As topre,vent the
decomposition, it is stored in "dark browocoloured bottle and
CI I % ethyl alcohol is added. This retards' the
decomposition
etc., it is rarely used as anaesthetic these days.] Hence. CI at01n cannot be replaced. Further si-hybridized
(c) Chloroform is kept with a little ethyl alcohol in a dark carbon is more acidic than sl-carbon.
brown coloured bottle. In allyl chloride, SN rea<;tion is easier since allyl carbonium
ion fonned after removal of Cl- is stabilized by resonance.
,422 , (I.R.B. Organic Chemistry jorCompetitions
+
H2C=CH-CH2Cl ,---+ cr + H2C=CH-CHz (0) The fonnation of the products giving the structures of
+
+---7 H2 C-CH =CHz] the intennediates.
H H2
(j) .• Why is free radical halogenation. of alkanes is seldom CC
'/il~ed for laboratory preparation of alkyl halides? Under (i) AA
what condition good yields. of ' monosubstituted 'H2C C OH
chlorides can be obtained? Hz H2
[ Solution: Several isomeric monosubstituted halides are CHZ) "
formed because alkanes have different types of hydrogen
+ I - " CH-'-CH2Cl + etc.
"CHz •
atoms. Their separation is difficult. Thus, free radical
halogenation method' is not used unless the parent
CH3
hydrocarbon possesses equivalent hydrogen atoms. Good H I
yields are obtained - in hydrocarbons such as
CH3 CH 3, (CH3)4C, cyclopropane, etc.]
(k) What effect should the following resonance of vinyl
(ii) .1!9... AA
HzC C CI
(only)
I-
But-3-im-l-ol
distance between positive and negative partial charges
H
increases,] zO
(1) 2-Chloro-3-methylbutane on treatment with alcoholic CI- +
H2C=CH-CH 2CH2CI ~ H2C-'-GHCH 2 CH 2
potash gives 2-methylbut-2-ene as the major product. 4-Chlorobut -l-ene
[ Solution: Elimination occurs in accordance to Saytzeff's and- for the cyclic prol\luct:
rule, i. e., elimination of hydrogen from the carbon which is
+ .---CH2 Cl--;
attached with least number of hydrogen atoms. ' H2 C--'CH ,I ---+
CH3-CJf-'>~CH-CH3 ---+ CH 3-C=CH-CH3 ] --:-"CH2
1\ '1-, , I . , ___ CH
CH3".CI" CH 3 2
' ... _' CIH2C-CH I
Major 'product -, --CH2
(m) Compare the rates of (i) S N I and (ii) S N 2 reactions of
In this reaction, the major product (4-chlorobut-l-ene). is formed by
allyl chloride and n-propyl chloride.
S 2 mechanism. Now the second product is formed by the initial
[ Solution: (i) Allyl chloride' is, much, more reactive than fgrmationof carbocation and attacked by the double bond on the
n-propyl chloride and the +charge of its' intermediate R+ is +ve carbon atom to form a second (cyclic) carbocation, which
. + +.
stabilized by resonance (H zC=CH-CH 2 ~ Hz C ' CH-CH z) twentually gives the product.]
(ii) Allyl chloride is again more reactive but not to the extent of
S I reaction and stabilizes the transition state.]
(n) When CH 3 CH=CHCH zCI reacts with alcoholic
potassium, cyanide, a mixture of isomeric products is
obtained.
[ Solution: It can undergo SN1 and SN 2 reactions.
H2C=CHCH2 CHCI
By SN 2 reaction only one product (A) is folmed. I
(Slow) CH 3
CH 3CH=CHCH2CI + CW --'----'+ 'CH3CH=CH-~H2···CI 4-Chloropent-l-ene
I-Chlorobut-2-ene SN 2 : •
CN In this reaction, the +I effect of CH 3 - group avoids cyclisation.]
By S I reaction, the intermediate is carbocation (resonance stabilized) of the following two reactions:
and ~ give a mixture of two isomeric products (A) and (B~
(Slow) ,
CH3CH =CHCH 2Cl ) (i) @-oNa + CB3Cl or
~I
+ +
CH)CH=CHCH 2
~Fast) 1cwo
~, CH)CHCH=CH z
(Fast) cw 1 (ii) @ - o l + CH30N~
CH 3CH=CHCH zCN CH3 CHCH=CHz] Which one (i) or (ii) is preferred?
, (A) dN [ Solutlon.(O ~Na + CICH ~ 3 @-o-cH3
(8)
Halogenated Aliphatic Hydrocarbons 423
Br
3 (xxiv) ~H
~Cl
2. (a) True; (b) False-form ethers;' (c) False-non-inflammable; 3
(d) False-insoluble; (e) True; (f)'rrue; (g) False-ethyl acetate; 5. (i) CSz + 3Cl z CCl 4 + SzCl z
AlCI )
f(h) True; (i) True; (j) False-does not form precipitate; (k) True; (ii) ~H5NHz + CHCI 3 + 3KOH ~ CJfsNC + 3KCl + 3HP
(I) True; (m) False-tertiary butyl alcohol; (n) True; (iii) C2HsOH + 41z+ 6KOH ~ CHI3+ HCOOK + SKI + SHP
(0) False-does not react; (P) True; (q) False-less reactive; . . . Cl 2
(r) True; (s) True; (t) True; (u) False-Friedel-Craft reaction; (IV) CaOCl 2 + H 20 ~ Ca(OH)z + Cl z ; C2H sOH ~
, . [0]
(v) True; (w) False- insoluble; (x) True; (y) True;
(z) False-undergo iodoform test. CH 3CHO CCl 3CHO . Ca(OHh) CHCl 3 +(HCOO)2 Ca
3. (i) (A~··6); (B-S); (C-7); (0-2); (E-I); (F-4); (G-3).
(ii) (A-4); (8--6); (C-I); (0-2); (E-'-3); (F-S). Cl z CI
(v) C2H sOH '[0]) CH 3CHO ---4 CCl 3CHQ
4. (i) cm 3; (ii) HC=CH, (iii) 'CCI 3NOz, (iv) CHCI 3; (v) C6HSNC, (Chloral)
(vi) CH 4, (vii) HzC=CHCHPH.(viii) No reaction,
(vi) C2HSBr + NaOC2HS ~. CZH SOC 2H s + NaBr
CH:l
(vii) CzHsBr + AgCN ~ C2HSNC + AgEr
I (viii) CCl 3CHO + NaOH ~ CHCl 3 + HCOONa
(ix) CH 3CH 2CH zLi, (x) (CH 3)4C, (xi) ICH2~C-CH2CH3'
. I (ix) CCl 4 + H zF2
SbF3
----'-7 CC1 2Fz + 2HCl
Br
(Freon)
, (xii) BrCH2HC=CH z, (xiii) BrCHz-CHz-CHzBr,
, (x) C zH sNH 2 + CHCl 3 + 3KOH ~ CzHsNC + 3KCl + 3H20
(xiv) R3 -C(CH 3 )z, (xv) CH3CH2~C(CHj)2 (Major),
(xi) CHCl 3 + 4KOH ~ HCOOK + 3KCl + 2H 20
. 1 I
OH OCzH s (xii) C2HSBr + Alc. KOH ~ CZH 4 + KBr + H 20
• (xiii) 2C2HSBr + 2Zn ~(C2Hs)2Zn + ZnBrz
CH 1
1 . H H •
(xvi) CH3-C-CHz-CH3 + CH 3-CH-CH-CH3 , .
(XIV)
I
H-C=O+CH3MgBr ~
I H10H
H-C-O.MgBr ~
H 20
I I I I .
Br CH 3 Br
CH]
(Major) (Minor)
Br CH 3CHzOH + Mg(OH)Br
(xix)
cgr
0 CH-CHZCHJ
I
Br
(Due to 1,2-hydride' shift),
(xvi)
CH 3
CH3~~-CH3
I
Tert.-BuOK'
DMSO ) CH 3-C=CH2
CH3
I
2-Methyl propene
CH 3 CH 3 Cl
1 'I AlCI 3
(xx) CH3-C=C-CH3 (Due to 1,2-methyl shift), (xvii) (CH3)3C-'-Cl + H 2C=CH z ~
CH 3
(CH3)3C-CH2CI:ilCI
1 I-Chloro-3,3-dimethylbutane
(xxi) 'CH~C=CHCH3 (Major),
" 424 G.R.B. Organic Chemistry tor Competitions
(ii) (A) CH 3CH=CH2; (B) CH 3CHOHCH 3; (C) CH3CHCICH 3;
(D) CH 3CH2CH 3 ' '
(iii) (A) CH 3CH=CH 2; (B) CH 3CH 2CH 2Br; (C) CH 3CH 2CH 2I;
(D) CH 3CH 2CH 2MgL,
(iv) (A) CH 3CH(Br)CH=CH 2; (B) CH 2=CH-CH=CH 2;
(C) CH 3CH(Br)CH=CH 2 and CH 3CH=CH-;-CH 2Br
6. (a) C2HSBr + Alc.KOH, (v) (A) CH 3CH 2CH(OH)CH 3; (B) CH 3CH 2CH(Br)CH3;
(b) C2HsBr + Na, (C) CH 3CH=CHCH 3.
(c) CzHsBr + (Aq.)NaOH or C2HSBr + AgOH, (vi) (A) CH 3-CH-Cl; (B) CH 3-CH-NH 2; .
(d) C2HSBr + NapC2H s,
(e) C:zHsBr + CH 3COOAg,
I I
CH 3 ' CH3
(f) CzHsBr + H 2(LiAlH 4 )·
7. (a) CHP + KOH ~ CH 30H + KCI (C) CH,-CH-NC
. I '
.
(b) CH 2Cl 2 + 2KOH -2KCi) CH
OH
Unstable
- H 20) HCHO
2
-H 0) HCOOH
(vii) (A)
CX 0;
CH 3
(Trans-)
Br
Br
.,
(B) (C) a OH
, 'Cl 2
G) CH 4 UV ) CH 3Cl
Nal
Acetone
) CH I
3
9. (i) (A) CH 3CH 2CH 2Br; (B) CH 3CH=CH 2; (C) CH 3CHBrCH 3;
(D) CH 3CHNH 2CH 3 .
14. (i) (a) >= (b) r (c)
!
0
Halogenated Aliphatic Hydrocarbons 425
(ii) (d) +,
CI Because tertiary halide reacts faster
than secondary halide due to greater
stability of tertiary carbocation.
16. C2BrCIFl It has six isomers:
I
448 (A)
Let the formula of the compound be RCIC==CH, i. e., NaNH,
R + 35.5 + 25 = 74.5 '
R = 14(CHz)
The compound is CH2 C==CH (3-Chloropropyne)]
I
CHr -C==C-C2Hs
Lindlar's catalyst
1VJ. .. II CH3CH=CHCzHs
J J
(C) ~i9 (D) Both are
CI Is does not have acidic . Jv~ Cis-form geometrical
hydrogen, so it does not CH3CH=CHC2Hs isomers.
3. An alkyl halide (X) offormula C 6 H 13 CI on treatment with react with Na or fonns Trans-form
potassium tertiary butoxide gives two isomeric alkenes (Y) metal acetylide (E)
and (Z) of formula q,H12 • Both alkenes on hydrogenation S. An organic compound (A), C4 H9CI on reacting with
give 2,3-dimethylbutane. Predict (X), (Y) and (Z). aqueous KOH gives (B) and on reaction with alcoholic
KOH gives (C) which is also formed by passing vapours of
(B) over heated copper. The compound (C) readily
G.R.B. Organic Chemistry for Competitions
decolourises bromine water. Ozonolysis of (C) .gives two be prepared from propyne on treatment with water in
compounds (D) and (E). Compound (D) reacts with NH2 OH presence Of Hg2+ and H2S04 , Identify (A) to (ll) with
to give (F) and the compound (E) reacts with NaOH to give proper reasoning.
an alcohol (G) and sodium s~lt (ll) of an acid. (D) can also
CH 3 CH:i
~ NaOH
(CH3hC=O + HCHO - - _ . . CH)OH + HCOONa
I
[Hint: CH 3-6-Cl Aq. KOH.. CH3-6-OH .
tH ~~
tH (}~~ ~~~.. (D) (E) (0) (H)
3 3 t;.0'"
(AI) (8) ~ O~ NH 20H
. Ale. KOH'
'----'----'-:.;..;..----_lI' (CH 3)2C =CH2 (CH)zC-;--NOH
(C) (F)
6. A 109 mixture of isobutane and isobutene requires 20 g of Now 58 g of.isobutane gives 137 g of tert-butyl bromide
. Br2 (in CC1 4 ) for complete addition. If 10 g of the mixture
:.10.25 g of isobutane gives 13.7 X 10.25 == 24.21 g of tert-butyl
is catalytically hydrogenated and the entire alkane is 58 .
monobrominated in the presence of light at 120°C, which bromide.]
exclusive product and how much of it would be formed? 7. Compounds (A) and (B) on reaction in ether medium and
(Atomic weight of bromine =80)
subsequent acidification and oxidation give 2,5-dimethyl-
[ Hint: Let isobutane be a g and isobutene b g. Thus
hexan~3-one. What are (A ) and (B)?
a+b==lOg
CH3
or H I CI ~ H I ·CI
CH2CH 3 CH 2CH 3
Ten.-butyl bromide (137)
(W) (Y)
Halogenated Aliphatic Hydrocarbons
H
CH 3
~ HI--t---CH2Cl
[~int:R-:-Li + HzO~ . CH3-rH-CHz-CH3 + LiOH
1
CH ZCH 3 CH 3
(Z) lsopentane
R-CI + Na + CI-R ~ CH3CHCHzCHzCH2CHzCHCH3
CH3 CH 3
I. I
or ClCH z ---1---=-- H ~
- tH=CH z
CICH z I
CH2CH 3
II CH)
2,7 -dimethyloctane
CH3
..
428 G.R.B. Organic Chemistry (or Competitions
OBJECTIVE OUESTIONS
SET I: This set contains the questions with single correct answer. (c) very repulsive characteristic odour 0
1. The derivatives not found in nature are: (d) none of the above 0
(a) alkanes 0 (b) carbohydrates 0 12. When the reaction between methyl iodide and sodium
(c) fats 0 (d) alkyl halides 0 ethoxide occurs, we get:
2. C2HSBr can be obtained in the laboratory by the action of (a) methyl acetate 0 (b) ethyl methyl ketone 0
ethyl alcohol with: (c) ethyl acetate 0 (d) ethyl methyl ether ' 0
(a) KBr 0' 13. The bad smelling subs~ce formed by the action of
'(b)NH4Br 0 alcoholic caustic potash on chloroform and aniline is:
(c) Br2 o (a) phenyl isocyanide 0 (b) nitrobenzene 0
(c) chloropicrin 0 (d) acetylene 0
Cd) KBr and conc. H 2S04 o 14•..... would be obtained'by boiling CHCl 3 with caustic
3. The reaction,
soda.
Alcohol + HCI ~ Alkyl halide + H 20 (a) Sodium acetate 0 (b) Sodium formate 0
is reversible. For the completion of the reaction ...... is (c) Sodium oxalate 0 (d) Methyl alcohol 0
used. 15. Heating together of sodium ethoxide and ethyl iodide will
(a) anhydrous zinc chloride .0 give:
(b) concentrated H2 SO4 0 (a) ethyl alcohol 0 (b) acetaldehyde 0
(c) excess of water 0 (c) diethyl ether 0 (d) acetic acid 0
(d) calcium chloride 0 16. Chloropicrin is:
4. Which one is an organometallic compound? (a) picric derivative 0 (b) nitrochloroform 0
(a) C 2H sONa 0 (b) C 2 H s SNa 0 (c) :1itromethane 0 (d) nitroethyl chloride D
(c) C2HSMgI 0 (d) All of these 0 17. CH 3 0H PI3 ) (A) ~ (B) Hydrolysis) (C)
'5. A Grignard reagent is prepared by the action of magnesium in The compound (C) is:
dry ether on: (EAMCET (Med.) 2006; CPMT 2008] (a) CH 3 0H o (b)HCOOH D
(a) C2H s OH 0 (b) C2 H 6 0
o (d) CH 3 COOH D
(c) C 2H s CI 0 (d) C 2H s CN 0
6. Iodoform is formed' on warming iodine and sodium 18. C H SBr KeN) (A) Hydrolysis) (B)
2
, Hel
hydrqxide with:
The compound (B) in above reaction is:
(a) CH 3 0H o ,(b) C2H sOH o (a) ethylene chloride 0 (b) acetic acid D
(c) HCOOH o (d) C2 H 6 o (c) propionic acid '0 (d) ethyl cyanide D
7. Ozone in stratosphere is depleted by: [AIIMS 2004] 19. Which of the following reactions is an example of
(a) C6F6 0 (b) CF2Cl 2 o nucleophilic substitution reaction? [CBSE (Med.) 2009)
(c) C 7 FI6 0 (d) C6H 6 Cl 6 o (a) RX+ Mg ~ RMgX D
8. Chloral is: (b)RX+KOH~ROH+KX CJ
(a) CC1 3 CHO o (b) CCl 3 CH3 o (c) 2RX +2Na ~R-R+2NaX D
o Cd) CCl 3 CH20H o (d)RX+H2 ~RH+HX D
9. The poisonous gas obtained by exposing chloroform to air 20. Chloroform can be obtained from:
and sunlight is: [CPMT 2004) (a) methanol 0 (b) methanal D
Ca) CH 2Cl 2 0 (b) COCl 2 0 (c)propan-I-ol 0 (d)propan-2-o1 0
(c) CH 20 0 (d) CH 3 CI 0 21. When iodoform is heated with Ag powder it forms:
10. Which is the correct formula of bleaching powder? (a) acetylene 0 (b) ethylene 0
[BHU 2005) (c) methane 0 (d) ethane 0
(a) Ca(OCI)Cl o (b) CaO(OCI) o 22. Which one of the following is'gem-dihalide?
(a) CH)CH2Br2 0 (b) CH2Br·CH 2Br 0
(c) Ca(OCI)2 o (d) Ca(OClhCI o
(c) CH 3 CHBrCH 2 Br 0 (d) CH 3 CHBrCH 2CH 2 BrD
n. When chloroform is treated with aniline and potassium
hydroxide we get: 23. Ethylene dichloride and ethylidene chloride are isomeric
(a) sweet odour 0 compounds. Identify the statement which is not applicable
(b) bitter almond odour 0 to both of them:
Halogenated Aliphatic Hydrocarbons 429
(a) they react with alcoholic KOH 0 35. The compound CCl 2 =CHCI is known as westrosol. Which
(b) they are dihalides 0 one of the following statements is wrong regarding this
(c) they react with aq.KOH and give the same product 0 compound?
(d) they respond to Beilstein's test 0 (a) It is obtained by treating westron with Ca(OHh 0
24. A sample. of chloroform before using as an anaesthetic, is (b) It is used as a solvent 0
tested by: [JIPMER 2003) (c) It is used in refrigerators 0
(a) Fehling's solution 0 (d) It is used as a degreasing agent 0
(b) ammoniacal cuprous chloride 0 36. Alcoholic solution of KOH is used for: ..
(c) ammoniacal silver nitrate solution 0 (a) dehalogenation 0 (b) dehydrohalogenation 0
(d) silver nitrate solution after boiling with alcoholic KOH
(c) dehydration 0 (d) dehydrogenation ~ 0
o 37. The reaction,
25. Ethyl alcohol is obtained when ethyl chloride is boiled with:
R-Br + NaCN ~ R-CN+ NaBr, is an example of:
(a) alcoholic KOH 0 (b) aqueous KOH 0 (a) elimination reaction IJ
(c) water 0 (d) H 2 0 2 0 (b) nucleop~ilic substitution 0
26. Which one of the following statements is wrong? (c) electrophilic substitution 0 .
(a) Lower alkyl halides are either colourless gases or (d) oxidation reduction 0
volatile liquids o 38. . ..... is usually added to chloroform to retard its
(b) Alkyl halides are very soluble in water o decomposition.
(c) Alkyl halides burn easily with green edged flame o (a) Ethanol 0 (b) Sodium carbonate 0
(d) The higher alkyl halides are colourless solids o (c) Ethyl chloride 0 (d) Ethyl borate 0
27. Alkyl halides are used for the preparation of: 39. AgN03 does not give precipitate with CHCl 3 because:
(a) alkanes 0 (b) alkenes 0
[BCECE (Med.) 2008)
(c) alcohols 0 (d) all of these 0 (a) AgN03is chemically inert 0
28. A silver salt of fatty acid on heating with alkyl halide gives:
(a) ether 0 (b) alcohol 0 (b) CHCl 3 is chemically inert 0
(c) ester 0 (d) aldehyde 0 (c) CHCl 3 does not ionise in water O·
29. The product obtained when ethyl alcohol is distilled with (d) none of the above 0
bleaching powder is: 40. Teflon is a polymer of:
(a) chloroform 0 (b) ethyl chloride o (a) ethylene 0 (b) vinyl chloride 0
(c) acetaldehyde 0 (d) chloral o (c) acetonitrile 0 (d) tetrafluoro ethene 0
30. Chlorination of CS 2 gives: 41. Which alkyl halide has maximum reactivity?
(a) carbon tetrachloride O. (b) chloroform 0 (a) CH 3 CH2 Br 0 (b) CH3Br 0
(c) both of these 0 (d) none of these 0 (c) CH 3 CH2 CH 2 Br 0 (d) CH3 CH 2 CH 2 CH 2 Br 0
31. Which will be obtained by boiling CH2 Cl 2 with caustic 42. Decreasing order of reactivity of alkyl halide is:
soda? (a)RI>RCI>RBr 0 (b)RBr>RCI>RI 0
(a) Sodium oxalate 0 (b) Sodium acetate 0 (c) RI > RBr > RCI 0 (d) RCI > RBr > RI 0
(c) Sodium formate 0 (d) Ethyl alcohol 0
[Hint: Formaldehyde is the fiFst product which undergoes
43. n-Propyl bromide reacts with ethanolic KOH to form:
Cimnizzaro's reaction to form methyl alcohol and [CET (Karnataka) 2008)
sodium formate] (a) propane 0 (b) propene 0
32. When CCl 4 is boiled with hot ethanolic KOH, the product (c) propyne 0 (d) propanol 0
formed is KCI and: . 44. The. bond angle in carbon tetrachloride is approximately:
(a) formic acid 0 (b) methyl alcohol 0 0018~ 0 0012~ 0
(c) formaldehyde 0 (d) potassium carbonate 0 (c) 109° 0 (d) 90° 0
33. Which one of the following statement is wrong? 45. Ethylidene chloride on hydrolysis with aq. KOH gives:
(a) Iodoform is used as an antiseptic 0 . [JIPMER 2004)
(b) Chloroform can be used as an anaesthetic 0 (a) CH 3 CHO 0 (b) CH 3COOH 0
(c) Chloropicrin is used as an insecticide .0 (c) CHCl 3 0 (d) CH3 CH2 0H 0
(d) Chloretone is used as an antiseptic 0 46. Chloroform on reaction with acetone yields:
34. In the reaction, CH=CH + 2Cl 2 ~ CHCI 2 -CHCI 2 , (a) insecticide 0 (b) analgesic 0
the product is: (c) isocyanide 0 (d).hypnotic 0
(a) called westrosol o 47. The chloro compound which is used as a fire extinguisher is:
(b) used as a solvent o (a) CCl 4 0 (b) CHCl 3 0
(c) used as a fire-extinguisher o (c) CH3 CI 0 (d) COCl 2 0-.
(d) used as an anaesthetic o
G.R.Br Organic Chemisto' (or Competitions
48. I-Chlorobutane when treated with alcoholic potash gives: 61. Which one of the following will produce a primary alcohol
(a) I-butene 0 (b) I-butanol 0 by reacting with CH 3 MgI?
(c) 2-butene 0 (d) 2-butanol 0 (a) Acetone 0 (b) Methyl cyanide 0
49. Which of the following is obtained when chloral is boiled (c) Ethylene oxide D· (d) Ethyl acetate []
with NaOH? 62. Grignard reagent adds to:
(a) CH3 Cl 0 (b) CHCl 3 0 (a) )C=O 0 (b) -C==N 0
(c) CCl 4 0 (d) None of these 0
50. Which of the following will not give iodofonn test?
[CPMT 2004; UGET (Med.) 2007]
(c) )c S 0 (d) all of these 0
(a) HCHO 0 (b) C2H s OH 0 63. For the reaction,
(c) CH 3CHO 0 (d) CH 3 COCH3 0 znX 2
C2 H s OH+HX ~ C2 HSX
51. Butanenitrile may be prepared by heating:
(a) propyl alcohol with.KCN 0 The decreasing order of reactivity of halogen acids is:
(b) butyl alcohol with KeN 0 (a) HI>HCl>HBr 0 (b) HI>HBr>HCI 0
(c) butyl chloride with KCN 0 (c) HCI > HBr > HI 0 (d) HBr > Ill> HCI 0
(d) propyl chloride with KCN 0 64. Which of the following alkyl halide is hydrolysed by SN I
52. A mixture of l-chlorobutane and 2-chlorobutane when
treated with alcoholic KOH, gives: [UGET (Med.) 2008] mechanism?
(a) I-butene 0 (a) (CH 3 hCHX o (b) CH 3 CH 2 X o
(b) 2-butene 0 (c) CH 3CH 2 CH 2 X o (d)(CH3 hCX o
(c) isobutylene 0 65. SN 1 reaction is favoured by:
(d) a mixture of I-butene and 2-butene 0 (a) non-polar solvents 0
53. The reagent used in the conversion of I-butanol to (b) bulky groups on the carbon atom attached to halogen
l-bromobutane is: atom 0
(a) CHBr3 . 0 (b) Br2 o (c) small groupson the carbon atom attached to halogen.
o (d) PBr3 o mom 0
54. Which reagent cannot be used to prepare an alkyl halide (d) none of the above 0
from an alcohol? 66. Only two isomeric monochloro derivatives are possible
(a) NaCI 0 (b) PCls 0 from:
(c) SOCl 2 0 (d) ZnCl 2 + HCI 0 (a) ethane 0 (b) 2,2-dimethylpentane 0
55. 'Ethyl bromide reacts with lead-sodium alloy to fonn: (c) neopentane 0 (d) 2-methylpropane 0
(a) tetraethyllead 0 . 67. An organic halide with fonnula C6H\3Br on heating with
(b) tetraethyl lead bromide 0 alc. KOH gives two isomeric alkenes (A) and (B) with
(c) both (a) and (b) .0 fonnula C 6 'H12 . On reductive ozonolysis of mixture (A) and
(d) none of the above ' 0 (B), the following compounds are obtained:
56. The nature of hydrogen atom in chlorofonn molecule 'is: CH 3COCH3 , CH3 CHO, CH3 CH2 CHO and (CH3 )2 CHCHO
(a) neutral 0 (b) acidic 0 The organic halide is:
(c) basic 0 (dj cannot be predicted 0 (a) 2-bromohexane 0
57. How many structural isomers are possible for C2H4Br2? (b) 3-bromo-2-methylpentane 0
(a) 1 0 (b) 2 0 (c) l-bromo-2,2-dimethylhexane 0
(c) 3 0 (d) 4 0 . (d) none of the above' 0
58. In the preparation of CHCl 3 from ethanol and bleaching 68. (CH 3 h CHCI + NaI ~ (CH3 h CHI + NaCI
powder, the latter provides: The above reaction is known as:
(a) Cl 2 0 (b) Ca(OHh' 0 (a) Finkelstein reaction 0 (b) Stephen's reaction 0
(c) both (a) and (b) 0 (d) none of these 0 (c) Kolbe's reaction 0 (d) Wurtz reaction 0
59. Which of the following processes does not occur during 69. In elimination reactions, the reactivity of alkyl halides is in'
formation of CH~13. from ethyl·alcohol and bleaching decreasing order:
powder? (a) T>S> P 0 (b) P>S>T 0
(a) Oxidation 0 (b) Chlorination 0 (c) S > P > T 0 (d) none of these 0
(c) Hydrolysis 0 (d) Reduction 0 70. Which of the following alkyl halides is hydrolysed by S N 2
60.. Which of the following is' 2° chloride? mechanism? .
(a) Isopropyl chloride . 0 (b) Isobutyl chloride 0
(c) n-Pr9Pyl chloride 0 (d) n-Butyl chloride 0 (a)H2 C=CHCH 2 Br 0 (b)(CH3)3CBr 0
(c) CH3Br 0 (d) None of these 0
Halogenated Aliphatic Hydrocarbons
71. Ethene on treatment with bromine in presence of NaCI (a) nitroalkane only 0
solution gives: (b) alkylnitrite only 0
(a) 1,2-dibromoethane 0 (c) a mixture of nitro alkane and alkylnitrite 0
(b) 1,2-dichloroethane 0 (d) acetylene 0
(c) a mixture of 1,2-dibromo and 2-bromo-I-chloroethanes 84. When ethyl chloride is heated with AgCN, the main product
o is:
(d) no reaction occurs 0 (a) ethyl cyanide 0 (b) ethyl isocyanide 0
72. The non-reactivity of chlorine atom in H2 C=CH-Cl is (c) ethyl amine 0 (d) ethyl nitrate 0
due to: 85. When a solution of sodium chloride containing ethyl
(a) inductive effect [] (b) resonance stabilization 0 alcohol is electrolysed, it forms:
(c) electromeric effect 0 (d) electronegativity . 0 (a) ethyl chloride 0 (b) chloral 0
. 73.· Ethyl orthoformate is formed by heating ...... with sodium (c) chloroform 0 (d) acetaldehyde [J
ethoxide. [DCE 2008] 86. When ethyl alcohol is heated· with a paste of bleaching
(a) HCOOH 0 (b) C 2H s OH 0 powder, we get a compound in which the function of
bleaching powder is:
(c) CHCl 3 0 (4) CH 3CHO 0
(a) as an oxidising agent 0
74. Whathappens when CCl 4 is treated with AgN0 3 solution? (b) as a chlorinating agent 0
(a) N0 2 will be evolved 0 (c) as a hydrolysing agent 0
(b) ~ white ppt. will be formed o (d) as chlorinating, oxidising and hydrolysing agent 0
(c) CCl 4 will dissolve in AgN03 solution o 87. Which of the following will not give iodoform test?
[UPSEAT 2004]
(d) No reaction takes place 0
75. Iodoform can be prepared in the laboratory by the action of
(a) Isopropyl alcohol 0 (b) Ethanol 0
iodine on sodium carbonate solution having: (c) Ethanal 0 (d) Benzyl alcohol 0
88. Which is detected by carbylamine test?
(a) ethanol 0 (b) ether 0
(c) acetone 0 (d) acetic acid 0 (a) H 2NCONH2 0 (b) CH3CONH2 0
76. Haloform reaction is used for preparing: (c) C2HSNH2 0 (d) All of these 0
(a) halogens 0 (b) alkyl halides 0 89. Terminal dihalides on heating with zinc and methanol, we get:
(c) CCl 4 0 (d) ·CHCI 3 0 (a) alkenes 0 (b) cycloalkanes 0
77. Upon reduction, iod9form yields as the first product: (c) alkynes 0 (d) alkanes 0
(a) methane 0 (b) methylene iodide 0 90. When an alkyl halide reacts with alcoholic potassium
(c) ethane 0 (d) mono-iodorflethane 0 hydroxide to form an alkene, the reaction is called as:
78. Chloroform on reduction with zinc and water gives: (a) dehydrohalogenation reaction 0
(a) acetylene 0 (b) ethylene 0 (b) elimination reaction 0
(c) ethane 0 (d) methane 0 (c) increase in unsaturation 0
79.. When carbon tetrachloride is reduced with Zn and H 2S04 ~d~~~~ 0
91. Tert. butyl chloride preferably undergoes hydrolysis by:
in alcoholic solution, it forms:
[DCE 2008]
(a) CH3CI 0 (b) CHCI 3 . o (a) S ~ I mechanism 0 (b) S N 2 mechanism 0
(c) C2Hs CI 0 (d) Cl 2 o
(c) any of (a) and (b) 0 (d) none of these 0
80. Pure chloroform may be prepared by:
92. Alkyl halide reacts with· alcoholic potassium hydrogen
(a) chlorination of methane o sulphide to form:
(b) partial reduction of CCl 4 o (a) alkanethiol 0 (b) thioether 0
(c) the action of bleaching powder and alkali on ethanol 0 (c) thioacid 0 (d) alkane 0
(d) distilling chloral hydrate with conc. aqueous alkali 93. Alkyl halide when heated with alcoholic solution of
solution 0 potassium sulphide, it forms:
81. When iodoform is heated with silver nitrate solution, we
(a) thioalcohol 0 (b) thioether 0
get:
(c) thioacid 0 (d) alkane 0
(a) a yellow ppt. of AgI 0 (b) a white ppt. of Agel d 94. The aliphatic halide which is used for the preparation of
(c) silver mirror 0 .(d) no precipitate 0 synthetic rubber, plastics and resins is:
82. When pure chloroform is shaken with silver nitrate solution,
(a) chloroform 0 (b) carbon tetrachloride 0
we get:
(c) allyl iodide 0 (d) vinyl chloride 0
(a) no precipitate 0 (b) a yellow ppt. of AgI 0 95. The antiseptic action of CHI 3 is due to: .
(c) a white ppt. of AgCI 0 (d) acetylene is liberated 0
83. When alkyl halide is heated with an aqueous ethanolic (a) iodoform itself 0
solution of silver nitrite, it gives: (b) liberation of free iodine 0
. 432' G.R.B. Organic Chemistry for Competitions
(c) partially due to iodme and partially due to CHI 3 itself (a) Carbylamine reaction 0
o (b) Cannizzaro's reaction 0
(d) none of the above o (c) Wurtz-Fittig reaction D
96. Which of the following is not an industrial solvent? (d) Reimer-Tiemann reaction 0
(a) CHCl 3 0 (b) CHI3 o 106. Which of the following compounds will give a yellow
(c) CCl 4 . 0 (d) (C 2H S h ° o precipitate with 12 and alkali?
(a) Acetophenone
IUPSEAT 2003]
0 (b) Benzophenone 0
97. The reaction conditions leading to the best yield ofC 2H s CI
(c) Methyl acetate 0 (d) Propionaldehyde 0
are:
+ Cl 2 ) (B)
o Sun light
Dark, Room temp. The product (B) can be used as a:
) o (a) fire extinguisher 0 (b) solvent o
.
(c) C 2 H6 +CI 2 (excess)
'UVlight
) o (c) insecticide 0 (d) all of these o
lOS. CH C=CH Dil. H2S0 4 ) (B) CHCI 3) (C)
(d) C2 H 6 +C1 2 UVligbt) o ,3 (HgS04) (NaOH)
9S. Arrange the following in order of their decreasing acid Compound (C) can be used as:
strength: (a) an anaesthetic 0 (b) an insecticide 0
(a) HCIO> HCI02 > HCI0 3 > HCI04 0 (c) a solvent 0 (d) a hypnotic 0
(b) HCI0 4 > HCI0 3 > HCI0 2 > HCIO 0 109. Treatment ofNH3. with excess of ethyl chloride gives:
(c) HCIO > HCIO 4> HCI0 3 > HCI0 2 0
(a) diethylamine 0
(d) HCI04 > HCIO> HCI0 2 > HCI0 3 0 (b) ethane 0
99. With conc. nitric acid, the chloroform forms a compound (c) tetraethylammonium chloride 0
which is used as an: (d) methylamine 0
(a) anaesthetic 0 (b) antiseptic 0 110. Chloropicrin is obtained by the reaction of:
(c) insecticide 0 (d) antiknock compound 0 [eBSE (Moo.) 2004; UGET (Med.) 2007]
100. The order of reactivity of alkyl halides depends upon: (a) steam on carbon tetrachloride 0
(a) nature of alkyl group 0 (b) nitric acid on chlorobenzene 0
(b) nature of halogen atom 0 (c) chlorine on picric acid 0
(c) nature of both alkyl group and halogen atom 0 (d) nitric acid on chloroform 0
(d) none of the above 0 111. Isobutyl magnesium bromide with dry ether and absolute
101. I-Bromopropane and 2-bromopropane on treatment with alcohol gives:
sodium in presence of ether gives: .
(a) (CH3 hCHCH 20Hand CH3CH2 MgBr 0
(a) n-hexane 0
(b) (CH3 h CHCH 2 CH 2 CH 3 and Mg(OH)Br 0
(b) 2,3-dimethylbutane 0
(c) 2-methylpentane 0 (c) (CH3 hCHand CH 3CH 2 0MgBr 0
(d) a mixture of all these different alkanes ' 0 (d) (CH 3 h CH, H 2 C=CH2 and Mg(OH)Br 0
102. Compound C4 H s Cl 2 (A)on hydrolysis gives a compound 112. Which of the following is an organometallic compound?
C4 H s O(B) which reacts with hydroxylamine and does not (a) Lithium methoxide 0
give any test with Tollens' reagent. What are (A ) and (By? (b) Lithium acetate 0
(a) 1,I-Dichlorobutane and butanal 0 (c) Lithium dimethylamide 0
(b) 2,2-Dichlorobutane and butanal 0 (d) Methyl lithium 0
(c) l,l-Dichlorobutane and butan-2-one 0 113. Which of the following will give a yellow precipitate with
(d) 2,2-Dichlorobutane and butan-2-one 0 12 /NaOH?
103. Seqondary butyl chloride on boiling with alcoholic potash gives: (a) ICH 2 COCH 2 CH3 0
(a}'-only I-butene . 0 (b) CH3 COOCOCH3 0
(b) only 2-butene 0 (c) CH3 CONH 2 0
(c) isobutylene 0
(d) CH3 CH(OH)CH2 CH3 0
(d) a mixture of I-butene and 2-butene 0
104. Which one of the following compounds is stable? 114. Which of the following will react with water?
(a) CH3 CH(OHh 0 (b) (CH3 h CH(OH)2 0 (a) CHCl 3 D (b) Cl 3 CCHO 0 .
(c) CCI 3 CH(OHh 0 '(d) None of these 0 (c) CCl 4 0 (d) CICH2 CH2 CI 0
105. Chloroform on treatment with phenol in presence of caustic
alkali forms salicylaldehyde. This reaction is known as:
. .
Halogenated Aliphatic Hydrocarbons 43~
D (b) CH~Br
D (d) CH3F
[AFMC 2005]
(a) anhyd. AICl 3 o (b) FeCl 3 o (a) CH3~H(Br)CH3 o (b) CH3CH 2 CH2 Br 0
(c) anhyd. ZnCl 2 o (d) Cu o (c) H2 C=CH-Br o (d) BrCH=CH-CH3 0
147. The major product in the following reaction is: 157; A compound (A) CSHlOCl2 on hydrolysis gives CSHIOO
. Aq.KOH which reacts with NH 20H, forms iodoform, Qut does not
CH3CH(CI)CH 2 CH 2 0H ) (AIIMS 2006] give Fehling test; (A) k .! .. ,
(a) CH 3CH=CHCH 2 0H o [DPMT 2005; MGIMS (Wardha) 2006]
(b) H 2 C CHCH2 CH 2 0H o
(c) CH3 CH-CH 2 o o
. I I
O--CH 2
(d) CH 3CH(0H)CH 2 CH 20H o
148. Which can \mdergo halo~orm reaction? (DCE 2006)
(a) (CH3)~C-OH 0 (b) (C 2Hs hC=0 0
(c) Acetophenone 0 (d) Benzophenone 0
149. Which of the following is a primary halide?
[PMT (Haryana) 2006; AIIMS 2008] o
(a) Is~propyl iodide 0
(b) Secondary butyl iodide 0
(c) Tertiary butyl bromide 0
(d) Neo hexyl chloride 0 o.
150. Among the halogens, the one which is oxidised by nitric
acid is: [AMU (Engg.) 2006] 158. Match List I with List II and pick the correct matching from
(a) fluorine 0 (b) iodine 0 the codes given below: (PMT (Kerala) 2006] .
(c) chlorine 0 (d) bromine 0 List I . List II
151. Freon used as refrigerant is: (Haloalkane/arene) (Applications)
[BHU (Screening) 2006; AFMC 2006] . A. Iodofolm 1. CF4
(a) F2C CF2 0 (b) CH2F2 0 B. BHC 2. Antiseptic
(c) CCl 2 F2 [J (d) CF4 0 C. Freon~14 3. Moth repellent
152. Which of the following is formed· when. the product of D. Halothanes . 4. Inhalative anaesth~tic
oxidation of chloroform is treated with ethyl alcohol? E. p-Dichlorobenzene 5. Termite pesticide
(EAMCET (Merl.) 2006]
(a) A-2,:8-4, C-5, 0-3, E - I 0
(a) Ethyl chloride .0 (b) Ethyl carbonate 0
(b) A-2, B-5, C-I, 0-4, E-3 0
(c) Chloral hydrate 0 (d) Chloral 0
(c) A-3,:8-4, C-2, D-I, E-5 0
153. Which of the following is added to chloroform to slow
(d) A-I, B-3, C-5, 0-2~E-4 0
down its aerial oxidation in presence of light?'
(e) A-5,:8-4, C-3, D-2, E-l 0
[EAMCET (Engg.) 2006; AFMC .2008]
Ale. KCN Dil. HCI .
(a) Carbonyl chloride 0 (b) Ethyl alcohol 0 159. In the reaction, RX ) {A)---? (B);
(c) Sodium hydroxide O· (d) Nitric acid 0 the product (B) is: (KCET 2006]
154; Ethyl chloride reacts with sodium ethoxide to form a (a) alkyl chloride 0 (b) aldehyde 0
compound 'A'. Which of the following reactions also yields (c) carboxylic acid 0 (d) ketone 0
'A'? (EAMCET (Engg.) 2006; AFMC 2008]
160. A compound called chloral whose formula is C2Cl 30H is
(a) C2Hs CI,KOH(alc.), A ·0
alan: [BHD (S) 2006] .
(b) 2C 2 Hs OH, conc. H2 SO4' 1400 C p (a) aldehyde 0 (b) alcohol 0
(c) C2H sCI, Mg (dry ether) • 0 (c) ketone 0 (d) alkanoyl chloride []
o 161. Which of the following haloalkanes is most reactive?
155. Maximum number of molecules of CH3 I that can react with . [GGS Indraprastha Univ. (Engg.) 2006]
(a) I-Chloropropane 0 (b) I-Bromopropane 0
a molecule of CH 3 NH2 is: (MGIMS (Med.) 2008]
(e) 2':Chloropropane 0 (d) 2-:Biomopropane. 0
(a) 3 0 (b) 4 0
162. In the ch~mical reaction,
(c) 2 0 (d) 1 n CH 3CH 2NH 2 + CHC1 3 + 3KOH---4 (A)+ (B)+3H 2 0
.
(a) (i), (ii) and (iii) 0 (bY (i) and (iii) 0 186. Methyl bromide reacts with AgF to give methyl fluoride and
(c) (ii) and (iii) 0 (d) (i) only 0 AgBr. This reaction is called: IPMT (Kerala) 2010]
(e) (i) and (ii) 0 (a) Finkelstein reaction 0 (b) Fittig reaCtion '0
178. The best method for the conversion of an alcohol into an (c) Swarts reaction D· (d) Wurtz reaction 0
alkyl chloride is by treating the alcohol with: (e) Wurtz-Fittig reaction 0 .
[CET (Karnataka) 2009] 187. Chemical fonnula of phosgene is : [AFMC 2010)
(a) PCls 0 (a) COCl 2 0 (b) CaOCI 2 · 0
(b) SOCl 2 in presence of pyridine 0 (c) CaC0 3 0 (d) COCI 0
(c) PCl 3 0 188. In the following reaction, . "
c5
(d) dry HCl in presence of anhydrous ZnCl 2 0
179. Which of the following on heating with aqueous KOH
produces acetaldehyde? IAIEEE 2009]
(a) CH 3 COCI 0 (b) CH 3 CH2 CI 0 The major product obtained is : [AMU (Med.) 2010]
(bla
(c) CH2 CICH zCI 0 (d) CH 3 CHCl z 0 CH2Br
180. Consider the
. .'
C2 H sCI + AgCN
follow~ng reaction:
EtOH/H 20 · .
) X (major)
which one of the following statements is true for X ?
6
(a) o
Br
o
r
0 (d)&. Br
o
(d) It has a cyanide group 0 189. If 1,3-dib~opropane reacts with zinc and NaI, the product.
181. An organic compound on heating with CuO produces CO 2 obtained IS : . [AFMC 2010]
but no water. The organic compound may be: (a) propene .0 (b) propane 0
ICET (Karnataka) 2009] . (c) cyclopropane 0 (d) hexane 0
(a) chlorofonn 0 (b) ethyl chloride 0 190. Chronic chloroform exposure may cause damage to liver,
(c) methane 0 (d) carbon tetrachloride 0 and kidney, due to the formation of :
182. Which one of the following does not undergo iodofonn [PMT (Kerala) 2010)
reaction? ICET (J&K) 2009] (a) phosgene 0 (b) methylene chloride 0
(~) Secondary butyl alcohol 0 (c) methyl chloride 0 (d) carbon tetrachloride 0
. (b) Iso propyl alcohol 0 (e) phosphoryl chloride 0
(c) Diethyl ketone 0 191. The correct order of reactivity of the halides, ethyl chloride
(d) Ethyl a l c o h o l ' 0 (I), iso-propyl chloride (II) and benzyl chloride (III) in S N 1
183. An ethereal solution of alkyl halide is heated with sodium reactions is: [PMT (Kerala) 2010)
metal. The reaction is l\nown as: IPMT (AMU) 2009] (a) III> II > I 0 (b) I> II> III 0
(a) Frankland's reaction 0 (b) Sandmeyer's reaction 0 (c) II > I > III 0 (d) I > III > II 0
(c) Wurtz-Fittig reaction 0 (d) Wurtz reaction 0 • (e) III> I> II 0
184. For the following reaction, 192. The order of rate of hydrolysis of alkyl halides 1°,2°,3° and
I'--.... (i) Mg, Et20 CH 3 X by the S N 2 pathway is.: [DUMET 2010)
V-Br >[A],
(ii) co 2 , (iii) H30+ (a) 1°> 2° > 3° > CH 3 X 0 (b) CH3 X > 3° > 2° > 1° 0
product [A] is: /pMT (AMU) 2009] (cl CH 3 X > 1° > 2° > 3° 0 (d) 3°> 2° > 1° > CH 3 X 0
Set II. This set contains questions with two or more. correct answers.
(a) [>-cOOH 0 (b) ([>-c00)2Mg [J
193. The compounds used as refrigerant are:
o (a) NH3 O. (b) CCl 4 0
(c)~~ ~./"1 o (d) [> o (c) CF4 0 (d) CF2 Cl 2 0
(e) CH2 F2 0
185. Which of the following IS the least reactive towards 194. Which of the following chemicals are used as moth repellents?
nucleophile? [PMT (Kerala) 2010]
CI
(a) CH 3 CH 2 CI
(c) H 2 C=CH-CH 2 CI
0 (b) CH3 CI
0 (d) C6 H sCI
0
0
(a)
Cl
;§r
0 o (b) Perch,oroethane o
(e) CH3 CH(Cl)CH3 0
G.R.B. Organic Chemistryfor Competitions
OO
(c)CHCI3 o (d) ····I~
. o
(a) Chlorinating agent 0 (b) Oxidising agent
(c) Hydrolysing agent 0 (d) None of these
0
0
~ # 199. Select the correct statement among the following:
195. Which of the following compounds will give iodoform test (a) S N 1 reactions involve two steps 0
wit~I2/NaOH? ,
o (b) S N 2 reactions involve single step 0
II (c) S N; reaction involves transition state intermediate 0
(a) CH3-C-H o
o (d) S N 2 reaction involves carbonium ion intermediate 0
I 200. Which of the following reaction products are correct?
(c) C2HS-C-H o (a) CH 3-Cl + Ag-CN ~ CH3 -CN + Agel 0
196. Select the correct addition products among the following: (b) CH3-CI+Na+CN- ~ CH 3-NC+NaCI 0
(a) H 2C=CHCH3 + HCI(aq. ) ~ CH3CHCICH 3 0
(c) CH3 -CI + Ag-N0 2 ~ CH3 -N0 2 + AgCI 0
(b) 'H2 C CHCH3 + HBr(aq.) ~ CH3CHBrCH 3 0
(d) CH3-CI + NaN0 2 ~ CH 3-O-N=O+ NaCI 0
201. Isobutene will be obtained on treatment of which of the
following compounds, by alcoholic KOH ?
(d) H2 CCHCH
,
3 + HI ~.',
CH 3CHICH 3 0 (a) (CH3 h C-CI . 0
197. What are the intermediate products involved in the (b) (CH 3 hCH-CH 2 CI 0
following reaction?
(c) CH 3-(CH2 h-CH 2 CI o
40H-) HCOO- + 3Cr + 2H2 0 CI
CHCl3
I
(a) CCI)" o (b) Cel 2 tJ (d) CH 3-CH....:...CH 2-CH3 o
(c) CH(OHh o (d) COCl 2 o 202. Which compounds among the following gives a positive
iodoform test? [PET (KeraJa) 2010]
198. Ethyl alcohol, on treatment ,with bleaching powder gives
chloroform. Which of the following is/are the function of (a) Ethanol 0 (b) EthanaJ 0
bleaching pOWder? (c) I-Butanol 0 (d) 2-Butanol 0
(e) . Phenylethanal 0 '
Following questions consist of an Assertion (A) and Reason (R) Reaction involves multiple Walden· inversion and the
(R). Use the following keys to select appropriate answer: product contains mixture of dextro and laevo isomer.
(a) Ifboth (A) and (R) are correct and (R) is the correct , 6. (A) Nucleophilic substitution' reaction on an optically
explanation of (A). active halide gives a mixture of enantiomers.
(b) Ifboth (A)and (R)are correct but (R)is not the correct (R) Reaction should be in accordance with S N 1
explanation of (A). mechanism. .
(c) If (A) is correct but (R)is incorrect. 7. (A) Ethyl chloride is more reactive than vinyl chloride
(d) If (A) is incorrect but (R) is correct. towards nucleophilic substitution reactions.
(e) If both (A) and (R) are incorrect, (R) In vinyl chloride, the -!.(;l is bonded to sp-hybridized
1. (A) The dipole moment of CH3F is greater than CH3 Cl. carbon of an alkene.
(R) C-F bond is more polar than C-CI bond. 8. (A) CH3 CH2 Br+ AgCN~ CH 3 CH2 NC+ CH3CH 2 CN
2. (A) The dipole moment of CH 3CI is greater than CH3F. . (Major) (Minor)
(R) Bond length C-CI bond is greater than C-F bond. (R)-CN is an ambident nucleophile, therefore, reaction
3. (a) S N 2 reaction takes place in single step. gives both cyanide and isocyanide.
(R) s 2 reactIon involves the reactivity order of alkyl Cl
·N I CH~CH=CHCH3
halides as 1° > 2° > 3° halides. 9. (A) CH 3 CHCH 2 CH 3 Ale. KOH)
4. (A) Nucleophilic substitution of iodoethane, is easier than
+KCI+H 2 0
chloroethane.
(R) Bond energy of C-I bond is less than that of C-CI Dehydrohalogenation reaction of 2-chlorobutane gives
bond. 2-butene. .
5. (A) Optically active 2-iodobutane on treatment with NaI in (R) Elimination reaction takes' place according to
~cetone undergoes racemization. Saytzeff's rule.
Halogenated Aliphatic Hydrocarbons ,439'
10. (A) Addition of HBr to alkene in preseg.ce of peroxide (R) .Benzyl radical is more stable than alkyl radical.
gives anti-Markownikoff product. . [AIIMS 2004]
(R) This addition follows ionic mechanism. 14. (A). Tert; butyl methyl ether is not prepared by the reaction '
, 11. (A) 2-Bromobutane, on reaction with sodium ethoxide in' of tert.' butyl bromide with'sodium methoxide.
ethanol gives I-butene as a major product. (R) SOdium methoxide is a strong nucleophile.
(R) I-Butene is less stable than' 2-butene. [AUMS 2005]
12. (A) Isobutanal does not give iodoform test. , 15. (A) Addition of HBr on but-2-ene gives two isomeric
(R) It does not have a-hydrogen. [AllMS 2004] products.
13. (A) Styrene on reaction with HBr, gives 2-bromo-2-phenyl (R) Addition ofHBr on bilt-2-ene follows Markownikoff's
ethane. rule. [AUMS 2006] ,
: ANSWERS I
OBJECTIVE QUESTIONS
1. (d) 2. (d) 3. (a) 4. (c) 5. (c) 6. (b) 7. (b) 8. (a) 9. (b) 10. (a)
11. (c) 12. (d) 13. (a) 14. (b) 15. (c) 16. (b) 17. (d) 18. (c) 19. (b) , 20. (d)
21. (a) 22. (a) 23. (c) 24. (c) 25. (b) 26. (b) 27. (d) 28. (c) 29. (a) 30. (a)
31. (c) 32. (d) 33. (d) 34. (b) 35. (c) 36. (b) 37. (b) 38. (a) 39. (c) , 40; (d)
41. (b) 42. (c) 43. (b) 44. (c) 45. (a) 46. (d) 47. (a) 4~. (a) 49. (h) 50. (a)
51. (d) 52. (d) 53. (d) 54. (a) 55. (a) 56. (b) 57.· (b) 58. (e) 59. (d) , 60. (a)
61. (c) 62. (d) 63. (b) 64. (d) 65. (b) 66. (d) 67. (b) 68. (a) 69. (a) 70. (c)
71. (c) 72. (b) 73. (c) 74. (d) 75. '(a,c) 76. (d) 77. ,(b) 78. (d) 79. (b) 80. (d)
81. (a) 82. (a) 83. (c) 84. (b) 85. (c) 86. (d) 87. (d) 88. (c) 89. (b) 90. (d)
91. (a) 92. (a) 93., (b) 94. (d) 95. (b) 96. (b) 97. (a) 98. (b) 99. (c) 100. (c)
101. (d) 102. (d) 103. (d) 104. (c) 105. (d) 106. (a) 107. (d) 108. (d) 109. ' (c) 110. (d)
111. (c) ,112. (d) 113. (a,d) 114. (b) .115. (b) 116. (c) 117. (d) 118. (d) 119. (a) 120. (d)
121. (b) 122. (a) 123. (b) 124. (d) 125. (b). 126. (b) 127. (c) 128. (c) 129. (d) 130. (a)
131. (c) 132. (b) 133. (c) 134. (4) 135. (a) 136. (c) 137. (b) 138. (a) 139. (a) 140. (b)
141. (d) 142. (d) 143. (a) 144. (d) 145. (b) 146. (c) 147. (d) 148. (c) 149. (d) 150. (b)
151. (c) 152. (b) 153. (b) 154. (b) 155. (a) 156. (a) '157. (a) 158. (b) 159. (c) 160. (a) .
161. (d) 162. (a) 163. (b) 164. (c). 165. (c) 166. (b) 167. (c) 168. (d) 169. ' (c) .170. (d)
171. (d) 172. (d) 173. (a) 174. (c) 175. (e) 176. (d) 177. (e) 178. (b) 179. (d) 180. (c)
181. (d) 182.. (c) 183. (d) 184. (a) 185. (d) . 186. (c) 187. (a) 188. (c) ,,189. (c) 190. (a)
191. (a) 192. (e) 193. (a,d) 194. (a,b,d) 195. (a,b,d) 196. (a,b,c,d) 197. (a,b) 198. (a,b,c) 199. (a,b) 200. (c,d)
201. (a,b) 202. (a,b,d)
1. (d) .2. (a) 3. (a) 4. (a) 5. (a) 6. (a) 7. (c) 8. (a) 9. (a) 10. (e)
11. (d) 12. (c) 13. (e) 14. (b) 15. (e)
440 G.R.B. Organic Chemistryfor Competitions'
extract].
* N02
, the C-Cl bond, hence, it gives test without preparing sodium
~
3. In which of the following pairs, the bromination of first Cl., CI CI CI
I
M
CICI
member is easier than the second member?
(a) Isobutane, butane 0 (b) n-Butane, isobutane 0 Ca) , o (b) CI o
CI
(c) Methane, ethane 0 (d) Noneofthese 0 Cl Cl Cl .
4. Tert.-alkyl halide is obtained as major product in:
f.Sr
(a) (CH 3 )3 CH ~
Br2
0 , CI' Cl C~1
hv
HBr (C)Ci~CID (d) Cl o
(b) (CH3)2CH-CH=CH2) 0 , CI
Peroxide CI
HBr' CI CI
(c) (CH 3 h CH-CH=CH2 ,----7 0 [Hint: Compound (c) has all equitorial substituent, hence, it is
most stable and undergo elimination with slowest state.]
(d) both Ca) and (c) 0 9. Consider the structures of the following two molecules:
S. Which of the following is ,fast de-brominated?
X:
(a)~
~Br
0 (b) 0 '
~Br
0 Y:
In which of these two, it is impossible for all the four
F-atoms to lie in the same plane?
'('--fBr (YBr (a) X 0 (b) Y 0
V
. (c) o (d) V o (c) Both X and Y 0 (d) None of these 0
10. Which of the following is least reactive towards nucleo-
philicsubstitution with aqueous KOH?
6. In .which of the following pairs both members on heating
with ale. KOH result in the formation of same alkene as
major product?
(a) (CH 3 )3 C-Br, (CH 3 )z CHCH 2Br
(b) n-Propyl iodide, isopropyl iodide
fr fr
0
0 o (b) 9 CI
OH
o
9
(c) (CH 3 hCH--'-C-CH 2 CH 3 , (CH3 )z.C-CH-C2HS
~:. I I Br
CH 3 CH 3
o o (d) o
(d) All of the above 0
7. Detection of chlorine is possible without preparing sodium
OH
extract in:
. Halogenated Aliphatic Hydrocarbons 441
. CH 3 15. Most reactive alkyl halide towards E2 mechanism is:
. 11. When Br--l-I---H reacts with KpH in presence of (a) (CH3 h C-CH2 Br o
CH2CH 3 /Br
water (through SN2reaction mechanism) then stereo~ CH CH
(b) ( 3 )2 -CH", o
. chemistry of product so formed will be: CH3
OOR 0
008 0 (c) (CH3 h C-CH2 CH 2 Br o
(c) mixture of Rand 8 0 (d) (CH3hC-CH-CH2Br [J
(d) Partial 8 + racemic mixture 0 I
[ Hint: Original compound is (R). hence, the product fonned C(CH3 )3.
wi\' ::e (S) due to inversion of configuration.] t 6. Which of the following compounds is the most likely to
12. Which o{t!1e following molecules represents freon~1,14? undergo a bimolecular nucleophilic substitution reaction
F F Cl Cl with aqueous NaOH?
. I I I I
(a) C1-r-f-H
Ct CI
D (b) F 4 - - r F
CI CI
o
(a) 0
~Br
Cl F F Cl F
I I I I I 0
(c) F-C-C-Cl o (d) F - r - r - r - F
I I
F. F Cl H ; F
13. In which of the following reactions, an optically. active
single product is formed?
OCH3
I
(a) CH30Na +. C~Br ) 0 02N'(XBr
/"- [ Hint: In I is activated for nucleophilic
H D ::::....N02
CH3 substitution by electron withdrawing group present at
I . ortho- position.] .
(b) NaI + C - B r ) 0 17. The major product obtained in the reaction,
/"-
CH3H
Ph Ph
I I
(c) HUII""'C-MgI + q-Br ) 0
,
CH
,"""9
CH H
is:
3 3
~H5 Ph
I I
(d) /C,,- MgBr+ /C,,- Br ) 0 o
CH3HCH3H
14. Which of the following will give acetoJlhenone a~ a
product?
o
CH3COCI
(a)O ) 0
AICl3
(c) Oil
~.
:-CH3
CI
Aq.KOH)
(a) carbene
(c) free radical
19. Iodoform is used as an:
0 (b) carbocation
0 (d) earbanion
0
0
(a) anaesthetic o
(b) analgesic
(d)' All ofthe above o (c) antiseptic o
(d) antifebrin
G.R.B, Organic Chemistry for Competitions
20. The trade name of trichloroethylene is: 27. Match List I with List II and select the correct answer using
(a) freon 0 (b) westron o the codes given below the lists:
(c) westrosol 0 (d) DDT o List I List II
21. In the reaction, Compound Action
R-Br + cr
----+ R-CI + Br-
(A) Teflon (i) Ozone layer depletion
the rates of reaction of ethyl bromide (I), n-propyl bromide
(II), isobutyl bromide (III) and neopentyl bromide (IV) (B) Pyrene (ii) Non-biodegradable
follow the order: insecticide
(a) IV> III> II> I 0 (b) I> II > III> IV 0 . (C) DDT' (iii) Non-stick cookwares and
(c) I> III> II > IV 0 (d) III> II > IV> I 0 .insulator
22. Arrange the following compounds in the decreasing order (D) Freon (iv) Fire extinguisher
of the boiling point:
CH3Br CH 3 CH 2 Br CH 3 CH 2 CH 2 Br Codes:
I II III A B C D
CH 3CH 2 CH2 CH 2 Br
rv (a) (i) (ii) (iii) (iv) 0
(a) I> II > III> IV o
(b) IV> IiI> II > I o (b) (iv) (iii) (i) (ii) 0
(c) I> III> II > IV o
(d) III> IV >1 > II o (c) (iii) (iv) (ii) (i) 0
23. In the reaction, (d) (ii) (i) (iv) (iii) . D.
Alc.KOH
CH3-CH-CH 3 --~) (A) HBr ) (8) NaI) (e)
. I. Peroxide .. Acetone 28. 11te intermediate compound fOJ1:ned in Frankland's reaction
Br is:
the compound (C) is: (a) RZnI 2 0 (b) R 2 Zn o
(a) CH 3-CH 2 CH 2 I (b) CH3-TH-CH3o o (c) RZnI 0 (d)R 2 ZnI o
29. The reaction given
I
CsHII
(d) CH 3 -CH CHI o CSHll
HIIIII:t-c1
OW
.. HO-Cc'III1H
-CI- \ CH
CH3 3
24. CCl 4 is used as ftre extinguisher because:
(a) of its covalent bond 0 is:
(b) of its low b.pt. 0 (a) SN 1 0 (b) SN2 o
(c) of its high m.pt. 0 (c) El 0 (d) E2 o
(d) it gives incombustible vapours 0 30. The major product of the reaction, ,
25. The correct order of reactivity of alkyl halides for SNI
'\~'/.
Halogenated Aliphatic Hydrocarbons 443
[Hint: CH3-CH-QH-Q--oH ~ CH 3
1
(a) CH3-C-CI o
, CH3--CH-CH2- Q - - o H I
CH 3
Br
, [CH3-CH2JH-Q--oH
I
~CH3-CHr--CH-Q--oH
(Less stable) ,
lsomerisation (b) CH3 -CH z -CHz-C1
(C)'C6H5~-CI
CH3 ,
o
o
Br CI o (d)f\vCI o
I I ~CH3
CH3 - C -CH3 , CH3-C-CH3
35. Ullmann reaction is given by:
(c) I. o (d) 1 o
CH3 -C--CH3 CH3 -C-CH3
(a) C6Hs--C1 0 (b) CH3- - Q - C I 0
1 I
Br I
32. Which of the following combinations is correctly matched?
Compound Reaction Stereochemistry (c) ~ )-CI
H
I N02
(a) CH 3-C--CI SN2 Walden inversion 0
I'
D
36. In the following comp,ounds, nucleophile and the leaving
groups are in the same molecule:
H
Br~.-.
I
Walden inversion o I. ..0: II. Br~fi:
(b) CH 3 -y-CI
D JII.Br~3: IV.Br~Q:
..
These dual nature species can undergo intramolecular and
intermolecular nucleophilic substitution. Intramolecular
SN 1 Retention in configuration
substitution reaction is possible in:
(a) I, II 0 (b) II, III 0
(c) III, IV 0 (d) IV 0
o [Hint: In I and II, intramolecular reaction will not be possible
because they will give strained ring.]
SN I Inversion in configuration 37. Compound Br~o- undergoes intramole-
cular nucleophilic substitution of the type .... giving .....
yield?
(c) both of the above are correct o
(d) intramolecular reaction is not possible o
444 G.R.B. Organic Chemistry for Competitions
38. Which is the most stable carbo cation formed as intermediate (a) Carbocation 0 (b) Carbanion 0
in nucleophilic substitution reaction? (c) Free radical 0 (d) A dianion 0
40. Only one of the following alkyl halides can be prepared as
the major product of the addition of HBr to an alkene:
Br
o
(a) ~Br 0 (b) ~ o
CJ (d)
e
0 o (c)~ o (d) 4 o
39. Transition state is accompanied by the formation of which
of the following species in SN2 reaction?
(8)6 (b) 0
BrY"ll
heterolytic ally (in step 1) to form a carbocation (as in S N I
reaction) in which (L-) is lost (rate determining step). The
carbocation (in step 2) loses a proton from the J3-carbon atom by a
base (nucleophile) to form an alkene. El reaction is favoured in
(yBr
(c) 0 (d) Cannot be predicted
compounds in which the leaving group is at· secondary (2°)'or
tertiary (3°) position.
In E 2 (elimination) reactions, two sigma bonds are broken
2. Consider the three types of C-H bonds in cyclohexene. and a1t-b()nd is formed simultaneously. E2 reactions occur in one
H step through a transition state.
l----- B
. Relative amount x 100
i ~G
Percentage YIeld of the product = - - - - - - - -
Sum of relative amounts
Relative amount = Number of hydrogen atoms on the
C
R++X- respective carbon x relative reactivity.
Carbocation NBS (N-bromo succinimide) is used for bromination at
intefI!1ediate E allylic and benzylic carbon, whereas Br2/hv gives bromination at
RNu+X" . benzylic, allylic and alkyl carbon.
Reaction progress ~ Answer the following questions:
1. Select most reactive. compound for chlorination in presence
Answer the following questions:
of light:
1. In SNi reaction, the hybridization changes in mte
6
determination step. Select the correct change among the CH3
following:
(a) from Sp3 to sp2 (b) fromsp2 tosp3 (a) (b)
2
(c) fromsp2 tosp (d) from sp to sp
448 G.R.B. Organic Chemistry for Competitions
yH 3
(b) C6Hs-r-CH2-CH3
CH3
'ALCOHOLS ORALKANOLS
, ).
. ~)."~Hl
(i) Methyl alcohol (ii) Ethyl alcohol . (iii) Tertiary butyl alcohol
H -H 20) ""-C=O
I / ""-O:H:
Unstabl~- ~
/
Carbonyl compOund (Stable)
CH 3 -C-OH
?! I . -00' /..,()';
CH 3 -C-OH -C -tOl~ -H20 C' -
(iv) Acetic acid
NH2·
(v) Acetaldehyde ammOnia . ~oa" ..) -:- ""-OH
These are not alcohols as carhonbearing -oH group is Unstable Acid (Stable)
attached to =0 in compound (iv) and to ~NH2· . [However. chloral hydrate is a stable compound although two
in compound(v). hydroxyl groups are attached to the same carbon atom. This is
due to intramolecular hydrogen bonding.] .
Classification
Alcohols are classified according to the number of 9:2 MONOHYDRIC ALCOHOLS
hydroxyl groups present in their molecules. Monobydric
Alcohols containing one hydroxyl group are known as
alcohols contain one hydroxyl group, dibydric two and
monohydric alcohols. These alcohols" may be saturated or
tribydric three, respectively. However, if an alcohol contains
two or more hydroxyl groups, it is generallycaUed as a unsaturated depending on the nature of hydrocarbon groups.
polybydric alcobol. Saturated monohydric alcohols form a homologous series· of·
·450 . G.R,B. OrlJpnic Chemistry for Competitions
"
the general fonnula C n H 2n + IOH. They are also represented as (iv) Allylic alcohols: In these alcohols, the -OH group
R-OH where R represents an alkYl group. They may be is attached to a sp3 -hybridized carbon next to the carbon-
regarded as derivatives of water, i. e., one hydrogen atom of the . carbon double bond, i.e., to an allylic carbon. For example,
water moiecule is replaced by ali alkyl group. 10 20
H 2C=CH-CH 20H H 2C=CH-CH- CH3 .
lIOH -H) ROH . 4 3 21 I '
Prop-2-en-I-ol
Water +R Alcohol
OH
(Allyl alcohol)
Monohydric alcohols are further classified according to
Primary (l" ) But-3-en-2-ol
the hybridisation of carbon atom to which the hydroxyl group Secondary (2° )
is attached. .
(a) Compounds ,containing Csp 3-0H bond: In these CH 3
30 1 .
',' alcohols, the -OH group is attached to a sp3 -hybridized H 2C=CH-C-CH3
carbon atom of an alkyl group. These are further subdivided as 1
OH
follows:
2 ~ Methyl but-3-en-2-ol
(i) Primary alcohols (1 0) .: In, these alcohols, the Tertiary (3°)
hydroxyl group is attached with primary (10) carbon atom.
They possess a characteristic group -CH 20H and their (v) Benzylic alco~ols: In these alcohols, the -Oil
general fortnula is RCH 20H.R may beH in the first member group is attached to a sp3 -hybridized carbon atom next to an
and alkyl group in the rest of the members. aromatic ring. For example,
Examples: , CH3 CH3
HCH 20H CH 3CH 20H; 20 1 30 1
C-OH ()C-OH
Methyl alcohol
.. CH 3CH 2CH 20H
Ethyl alcohol
~ )H
( I I .
'~, CH3
I 1
n-Propyl alcohol
Primary Secondary Tertiary
Isobutyl alcohol So, allylic and benzylic alcohols may be. primary,
(ii) Sec()~dary alcohols (2°): In these monohydric secondary or tertiary.
alcohols, ,the hydroxyl group is attached with secondary (2°) • (b) Compounds containing C sp2 -OH bond: In these
carbon atom. They possess a characteristic group >CHOH alcohols, the -OH group is attached to a carbon atom of the
, ,. R"",,- double bond, i.e., vinylic carbon or to an aryl carbon. For
and the general formula :/CHOH (R and R' may be same or example,
., R,':/ Vinylic . alcohol: H 2C=CH-OH, vinyl alcohol
·
different). (unstable)
Examples: Phenols:
CH 3 -CH-CH3 ; CH 3 -CH-CH2CH3 .. CH3 OH
ex
OR 'OH
~OH 0-.,
, 1 1 .
OH OH
, I
. Isopropyl alcohol ' Sec. butyl alcohol
(iii) Tertiary alcohols (3°) ,:, In these monohydric
alcohols, the hydroxyl group is attached with tertiary (3°)
V
Phenol
U
;J)-OH ;
o-Cresol
~
Catechol
OH
~
Pyrogallol
OH
OH
, I
CH3CH2CH20H CH3-CH-CH3
n-Propyl alcohol Isopropyl alcohol
. OH '. Cyclohexanol Phenylmethanol
I (Benzyl alcohol)
CH3CH2CH2CH20H ; CH 3CH2CH-CH 3
n-Butyl alcohol Sec. butyl alcohol 9.4 ISOMERISM
Oll Monohydric saturated alcohols show following three types of
I isomerism:
CH3 - 'CH-CH20H CH3 - C -CH3 1. Chain isomerism : 'Chain isomerism exists due to
I ' I , difference in the ,structure of the chain containing four or more
CH 3 CH3
Isobutyl alcohol Tert. butyl alcohol carbon atoms attached to the hydroxyl group.
Examples:
2. Carbinol system: The simplest monohydric alcohol,
CH30H, is called carbinol. All other members are considered CH3CH2CH2CH20H atld CH 3 -CH- CH20H
its alkyl derivatives. The alkyl groups attached to the carbon Butan-l-ol " ,I
(n-Butyl alcohol) CH 3
atom canying -OH group are named in alphabetical order.
H3 C, ' 2 - Methyl propan -1- 01
(Isobutyl alcohol)
CH 3CH 20H ; 'CHOH' are chain isomers.
Methyl carbinol H3 C/ ' 2. Position isomerism: This isomerism is due to the
Dimethyl carbinol difference in the position of the hydroxyl group when the
carbon chain of three or more carbon atoms is the same.
Examples:
CH3CH2CH20H and CH3CHOHCH3
Propan-l-ol Propan-2-01
(n-Propyl alcohol) (Isopropyl alcohol)
Ethyl methyl carbinol
are position isomers.
H3 C, . C2 H s" , CH3CH2CH2CH20H and CH3CH2CHOHCH3
H 3C -=-'C-OH C 2H s7 C-OH
H3C . "7 C2H S ,Butan-l~ol
(n-Butyl alcohol)
'Butan-2-ol '
Trimethyl carbinol Triethyl carbinol '(Sec. butyl alcohol)
are position isomers.
3. ,IUPAC system According to this system, the, 3. Functional isomerism ,Saturated monohydric
alcohols are called alkanols, i. e., by replacing -e from the name alcohols containing two or more carbon atoms show functional
of alkane by -01, i.e., isomerism with ethers. Both have the general formula
Alkane (- e) + 01= Alkanol CnH 2n + 20. The alcohols contain a hydroxyl group whereas
Examples: ethers have ethereal oxygen (-0-). '
CH 30H CH3CH2CH20H; Examples :'
Methanol Propan-I-ol
3
C2 H SOH and CH30CH3
CH 3 CH3 Ethyl alcohol DImethyl ether
3 12 I 21 are functional isomers.
CH 3 -CHCH 20H CH3-C-OH, CH3CH2CH20H and C2HsOCH3
2-Methyl propan-I-ol II ' Propan-I-ol Ethyl methyl ether
CH 3 (Methoxy ethane)
, 2-Methyl propan-2-01 are functional isomers.
OH CH3 Besides the structural isomerism, alcohols having' asym- ,
metric 'carbon atom exhibit optical isomerism (enantio-
3 Iz I 4 3 12 I
merism) also.
CH 3 -CH-CH3 CICH2CH2CH-C1I20H;
Propan-2-ol , 4-Chioro-2-methyl butan-l-ol Examples:
OH " H, /AS,ymmetric,
4 3 2 I 4 • 3 12 I I /. _.
carbon atom
CH3CH2CH2CH20H CH 3 -CH 2 -CH-CH3; Butan -2-01 CH3-C-OH'
Butan-l-ol , Butan-2-ol ,(Sec. butyl alcohol) , I ' '
C 2 HS
G.R.B. Organic Chemistryfor Competitions
H /AsymmetriC
.I /" carbon at.om
Pentan -2 ~ 01 CH 3 -C-OH (b) (1)
(Sec. amyl alcoh.ol)
I Cycl.obutan.oI Cycl.opr.oPyl methan.oI
C3H 7
.~
addition ofborane follows Markownikoff's rule.]
(yCH2 Hydroboration method has entirely replaced peroxide
V + Hg(OAch
_--'-'--_
(ii)NaBH4 V ..H CH3
initiated addition of HBr reaction for anti-Markownikoff's
addition.
This two step process is called oxymercuration 3. Hydrolysis of ester: Esters on hydrolysis by mineral
reduction or oxymercuration-demercuration and forms acids or alkalies form alcohols and carboxylic acids;
alcohol.
Alcohols or Alkanols 455
0, 0
II : . II
CH3C70-C2Hs +HOH~CH3-C-OH+ C2HSOH
Ethyl acetate Acetic acid Ethyl alcohol
This method provides industrial preparation of those alcoholswhich naturally occur as esters.
Note: Tertiary halides do not give a satisfactory yield of alcohols on hydrolysis. These are first converted into esters and then by doing hydrolysis,
tertiary alcohols are obtained in good yields ..
R3CX + CH3COOAg -----;, CH 3COOCR) + AgX .
Tertiary Silver acetate ' Ester
halide
CH3COOCR3 + H 2 0 ---7 CH 3COOH + R1COH
alcohol
4. Hydrolysis of ethers: Ethers when heated with dilute sulphuric acid under pressure are hydrolysed to the corresponding
alcohols.
ROR' + HOH_H_2S_O_4_(d_il_.)-;) ROH + R'OH
8 .
H zS0 4 (dil.)
C2HsOC2HS + HOH ----~) 2C2HsOH
Diethyl ether 8 Ethyl alcohol
H 2S0 4 (dil.)
CH 30C 2H s + HOH-----;) CH 30H + C2HSOH
Ethyl methyl ether 8 Methyl alcohol Ethyl alcohol
5. Action of nitrous acid on primary amines: Primary alco~ols are formed when primary amines are treated with nitroQs
acid (NaN0 2 + HCI dil. ).
I I
6. Reduction of carbonyl compounds including carboxylic acids and esters: Aldehydes, ketones, acids and acid
derivatives on reduction yield alcohols. A number of reducing agents like ZnlHCI, Na1.C2H s OH, LiAlH4 or NaBH4 can be used
for this purpose. Aldehydes and ketones are also reduced to corresponding alcohols by catalytic hydrogenation (addition ofH 2)
with finely divided platinum, palladium, nickel or ruthenium, etc.
(i) Bouveault-Blanc reduction: The reducing agent used is sodium and ethanol. The aldehyde, ketones and esters etc., are
reduced by nascent hydrogen into corresponding alcohols.
RCHO +2H Ni or Pt ) RCH. 2 OH
Aldehyde or Pd Catalyst· Pri. alcohol'
. H2 /Nior Nal alcohol
CH 3CHO+2H " . ) CH3CH 2 0H
Ethanal or LiAlH4 or NaBH4 Ethanol
R, . R
" /'
" CO +2H Ni ) . """ CHOH
R" /' ,orPt RV
Ketone Sec. alcohol
H2/Ni or Na/alcohol H 3C"",, .
or LiAlH4 or NaBH4 ) / ' CHOH
H3 C
. Propan-2-o1·
LiAlH4 . . .
RCOOH + 4H --,.....,...:..;;.. ----7) RCH 20H + H 2 0
, 'Acid or B2H6/ether
(i) LiAlH4 .
CH 3COOH + 4H . ) CH3CHZOH+ H 2 0
Ethanoic acid (ii) H3 0 + Ethanol
LiAlH4
" CH 3CH=CHCOOH + 4H------7) CH 3 CH=CHCH 20H + H 20
o
I LiAlH
. CH 3 -C- OCH 3 _ _....:.4~) CH 3CH 20H+CH 30H.
Alcohols or Alkanols
LiAlH
(CH3COhO-_...;.4~) 2CH3CH20H
°II LiAlH
CH 3-C-CI _ _...:.4~) CH3CH20H + LiCI + AlC13 .
-
....
-CHO -CH 20H· LiAlH4, NaBH4, B2H6/THF; Ni/H2
)c=o
-COOH
'"
/CH-OH
-CH 20H
-'-iio-.
LiAlH4. B2H6/THF
-COCl - CH20H LiAl~. NaBH 4, B2H6/THF
(RCOhO R-CH20H. LiAlH 4• B2H6/THF, H2/Ni
)c=>c( -CH2-CH2- H2/Ni. B2H6/THF
.-COOR -CH 2 0H LiAlH4, B2H6/THF, H2/Ni
-CH 20H -CH3 RedPII2
7. Addition of Grignard reagents to aldehydes and ketones: All the three types of monohydric alcohols can be prepared
by the use of Grignard reagents. Grignard reagents fonn addition compounds by nucleophile attack with aldehydes and ketones
which on hydrolysis with dilute acid yields an alcohol.
10
-C=O+R--MgX+
.
Dry) -C
l/oMgX
.
H 0/H+
2
l / o H ' ./OH
) -C, +Mg,
Aldeh~gnard ether . "-.....R Hydrolysis .. 'R . 'X
or ketone reagent .Addition compound Alcohol
(i) Primary alcohols: Primary alcohols are obtained when Grignard reagent is reacted with oxygen or fonnaldehyde or
ethylene oxide.
, H O/H+ /OH
(a) RMgX+-2102 ---7Rn:,MgX' 2 ) ROH. +M~ .
. H:OH' Hydrolysis 1" Alcohol , X
"
1 . HO /OH
C2H SMgBr +'2°2---7 C2H sOMgBr 2 ) C 2HSOH + Mg"-.....
Ethyl magnesimn Addition product Ethyl alcohol Br
'bromide
The alcohol has same number of carbon atoms as present in the alkyl group of the Grignard reagent.
H" . Dry H " /OMgX H 2 0 . /OH
(b) /C=O + RMgX )
/C, ) RCH 20H + Mg, .
H/ ether H/ 'R H+ I" Alcohol 'X
Formaldehyde
H" H " /OMgBr
/"C=O +CH3CH2MgBr ---7 /C"-.....'
H
2
° )
/OH
CH3CH2CH20H + Mg"-.....
H Ethyl magnesimn H CH2CH3 Propan-l-01 Br
Formaldehyde bromide Addition product (n-Propyl alcohol)
The alcohol has one carbon atom more than the alkyl group of the Grignard reagent.
2
(c) I
CH " /0
" +RMgX
CH 2
Ethylene oxide
(oxirane)
G.R.B. Organic Chemistryfor Competitions
~, ~ . /00
I /0 + C2HsMgBr ~ C2HsCH2CH20MgBr-~) C2HsCH2CH20H + Mg"
CH2/ Ethyl magnesium Addition product Butyl alcohol Br
Ethylene oxide bromide
The alcohol has two carbon atoms more than the alkyl group of the Grignard reagent.
(ii) Secondary alcohols: Secondary alcohols are obtained when Grignard reagent is reacted with an aldehyde other than
formaldehyde.
(a)
R,
'C=O+R'MgK Dry)
R, OMgK H
)C/.
2)
R, /OH
"c +Mg/
OH°
H/ . ether H / "R' W H / ':--..R' "X
Aldehyde Sec. alcohol (2°) .
H 3C",,- o H 3C, /OMgI HO H 3C,,- /OH
/C---:-O + CH3MgI ry ) 'C/ 2) /CHOH +Mg"
H . Methyl magnesium ether . H / ""-CH 3 H+ H3 C/ . I
Acetaldehyde iodide Addition product Propan-2-01
(Isopropyl alcohol) .
I CH3 CH 3
o I H 0 I . /OH
~. +RMgK
2
(b) ~ RCH2 -'CH-OMgK ---"~) RCH 2-C-OH + Mg"
3 2
Addition product W I X
2-Alkyloxirane
H
2° Alcohol
(The ring is opened from least hindered site to form addition product).
The alcohol has three carbon atoms more than the alkyl group of the Grignard reagent.
(iii) Tertiary alcohols: Tertiary alcohols are obtained when Grignard reagent is reacted with ketones.
R, . R, H R '- /OH°
(a) "C=O + R" MgK Dry) R' "C-OMgK
R'/
Ketone
ether R,7
2 ) R'- "C-OH + Mg
. H+ R"/
Tert. alcohol (30)
"X
H 20 H C" 3 /OH
+ ) H3C /C-OH + Mg"
H H3C/ I
2-Methylpropap. -2-01
(Tert, butyl alcohol)
Rl Rl
. I H20 I /OH
.
(b) +RMgK ~RCH2-C-OMgK ) RCH2-C-OH+Mg,.
I W I ... x
2,2-Dialkyl oxirane R2 R2
Addition product 3° Alcohol
(c) Esters (RCOOR,) on treatment with Grignard reagent first forms ketone which then reacts with second molecule of
Grignard reagent and forms tertiary alcohol.
o 0
II ~------------- Dry II /OC 2 Hs
CH 3-C--f-OC2H s + BrMg :C2HS --'-~) CH3-C-C2Hs +Mg"
Ethyl·acetate- - - - - - - - - - - ether Ethyl methyl ketone Br
C2 H S, /C=O + C2HSMgBr
H20lW
.
,I
)C2 HS-C-C2H S
CH 3
CH3/
Ethyl methyl ketone
Ethyl magnesium
bromide
I
OH
3-Methyl pentan-3-01
Altemative reactants can be selected for the same product using Grignard reagent:
Alcohols or Alkanols 459
. 0 OMgBr OH
. (yMgBr
(a)
~
I
Phenyl magnesium
bromide .
I
+ CH 3 -C-C2H S ~ CH 3 -C-C2H S
Ethylmethyl ketone
!? .
~ .
6 I
I
I
6····
HOH/HCI ) CH 3 -C-C2 Hs +Mg/
/Br
'OH
Adduct 2~Phenylbutan-2-o1
or
o
. I
CH3MgBr +
VI
, .
C-C2Hs~
(b)
IMgCl+~H HOHlHCl
'Y(
OH
4-Methyl hexan-2-o1
or
0
II HOHlHCI
I G - H + CH3MgCI II
'Y(
3-Methyl pentanal OH
The fermentation of sugar is completed in about three days and the optimum temperature is 27°C. The carbon dioxide is
recovered and sold as a byproduct.
B. maceranus '' H OH
(C 6 H lO O S )n 0) CH3COCH3 +CH3CH2CH2C 2
Starch 3()""'35 C Acetone (30%) n-Butyl alcohol (60%)
9. Oxo-process(lndustrial method) : This reaction is also called as carbonylation or hydroformylation. In this reaction,
alkene is converted to alcohol with one carbon atom more. Catalyst used in this process is cobalt carbonyl or cobalt carbonyl
hydride [COH(CO)4]' In this process first of all aldehyde is formed, which is reduced to obtain alcohol, e.g.,
[CoH(CO)4 ]
H2C=CH2 +CO + H2 -------'---7. ), CH CH CHO
3 2
Ethene High temp. and pressure Propanal
CHO
I
[CoH(CO)4] ) CH 3 -CH-CH 3 +CH3CH2CH2CHO H2 ~ CH3CH2CH2CH20H
2CH3 -CH=CH2 +2CO +2H2
Propene Zn-Cu Butan-l-ol'
CH 20H
I
CH3-CH-CH3~-=~
H2
, . 2-Methyl propan-l-ol Zn-Cu
CH 3 CH3'
I , I
CH 3-C-CH2-C=CH 2 +CO + H2 [CoH(CO)4] ) CH3_C_CH2_CH_CH2_CHO-,--H.;;;;.2_/Zn-_C_u--?)
, I I . I I -'
CH3 CH 3 CH3 CH 3
2,4,4-Trimethyl pent-l-ene (Major)
CH3
I
CH 3 -C-CH2 -CH-CH2 -CH20H
I I .
CH 3 CH 3
3,5,5-Trimethyl hexan-I-ol
,9.6 GENERAL CHARACTERISTICS OF a+ a- a+ a- a+ a- a+ a- a+ a-
ALCOHOLS H-O---H-O--- H-O--- H-O---H-O
Physical properties : (i) The lower members upto CII
I I' I I l
H R H R H
are colourless mobile liquids. Higher members are wax like Fig. 9.1 Hydrogen bonding between water and alcohol
solids. The solubility of higher members in water is less. This can
(ii) The lower members have a characteristic smell be explained in the following manner. The alcohols possess
(alcop.olic) and a burning taste while solid members are almost ,both hydrophilic (waterioving or waterlike, -OH group) and
colourless and tasteless. hydrophobic (water hating, alkane like due to carbon chains)
(iii) Alcohols are toxic substances. Methyl alcohol is moieties. Thus, with increase in molecular mass the
highly t~xic in nature while ethyl alcohol is less toxic. hydrophobic part of the alcohols increases. This reduces their
(iv) Alcohols are neutral substances. Theyare lighter than water solubility. Another interesting feature in this connection
water. is that among the isomeric alcohols, the solubility increases
(v) The first three members are highly miscible with with increase in branching. This can be attributed to decrease
water. However, the solubilitY in water decreases with rise of hi relative volume of hydrophobic portion.
molecular mass. The solubility in water is due to hydrogen (vi) Boiling points of alcohols increase gradually with
bonding as -OHgroups present both in alcohol and water are increase of carbon chain. The difference between boiling
highly polarised. points of two consecutive members is about IS-20°C.
Alcohols or Alkanols 461.
r
5- ~H5+
. ·l5.l,:;""~3G', I~~::li;':c,'s;;,- i:';.::~:.':
~~ -.,'1: Ia
Methanol CH3OH' 64.5 _C + ~ t
Ethanol C2HsOH 78.3 I •. I
Propan-loOl C3H, OH 97.0 Polar bonds
Butan-IoOl 'C4HejOH 118.0 c-o bond is weaker in the case of tertiary alcohols due to
Pentan-I-ol CsH1l 0H 138.0 +[ effect of alkyl groups while o-H bond is weaker in
Among isomeric alcohqls, the boiling points are in the primary alcohols as electron density increases between O-H
following order: " bond and hydrogelltends to separate as a proton,
Primary > Secondary > Tertiary H Weaker Weaker
Butan-I-ol > 2-Methyl propan-l.,ol I R
'bond . R bond
R+-C-O _.1-_ H; "CH--a--:H; R ~C -,.1-_ O-H
(CH 3CH2CH2CH20H) ( CH 3 -CHI-CH20H) 1 R? R7
b.pt. 118GC H Secondary Tertiary
CH 3 , Primary
b.pt. 108GC Thus, primary alcohols are most reactive when there is
> Butan-2-01 > 2-Methyl propan-2-01 cleavage of 0- H bond while tertiary alcohols are most
reactive when there is cleavage ofC-O bond.
. Hence, in O-H cleavage, the order of reactivity is,
[CH3CH2CH(0H)·CH3 ] CH3-rOHl' Primary> Secondary> Tertiary,
, b.pt. 9~C [
CH3 and in C-O cleavage, the order of reactivity is,
b.pt. 83°C Tertiary> Secondary> Primary.
The boiling point decreases with branching. During 0 -H cleavage, proton is given out showing that
The boiling points of alcohols are much higher as com- alcohols are acidic in nature. However, alcohols are weaker
pared to the corresponding alkanes, etQers and alkyl halides. acids than water. This is because the alkyl groups in alcohols
The reason for the higher boiling points than expected is due to have a +I effect. The negative charge on oxygen makes the
intermolecular association of a large number of molecules due release of proton bit difficult. Tertiary alcohols are least acidic
to hydrogen b9nding as -OH group is highly polarised. due to maximum +[ effect of three alkyl groups. Acidic nature
R R R R increases from tertiary to secondary and from secondary to
I I I I primary as +I effect decreases. Thus, the following order is
- - -O-H - - - O-H - - - O-H - - - 0 - followed in the acidic nature of alcohols. '
~ CH30H> Primary alcohol> Sec. alcohol> Tert. alcohol
Hydrogen bonding
In general, the reactions of alcohols may be divided into
No hydrogen bonding is present in alkanes, ethers and
the following three categories:
alkyl halides.
(a) Reactions involving the cleavage of oxygen-hydrogen
(vii) Lower alcohols form solid derivatives with certain I
metallic salts. bond [C-O-+-- H] with substitution or removal of hydrogen as
I
CuS04 ·2CH 30H CaC12,4CH30H MgCI2· 6CH30H I
CuS0 4 ,2C 2H sOH CaCI2·4C2HsOH MgCl2'6C 2H SOH proton (i,e., alcohols act as nucleopbiles).
For this reason, alcohols cannot be dried over anhydrous H
calcium chloride. .~ ·r-I+ I
"C- ~ R..LC-C- ~
R-O-H+/
Chemical properties: The hydroxyl group present in ••
Nucleophile Electrophile
•• I
alcohols, is a very reactive group and the. characteristic
reactions ofa1cohols are the reactions of the - 'OHgroup. The I
reactions of the hydroxyl group consists of either cleavage R-O-C- + H+
(breaking) of c-o bond or the cleavage of 0- H bond as I
both are highly polarised with negative end of both the dipoles (b) Reactions involving the cleavage of carbon-oxygen
I
at oxygen. Moreover oxygen has two unshared lone pairs of
bond [C-: OH] with substitution or removal of -OH group
electrons and has partial negative charge so alcohols (or I,
phenols) possess a net dipole moment. Methanol has a dipole (i.e., alcohols act as electropbiles).
moment of 1.71 D. Due to this dipolar nature, alcohols (or The protonated alcohols react as follows:
phenols) form intermolecular hydrogen bonding.
·462' G.R.B. Organic Chemistry for Competitions
Note: Al. isopropoxide is a specific reducing agent,for aldehydes and On tre~iting an alkoxide ion with water, the starting alcohol
ketones (without affecting >
C=C< , -C-C:-,-, -N02
..
is obtained.
~ n·.. ..... ..-..
and ether etc).
~L tert. butoxide is used as a catalyst in oppenauer oxidation. It .....
R-O: + H-O-H~ R-O-H + :O-H
oxidises 1° and ~ alcohols into aldehydes and ketones. Base Acid Conjugated acid CoI\iugate base
Metal hydride (M+ H-) or metal amides (M+NH2") are (Alkoxide ion) (Water) (Alcohol)
strong bases and on reaction with alcohol also forms alkoxides. Comparison of acidic character of primary, secondary "
R-:.....OH+ Na+H- ~ R-ONa +112 and tertiary alcohols
Sodium hydride Sodium alkoxide
. The acidic character of alcohols is due to the polar nature
+ -
CH3CH20H + NaNH2 ~ CH 3CHiONa + NH3 of Q-H bond. An electron releasing group (R) increases
Sodamide .Sod. ethoxide electron density on oxygen tending to decrease the polarity of
Alkoxides are extensively employed for the preparation of Q-H bond. This decreases the acid strength, and so, the acid
ethers on treatment with alkyl halide (Williamson synthesis). strength of alcohols decreases in the following order:
R-0Na+ XR' ·~R-O-R·'+NaX H R R
Alkyl halide Ether . I t t
R -+-C-0H > R -+---C-OH > R -+-C-OH
- + B "Heat 1 I . ~
C2H S0 Na + rC 2H s ~C2Hs-0-C2Hs+NaBr
Sodium ethoxide Bromo ethane Ethoxyefuane H H R
(Diethyl ether) 1° Alcohol 2° Alcohol
Alcohols orAlkanols 463'.•
The +1 effect of alkyl group would be maximum in tertiary of esters. The process is known as acylation. When the
(3°) alcohol and ·minimum in primary (10) alcohol. In other hydrogen of -OH group is replaced by CH3CQ- (acetyl)
words, primary alcohols are the strongest acids and tertiary the group, the process is termed acetylation.
weakest. o 0
CI~R'
2. Reaction with mono carboxylic acids: Alcohols
react with organic acids to form esters. The process is known as R-OH + Base) RJR' + HCI
.esterification. It is a reversible reaction and hence it is carried
out in presence of a dehydrating agent like cone. H 2S0 4 or dry CzHsOH + CIOCCH 3 Pyridine) C 2H s OOCCH 3 + HCI
HCI gas which catalysis the forward reaction and also act as a Ethyl alcohol Acetyl chloride Ethyl acetate
protonating agent. With 3° alcahols, the reaction is usually accompanied by
dehydration of alcohols to alkenes or by the formation of 3°
RCOOH + HOR' H 2S04 (conc.) ) RCOOR' + H 0 alkyl chloride.
2
. Acid Alcohol Heat Ester
When HCI gas is used as a catalyst, the reaction is usually
o 0 .
referred to as Fischer-Speier esterification. II Hcl 11 :
CH3-C-CI + HO-C(CH3h-~ CH3-C-Q-i-C(CH3)3
I
Water is removed as soon as it is formed to drive the
equilibrium in the forward direction.
o
H 2S04 (conc.) HCI' II
CH3CooH + HOC 2H s ) CH3COOC2Hs + H20 ~ (CH3)3 C-CI + CH3 -C-QH
Acetic acid Ethyl alcohol Heat Ethyl acetate
FQr alcohols (CH 30H> 1° > 2° > 3°) ROH + (R'CO)zO Base) RooCR' + R'COOH
and the acids are in the order: Alcohol Acetic anhydride Ester Acid
HCooH > CH 3COOH > RCH 2COOH> R 2CHCOOH
>R3CCooH C2 H SOH + (CH 3CO)z0 Pyridine) C2HsOOCCH3
Reversible esterification may be achieved by the following . Ethyl alcohol Acetic anhydride Reflux Ethyl acetate
scheme of reaction.. +CH3COOH
o 0 Acetic acid
II PCls or II C2H sOH The process of acetylation is used to protect the hydroxyl.
CH 3 -C-QH ---'-~) CH3 -C-CI ~----'--~) groups in various reactions. The acetyl derivatives of alcohols
SOCl 2 .
readily hydrolysed to regenerate the alcohols.
o . 5. Alkylation : When alcohols react with dialkyl
II sulphates, the hydrogen ofthe hydroxyl group is replaced by ail
CH3-C-QC2HS +HCI
alkyl group resulting in the formation of ethers.
Mechanism of esterification was contlrmed by isotopic
ROH+R2S04 ----) ROR' +R'HS04
labelling.
C 2H sOH + (CH 3h SO 4----> C2HSOCH3 + CH 3HS0 4
Dimethyl Ethyl methyl Methyl hydrogen
sulphate ether sulphate
I I Note: Ethers can also be obtained when alkoxides are heated with 'alkyl
. In esterification, it is the ~OH group of acid and not that. . halides.
of alcohol that cleaves. /1.
3. Reaction with inorganic acids: Alcohols react with
C2Hs ONa + BrC2HS -=-+ C2H50~H5 + NaBr
Sod.. ethoxide Ethyl bromide Diethyl ether
inorganic acids (except halogen acids) to form inorganic esters. This reaction is tenned WillialJ}.!iOn·s synthesis.
C 2H s OH+HOS020H(conc.)----> C2 H sOS020H +H20 6. Reaction with Grignard reagents : Hydrogen
Sulphuric acid Ethyl hydrogen sulphate (acidic) is provided by alcohols which combines with-alkyl
group of the Grignard reagent to form alkane.
M<
C 2H sOH + HQ-N0 2 (conc.) ----> C 2H sO-N02 + H 20 .. OR .
Ror~.:E~~lMgX---->
Nitric acid Ethyl nitrate
4. Acylation or reaction with acid chlorides and acid + R'H
Alcohol Grignard X Alkane
anhydrides: When alcohols react with acid chlorides or. reagent
acid anhydrides in presence ofa base catalyst, (such as pyridine . /OC 2H s
or dimethylaniline) the hydrogen ofthe hydroxyl group is C2HSOH +. CH3MgI ---->Mg""" + CH4
replaced by an acyl group (RCQ-), resulting in the formation Ethanol Methyl magnesium I· Methane
iodide
G.R.B. Organic Chemistry for Competitions
Reactions Involving the Cleavage ofC-·OH Bond In 3° (and 2°) alcohols, the SN1 mechanism operates.
The order of reactivity in this type of reactions is: however, with tertiary alcohols, no such catalyst is required.
Tertiary alcohol> Secondary alcohol> Primary alcohol. Room temp. ) (CH 3hC-C1 + H 0
(CH3hC-OH + HCI 2
7. Reaction with hydrogen halides: Halogen acids 2-Methyl 2-Chloro-2-
react with' alcohols to form alkyl halides. The reactivity of propan-2-ol (3") methyl propane
halogen acids is in the order of HI .; HBr > HCI > HF and the
reactivity of ROH is in the order of allyl, benzyl> 3° > 2° > 1°. .~Hr -H20
R3C-OH ••=~~ R3 C- OH; . ..
The reaction follows a nucleophilic substitution mechanism. •• . Slow
3" Alcohol
ZnCI
2
ROH + HX ----.,;;;...;...---+) R-X + H 20
Anhydrous
0-·
R3C+ - - - 4 R3C- X
znCI 2
C2H sOH + HCI ) C2H sCI + H 20 Fast 3" Haloalkane
Ethyl alcohol Anhydrous, heat Ethyl chloride
While in primary (l0) alcohols, the rearrangement does not
. ZnCI 2 take place as they follow SN2 mechanism.
CH 3 -CH-CH3 + HCI ) CH3 -CH-CH3 + H20
I Anhydrous I + a- a+
R-OH2 + X- -H X ---R ---OH 2 ]~ R-X +H 20
OH CI (Protonated Transition state I" Alkyl halide
Propan-2-o1 2-Chloropropane I" alcohol)
(2° Alcohol)
H2S0 4{conc.)
. In case of higher alcohols, i.e., the intermediate is 2° C2HSOH + HBr ) C2HSBr + H 20
Ethyl alcohol Heat Ethyl bromide
carbocation that can change to more stable 3° carbocation by
1,2-hydride shift. .
C2HSOH + HI Heat) C2HsI + H 20
CH3 CH 3 Ethyl iodide
I I In case of branched primary alcohol, SN1 mechanism is
CH 3-.CH-· CH-·CH 3 +HCI----tCH3-C-CH2CH3
I ·1 involved, e.g., .
. OH CI CH 3 CH 3
3-Methyl butan-2-o1 (Major product) I HrX- I +
CH 3 CH 3-C-CH20H.. ' CH3-C-CH20H2
I I I·
+ CH3-CH-CH-CH3 CH3. CH3
2,2-Dimethyl propan-I-ol
I CH3
CI
(Minor) -H20 I +
There can be 1,2 hydride shift to get more stable (30) )CtH3-<[-CH2
carbocation. CH3
CH 3 CH 3 CH 3 Methyl shift
I . H+ I -H 20 I +
CH 3CHCHCH 3 ~CH3CHCHCH3--=----+) CH3CHCHCH3
CH 3 CH 3
6H COlH+2 1 2" C~cation·
(less stable)
• I
CH3-·C-.· CH 2 -CH 3 f----CH3-C-CH2-CH3
x- I
3-Methyl butan-2-o1 1,2-Hydriqe shift I . +
X
CH 3 .. CH 3 ::-::N:-"ot:-e-:--:I;;;f,-'-h-ow"":-e-v-er-,-:al-co-'-h--:ol;-:is"""'h:-e-ate-d""'w--"':ith:-c""o-"-nc-.-;;OHI::::--an--:d:-red--=-p""'h-os-p"::""ho-rus-
I . Cl-·· .. I it is converted into alkane.
CH3CCH2CH3 ~CH3C+CH2CH3 RedP
C2 HSOH + 2HI . ) C2H6 + 12 + H20
I
CI
3" Carbocation
(more stable)
Heat
2-Cbloro-2-methyl 8. Readion with phosphorus halides : react
butane with phosphorus pentahalides (PX 5) and phosphorus trihalides
The reaction of 1° and 2° alcohols with HCI gas in presence (PX 3) to yield alkyl halides.
of anhydrous ZnCl 2 is called Groove's method. 3ROH + PX 3 ----t 3RX + H 3P0 3
. Alcohol Phosphorus Alkyl Phosphorus
trihalide halide acid
.Alcohols orAlkanols
Cyclohexanol
80% H 3P04
170·C o
Cyclohexene
minor product.
H+
, CH3CH2CH2CH20H--=---7CH3CH2CH2CH20H2
Butan-I-ol Protonated alcohol
+ -H 20.
)
6>6>6
H 3 C, .' H3 C. , .
"CHOH [0]) . "C=O
H3C/ '.H3 C / ·
Isopropyl alcohol . Acetone
(3C-atoms) (3C-atoms)
11. Dehydrogenation (Action of hot copper) : Primary,
Other reagents for oxidation are:
secondary and tertiary alcohols differ in their behaviour when
Jones reagent (cr0 3 , aqueous H 2S04 and acetone as
the vapours are passed over hot reduced copper at 3000C.
(i) A primary alcohol loses hydrogen and fonnsan solvent) oxidises alcohol without affecting carbon-carbon
aldehyde., multiple bonds, aUylic or benzylic C-H bonds and other acid
sensitive groups. This reaction is carried out at O°C.
RCH 20H Cu) RCHO + H2 (Dehydrogenation)
(1°) Alcohol 3000C Aldehyde cr0 3 , acetone, aq. H2S04
HC==C-CH=CH-CH20H ,)
, onc
CH 3CH 20H . Cu ) CH3CHO+ Il2
HC=C-,cH=CH-CHO
Ethyl alcohol 300"C Acetald~hyde
(ii) A secondary alcohol loses hydrogen and forms a At higher temperature (~bove 25°C), aldehydes convert
into carboxylic acids.
ketone.
Aluminium tert. butoxide, [(CH 3 h COh AI in acetone
R", oxidises I ° and 2° alcohols (particularly) into aldehydes and
CHOH Cu ) R"",C=O + H2 (Dehydrogenation)
R/ 300°C R/ ' ketones (Opplmauer oxidation).' N-Bromosuccinimide
(2°) Alcohol Ketone (NBS) also oxidises primary and secondary alcOhols to
C aldehydes and ketones.
H3C"" H3 " " ,
CHOH > Cu) _ /C=O +H2 Pyridinium chlorochromate (PCC) in CH 2C1 2 (Sarret
H 3C/ 3000C H3 C" '.
reagent) oxidises primary alcohols t-o aldehydes;· [pcC is an
Isopropyl alcohol Acetone
equimolar . mixture of cr0 3, HCI and pyridine i. e.,
(iii) A tertiary alcohol however, undergoes, dehydration to Cr03 ·CsHsN·HCI or (CsHsNH)+CICrOi or Corey's
form alkene.
reagent].
H 3 C"",- /OH C
H3 "/C=CH 2 + H20 Pyridinium dichromate (PDC) is (CsHs NH+h Cr20;-
C Cu)
H3C/ "CH 3 3000C H3Cth, (Dehydration) and it oxidises primary alcohols to aldehyde and secondary
Ten. butyl alcohol 2·Me yl prop-I-ene alcohol to ketone (in excellent yield) without affecting
OO)Alcohol (lsobutylene) carbon-carbon mUltiple bonds. .
This property is utilized to distinguish between primary,
PDC/CH CI '
Secondary and tertiary alcohols. C 6 H sCH=CHCH 20H _ _ _2--,-;Z~) C6 H SCH =CHCHO
13. Oxidation: The nature of the oxidation products
depends on whether the, alcohol is primary, secondary or N, 'N°
~~"y
",O,.H,
tertiary. The oxidising agents usually employed' are acidified
potassium dichromate (K2Cr2071H2S04), acidified, or Y
CH20H ' CHO
"
468 G.R.B. Organic Chemistry (or Competitions
DMSO in (COClh and (C2Hs),3N also oxidises primary It selectively oxidised allylic and
benzylic 10 and 2" alcohols to give
alcohols to aldehyde without affecting carbon-carbon m~ltiple
aldehyde and ketones respectively.
bonds (Swern re~ction).
, Tosyl derivative of alcohols is also oxidised by DMSO. 6. Ag2C0 3 ,in benzene 10 alcohol to aldehyde and 2° alcohol to
ketone.
R-:....CH OH (i) TsCI, ., ) R-CHO , 7. Ceric Ammonium nitrate 1° alcohol to aldehyde and aromatic
.2 (ii)DMSOINaHC0 3 , (CAN) -CH3 group into -CHO.
MnOz selectively oxidises the -OH group of allylic and 8. Sodium hypochloride 2° alcohol to ketone without affecting the
benzyUr 10 and 20 , alcohols to aldehydes and ketones (NaOCJJCH3 COOH) 1° alcohol.
respectively and so is Collins reagent (one mole ofCr03 and 2 14~ Reaction with halogens: Halogens, oxidise primary
moles of pyridine inCH2CI2)' and secondary alcohols to aldehydes and ketones respectively.
The oxidation product then undergoes halogenation.
Mn°2
H2C ,CH-CH20H----=--~) H2C=CH-CHO CI
(acetone)
CH3CH20H ,, 2 ) CH 3CHO -~ CCl 3CHO
Ethyl alcohol [0] Acetaldehyde Chloral
0IH 0
Mn0 2 I , H 3C", Cl C ,
2 ) H3 "/CO Cl
2
CCl 3
C6Hs -CH-,CH3 ---=-~) C6HS -C-CH3
(CCI 4 ) /CHOH )CO
H3C/ [0] H3 C / CH3/
Ketones, are difficult tb be oxidised further, but' on Isopropyl alcohol Acetone . Trichloroacetone
prolonged action of oxidising agents, these are oxidised to 15. Reaction with,' bleaching powder : When the
carboxylic acid or a mixture of acids each containing lesser mixture of ethyl alcohol and bleaching powder is heated,
immber of carbon atoms than the ketone or original alcohol.
,
chloroform is formed. The conversion occurs in three steps.
3 Bleaching powder brings oxidation in first step, chlorination in
H C",CO [0]) CH3COOH + HCOOH [0]) CO 2 + H2 0 second step and hydrolysis in third step respectively,
H3C/ Acetic acid Formic acid
(3C-atotm) (2C-atoms) (IC-atom) CH3CH20H + CaOCl 2 Oxidation) CH3CHO
Ethyl alcohol Bleaching powder Acetaldehyde
(iii) A tertiary alcobol having no oxidisable hydrogen
Hoked to carbon atom bearing hydroxyl group, is stable to +CaCI 2 +H 20
pXid~tio~ under ordinary conditions. However, under drastic
2CH3CHO+6CaOCI2 Chlorination) 2CCl 3CHO
oxidation the carbon chain is ruptured and ketones and acids Chloral
are formed both having fewer number of carbon atoms than the
+3Ca(OHh +3CaC12
original alcohols.
Hydrolysis
H
" ,I ,3
2CH3-C-,-OH
[0] [ 1H3
) CH3 -,C-CH2
]4[0]
)
2CC1 3CHO+Ca(OHh . ' ) 2CHC1 3 ,
Chloroform
+ (HCOOhCa
I ' Conc. HN0 3 2-MethyJpropene ' Calcium formate
' . CH 3 ' (Isobutylene) 16. Haloform reaction: Ethyl alcohol when' heated
Teri. butyl Illcohol with iodine and sodium hydroxide or aqueous sodium
CH 3 carbonate forms a yellow crystalline solid, iodofor,m.
I
CH 3 -C=O ~[O]) CH3COOH + C0 2 + H2 0 C 2H sOH +412 +6NaOH Heat) CHI 3 + 5Nal
Acetone ~ Acetic acid Ethyl alcohol Iodoform Sodium iodide
Some spetifi~ oxidising agents are: + HCOONa + 5H20
Sodium furmate
This reaction like the preparation of chloroform also
1. Chroinic acid,H2Cr04, 1° alcohol to' carboxylic a~id. occurs in three steps:
','
Methyl alcohol does not respond to the iodofonn test. (c) If the solution remains clear, i. e:,no cloudiness is
In place of iodine, bromine or chlorine can be taken when fonned, the alcohol is primary. P
the corresponding compounds bromofonn orchlorofonn are to Note: Primary alcohols do. not react. with Lucas reagent <let· room
be fonned. This reaction in general is known as haloform temperature. It requires high temperature. The benzyl and ·allyl .
reaction. alcohol reacts as rapidly as tertiary alcohols with Lucas reagent
because their cations. are resonance stabilized and stable as 3"
C2HsOH+4Br2 +6NaOH~ CHBr3 +5NaBr cations.
Bromoform
Lucas reagent . ..
+HCOONa +5H 20 H2 C=CHCH 20H ---.=.-...:;) Turbidity within a minute
LUcas reagent
C2HsOH+4Cli +6NaOH~ CHCl3 +5NaCI CH 3CH 2 CH2 0H ; Response lifiera longtime
Chloroform .
+ HCOONa + 5H 20 2. Dichromate test (oxidation test): The test is based
17. Reaction with acetaldehyde: In presence of dry on the fact that thre~ types of monohydric alcohols give
hydrogen chloride, ethyl alcohol combines with acetaldehyde different oxidation products on oxidation. (For details see
forming hemiacetal and acetal. section 9.6-13).
The unknown alcohol is treated with sodium dichromate in
H~l
OH
CH3CH=O+ HOC 2H s Dry gas) CH 3C J / dilute sulphuric acid (orange solution) at room temperatUre ..
Acetaldehyde Ethyl alcohol 100 C ""OC 2 H s The oxidation products are identifIed.
. Hemiacetal (i) A carboxylic acid with same number of carbon· atoms
.. ~~~=~?JOC2Hs (-H 0) ... . /OC2 H S as hi th~alcohol if fonned confinns the primary alcohol:: The·
CH3CH, 2 ') CH 3CH, colour of the solution' changes from orange to green.
'OC 2H s -~'. 'OC 2H 5
(ii) A ketone with same number of carbon atoms as in the
Acetal
(Diethoxyethane) alcohol if fonned confinns the secondary alcohol. The colour
18. Reaction with P2SS: On heating yields thioalcohol. of the solution also changes from orange to green.
(iii) In case the colour of the solution does not change~ i. e.,
5C2HsOH + P2S 5 ~ 5C2H 5SH + P20S it remains orange, the unknown. alcohol is tertiary as it cannot ...
Ethanol Ethanethiol be oxidised under these conditions.
9.7 METHODS OF DISTINGUISHING BETWEEN Primary Secondary . Tertiary
PRIMARY, SECONDARY AND TERTIARY
ALCOHOLS RCH20H
1
[0] Na2Cr20] + H2S04 /1
'" . . .
R"-. .
CHOH
R,
f,,7 C-OH ..
.
I
.n
The following methods are used for distinguishing thr~e types Na :tCrt07
RCHO . Na2C120]
of-monohydric alcohols: [0] +H'SO [0] +H2S04.
Aldehyde . 2 4
1. Lucas test: Alcohols react with an equimolar mixture
of concentrated hydrochloric acid and anhydrous zinc chloride
at room temperature to fonn alkyl halides. [0]1 Na2CriJ7 + H2S~:r ,.;)co . " No reaction (solution
remains or~.ge)
RCOOH ' . '.
ZnCl 2 Acid Ketone
R-OH + HCI ) R-CI +H 20 ·(Orange solution
(Cone.) Anhyd. Alkyl halide (Orange· solution
becomes green) . becomes green)
The three types of alcohols undergo. this reaction at
different rates. The rates of reaction with Lucas reagent conc. t Note: Sodium dichromate in presence of dilute H2So'4 acts as an
HCI + ZnCl 2 (anhydrous)] follow the following order: oxidising agent. It is converted into chrcimicsulphatewhich is
Tertiary alcohol> Secondary alcohol> Primary alcohoi green in colour. The potential equation is:
Na2Cr207 +. 4H2S0C-7 Na2S04 + Cr2(S04)3 + 4HiO + 30
Lucas test is based on this order. An unknown alcohol Sodium dichromate .. Chromic sulphate
(monohydric) is mixed with conc. HCI and anhydrous ZnCl 2 at (orange) .. (ween)· .
room temperature. The alkyl chloride fonned is insoluble in the 3. Victor Meyer's test: In this test; the following steps
medium, thus the solution becomes cloudy before it separates are involved:
as a distinct layer. The following observations are made: (i) Alcohol is reacted with cone. HI or red phosphorus and
(a) If cloudines.s (white turbidity) appears immediately, iodine to fonn the corresponding alkyl iodide.
the alcohol is tertiary. Oi) Alkyl iodide is treated. with silver nitrite when
(b) If cloudiness appears within 5 minutes, the alcohol is corresponding nitroalkane is fonned.
secondary.
470 G.R.B. Organic Chemistryfor Competitions
(iii) Nitroalkane is treated with nitrous acid (NaN02 + .3. Acylation test: Acetyl chloride or benzoyl chloride
H 2S0 4) and th~ solution is made alkaline by addition of excess is added to the given compound or its solution, if hydrogen
of caustic soda. chloride is evolved, it shows that the organic compound is an
alcohol.
I
RCH 1 I
AgNO,
R/l AgN02
method for its preparation was by destructive distillation of
wood. It ocours in combined state in some essential oils, e.g.,
oil of winter green (methyl salicylate), oil of cloves (methyl
R" .
~/CI-N02
benzoate), oil of orange flowers (methyl anthranilate), etc.
General methods of preparation: Methyl alcohol can
RF::' . HONO.
be obtained by the general methods of preparation of
monohydric alcohols .
Manufaeture or Industrial Preparation
1. On a large scale, methyl alcohol is obtained from wood
R-C-N02 No reaction
by its destructive distillation method.
II 1NaOH
NOH
(FLOW-SHEET)
Nitrolic acid Pseudo nitrol Colourless
Manufacture of Methyl Alcohol by Destructive Distillation
1 NaOH . . _... 1
NaOH WOOD
Blood red eolour Blue eolour I
Destructive distillation .
4. Catalytic dehydrogenation: It involves the passing
of vapours of ~lcohol over reduced copper at 300°C and the Volatile Non-volatile residue
product thus formed is identified. products (Charcoal)
(i) Primary alcohols give aldehydes (dehydrogenation). Passed into condenser
(ii) Secondary alcohols give ketones (dehydrogenation).
(iii) Tertiary alcohols form olefins (alkenes). This is
dehydration. Uncondensed gases Distillate
(Wood gas) allowed to settle
(For details see section 9.6-12.)
9.8 ANALYTICAL TESTS FOR ALCOHOLS
I
The presence of a hydroxyl group in an unknown organic Lower coloured Upper layer
layer (Wood tar) (pyroligneous acid)
compound may be detected with the help of following tests. If or creosote (used as Acetic acid 10%, methanol 2.5%
the compound is a solid it is dissolved in an inert solvent, e.g., a timber preservative) and acetone 0.5%
dry ether or benzene.
1. Alcohols are neutral substances towards litmus :The Passed ihrough milk of
lime and distilled
colour of blue or red litmus does not change when alcohol is
added to it.
2. Cerlc ammonium nitrate test : The freshly pre- Distillate Residue
pared solution of ceric ammonium .nitrate (CAN) has yellow (Methanol andacetone) (Calcium acetate)
colour. When few drops of this reagent are added to the given.
compound or its solution if colour changes from yellow to red, Distilled
with
the compound contains a hydroxyl group .. H2S04
2R-OH + (NH4hCe(N03)6 ~ [(ROHhCe(N0 3 )4] Acetone (impure) Methanol (impure)
(b.pt. 56°C) (b.pt. 64SC)
CAN Red complex CH3COOH
Purified by anbydious
Acetic acid
+21~tL calcium chloride
Alcohols or Alkanols
•
2. From water.gas: Now-a~days metha~olis most~y (vi) in the preparation of dyes, medicines and perfumes.
manufactured by this method. Methanol obtamed by thiS Methyl salicylate and methyl anthranilate are used in
method is about 99% pure. The yield is also quantitative. 1?erfumery.
Water gas is formed by passing steam over coke at 1300°C
Analytical Tests of Methyl Alcohol'
C + H 20 1300°C) CO+H 2 1. When W!\fllled with a little salicylic acid in presence of
'---.r--' few drops of conc. sulphuric acid, it gives a characteristic
Water gas
Water gas is mixed with half its volume of hydrogen. The ,OH
.
fragrant smell of oil of winter green (methyl salicylate). ' '
OH
mixtu,re is compressed to approximately 200-300 atmosphere.
01'
It is then passed over a catalyst (ZnO + Cr203) at 300°C.
Methyl alcohol vapours are formed which are condensed.
ZnO + Cr203
CH30H+
, 1 '
0
COOH H2S04(conc,)
~,
,,"
Salicylic acid
Heat ~
COOCH3
Methyl salicylate
+ H20
(iii) as a solvent for paints, oils, perfumes, dyes, varnishes, gums, etc.
(iv) as a preservative for biological specimens.
(v) in the manufacture of acetaldehyde, acetic ,acid, ethyl halides, ethyi acetate, chloroform, iodoform, etc .
. (vi) as an antifreeze in automobile radiators.
(vii) as a low freezing and mobile liquid in scientific apparatus such as thermometers and spirit levels.
(viii) in hospitals as an antiseptic.
(ix) as a fuel in spirit lamps and stoves.
(x) as a petrol substitute (power alcohol).
(xi) laboratory reagent a~ a reaction medium, extractant and crystallizing solvent.
(xii) for making solid alcohol fuel. It is prepared by mixing ethyl alcohol with saturated calcium acetate solution. A solid gel is
fcrmed which is known as canned heat or solid alcohol. It bums like alcohol.
Analytical Tests of Ethyl Alcohol
1. Iodoform test: When a few drops of ethyl alcohol are warmed with iodine and potassium hydroxide, yellow precipitate
of iodoform with characteristic smell is obtained. .
2. Ester test: When ethyl alcohol is heated gently with sodium acetate and concentrated sulphuric acid, a characteristic
fruity odour of ethyl acetate is formed.
3. Acidified potassium dichromate test: 'Ethyl alc()hol when heatat with potassium dichromate and dilute sulphuric acid is
oxidised to acetaldehyde which has characteristic pungent smell. If a paper dipped in ammoniacal silver nitrate solution is dipped
in this solution a black spot appears on the paper due to reduction of silver nitrate by acetaldehyde.
4. eeric ammonium nitrate test: With a few drops of alcohol and dilute ceric ammonium nitrate, a red colour indicates
alcoholic hydroxy group. .
Name Percentage of alcohol '. Source' Name Percentage ·of alcohol Source
Beer 3-6 Barley Whisky 35--40 Malt
Cider 2-6 Apples Rum 45--55 Molasses
Wine (Champagne) 8-lO Grapes Gin 40-45 Maize
Claret 7-13 Grape juice Brandy. . 40--45 Grape juice
Port and Sherry (Fortified) 14-24 Grape juice . Cognac 40--50 Grape juice
Alcoholic beverages when taken in small quantity act as stimulants but when taken regularly in excess, may decrease the
energy of the body, retard the mental powers and damage the liver causing cirrhosis of liver.
The process of determining the percentage of alcohol in a given sample is known as alcoholometry. This is done by
measuring the specific gravity of the sample with the help of hydrometer and then reading the percentage of alcohol against this
value of specific gravity from a standard reference table.
An alcohol water mixture having specific gravity 0.91976 at 15°C and containing 57.1 % of ethyl alcohol by volume or 49.3%
by weight is called proof-spirit. A sample havinghigher percentage of ethyl alcohol in comparison to proof-spirit is referred to as
over-proof (O.P.) and the one having lower alcohol content than proof~spirit is known as under-proof (D.P.). Thus, 15 U.P.
means that 100 mL of the sample contains as much alcohol as 85 mL of proof-spirit. Similarly, 15 O.P. means that 100 mL of the
sample contains as much of alcohol as 115 mL of proof-spirit.
474:··. G.R.B. Organic Chemistry for Competitions
9.11 INTERCONVERSIONS
1. Conversion of primary alcohol into isomeric secondary alcohol, e.g~, n-propylalcohol into isopropyl alcohol:
Br OH
HiS04(conc.) ~r I . . KOH (aq.) ) CH I .
CH3CH2CH20H ) CH 3CH=CH 2 .) CH 3 -CH-CH3 3 -CH-CH 3
n-Propyl alcohol -H2 0 Propylene IsOpropyl bromide or AgOH Isopropyl alcohol
2. Conversion of primary alcohol Into isomeric tertiary alcohol, e.g., isobutyl alcohol into tertiary butyl alcohol
or (2-Methyl propan-1-o1 into 2-methyl propan-2-(1):
Br OH
i CH 3 -cl-
H 2S04 (conc.)
CH 3 -CHCH 2. 0H ---==---'----7) HBr CH
CH 3-C=CH 2 """::'=':"'-7) 3-c- CH 3 KOH (aq.)
----'--7)
CH 3
I -H 20 I I .. I
CH 3 CH 3 OH 3 CH 3
Isobutyl alcohol Isobutene Tert. butyl bromide· Tert. butyl alcohol
3. Conversion of secondary alcohol into iSomeric tertiary alcohol, e.g., 3-methyl butan-2-ol into 2-methyl butan-2-o1:
Secondary alcohol having -OH group adjacent to tertiary carbon atom can be converted into a tertiary alcohol.
CH 3 OH CH 3 CH 3 CH 3
I I H 2 S04 (conc.) I HBr I· I
CH3-CH-CH-CH3 ) CH 3 -C=CH-CH 3 ) CH 3 -C-CH2CH 3 CH 3 -C-CH2CH3
3-Methyl butan-2-o1 H 20 2-Methyl but-2-ene I I
Br OH
2-Br~:llno-2-methyl butane 2-Methyl butan-2-ol
Note: Conversion of tertiary or seconaary into lsomenc seconaary and pnmary alcohol IS not poSSIble. However, hIgher homologues can be converted
into l<)wer homologues.
Ascent of Series
1. Conversion of lower primary alcohol into higher primary alcohol
(a) By cyanide synthesis:
P+ . HNO
RCH20H ----7 RCH 21 KCN) RCH2CN 4H) RCH 2CH 2NH 2 2) RCH 2CH 20H
(ii) CH3CH20H _P_+---7 CH 3CH21 Mg) CH 3CH 2MgI HCHO ) CH3CH2CH20MgI _H_2.,-0-7) CH3CH2CH20H
Ethyl iodide Ether Ethyl magnesium Addition product W n-Propyl alcohol
iodide
CH MgI
3
I H20 I
) CH 3 -C""'-()MgI ---.,;~) CH 3 -C-OH
I H+ I
CH3 CH3
Addition product Tert. butyl alcohol
Descent of Series
1. Conversion of higher primary alcohol into a lower primary alcohol:
(a) RCH 2OH ~ RCHO [OJ) RCOOH NH3) RCOONH 4 Heat), RCONH 2
(b) RCH
2
()H [0\ RCHO [0]) RCOOH NaOH) RCOONa Soda lime) RH e12 ) RCI KOH(aq.» ROH
UV
2. Conversion of higher secondary alcohol into a lower primary alcohol:
OH 0
I H 2S0 4(conc.) 03 / "- 2
CH 3CH 2CHCH 3 ) CH3CH=CHCH3 ----+ CH3CH CHCH 3 Zn/H 0 ) 2CH 3CHO Reduction) 2CH CH 0H
3 2
Sec. butyl alcohol A,-H20 But-2-ene I I Acetaldehyde Ethyl alcohol
0-·-0
3. Conversion of a tertiary alcohol into a lower secondary and a primary alcohol:
H 2S04(conc.) Ozonol",,'s
(CH 3hCOH - - - - i - ) ( CH3hC=CH 2 . J-) CH3COCH3+ HCHO Reduction) CH OH
Tert. butyl alcohol 8, -H20 lsobutene Hydrolysis Acetone Fonnaldehyde LiAlH4 Methlalcohol
(Primary)
I Reduction) CH CHOHCH
LiAlH4 lso~ropYI
alcohof
(Secondary)
Problem 4. How will you distinguish? (i) Methyl alcoholfrom ethyl alcohol, (ii) Ethyl alcohol from chloroform.
Solution: (i)
1. Iodoform test
On heating with 12 and NaOH No yellow compound is formed. ellow compound with characteristic odour is
formed. ' .
2. Oil of wiDter green test
On heating with salicylic acid and cone. H 2S0 4 . Gives characteristic odour of oil ofwinter green. Does not give odour of oil of winter green.
3. Ester test
On heating with glacial acetic acid and cone. H2S04. methyl acetate·· with chaJ:aQt(risti.cIForffis ethyl acetate. which has fruity odour.
. odour.
476 G.R.B: Organic Chemistry for Competitions
(il)
-- Tests Etbylalcohol Chloroform _
1. Iodoform test
On heating with 12 and NaOH Forms yellow crystals with characteristic odour. Does not give the test.
2. Isoc;yaoide test
On heating with aniline and alcoholic KOH No reaction. Forms phenyl isocyanide which has a characteristic
bad odour.
3. Solubility test It is soluble in water. It is insoluble in water.
(CH 3COhO
Acetic anhydride
~~\
CH3CHO
Acetaldehyde
1 [0] •
HCI, d Conc. NH3
-----'..;...;.:..---'-~) C 2H s CI ----..:!.-~) C2HsNH2
C 2H sCN---=::c.:.:...:.=---,-+) C 2H sCOOH
Propionic acid
I Reduction
C2HsCH2NH2
Propylamine
CH 3CH 2CH20H
n-Propyl alcohol
!
160-1700 C
heat with
H2S04(conc.) _
H C=CH Ozonolysis - HCHO [0] ) HCOOH
2EthyleQe 2 - Hydrolysis Formaldehyde Formic acid
~CH3CH2Br----'-'N::::a/-"'ethe=-r--+)
I
CH 2Br
I
CH 2Br
.
KOH(aq.) )
Ethyl bromide
CH 20H
I
CH 20H
CH 3CH2CH2CH 3
Butane
CH 2 0H I I
(i) DU. KMn04
9.12 ETHYLENE GLYCOL, I ; -C-C-.
CH 2 0H (ii) Dil. OW I I .
(ETHANE-1 ,2-DIOl) OH OH
Ethylene glycol is the simplest and most important dihydri,c
I I (Syn -hydroxylation)
-C=C
alcohol. The following methods cim be used for its preparation: OH
1. From ethylene (Lab method): (a) Ethylene is
passed through cold dilute alkaline solution of potassium ,---R_CO...;.2_0H~_b_b__
\/
H 20)
H+
-l-h-
I I
permanganate (Baeyer"s reagent) when it is oxidised to glycol
(Hydroxylation of alkenes) .. o OH '
(Anti-hydroxylation)
rn 2 _ CH 200
I + [0] + H 20 _Ba_ey,,-er_'s_r_ea=ge_nt~) I Note: A compound containing both -OH and -CH20H groups, can
CH2 CH 20H be obtained from alkenes by the addition with formaldehyde in
Ethylene Ethylene glycol presence o,facid as a catalyst. This addition reaction is known as
Prins reaction.
OR + '
. CH2 CH 20H . R-CH=CH2 HCHOtH ) R-C;;.H-CH -CH OH
Alkene HOH I' 2 2
311 +2KMn0 4 +4H20~ 31 '. +2Mn0 2 +2KOH OH ,
CH 2 CH 20H A1kanediol
Ethene Etbane-I,2-diol ?H
Higher alkenes give cis-glycols, CH3-C;;=ffi2 HCHOIH+) CH3-(:-CH2-CH20H
I HOH I
CH3 -CH CH 3 -CH-OH CH3 CH3
II +[0]+H20~ I 2-Methyl propene 3-Methyl butane-l,3-diol
CH 2 CH 2 -OH The -OH group always adds on the doubly bonded carbon
Propene . Propane-l,2-diol which has least number Qfhydrogen (or doublybonaed carbon
CH3CH=CHCH3 + [0] + H 20 ~
But-2-ene
CH3-CH-0H.
CH 3 -CH-OH
I '. 0
. which can form stable carbocation).
..
1 ,
HCHO{H+)I
HOH
Buuine-2,3-diol Cyclohexene
o
Cyclopentene
KMn04 0r
. + [0] -.-OS-0-4~)
(;\H
~OH' OH
Cis-I,2-cyclopentanediol
(b) Ethylene is fIrst converted into ethylene oxide by
passing a mixture of ethylene and air under pressure over silver
catalyst at 200--4000C.
CH 2 A (C I ) CHi"-
.
H 0 Ii ,.... C H 20H
I + 10 2 g. ata yst) I . "0 2') , I
Hydroxylation of a double bond can also be done by the CH 2 2 300°C CH~ Dil. HCI CH 20H
action of osmium tetroxide (OS04) and the cyclic osmate ester Ethylene Ethylene oxide Ethylene glycol
thus, formed on decomposition with ethanolic Na2S03
solution gives glycols in quantitative yield. ' Ethylene oxide can also be obtained by treatment of
ethylene with per acid.
CH 2 0)0\0
# s<
CH 2 CH 2"'-. .
I
CH 2
+
0
Ethylene Osmium tetroxide
£)
~
Pyridine) ,H 2 -O""-os(O
. CH2 -0/ .
Cyclic osmate ester
(Coloured con:plex)
"0 I +C6HsCOOOH-~) /0+C 6H sCOOH
CH 2 . Perbenzoic acid CH 2
1
I
HOH/HCI
CH 2 0H
C.H 20H HO,,- (0
I + _ /Os~ I
(HOH) CH20H . HCY ~O CH 20H
Ethylene glycol Osmic acid Ethylene glycol
Ethylene oxide undergoes hydrolysis when treated with
dilute hydrochloric acid to form glycol. This is an industrial .
method. .
G.R.B. Organic Chemistry (or Competitions
Cyclic ketals or acetal are also called as dioxolanes. it is known as glycerine. It Occurs in combined state as esters of
Formation of dioxolane is a method of protecting carbonyl . higher fatty acids like palmitic (C 1s H 31 COOH), oleic
group for a reaction to be carried out in basic medium. (C17H33COOH) and stearic (C17H3SCOOH) in natural fats
Carbonyl group may be regenerated by either hydrolysis in and oils. These esters are called glycerides.
acid medium or by the addition of periodic acid. , Manufacture
H3~
2
.C SH
: ~ O-CH2
/C4"O!..I+ ---t
H3C",,- . /O-CH2
Superheated steam )
.
CH20H
~HOH
H3C" CH20H H 3C" ' Under pressure I
/C=O+ I /C=0+2HCHO CH20H
C7HS CH20H C2Hs Glycerol
Uses: Ethylene glycol is used: + 3RCOOH
(i) as an antifreeze under the name preston in car radia- Fatty acid
tors. (Waxy solid used in
(ii) in the manufacture of dacron, (terylene), glyptal, di- candle manufacture)
oxan and ethylene oxide. Some examples of fatty ~cids are: .
(iii) as a solvent and as a preservative: C17H3SCOOH Stearic acid (formed by hydrolysis offat)
(iv) as a cooling agent in aeroplanes. ':""'-i"':;'
(v) as an explosive in the form of dinitrate. C 1s H 3iCOOH Palmitic aci~ (formed by hydrolysis offat)
. Pinaeol; 2,3-Dimethyl butane-2,3-diol C 17 H 33 COOH Oleic acid (formed by hydrolysis of oil)
CH3 CH3 r CH 3CH3 The hydrolysis is carried out either by alkali solution (Lye)
I I . ~+~~ I I or by superheated steam.
H3C"",-C= C-CH3 . ) H3C-C-C-CH 3 ,..----------1·
2,3-Dimethyl but-2-ene Dd. alk. KMn° 4 I' I CH2qOCR Naq H CH20H
I ~HOH
I I
OH OH I I
Hydrolysis)
Pinacol CHO: ~ + Naq H
Pinacol on treatment with mineral acids (HCl) undergoes I I
1
I
1 I
CH2Q.QCB ___ Na..Q H CH 20H
dehydration and reamingement to form ketones (pinacolone). Glycerol
Fat or oil Alkali
CH3CH3 CH3
+ 3RCOONa
I I I Soap
H3 C-C- C-CH 3 H+) H3C- C-C-CH3 (Sodium salt of
. I I I I bigher fatty acids)
OH OH 0 CH 3
2,3-Dimethyl butane-2,3-diol 3,3-Dimethyl butane-2-one Since, sodium or potassium salts of higher fatty acids are
(Pinacol) (Pinacolone) called soaps and this alkaline hydrolysis of oils and fats is
This conversion of pinacol into pinacolone is an example called 'saponification'.
In the manufacture of soap (sodium salt of higher fatty
of 1,2-alkylshift and is termed Pinacol-Pinacolone
acids) and fatty acids (required in candle industry), glycerol is
rearrangement (or simply pinacol rearrangement).
obtained as byproduct.
CH 20H 2. By fermentation of sugars: During alcoholic
I . fermentation of sugar about 3% glycerol is formed. However,
9.13 GLYCEROL OR GLYCERINE, CHOH if the fermentation is done in presence of sodium sulphite, the
I,
CH 2 0H
yield can be increased to 25%.
Yeast
." ...
Glycerol is a trihydric, alcohol. It may be considered as C6H1206 -~~) C3HS03 + CH 3CHO + C02
Glucose Na2S03 Glycerol Acetaldehyde
derivative of propane, obtained by replacement of three (Aq. solution)
hydrogen atoms from different carbon atoms by three hydroxyl
groups. Its IUPAC name is propane-I,2,3-triol and in industry,
4Bo G.R.B. Organic Chemistry tor Competitions
3. Synthesis (from pro.pene): Today much of glycerol is obtained from propene (a product of catalytiC cracking of
petroleum).
CH 3 CH2CI CH20H CH 2 0H CH 20H.
I
CH C1 2 ) ~H NaOH (dU.) ) ~ HOC1) ~HCI NaOH(aq.» ~HOH
I 600"C I or Na2C03(aq.) I I I.
CH 2 CH 2 CH 2 CH 20H CH20H
Propene Allyl chloride Allyl alcohol ~-Monochlorohydrin Glycerol
4. From acrolein : Acrolein on reduction with LiA1H4 gives allyl alcohol, which on treatment with Baeyer's reagent gives
glycerol.
CH 2 CH 2 CH 20H
I
CH
LiAlH4 )
- CH
I1 (1% alkaline KMn0 4 cold) I
)CHOH
I [H]. I or H 20 2 I
CHO CH 20H CH20H
Acrolein Allyl alcohol Glycerol .
Physical properties: (i) It is a colourless, odourless, viscous and hygroscopic liquid.
(ii) The liquid is sweet in taste and non-toxic "in nature and steam volatile.
(iii) it is soluble in water and ethyl alcohol but insoluble in ether.
(iv) It has high boiling point, i. e., 290°C. The high viscosity and high boiling point of glycerol are due to association through
extensive intennolecular hydrogen bonding. .
Chemical properties: The molecule of glycerol contains two primary -OHgroups and one secondary -OHgroup. Thus,
it shows characteristics of both primary and secondary alcohols. The carbon atoms in glycerol are indicated as a., ~ and a.'.
a. CH 20H-Primary alcoholic group
I . .
~ CHOH-.Secondary alcoholic group
I
a.'CH 20H-Primary alcoholic group
In general, primary -OH groups are more reactive than secondary -OH group.
(i) Reaction with sodium: Only primary alcoholic groups are attacked one by one and secondary alcoholic group is not
attacked. Sodium forms monosodium glycerolate at room tempemture and disodium glycerolate at higher temperature.
CH 20H CH20Na CH20Na
I ' 1 I
CHOH N a ) CHOH Na CHOH
I Room temp. I High temp. I
CH 20H CH 20H CH 20Na
Monosodium glycerolate Disodium glycerolate
(iOReaction withPCl s , PBr3 and PI 3 : All three -OH groups are replaced by halogen atoms.
CH 20H CH 2 CI
1 I
CHOH +3PCI s ----7 CHCI +3POCI 3 +3HCl
I . I .
CH20H CH 2CI
1,2,3-Trichloropropane
(Glyceryl trichloride)
CH20H CH 2Br
I I
CHOH .+ PBr3 ----7 CHBr + H3 P0 3
I I .
CH 20H CH 2Br
1,2,3-Tribromopropane
Alcohols or Alkonola
!::H
I·
PI, [tI]---->
I
+ ~'.
I
--> + I,
I (Conc.) I
CH20H CH20N02
Glycerol GlYcerYl trinitrate (T.N.G.)
Glyceryl trinitrate is an yellow oily liquid. It is poisonous and causes headache. It explodes violently when heated rapidly or
subjected to sudden shock. Nitroglycerine is not only an explosive but it is also, a medjcine for heart patients as vasbdiiatof.It
releases large volume of gases and occupy 10,900 times the volume of nitroglycerine. '
4C3Hs(ON02h~12C02 +lOH20+6N2 +02'
It becomes a safer explosive when absorbed on kieselguhr. In this form, it is known as dynamite. Dynamite was discovered by
Alfred Nobel in 1867. The other important explosives prepared fro~ glyceryl trinitrate are: .
<a) Blastinllelatin-A mixture of glyceryl trinitrate and cellulose nitrate (gun cotton).
(b) Cordite-It is obtained by mixing glyceryl trinitrate with gun cotton and vaseline. It is smolceless explosive.
G.R.B. Organic Chemistry/Or Competitions
. (vi) Reaction with CH 3 COOH, acetic anhydddeor acetyl chloride: Mono-, di~ and tri-esters are fonned.
CH 20H CH 20COCH 3 ·CH 2OCOCH 3 CH 20COCH 3
• I' " C H3COOH I CH 3COOH I, ' CH 3COOH I '
CHOH' ) CHOH ) CHOH ) CHOCOCH 3
1 or CH3COCI l o r CH3 COCI I or CH 3 COCI I
CH20H CH 20H CH 20COCH 3 CH2OCOCH3
Glycerol Monoacetate Diacetate " Triacetate (Triacetin) ,
, ,(Monoacetin) (Diacetin),
(vii) Reaction with oxalic acid: Different products are fonnedunder different conditions.
(a) At llOOC and witbexcess of oxalic acid, fonnic acid is fonned.
CH 20H •. CH2OOC--COOH CH 200CH CH20H,
1 1 I' ' H 20 I
CHOH +:HOOC--CooH lGO-IlOOC) CHOH ) CHOH ---,,-~) CHOH + HCOOH
I, Oxalic acid -H20 1 1
I Formic acid
CH20H CH 20H CH20H CH 20H
Glycerol Glycerol Glycerol Glycerol'
, IOOno-oxalate' monofo~te
(b) At 2600C, allyl alcohol is fonned.
CH20H ' CH200C
I HooC 2HO ,I I
CHOH + 1 - 2 ) CHOO C
I HOOC I
CH 20H Oxalic CH20H
acid '
Glycerol , Glycerol dioxalate Allyl~cohol
(viii) Dehydration: 'Glycerol when heated alone or with dehydrating agents such as potassium hydrogen sulphate or
phosphorus pentoxideor concentrated sulphuric acid, acrolein or acraldehyde is fonned which has a characteristic bad smell.
H
Ir---~
H-' c+on: CH 2
I
r---~
1
I
I
I
I '
Tautomerises )
: :I
IHO+-C-'-H: L ___ _
CH
I
~_Jl+I-OH CHO
Unstable Acraldebyde or Acrolein
, H (a, P-Unsaturated aldehyde)
Glycerol , or Prop-2-en~l-01
~HOH~" "
,!to]
CH20H .' fO . Ca2 0H CH 20H COOH
I '
Glycerol, 'I, . I . [0] I [0] [0]
COOH
, CO) CO ) CO ) I [O])CO 2,+H 20
I I , I CooH
Oxalic acid
CH20H CooH CooH
Dihydroxy acetone, Hydroxy pyruvic acid Mesoxalic acid
Alcohols or Alkanols
,
HIO 4 is specific reagent for cleavage ofC-Cbond if two -OH groups or -OH and carbonyl group or only carbonyl - C -
( II 1
group are present at adjacent carbons.
CH3 - 'CH-OH " , "
e.g., , I,,+mOr--~CH3CHO+C2H5CHO+m03 +H20
C2H5-CH-OH
C 2 H 5 -CH+C-CH 3 +HI0 4 :---->C 2:H 5 - 'CHO+CH3COOH+HI03
, I :I I ' , ',
OH :0 , "
(x) Formation of cyclic acetal': Glycerol gives acetal when mixture of glycerol and benzaldehyde is heated or treated with
HCI in cold.
CH20H H
I' I
CHOH +·0=C-C6H5
I Benzaldehyde
CH 20H
Glycerol
(xi) Fermentation:
I 2OH~"m
, CH ;ntlS bUtyt
B~'
lC
,
,CH3CH2CH2CH20H
•
n-Butyl alcohol
'
CHOH ' ,
where wis the amount ofalkali, Wamount ofacetyl derivative, Mis the molecular mass ofalcohol and n number ofhydrqxyl groups.
0.336 . ' .
0.436 (92 + 42n) = 56n
or . 92 +42n 0.336=
0.436 x56 =218
n 3 n
or 276+126n=218n or n=3 (The alcohol is trihydric.)
",9.15 UNSATURATED ALCOHOLS
Vinyl alCohol, H 2 C=CHOH, is still unknown. Whenever an attempt is made to prepare vinyl alcohol; acetaldehyde is formed in
its p l a c e . " . .
H 2C=CHBi: + AgOH ~ [H 2C=CHOH] ~ CH3CHO
. Vinyl bromide Acetaldehyde
However, allyl alcohol, CH 2 =CHCH 20H, is known.·
It is prepared by the application of following Inethods:
: (1) From allyl halide: Allyl chloride or allyl bromide undergoes hydrolysis when boiled with water. The fonnation of allyl
alcohol occurs ..
H 2 C=CH--'-CH 2 Br + H 2 0 ~ H 2 C=CH-:-CH 2 0H + HBr
Allyl alcohol
(2) By healing' glycerol with oxalic acid at 260°C •.
CH
.11 .2
Heat)
CH
-2C02
I
CH 2 0H
Allyl alcohol
A/wals or Alkana/s
Properties: It is a colourless pungent smelling liquid. It is soluble in wa~r. alcohol and ether in all proportions. It shows the
properties of an unsaturated compound and a primary aicohol.
CH3CH2CH20H
Pt Propan-I-ol
Br2
CH 2BrCHBrCH20H
2,3-Dibromopropan -1-01
HBr
CH2BrCH2CH20H
3-Bromopropan -1-01
HOCI'
CH 20HCHCICH20H
Glycerol p"monochlorohydrin
A1k. KMn04
CH20HCHOHCH20H
(0+ H 20) Glycerol
Na
H~=CH--CHPH
(AUyI alrohol)
CH 3COOH
H2C=CH-CH200cCH3
Allyl acetate
Hel
H 2C=CH-CH2CI
Allyl chloride
'COOH
Oxidation
I '+ HtOOH
COOH Formic acid
Oxalic acid
CH2-CH-CH2 ' CH2-CH-COOH
Br2
I ' ,I 'I,' . [OJ. ) I' I '"
'Br Br OH HN~, Br Br_
6
CH20H
I Ans tb)]
~) 4. Glucose on fermentation in presence of sodium 'sulphite
gives mainly: '
(a) ethylene glycol and acetaldehyde
(C)~OH
(b) glycerol and propionaldehyde
(c) glyCerol and acetaldehyde '
Ph ,(d) ethyl alcohol and propionaldehyde
[ Ans: (a) But-3-en-2-ol, (b) I-Cyclopentenyl methanol, [Ans ~c)l
(c) 2-Phenylpropan-2-o1] 5. What is the product (A) in the following reaction?
2. A compound soluble in conc. H2S04' It does not (i) BH3/THF ) (A)
decolourise bromine in CCI4 but oxidised by chromic ~ ''(ii)H20 2·OIr
anhydride in aqueous H2S04 within two seconds, turniqg
orange solution to blue, green and then opaque. The original (a) PentaD-I-ol
compound is : (b) 2-Methyl butan-I-ol
(a) an alkene (c) 2-Metbyl butl.)n-2-o1
(b) a primary alcohol (d) 3-Methyl butan-l-ol
(c) a tertiary alcohol [ Ans tal]
(d) an ether 6. Acrolein on complete reduction gives:
(Ans \1»] (a) propanal'
486: G.R.B. Organic Chemistry (or Competitions
Problem 7.. Prepare pentan-I-olfrom (a) Pent-l-ene. (b) I-Bromopentane, (c) I-Bromobutaneand (d) I-Bromopropane.
B2H6 . H20 2
Solution: (a). CH3CH2CH2CH=CH2 ) (CH3CH2CH2CH2CH:zhB OH .) CH3CH2CHlCH2CH:zOH
Pent-I-ene THF Pentan-loOl
OWIH 20
(b) CH3CH2CHiCH2CH2Br ) CH3CH2CH2CH2CH20H + HBr
. I-Bromopentane Pentan-I-ol
, .H
Mg· . HCHO . .• I .' .H 20 ..' . . .' .
(c)ClhCH2~H2CH2Br-~)CH3CH2CH2CH2MgBr )CH3CH2CH2CH2COMgBr~+ CH3CH2CH2CH2CH20H
I-Bromobutane Ether.' .' I.H
H
Mg Ethylene oxide H+ .
(d)CH3CH2CH2Br ) CH3CH2CH2MgBr .' ) CH3CH2CH2CH2CH20MgBr~CH3CH2CH2CH2CH20H
I-Bromopropane Ether
Problem 8. How will you synthesise? .
(a) n-Butyl alcoholfrom acetylene, (b) Allyl alcoholjivmpropane, (c) Glycel'olfrom acetylene.
Solution:
O. . 0
CH2-CH-CH2 LiAiH CH2-C-CH2 . .
KOH(aq.)·
I I
I I I ( 4 I I I L
, CICH 2 -C-CH2CI (~
CI 2
CH3 -C-CH3
OH OH OH OH 0 OH
Glycerol
. @I,
H......Q-CH2 -CH 3 • 'r I' ,
00 .'
..
)CHJCH2--~CH2CHJ--4
+
..
..
CH 3CH2 --~CH2 -CH3
(c)The hydroxyl group in 3,3~dimethyl butan-2-01 undergoes protonation followed by dehydration to form a secondary
carbocation which undergoes a methyl shift to form a more stable tert. carbocation and the removal ofH+ gives a double bond.
",'. H .Me' . . H Me - Me
I .I H+
CH 3 --C-e-CHJ --4 CH3 --C--C-CHJ
I I -H 20 + I 1,2 Methyl shift
) CH3 --CH-C-CH 3 ----''-----'---...,
I I ...I I I
..
:OH Me
3,3-DimethyJ butan-2-o1
H:OH Me Me
[Me=CH J ]
Me Me
I ." ~ ,:-H+ I
CH3 -C=C--CH3 ( , CH 3 -CH-C-CH3
I . I +'
Me Me
2,3-Dimethyl but-2-ene 3° Carbocation
Problem 11. An alcohol (A) .when heated with concentrated H2S04 gives an alkene (B). Whe,! (B) is bubbled through
bromine water and the product obtained is dehydrohalogenated with exc.ess ofsodamide, a new compound (C) is obtained. The
compound (C) gives (D) whim treated with dilute H 2S04' in presence OfHgS04' (D) can also be obtained either by oxidising (A)
with KMn0 4 or from acetic acid through its calcium salt. Identify (4), (B), (C) and (D).
Solution: (D) is obtaitled by heating calcium acetate. It should be acetone.
(CH 3COOhCa --4 CHJCOCHJ +CaC03
(D)
,Acetone '
i. propan-2-ol.
(D) can also be obtained by oxidation of (A). Thus, (A) is secondary alcohol, e.,
H3 C , •
/CHOH [0], ) CH 3COCH 3 + H2 0
H3C KMn04 Acetone ,
(A)
(A) with cone. H 2S04 gives an alkene (propene).
Cone. H2 S04
CH3CHOHCH3 , . ' ) CHJ -CH=CH2
Heat (8)
Propene
(B) reacts with bromine to form 1,2-dibromopropane which on dehydrohalogenation yields propyne.
. ,NaNH2 HgS°4
CH J -CH=CH 2 + Br2 --4 CH3CHBrCH2Br ) CHJC==CH ) CH3COCH3
Propyne(C) , H2S04 Acetone (D)
ProblemJ2. An organic compound ofthe formula, CJHgOJ, gave thefollowing reactions:
(a) On oxidation with nitric acid, it gave a dibasic acid.
(b) With P40 10 , it gave an unsaturated aldehyde.
(c) With PCls , it gave a chlorinated hydrocarbon, with vapour density, 73.5. What structuralformula would you assign to the
compound? .
Solution: The expected compound is glycerol.
Alcohols or Alkanols
CH 2 CH 2°H. COOH
I . P4010 I I
CH ~(-~- CHOH CHOH
I -2Hp I I
eHO CH20H CooH
Acrolein Glycerol TartrOmc acid
1
(An unsatw'ated (A dibasic acid)
aldehyde)
PCI,
CH 2CICHCICH 2CI
Chlorinated hydrocarbon
with V.D. 73.5
Problem 13. Compound X' (molecular formula C s HgO) does not react appreciably with Lucas reagent at room
temperature but gives a white precipitate with ammoniacal silver nitrate solution. With excess ofMeMgBr, 0.42 g of x' gives 224
mL ofCH4 at STP. Treatment of x' with H2 in presence ofPt catalyst followed by boiling with HI, gives n-pentane. Suggest the
structure for x' and write the equations involved.
Solution: Since, the compound does not react appreciably with Lucas reagent, it is a primary alcohol, i.e.., consists
-CH 20R The compound gives a precipitate with AgN03, hence it consists -C::sCHgroup at the extreme. Thus, the compound
maybe:
54321
HC::sC-CH 2 -CH2 -CH20H
4-Pentyn-l-01
Molecular mass of 'X' = 84 g
0.42 g of compound = °8~2 = 0.005 mol
224
224 mL ofCH 4 = 22400 =0.01 mol
0.005 mol of the compound 'X' produces 0.01 motofCH4 with excess ofMeMgBr, it shows that the compound consists two
active hydrogen atoms, one due to hydroxyl group and other due to HC::sC- group. The equations of the reactions involved are:
AgN°3 .
(i) HC::sC-CH2 -CH2-CH20H . ) Ag-C::sC-CH2 -CH2 -CH20H
H 2C=CH-CH20H
Cr03·2CsH sN ) (W) CH30H (
) X
)
(CH 2CI 2 ) H+
[Roorkee 2000]
G.R.B. Organic Chemistry for Competitions
Solution:
1 H,O,H,O
CH 2- 'CH-CHO
1 ,1-'
OH OH
(Z)C 3H60 3
Al .0 (i) HI
Problem 16. (A) , 2 3 ) (B)---'-"---~) (C)
250°C (ii)AgOH
In the above reactions scheme (A) and (C) are isomers. (B) has aformula OfCsHIO' which can also be obtained from the
product ofthe reactions OfCH3CH2 MgBr and (CH3 hCo. Give structures of(A), (B) and (C). IRoorkee2000]
Solution: An alcohol
.o
Al2 3 ) Alkene (i)HI ~ (C)
(A) 2S00C (B) CsHIO (ii) AgOH ,
CH 3 CH 3
I I
CH 3CH 2MgBr +CH 3-C=O ----+ CH3 -C-OMgBr
, ' 1 "
, CH2 CH 3
1 H.oH,H+
CH 3 CH 3
, 1 -H2.o 1
CH 3-C=CH-CH3 E ". CH 3-C-OH
" (Major) Alkene . DehydratIOn
1
CH 2CH 3 .
CH 3 CH 3 CH3
I , Al2.o3 1 (i) HI 1 Al2.o3
, So, CH 3-CH-CH-CH3 ---"-~) CH 3-C=CH-CH3 --':;'':''---4) CH 3- C -CH2CH3 ---=---:=--~)
I ' 250°C (B)CsHIO (ii) AgOH 'I 1500C, (-H2.o)
OH OH
~ q
CH 3 CH3
, 1 (i) B2H6 1 '
CH3 -C=CHCH3 ----=-=----4) CH 3-CH-CH-CH3 ' '
(B) (ii) H 20 2 , .oH- , I'
OH
(A)
Alcohols or Alkanols
Problem 17. Two different Grignard reagents (X) and (Y) produce C6HsCH2C(CH3hOH on reaction with (P) and (Q)
respectively. Give the. structures of (X), (y), (P) and (Q). [Roorkee 2000]
Solution: Grignard reagent (X) + (P) - - - - ,
CH 3
So, HOH, H+ ) CH
3
-~-OH
I
CH 2C 6H S
CH3
HOH,H+
. )C6HsCH2--C-OH
I
I
CH3
o Reduction with LiAlH 4 : It reduces aldehydes, ketones, o Reactions involving the cleavage of O-H bond: The
carboxylic acids and their derivatives into alcohols (even reactivity order is: CH3> 1° > 2° > 3°.
without affecting the> C=C<).
o Action of alkali metals: Formation of alkoxides or
alcoholates (R-ONa).
o Reduction with NaBH4 : It also reduces )C=O o Action of monocarboxylic acids: Formation of esters
compounds to alcohols without'attacking >C , C<
(R-, COOR f).
o Action of inorganic acids (H2S04 or RNO]) :
o Addition of Grignard reagents to aldehydes and ketones
followed by hydrolysis. Formation of inorganic esters (alkyl hydrogen sulphate or
o Primary alcohols are obtained when GR is treated with alkyl nitrate).
oxygen or formaldehyde or ethylene oxide.
o Action of acid halides, acid amides and acid anhydrides:
o Secondary alcohols are obtained when GR is treated with Formation of esters (RCOOR f) in presence of pyridine
an aldehyde other than formaldehyde. (base catalyst).
o Tertiary alcohols are obtained when GR (1 mole) is o Alkylation (action of dialkyl sulphates): Formation of
treated with ketones. GR (2 moles) on reacting with esters ethers (R-O-R f).
(RCOOR f) also form tertiary alcohols. o Action of Grignard reagent: Formation of alkanes
o Fermentation of carbohydrates : Alcohols can be corresponding to the alkyl (R-) group of GR.
prepared by the fermentation of carbohydrates under the o Reaction withjJIX: Alcohols react with HX to form
influence of certain enzymes. corresponding i1~-)X. The order of reactivity ofHX is :
Diastase converts starch into maltose. HI > HBr> HCl > HF. Hence, HCI reacts only in presence
Invertase converts molasses (sucrose) into a mixture of of a catalyst (anhyd. ZnCI 2 or AlCI 3). The increasing order
glucose and fructose. of reactivity of alcohols towards HX is: CH30H < 10
MaJtase converts maltose into glucose. alcohol < 2° alcohol < 30 alcohol < benzylic and allylic
Zymase converts glucose or fructose into ethyl alcohol. alcohols.
o Oxo process: Amixture of alkene, carbon monoxide and o Reaction with conc. HCI jn presence of anhyd. ZnCl2
hydrogen reacts together 'at high temperature under (1: 1) is Lucas reaction. ",
pressure in presence of catalyst cobalt carbonyl or cobalt o Reaction with PCl s and PBr3 : Alcohols react with
carbonyl hydride to form an aldehyde which is reduced (by PCls or PBr3 (Br2 and red P) or PI 3 (I2 and red P) to yield
Zn-Cu) to obtain alcohol. It is also called carbonylation alkyl halides. '
or hydroformylation. o Reaction with thionyl chloride (SOCI 2) : Alkyl
o From alkanes: A mixture of methane and oxygen (9 : 1 , chlorides (pure) are formed when an alcohol reacts with
by volume) is passed over copper catalyst at 250°C under SOCl 2 in..presence of pyridine base.
pressure, oxidises to methanol. ' o Reaction with NH3 (ale.) : Alcohols react with alc.
o Alkanes having 3° H atoms are o~idised by KMnO 4 or solution ofNH 3 when their vapours are passed over heated
cr0 3 to 3° alcohol. Al 20 3 at 400-500DC to form a mixture of 1D, 20 and 30
Physical properties :
amine.
o Lower alcohols are volatile liquids having characteristic Reactions involving both the cleavage of R- and-OR
smell (alcoholic) and burning taste. Alcohols are neutral groups:
and highly toxic substances. The lower alcohols are o Dehydration of alcohols : Alcohols on dehydration
completely soluble in water arid solubility decreases as the 'yield alkenes. The order of ease of dehydration is : 30> 20 >
molecular weight increases. The solubility in water is due 1°. Dehydrating agents for alCOhols are : conc. H2S84/~
to intermolecular, H-bonding between water and alcohol, H3P04/~ anbyd. Al203/~ KHS04/~ anhyd. ZnCl2/A
molecules due to their polar character. Isomeric alcohols and P20s/Aetc.
have solubility in the order: 1° > 20 > 30. o 2° and 30 alcohols 'always' give El reaction. More
The b.pts of alcohols are much higher as compared to the
substituted alkene is more stable.
corresponding alkanes, ethers and alkyl halides, it is due to
intermolecular association of their molecules through
o The less stable carbocation undergoes l,2-hydride or
1,2-methyl or l,2-phenyl shift to form more stable
H-bonding. Among isomeric alcohols, the'b.pts are in the
carbocation.
order: 1° > 20 > 30.
Chemical properties: R-OH o 1° alCohols whose P-carbon atom is 10 or 2° gives E2
o Primary alcohols are most reactive when there is a cleavage reaction.
of O-H bond while tertiary alcohols are most reactive o Dehydration of alcohols depends upon the temperature of
when there is a cleavage of C-O bond. the reaction. With conc. H2S04 at 170°C or Al 2 0 3 at
Alcohols or Aikanols
350-400°C, alcohols give alken~, while conc. H 2S0 4 at o Lucas test: An equimolar mixture of conc. Hel and
140°C or with Ah03 at 250°C, ether is fonned. anhyd. ZnCl 2 (Lucas reagent) is added to an alcohol to·
o Dehydrogenation with copper catalyst at 300°C : fonn alkyl halides.
1° alcohol loses hydrogen and fonns an aldehyde. "20 If cloudiness or turbidity or thick oily layer appears
alcohol loses hydrogen and fonns a ketone. A 3° alcohol immediately it will be 3° alcohol.
undergoes dehydration rather than dehydrogenation to give Ifcloudiness appears within 5-10 minutes, the alcohol is 2°.
an alkene. This property is used to distinguish between 1°, If the solution remains clear, i.e., no Cloudiness is fonned at
2° and 3° alcohols. room temperature, the alcohol is 1°.
o Oxidation: The compound that is fonned by oxidation o Victor Meyer's test: This test is based on the fact that
depends upon the nature of alcohol (10 or 2° or 3°). The 1°, 2°, 3° nitroalkanes behave differently towards HN02
oxidising agents used are K2Cr2071H2S04, acidic or and alkali. The three aIeohols react with ll1I2' AgN02,
alkaline KMn0 4, dil. HN03, etc. NaN021H2S04 or HN0 2 and made alkaline with NaOH
o Primary (1°) alcohols are oxidised to aldehydes, which are, orKOH.
in tum easily oxidised to carboxylic acids both containing o 1° alcohol gives blood red colour, 2° alcohol blue colour,
the same number of carbon atoms as the original alcohol. while no colour with 3° alcohol.
o Secondary (2°) alcohols are oxidised to ketones containing Dihydric alcohols
same number of C-atoms .. Ketones on oxidation under Two -OH groups on adjacent (vicinal) carbon atoms are
drastic condition fonns mixture of acids each having lesser called glycols. Their common name is alkylene glycol and
number of C-atoms than the ketone or original alcohol. IUPAC name is alkanediol.
o Tertiary (3°) alcohols do not easily undergo oxidation. But Methods of preparation
on vigorous oxidation gives several produCts, i.e., an o From alkenes : By hydroxylation with cold, dil. alkaline
alkene, a ketone (containing less number ofC-atoms) and KMn0 4 (Baeyer's reagent) or by oxidation with
then carboxylic acids (containing even more less number of Os04/ethanolic Na2S03·
C-atoms). o By passing a mixture of ethylene and air under pressure
o Reaction with halogens: Halogens first oxidise primary over silver catalyst at 300°C to fonn ethylene oxide which
and secondary alcohols to aldehydes and ketones on hydrolysis in presence ofdil. HCl gives ethylene glycol.
respectively. The oxidation product then undergoes o By passing ethylene through hypochlorous acid followed
halogenation. S02Cl2 also acts both as an oxidising agent by hydrolysis with NaHC03 yields glycol.
and halogenating agent. o From glyoxal: By reduction with LiAlH4 .
o Reaction with bleaching powder: When a mixture of o From 1, 2- dibtomoethane : By hydrolysis with boiling
ethyl alcohol and bleaching powder is heated, CHCl3 is Na2C03 solution.
fonned.
Properties
o Haloform reaction: Ethyl alcohol when heated with 12 o Glycol is colourless, syrupy hygroscopic liquid, b.pt.
. and NaOH or aq. Na2C03 fonns a yellow crystalline solid, 197°C, highly soluble in water (due to H-bonding).
iodofonn. The iodofonn test is given by C2HSOH, o There are two primary alcoholic groups present in glycol
o molecule. Its reactions are therefore, those of primary
I alcohols (-CH 20H) twice over.
CH3CHO, CH3COCH3, -C-CH3 group,
o Action of alkali metal (Na or K): Fonnation of mono
CH3CH(0H)-. group, 2-01s, CH 3CH(OH)COOH and and disodium glycollate at 160°C.
o o Action of PCls or PBr3: Fonnation of 1,2-dihalo
II (chloro or bromo) ethane.
CH3 -C---,-COOH, etc.
o Action of PI 3 : Fonnation of ethylene iodide (unstable)
o Reaction with acetaldehyde: Ethyl alcohol combines
and finally ethylene.
with· acetaldehyde in presence of dry HCl gas to fonn
hemiacetal and acetal. o Action of HCI gas at 200°C : Fonnation of 1,2-
dichloroethane.
Distinction between 1°, 2° and 3° alcohols
o The following methods are used for distinguishingpri., sec. o Action of CH3COOH or SOCI 2 : Fonnation ofglycol
and tert. alcohols. diacetate.
o By catalytic dehydrogenation: Heating with copper o Action of conc. HN03/conc. H2S04 : Formation of
catalyst at 300°C. ethylene dinitrate (used as an explosive) ..
o By oxidation method (Dichromate test): Using strong o Action of he~t at 500°C: Fonnation of ethylene oxide.
oxidising agent like acidified K2Cr207' o Oxidation with dil. HN03: Fonnation of oxalic acid.
'494 . G.R.B. Organ.ic Chemistry [or Competitions
/'·1
(iii) CO + H2 300"C, 200 aim.)
•
(C»(D) (E»
.
D
(xii) C 6H 6 + H2C=CHCH2CI AlCI 3 ) (A) (i) BH3/THF )
(xxviii) CH3 -CH-CH 2 . PCI~ (A) l(OH(aq.» (B) P13 ) (C)
(ii) H 20 2, Olr·
(B)~C9HlO(C)
Heat .
"'/
(i) NaNH2
o .
H 2/Pd-BaS04
(xxix) CH3CH2C-CH. ) (A) )
(xiii) RCH=CH2 Hg(OAch) (A) NaBH4 )(B) (ii) CH 3CH2Br
THF, -H20
(B) Alkaline KMn04 ) (C) [nT 2002]
(xiv) CH3CH2CH=CH2 H2S04 ) (A) HOH ) (B)
C2H S
(xv) CH 3CH=CH2 ~H6) (A) H20 2 ) (B) (xxx) CH3CH 2-C=CHCH3
I Hs(OAc)2
/H
20) (A)
~H3CH=CH2 . NaBH4
(xvi) (i) H+
° ) (A)
(ii) O2 (A) . ) (B)
(m)·lfv
~B}
, (b) n-Butyl alcohol from acetylene.
(c) Allyl alcohol frOm propene.
(d) 'Glycerol from acetone or isopropyl alcohol or propene.
(e) Glycerol from carbon and hydrogen or acetylene.
.
(h) 'Isopropyl alcohol from acetaldehyde. (k) I-Phenylethanol from styrene (vinyl benzene).
, (i),2-methyl propan-l-ol from formaldehyde. (I) Tert: amyl alcohol from methyl magnesium iodide.
(j)' Cyclohexyl methanol from formaldehyde. (m) 3,5-Dimethyl hexan-3-o1 from butan-2-one.
tHlnt: (a)CH3CH 2CH3 ~ CH 3CHCICH3 KOH(aq.» CH3CHOHCH 3
, " h ,
lNoNH, .
H~C==C-Na CHFHzBr) HC==CCH2CH3 Hz ) H 2C=CHCH2CH3 _.2HB~r~
(Lindlar's catalyst) , , H 20 2
BrH2CCH2c;H2CH3KOH(aq.) ) HOCH2CH2CH2CH3
H
" Alternative CH 3CH 2CH ' CH z '(i) B2 6 ' ) CH3CH 2 CFI2CH20H
, ',', (ii) H 0 /0H-
2 2
LiAlH H3C"-..
. 4) /CHOH
H3G' ,
Isopropyl alcohol
(e)
O.
(g).
"6·
MgB,.. '·1 .
(j) , ., "+H-C=O OOH+ Mg(OH)B'
" ". ,Formaldehyde
Cyc1Qne:otylmiig. CyCiohexyl
bromide' methanol
, ' '
~CH2 +~
HCH3
, Vinyl belizene',
, (~t]'rlT~e)
_H;:..20_/H_+
6, /
I-Phenyl ethanol
Alcohols or Alkanols
(I)
~
OH
H 20IH+ . I
(m) CH -CH-CH2MgX + CH - C -CH2CH3
3 3 . ~ CH 3 -?H-CH2 -?---, CH2CH 3]
I Butan-2-one
CH 3 . CH3 CH3
Isobutyl mag, halide, 3,S-Dimethyl hexan-3-o1
rr HSO.'
lnt : HC=CHH~O: ) CH 3CHO
Red',
n
~C2HsOH Lu:: 1
J
r
(e) n-Propyl alcohol from ethyl alcohol (four steps).
. Na~~(aq)··· . 1
CH3CH2CH2CH2 CI ., . ) CH3 CH2 CH2CH2 0H J
·sott . · . G.R.B. Qrganic Chemistry fOr Competitions
[
: Hint:C2HsOH + 12 + NaOH
' . .
~ CHl3~
Heat
CH=:=CH ]
C2H s MgBr
-Mg(OC H )B:
I. H 20
O..:..H)-B4/ CH3-i-C2Hs
Clh-i-C2Hs ---M-d,......
I ]
2 s
IS.How will you distinguish among the following pairs? C2HS C2HS
(~t n-Propyl alcohol and isopropyl alcohol. . (b) Give the structures or" Grignard reagent and the
./ [ Hint :!I-Propyl .alcohol .does not give iodofonn test while substrate (aldehyde or ketone) that would react to form
, isopropyl alcohol fonns yellow crystalline iodofonn when 2,4-dimethylpentan-3-ol. .
.,,, treated with 12 and NaOH.] . Hint:Striicture of2,4-dimethyl pentan-3-ol is,
[
(b)' p-Butyl, sec. butyl and tert. butyl alcohols. ...:c. CH 3 CH 3
.' [Hint:Perf0 Lucas test. Tert. butyl alcohol reacts imniediately
ntl I I
CH3-CH- CH-CH- CH3
. with (znC1 2 + HCl) Lucas reagent to fonn cloudiness,
secondary butyl alcohol reacts within 5 minutes while
. I
OH
n-butyl alcohol does not react at all at room temperature.] This is fonned by reacting (C.H 3h CHCHO with (CH 3h CHMgX.
(c) Ethanol and chloroform. ' . . CH 3 H H
[ Hint :Chlorofoim gives isocyanid; test. This testis not given by
.' I I .' '1
CH3-CH-C=O+(CH3hCHMgX~ (CH 3hCH-C-OMgX
ethanol. Ethanol gives iodofonn test. This test is not given I j
by cj1lorofonn.] . . ........ . . CH(GH3h
[ Mg<~
(d) Ethanol and acetone.
[ Hint:Ethanol undergoes oxidation with dilute acidified
+ (CH 2),CH H-CH(CH2J,' ",0 I
. K2Cr207 and gives pungent odour due to fonnation of
. acetaldehyde. Acetone gives a red colour with sodium
T
OH
nitroprusside in the presenc~ofNaOH.] (c) By giving one chemical reaction prove that glycerol is
.(e) Ethanol and propan-I-ol. an alcohol.
[ Hint :E.thyl alcohol (ethanol) gives iodofonn test. This test is not [ Hint :Give reaction with acetyl chloride or PCl s or sodium.
'. . .given bypropan~l:01.] These reactions show that -OH gr:oups are present in
glycero1.]
(f) Glycerol and sugar solution.
(d) Give one specific example to prove that enzymes are
[ Hint :Glycerol on heatirig With KHS0 4 fonns a pungent odour
very specific in their action.
'" . compound, acrolein. This test is not given by sugar
(e) Write dcwn the names and structures of two
solution. The pink colour of borax and phenolphthalein
disappears when glycerol is added" to it in cold but, compounds obtained by dehydration Of ethyl alcohol.
reappears on heating, however,. it again disappears on (f) List the reagents commonly used to reduce carbonyl
cooling. This test is not given by sugar solution.] functional groups to alcohols. .
(g) Allyl alcohol and n-propyl alcohol. . (g) Give the expected r~duced product from the reaction of
[Hint :Allylalcohol reacts immediately with Lucas reagent and (a) CH 3COCH 2COOH, (b) OHCCH2COOCH3,
(c)CH 3CH 2COCH 2CH 2Br, (d) P -02N-C6H4CHO
gives white turbidity.in less than one minute while
with (i) NaBH 4, (ii) LiAlH4. . _
n-propyl alcohol does not react.]
19. Write short notes on: . (h) Give the product of the oxidation with Mn02 of: .
(a) Fermentation, (b) EnZyni.es, (c) Power alcohol, (a) CH3CH2CH=CHCH20H .
(d) Iodoform test, (e) Methylated or denatured spirit, . (b) C6HsCH20H
(f) DestructivedistIDation of wood, (g) Absolu,t~ al~ohol, (c)C6HsCH(OH)CH2CH20H
(h) Rectified spirit, (i) Proof-spirit, (j) Dynamite, (d) CH3CH=CHCH2CH2CH20H
(k) Alcoholometry. '. (i) Give the product ofthe oxidation with Jones reagent of:
20.(a) Write the structural formula of the main. orgamc (a) CH3CH=CHCH(OH)CH3 (b) C6HllCH20H
product formed when ethyl acetate is treated with twice CD How can a primary alcohol be. oxidised to an aldehyde?
the'molar quantity of ethyl magnesium bromide and the 21. (i) Arrange the following in order of their increasing
reaction mixture is poured into water. basicity:
.' 0 OMgBr ,H20,.OH- ,CH30H, CH30-
". . . II CiHsMgBrl . (ii) Arrange the following in order of their increasing
Hint~H3~G-OC2Hs ---=--"---=---4) CH3-C-OC2Hs
boiling point:
I n-butane, ethanol, water,propane.
C2HS
, .'"
j:
•
Alcohols or Alkanols 501
,-
(iii) Arrange the following in order of their increasing (x) Why is it not pos~ible to obtain a halide by reacting
boiling point: ROHwithX-?
n-butane, n-butanoI, n-butyl chlonde, isobutane. mint: OH- is a very poor leaving group. Acid con~erts it to H20,
(iv) Arrange the primary, secondary and tertiary alcohols a better leaving group.]
into decreasing order of reactivity towards sodium. (xi) CICH2CH 20His stronger·acid than CH 3CH 20H.
(v) Arrange the primary,secoBdary and tertiary alcohols Jli:in't: The electron withdrawing CI deloca\i~es the negative
into decreasing order of acidity. charge on the oxygen atom of the OH group.]
(vi) Arrange the following in order of their decreasing (xii) Hydration6f 3-phenylbut-l-ene in dil. H 2S04 forms
boiling point: 2-phenylbutan-2-011nstead of3-phenylbutanc2-oL
pentan" 1-01, 2-methyl butan-2-01, 3-methyl butan-2-01. /"
Jli:int: Hydration gives an intennediate 2° C+, Which undergoes a
(vii) Arrange the following in decreasing order of rate of
hydride shift to more stable 3° carbo cation. .
dehydration with cone. H2S04:
H+ . + ". . Hydride shift
CH3CH2CH(OH)CH2CH2CH3 (A) H3C-CH-CH=CH2-=---7H3C-CH-CH-CH3 .)
1 . 1 "---""
(CH3 hC(OH)CH 2CH 2CH 3 (B)
C6H S G6 HS
(CH3hC(OH)CH(CH 3h (C) (2°)
CH 3CH 2CH(OH)CH(CH 3 h (D) "(' '" ..;,. OH
+ " . ~H- I' 1
CH3CH2CH2CH2CH2CH2CH20H (E) H3C-C-CH2CH3 --==---? H 3C-C-CH 2CH 3 J
22. Give reasons for the following: 1 I' .
(i) Molecular mass of ethanol and dimethyl ether IS the C6 HS C6Hs'
(3°)
.same, however ethanol is a liquid at room temperature . (xiii) The compound (CH3 h C-CH(OH)CH3 on treatment
. but dimethyl ether is a gas. with cone. HCl forms (CH3 h C(Cl}--C:H(CH 3h
mint: Hydrogen bonding in ethanol.] instead of (CH 3 h C-CH(Cl)CH3.·
(ii) Anhydrous CaCI 2 · cannot be used for drying ethanol. Jli:int: The first fonned 2° C+ re~anges by a CH3 shift to more
Jli:int: EthanoHonns an addition compound with CaCI 2.] stable 3° C+, which then gives the 3° chloride.]'
(iii) Tertiary alcohols form the turbidity fastest in Lucas (xiv) Acidcatalysed dehydration of (.butanol is fa~ter than
test while primary alcohols' form slowest. that of n-butanol.
mint: The acid catalysed dehydration ofiln alcohol proceeds via ;;
mint: Positive inductive effect is maximum in tertiary alcohol
the fonnation of acarlxication: .
and hence -OH removal is facilitated.]
H C~ H ~~- /
(iv) Ethyl alcohol reacts with HI but not with HCN. 1 1 +H+ I I -H20
mint: C2H sOH is a weak base and hence reacts with stronger H-'--C-C-CH3 ~ H-C-C-CH3 ' '
acid.] 1 1 1 I.
HOH H +OH 2
(v) Sodium metal can be used for drying diethyl ether but
H Cfh
H CH 3
not ethanol. 1 ~H+ I'
1 1
mint: Ethanol has active hydrogen atom which reacts with H-C-C-CH3 ~ H-C=C-'·"CH 3
sodium.} 1 + ..~ ,
(vi) Propanol, unlike propane is soluble in water. H
mint: Propanol can fonn hydrogen bonding with wat~r but Since, 3° carbocation is more stable than 1°, the
propane does not possess this property.] dehydration in 3° proceeds. faster than 1 ° . ] '
(vii) Propanol boils at a higher temperature than propane. (xv) When (-butanol and n-butanal are separately treated
mint: In propanol, there is intennoleeul~r hydrogen bonding but with a few drops of dilute KMn0 4, in one case only,
in propane, there is no hydrogen bonding.] the purple colour disappears and a brown precipitate
(viii) Why glycerol has high viscosity and is miscible with .is formed. Which of the two alcohols gives the above
water in all proportions? reaction and what is the brown precipitate?
Sint: n-Butanol is oxidised by KMn04 and not t~butanol as the
mint: Hydrogen bonding is responsible for high viscosity and
latter does not contain H atom attached to carbinol'carbon
solubility in water.] atom.
(ix) Reactivity ofRK with alcohols is in the order, . +--
CH3CH2CH2CHiQH + KMn04 -7 CH 3CH 2CH 2COOK + Mn0 2
HI> H~r> HCl> HF. n-Butanol Purple PotassiJIIII 'f Brown
mint: Bond dissociation energy of HX is in the order, (I ° alcohol) benzoate· - ppt.
HI < HBr < HCI < HF.] +KOH
G.i.B..Organic Chemistry for Competitions·
CH 3 (E)C2HsCONH 2 1
mOOH ·CR3
(ii)~
OR
(C)©()
(iii) ~
OR
(iV
ANSWERS
lQ1: (xiii) (A) RCH---'CH2
OH
I I
HgOAc
(xiv) (A) CH3CH2~CH~CH3; (E) CH3CH2-CH-CH3
I
(E) R-CHOHCH3"
I
. HS04 OH
1. (a) alkane, different; (b) methyl alcohol; (c) (CH3hCHOMgBr, (xv) (A) (CH3CH2CH2hB; (E) CH 3CH 2CH 20H
H 20/H+ ; (d) zymase; (e) invertasej (f) ketone; (g) thioalcohol; (h)
ethanol; (i) absolute alcohol; oj two, secondary; (k)sweet, conc...
(xvi) (A) CH3-
y
H-CH 3 ;. (xvii) (A)CH 3 - H-CH 2D
y
OD OH
HN03/conc. H2S04; (l)'decreases; (m) dehydration; (n) ketones;· CH 3
(0) distilled; (P) undistilled; (q) acetone; (i) acetaldehyde; (s)
95.57% ethyl alcohol and 4.43% water; (t) not bej(u) higher; (v)
I .
-(xviii) (A)CH 3-C-CH2CH 2D; (xix) (A) (CH 3hC=CHCH 3
alcohol, esterification; (w) C2HsHS0 4; (x) unfit; (y).nitro· . I
glycerine; (z}tertiary, primary. OD
2. (a) False-gives tertiary butYl alcohol; (b) False-no reaction;
... (c) True; (d) False-does not give iodoform test; (e)FaIs~
contains methyl alCOhol, acetic .acidand acetone; (f) True; (g)
(xx) (A)·.~
True; (h) True; (i) False-secondary and tertiary alcohols· are OH
dehydrated easily than primary alcohols; G) True; (k) True; (I) (xxi) (A) (CH 3 hCH-:--C-(C2H s)2
False-forms chloral; (m) True; (n) Truej(o) False-weaker acids·· . I
OH
than water; (P) True; (q) True; (r) False-less acidic than primary
alcohol; (s) False-it can act as a base; (t) False-is a dihydric
alcohol; (u) False-miscibility decreases with increaseiri
(xxii) (A)'~
molecular mass and increases with branching of chains; (v) TrUe; OH
(w) False-forms acrolein; (x) False-contains two primary and o
one secondary alcoholic groups; (y) True; (z) True. (xxiii) (A) (CH3hCH--::-C-ONa
I
,1. (i) (A-8); (B-5); (C--7); (1)--6); (B-2); (F-:3); (Q--:-I);
(H-4).
(ii) (A:--7); (B-li); (C-I); (0-8); (E-3); (F-2); (G---5);
(xXiv) (A) ~ .
(H-4)1 o
. Z .
.... (i) C6H120 6 . ymase) 2C2HsOH + 2C0 2 o
. . II
;I,'
I I '
(11) 2(C6H120S)n + nH 20
• • • Malt extract
.
..
) n(C12H 22 0 11 ) (xxv) (A) RCH 2yH-OTs; (~) CH3-C~O:--yHCH2R;
Starch (DIastase) Maltose . CH3 . CH 3
ZnO+CrO
(iii) CO + 2H2 2 3) CH3 0H (C) HO-CH-CH2R .
·30O"C, 200 aim. Methyl alcohol
. ~H3."·
(iv) C12H22011 + H 20 Invertase) C6H1206 + C6H120 6 (-)
Sucrose Glucose Fructose
O~ /O,~
(v) ~HsOH [OJ) CH3CHO~ CI3CHO NaOH) CHIj C. ~H2
+HCOONa·
(xxvi) (A) I I
(vi) At 110°C HCOOH andat 260·C allyl alcohol. o-?'C'o/CH2
(vii) (A) CHjCH=CH 2; (B) CH 3CHBrCH3 ;
(e) CH 3CHOHCH 3
(viii) (A) C2H sCI;
1
(B)C2H sCNj
(B) [Y=o;
(e) ~HsCOOH; . (D) C2HsCOONH4;
:i
Alcohols or Alkanols '503
C H OH
Na ) C H OH
2 5
..
CH3COCI + HOC2 H s - - t CH3COOC2Hs + HCl 2 s
(e) Iodoform is formed. (d) CH3COOH LiAlH4) CzHsOH
C2 H sOH [01) CH 3CHO ~ CI3CHO NaOH) CHI3 + HCOONa (e) C:iHsNHz + HN0 2- - t CzHsOH + N2 + HzO
Na/C 2HsOH
(1) Chloroform is formed. (1) CH3CHO I ) C 2H s OH
,or Pt/H2
(g) Dioxane is formed. v'O _ .
CH20H HO-CH2 H-"O . /CH2-CH2",-
I ."
(g) HCHO + CH3Mg8r -'} CH3CH20MgBr ~C2HsOH
. H °
. H
I + I:r 4 ) 0 0 + 2H 20
''+Mg(OH)Br
CH 20H HO-CH2 Heat "'-CH2 -CH2/ ...•.... 11. See properties of ethyl alcohol.
12. (a) C 2 H sOH + PCls
(b) C2 H sOH + CH3COCI·
(c) C2H sOH + K2CrZ07/HzS04 '
(i) At room temperature, ethyl hydrogen sulphate is formed. (d) CzHsOH + I z + NaOH
(I) C 2H sOH + H 2S0 4 - - t C 2H sHS0 4 + H 2 0 (e) C 2H sOH + Conc. H 2S04 at l70°C
(2) At 140°C, diethyl ether is··formed. (1) C2 H sOH + H 2S0 4 at 140·C
HzS04 CzHsOH PCl s '[II] .
CzHsOH ) CzH sHS04 ) C2HsOC2HS + H 2S04 (g) CzHsOH ~ C 2H sCI ~ CZH 6
(3) At 170°C, ethylene is formed.
(h) CzHsOH ~ C2H sCI . NaNH2 ) C2 H SNH2
H 2S04 170"C (i) C 2 H s OH + CaOCl 2 (Bleaching powder).
C2H sOH ) C2H sHS04 ~ C2~ + H 2S04
14. (a) heat with KHS04 or P20 S, (b) heat with oxalic add at 260°C,
(4) While at O°C., ethyl oxonium hydrogen sulphate is
formed. (c) treat with large amount of HI, (d) treat with a mixture of cone.
H 2S04 and fuming nitric acid, (e) treat with pci s • (1) treat with
conc. HN0 3_ . ' .
G.R.B., Organic Chemistry for Competitions
IS. (a) heat with conc. H2S04, (b) treat with PCIs, (c) oxidise with Addition of water to both these alkenes give the desired alcohol.
conc. HN03 , (d) heat at 600°C, (e) heat with zinc chloride.
20. (e) (i) Ethylene, CH2=CH2 and(ii) Diethyl ether, C2H sOC2H s .
(f) H2/catalyst, LiAlH4• NaBH 4, NaH.
(g), (a) (i) CH 3CH(OH)CH 2COOH, .
CY 3
I-Methylcyclo
CH
L 0~CH3.lt-
3° Carbocation
()'
Methylene
(ii) CH3CH(OH)CH 2CH20H hex-I-ene ! •• cyc10hexane
(b) (i) HOH 2CCH2COOCH3, (ii) HOH 2GCH 2CH20H H20:
(c) (i) CH3 CH 2CH(OH)CH 2CH2 Br,
(ii) CH3CH2CH(OH)CH2CH3
(d) (i) p-02N:-C6H4CH20H, (ii) p-H2N-C6H 4 CH2 0H
[LiAlH4' being a more reacth:e reducing agent than NaBH 4, a SH3
O-R .::!!-
q+ + O .
CH
OR3
' -H20
OH (Dehydration)'
'.
av if'Pentan-2-o1
.
"
.,".
+
~
OH
Pentan-3-o1
,
,
cr ifLOj'Lif
H2 0 to alkenes occurs in accordance with the Markownikoff's 2-Cyelohexyl 2-Cyclohexyl 2.Cyc1ohexylidene
rule. . butan-2~ol but-2-ene butane
(i)
O
CR
OR3 -H20
(Dehydration) I
CYI . CR
3
'+
. '.
CR2 Addition of H20 to both alkenes give the desired alcohol.
I-Methylcyc1o '
hexan-I-ol
I-Methylcyclo
hex-I-ene
6¥
. Methylene
cyc10hexane
2-Cyclohexyl .
bUI-2-...
-H+! H 0: 2-Cyc1ohexylidene
butan,
2-Cyclohexylbutan-2-o1
Alcohols or Alkanols
OBJECTIVE OUESTIONS
Set I: This set eontalns the qilestions with single eorreet answer. ll. When vapours of secondary alcohol are passed over hot
I. The general molecular formula, which represents the copper at 300°C, the product formed is:
homologous series of alkanol is: (CBSE (Med.) 2006) (a) aldehyde 0 (b) ketone 0
(a) CnH2nO 0 (b) C".H 2n +I O 0 (c) alkene 0 (d) alkane 0
(c) CnH2n+20 0 (d) CnH2n 0 2 0 12. Which of the following is soluble in water?
2. Which one is a primary alcoholic group? (a) CH 30H 0 (b) CHCl 3 0
(c) 'CCI4 0 (d) CS 2 ' 0
(a) -CH20H 0 (b) )CHOH 0
13. CO+ H2 X (catalyst) ) CH 3 0H, the catalystXis:
(c) ~-OH 0 (d) "'-C--e./ 0
300"CJ300 atm
/ ./1 1"'- (JEE (Orissa) lOI 0)
OH OH (a) Fe 0 (b) Cr203/ZnO 0
3. Butan-2-01 is a: (c) V2 0 S 0 (d) Al 2 0 3 0
(a) primary alcohol 0 (b) secondary alcohol 0 14. Hydrogen bonding is maximum in:
(c) tertiary alcohol 0 (d) dihydric alcohol 0 . (a) ethanol 0 (b) diethyl ether 0
4. Total number ofisomeric alcohols with formula C4H lO O is: (c) ethyl chloride 0 (d) triethylamine 0
IS. Reason for excessive solubility of ethyl alcohol in water is
(a) 2 0 (b) I 0
due to:
~3 D~4 0
(a) covalent bonding 0
S. Number of isomers represented by molecular formula
(b) ionic bonding 0
C4 HlO Ois:.
(c) hydrogen bonding with water 0
(a) 3 0 (b) 4 o (d) none of the above 0
(c) 7 0 (d) 10 o 16. Alcohols of high molecular masses are:
6. An isomer of ethanol is:
(a) soluble in water 0
(a) methanol 0 (b) dimethyl ether • o (b) soluble in water on heating 0
(c) acetone 0 (d) diethyl ether o (c) insoluble in all solvents 0
7. Lucas reagent is:
(d) insoluble in water 0
(CET (Punjab) 2006; JIPMER (Med.) 200B)
17. HBr reacts fastest with:
(a) anhydrous ZnCl 2 and conc. HCI . 0
(a) 2-methylpropan-2-oID (b) propan-l-ol [J
(b) anhydrous ZnCl 2 and conc. HN03 0
. (c) propan-2-o1 0 (d) 2-methyl propan-l-ol 0
(c) hydrous ZnCl2 and conc. HN0 3 0
lB. An industrial method for the preparation of methanol is:
. (d) hydrous ZnCl2 and conc. HCI 0
(a) by reacting CH4 with steam at 900°C with a nickel
B. Which one of the following alcohols reacts most readily
catalyst . 0
with Lucas reagent?
(b) by reduction of HCHO with LiAlH4 0
(a) CH3CH2CH20H o (c) by catalytic reduction of CO in presence of
ZnO-Cr203 0
(d) byreactionofHCHOwithNaOH(aq.) 0
CH3
I 19. Reaction, CO + H2 + H2 673 K, 300 atm. )?
(c) CH 3-C-OH o ~
Water gas .
Cr203-Zno
I may be used for manufacture of:
CH3
9. Primary, seCondary and tertiary alcohols are distinguished (a) HCHO 0 (b) CH 3COOH 0
by: (c) HCOOH 0 (d) CH30H 0
(a) oxidation method 0 20. Which reagent can bring about,
(b) Lucas test 0 RCOOH ~ RCH 20H transformation?
(c) Victor Meyer's method 0 (a) Sn + HCI 0 (b) LiAlH4 in ether 0
~~~~~~ 0 (c) Na and C 2H sOH 0 (d) H2 and Pt 0
10. the product of reaction CH3CH 20H 300"C)? is: 21. Which of the following is an alkoxide?
Cu (a) CH2=CH2 0 (b) CH3MgI 0
(a) C 2H 6 0 (b) CH3COCH 3 0 (c) (CH3COhO 0 (d) CH3CH2CH20Na 0
(c) CH 3 COOH 0 (d) CH 3 CHO 0
Alcohols or Alkanols 507
22. Rectified spirit contains: 35. Absolute alcohol cannot be obtained by simple fractional
(a) 75% alcohol 0 (b) 95.5% alcohol o distillation because:
(c) 56% alcohol 0 (d) 100% alcohol o (a) pureC2HSOHis unstable 0
23. Enzymes are: (b) C 2H s OHforms hydrogen bonding with wa.ter 0
(a) carbohydiates 0 . (b) lipids o (c) boiling point of C2HsOH is very close to that of water 0
(c) proteins 0 (d) none of these o (d) constant boiling azeotropic mixture is formed with
24. When wine is put in air, it becomes sour due to: water 0
(a) oxidation ofC 2H sOH o 36. Wood spirit is known as: [AFMC 2004)
(b) reduction ofC2H s OH o (a) ethanol . 0 (b) methanol 0
(c) formation of C2HsNH2 o (c) acetone 0 (d) benzene 0
(d) dissolution of CO 2 o 37. Isopropyl alcohol on oxidation forms:
25. Witt~ contains: (a) acetone 0 (b) ether 0
(a) CH3 0H o (b) C2H sOH o (c) methane 0 (d) acetaldehyde 0
(c) C6 Hs OH o (d) glucose o . 38. Primary amine on treatment with NaN0 2 and HCI yields:
26. Fermentation is anla:
(a) nitro compound 0 (b) ammonia 0
(a) endothermic reaction o (c) secondary alcohol 0 (d) primary alcohol 0
(b) exothermic reaction o 39. Identify (2) in the reaction series,
(c) polymerisation reaction o
(d) condensation reaction o H 2 C=CH2 ~ (X) Hydrolysis) (y) NaOH ) (Z):
27. Glucose and fructose are converted into C2H s OH in . I 2 (excess)
45. The compDund (B) fDrmed in the fDllDwing. sequence Df 59. Out Df n-butyl alcDhDI, sec. butyl alcohDI, tert. butyl alcohDI,
reactiDns, the highest bDiling PQint is expected fDr:
PCI AI 0 (a) n-butyl alcohDI 0 (b) sec. butyl alcQhDI 0
CH3CH2CH20H---4 (A) c. K! H ) (B)is:
(c) tert. butyl alcDhDI 0 (d) same fDr all 0
(a) propene 0 (b) prDpyne o 60. When ethyl alcohol is dissQlved in water, it is accDmpanied
(c) prDpane 0 (d) propanal. o with:
46. EthanDI cDntaining SDme methanO'l is called: (a) absorptiDn .of heat and contractiQn in vDlume 0
(a) methylated spirit 0 (b) rectified spirit. o (b) eVDlution Dfheat and cDntractiDn in vQlume 0
(c) absDlute spirit 0 (d) nDne .of these o (c) absQrptiQn .of heat and'increase in vDli.une 0
47. Rectified spirit can be dried with: (d) eVQlution of heat and increase in vQlume 0
(a) CDnc. H2S04 0 (b) CaO 0 61. 23 g .of sQdium metal shall react with methyl alcDhQI to' give:
(c) anhydrDus CaCl2 0 (d) slaked lime 0 (a) I mQle .of Dxygen 0
48. When vapQUrs Df an alcDhDI are passed Dver hDt reduced . (b) I mQle QfhydrQgen 0
copper, alcohDI is cDnverted intO' alkene, the alcOhDI is: (c) 112 mQle DfhydrQgen 0
(a) tertiary 0 (b) primary 0 (d) 1/2 mQle Df .oxygen 0
(c) secondary 0 (d) none Df these 0 62. Which Dne .of the fQllQwing statements is wrQng?
49. Ethyl alcDhDI .on DxidatiDn with dB. acid K2Cr207 ~ves: (a) CH30His used fDr drinking purpQses D.
. (a) fQrmic acid 0 (b) fQrmaldehyde 0 (b)CH30His highly pDisQnQus cQmpQund 0
. (c) acetic acid 0 (d) acetaldehyde 0 (c) CH3 0His most acidic alcQhol 0
50. Lucas reagent is used to' distinguish amDng primary,
(d) CH30His sDluble in water 0
63. Which .of the fQIIQwing alcDhDls is least sQluble in water?
secQndary and tertiary: •
(a) alkyl halides 0 (b) aliphatic amines o (BHI:1 2002)
(c) arDmatic amines 0 (d) alcDhDls o (a) CH30H 0 (b) C3H70H o
51. . Lucas test is used for the determinatiQn Df: (c) CIOH210H 0 (d) C4 H9 0H o
64. InglycerQI mQlecule, there is:
[eET (Karnataka) 2009)
Ca) aldehydes 0 (b) phenQls 0 (a) .one primary alcQhDlic grDUp 0
(c) carbDxylic acids 0 (d) alCDhQls 0 (b) DIle secondary alcQhQlic grQUP 0
(c) twO' secQndary alcQhQlic grQUPS 0
52. ChlDrine reacts with ethanO'l to' give:
(a) ethyl chlQride 0 (b) chlDrQfQrm 0 (d) twO' primary and .one secondary alcohQlic grDUpS 0
(c) acetaldehyde 0 .(d) chlDral 0 65. FQr .one mQle Df glycerQI, mDles .of acetyl chlQride required
53. ThecQmpQund that will nQt give iQdQfQrm test with alkali fQr cQmplete acetylatiDn are:
and iQdine is: (a) .one ' 0 (b) twO' 0
(a) diethyl ketQne o (b) ethanQI 0 (c) three 0 (d) fQur 0
(c) acetone 0 (d) iSQprDpyl alcDhDI 0 66. The alcQhQI which fQrms fats with fatty acids is:
54. TO' prepare prop~-2-QI frQm ~ethyl magnesium iQdide, the
. (a) ethanQI 0 (b) methanQI o
chemical reagent required is: (c) iSDprQPyl alCDhQI 0 (d) glycerQI o
(a) CH3CHO 0 (b) HCHO 0 67. AcrQlein is fQrmed when glycerQI is heated with:
(c) CH3COCH3 0 (d) CO 2' 0 (a) acidified KMn04 0 (b) Br2 water o
55. FQr a given alcQhQI, the Drder .of reactivity with halQgen . (c) KHS0 4 0 (d) HN0 3 o
acids is: 68. GlycerDI Dn treatment with .oxalic acid at llO"C fQrms:
(a) HI> HBr> HCI 0 (b) HI> HCI> HBr 0 (a) allyl alcDhDI 0 (b) fQrmic acid o
(c) HCI > HBr> HI 0 (d) HBr> HI > HCI .0 (c) CO2 and CO 0 (d) glyceric acid o
56. Which is u.P. spirit (containing ethyl alcQhDI by vQlume)? 69. The explQsive nitrO' glycerine is: ,I
(a) CH3 -CH-CH2 o (b) CH3-CH,-CH 2 o 107. Dehydration of methyl alcohol gives:
I I I I (a) methane 0
NH2 NH2 OH OH (b) ethane 0
o (d) CH3-C=CH2 o (c) methyl hydrogen sulphate 0
(c)CHr-C==CH
I . (d) dimethyl ether 0
OH lOS. UpOn oxidation, an alcohol gave a carbonyl compound
.containing same number of carbon atoms. The alcohol is a:
95. Denatur.ed spirit is mainly used as a:
(a) drug 0 (a)' primary alcohol 0
(b) good fuel . 0
(b) secondary alcohol 0
(c) material in preparing oils 0 (c) tertiary alcohol' 0
(d) solvent in preparing varnishes 0 (d) primary or secondary alcohol 0
96. The product formed, when glycol is heated with zinc 109. Liquor poisoning is (,iue to the presence of:
chloride, is: . (a) methyl alcohol 0
(a) acetaldehyde . 0 (b) glyoxal 0 (b) ethyl alCohol 0
(c) carbonic acid 0
(c) oxalic acid 0 (d) ethylene oxide· 0
97. The product formed, when glycol is heated withconc.
(d) bad compound in liquor 0
110. An enzyme which changes cane sugar into glucose and
H2S04, is:
fructose, is known as: .
(a) ethylene DJb) dioxane o (a) zymase 0 (b) maltase 0
(c) ethylene oxide 0 (d) glyoxal o (c) invertase 0 (d) diastase 0
9S. Oxalic acid is formed when glycol is treated with:
111. An enzyme which changes maltose into glucose is known
(a) H2S04 0 (b) H3P04 o as:
(c) HCI 0 (d) HN03 o (a) zymase 0 (b) maltase 0
99. Which of the following is generally present in tonics?
(c) invertase 0 (d) diastase 0
(a) Ethanol 0 (b) Ether 0
(c) Ethanal 0 (d) Chloral 0 111. Methylated spirit is:
(a) 100% alcohol 0
100. The compound formed by reaction of ethylene glycol and
(b) 95.6% alcohol + 4.4%.water 0
periodic acid (HI04) is: (CBSE (Med.),lH9)
(c) 90% alcohol + 9% methanol + pyridine, etc. . 0 .
(a)' carbon dioxide 0 (b) formic acid 0 (d) power alcohol 0
(c) formaldehyde 0 (d) glyoxal 0 113. Denatured spirit is a mixture of ethyl alcohol, methyl
101. Dynamite is prepared by mix,ing nitroglycerine with: alcohol and:
(a) saw dust and ammonium nitrate 0 (a) acetic acid 0 (b) pyridine 0
(b) cellulose nitrate 0 (c) acetone 0 (d) water 0
(c) saw dust alone 0
114. Ethanol is used for the preparation of:
(d) conc. sulphuric acid 0
(a) Tincture iodine 0 (b) Toluene 0
101. When 3,3-dimethyl butan-2-o1 is heated with conc. H2S04
(c) DDT 0 (d) Carbon tetrachloride 0
the major product obtainedis: (PMT (Kerala) 1007;
115. In the following reaction, what is (X)?
Punjab CET (Engg.) lOOS)
(a) 2,3-dimethyl but-I-ene o (X)
Na2S03
) Glycerol + acetaldehyde + C02
(b) 3,3-dimethyl but-I-ene IJ
(a) Ethyl alcohol 0 (b) Glucose 0
(c) 2,3-dimethyl but-2-ene o (c) Glycol 0 (d) Allyl alcohol 0
(d) cis and trans isomers of2,3-dimethyl but-2-ene o 116. Glycerol on oxidation with bromine water or sodium
[Hint: See solved problem 13(c}]
103. Isobutyl alcohol is Ii: . hypobromite or Fenton's reagent yields:.
(a) primary alcohol 0 (b) secondary alcohol o (a) oxalic acid 0 (b) meso-oxalic acid 0
(c) tertiary alcohol 0 (d) diethyl ether o (c) formic acid 0 (d) glycerose . 0
. 104. The hydrolysis of oils and fats with alkali is called: 117. When glycerol is treated with phosphorus tri-iodide, the
(a) esterification . 0 (b) saponification 0 main product obtained is: .
(c) dehydration 0 (d) .acetylation 0 (a) . glyceryl tri-iodide 0 (b) propene 0
105. Which is used in alcoholic beverages? (CPMT100S) (c) allyl iodide 0 (d) isopropyi iodide 0
(a) Phenol 0 (b) Glycerol 0 US. Glycol on treatment with PI3 gives mainly:
(c) Methanol 0 (d) Ethanol 0 (a) ethylene 0 (b) ethylene iodide :0
106. When ethyl alcohol reacts with nitric acid, it forms: (c) ethyl iodide 0 (d) ethane 0
(a) nitromethane 0 (b) nitroethane o
(c) ethyl nitrate 0 (d) diethyl ether o
Alcohols or Alkanols 511
(c)~ o (d),0. o
(a) elimination of water
(b) fonnation of an ester
(c) fonnation of carbocation
0
0
. 0
OH OH (d) protonation of alcohol molecule . 0
154. The reaction of Lucas reagent is fastest with: 163. Which of. the following functional groups, cannot be
. . : (PMT (MP) 2M) reduced to alcohol using NaBH4in ethanolic solution?
(a) (CH3hC-OH 0 (b) (CH3hCHOH 0 pJPSEAT1004]
(c) CH3(CH2hOH 0 (d) CH3CH20H 0 (a) R~R 0 (b) RCOCI 0
ISS. Propan..l-ol may be prepared by,the reaction of propene (c) R-COOH D (d) R-CHO 0
w~: (CBSE (Moo.) 2_; AIIMS (Moo.) 20031 164. Acetyl bromide when reacts with 'excess of CH3MgI
(a) H3B03 0 (b) B2H6/NaOH-H202 0 followed by treatment with saturated solution of NH4CI it
. 0
gives: IAIEEE 10041
. II·",' . (a) acetone 0
(c) H2S04/H20 0 (d) CH3 -C-O-O-H 0
(b) acetamide 0
, 156. What is fonned when glycerol reacts with ID0 4? '
(c) 2-methyl-2-propanol 0
(DPMT2_) (d) acetyl iodide . . 0
(a) Two molecules of fonnic acid and one molecule of 165. Among the following compounds which can be dehydrated
fonnaldehyde' 0 very eaSily? (AIEEE 1004)
(b) Two molecules offonnaldehyde and one molecule of (a) CH3CH2CH2CH2CH20H 0
fonnic a c i d . 0 OH
(c) Three molecules offonnic acid . 0 I'
(d) Three molecules of formaldehyde 0 (b) CH3CH2CH2CHCH3 0
157. The compo1,llld that will react most readily with NaOH to CH'
fonnmethanol is: (liT (S) 2001] I 3
+ (c) CH3CH2-C-CH2CH3 ' 0
(a) (CH3)4Nr 0 (b) CH3-O-CH3 0 . I '.
(c) (CH3 hSr; 0 (d) (CH 3 hC-C1 0 OH
158. Ethanol when reacted with PCI 5 gives (A), POCl3 and HCI. (d) CH3CH2CHCH2CH20H o
. I '.
(A) reacts with silver nitrite to fonn(B) (major product) and cn3
AgCl, (A) and (B) are respectively:' (EAMCET 2001)
(a) C2HSCI and C2HsOC2HS 0 166. Which of the following is industrially prepared by passing
(b) C2 H 6 and C2HsOC2HS 0 ethylene i'nto hypochlorous acid? [BHU 1004)
(c)C2HsClandC2HSN02 0 (a) Ethylene glycol D·
(d) C2H6 and C2HSN02 .. 0 (b) Ethylene oxide 0
159. Given are cydohexanol (I), acetic acid (II), 2,4,6- (c) Ethyl~me din,jtrate 0
trinitrophenol-(III) and phenol (IV). In these the order of (d) Ethane . 0
decreasing ,acidic character will be: . .. 167. The -Ollgroup of an alcohol or the -('DOH (carboxylic
'(CBSE (PMT) Prelims 2010) acid) can be replaced by -CI using:
(a) II>III>IV>I 0 (b) II>III>I>IV 0 (CUSE (Moo.) 1004; UGET (Moo.) 1007]
(c) III>II>IV>I 0 (d) UI>IV>II>I 0 (a) phosphorus p,Slntachloride '0
160. Excess of ethanol when heated with cone. H2S04 at 140°C, (b) hypothlorous acid, 0
(c) chlorine , .\ 0
the compound obtained is: (AFMC 2~2]
(a) ethene 0
(d) hydrochloric acid r: 0
(b) diethyl sulphate 0 168. ~CH3 ~ [F] ~ 'C4Hg Br2! j"'
169. The best reagent to convert pent-3-en-2-01 into pent-3-en- 177. When phenyl magnesium bromide· reacts with tertiary .
2-one is: (AIEEE 2005] butanol, the product formed will be : [llT (8) 2005]
(a) acidic penrianganate 0 (a) phenol 0
(b) acidic dichromate 0 (b) benzene 0
(c) c~mic anhydride in glacial acetic acid 0 (c) tertiary butyl phenyl ether 0
(d) pyridinium chlorochromate 0 (d) tertiary butyl benzene 0
170•. Acid catalysed hydration of alkenes except ethene leads to 178. Which is the best reagent to convert cyclohexanol into
the formation of: (AlEEE 2005) cyclohexene? [llT (8~ 2005)
(a) primary alcohol 0 (a) Cone. HCI 0
(b) secondary or tertiary alcohol 0 (b) Cone. HBr 0
(c) mixture of primary and secondary alcohols 0 (c) Cone. H 3P0 4 0
(d) mixture of secondary and tertiary alcohols d (d) Cone. HCI with ZnCl 2 0
171. When alcohol reacts with cone. H 2.S04 , intermediate 179. Match the List I with List n and pick the correct matching
compound formed is: (AFl\fC 2005) from the codes as given below: [PMT (K;erala) 2006]
(a) carbonium ion 0 List I List II
(b) alkoxy ion 0 A. Propane-I,2,3-triol 1. Cyclic ether
(c) alkyl hydrogen sulphate 0 B. Ethane-I,2-diol 2. Absolute ethanol + petrol
(d) none of the above 0 C. Tetrahydrofuran 3. Dynamite
172. The only alcohol that can be prepared by the indirect D. Power alcohol 4. Denatured alcohol
hydration of alkene is : lAFMC 2005) E. Methylated spirit 5. Terylene
(a) methyl alcohol 0 Codes:
(b) ethyl alcohol 0 (a) A--::-I, :8-:-2, C-3, 0-4, E-5 0 /
(c) propyl alcohol 0 (b) A:'::"'l, B-3, C-5, 0-4, E-2 0
(d) isobutyl alcohol 0 (c) A-3, :8-:-2, C--4, 0-5, £:--1 0
173. Among the following the most stable compound is : (d) A-3, B-5, C-l, 0-2; E--4 0
(AllM82005) (e) A--4,B-I,C-5,0-3,E-2 0
(a) cis-I,2-cyclohexanediol 0 180. In the Victor Meyer's test, the colours given by 1°,2° and 3°
(b) trans-I, 2-cyclohexanediol 0 alcohols are respectively: (PMT (Kerala) 2006)
(c) ciS-I, 3-cy~lohexanediol 0 (a) red, coloUrless, blue 0 (b) red, blue, colourless 0
(d) trans-I, 3-cyclohexanediol 0 (c) colourless, red, blue 0 (d) red, blue, violet 0
174. Which will give chiral molecuie? [DPMT 2005] (e) blue, red, violet 0.
181. Phenol can be distinguished from ethanol by the follOWing
o reagents except (PET (Kerala) 2006]
(a) sodium 0 (b) NaOHlI 2 0
o (e) neutral FeCI 3 0 (d) Br21H20 0
(e) phthalic anhydride/cone. H2S04 and NaOH 0
o 182. The major product formed in the following reaction is:
184. Reaction of esters with Grignard reagents give rise to:. (a) C2H s CI 0 (b) C2H s COOCH3 0
IPMT (HP) 2006) (c) C2 H sOH 0 (d) C2H 6 0
(a) primary alcohols 0 (b) secondary alcohols 0 194. In the following sequence of reactions,
(c) tertiary alcohols 0 (d) ketones 0
185; Glycerol on oxidation with bismuth nitrate prodUces:
CH3CH 20H P+I2)(A)~(B) HCHO) (C) H20) (D)
ether .
. IBHU2006] the compoundD is: [AIEEE 2007]
(a) glyceric acid 0 (b) glyoxalic acid 0 (a) propanal 0 (b) bu~al 0
(c) oxalic acid 0 (d) meso oxalic acid 0 (c) n-butyl alcohol 0 (d) it-propyl alcohol 0
186. The end product of the reaction is: IBHU2006] 195. A fruity smell is obtained by the reaction of ethanol with:
C2H sOH ~ (A)
0 [BCECE (~ed.) 2007; JIPMER (Med.) 2008]
KCN) (B) H3 +) (e)
(a) CH3COCH3 0 (b) PCIs 0 .
(a) propanol 0 (b) propanoic acid ·0 (c)" CH3COOH 0 (d) CH3CHO 0
(c) propanamide 0 (d) none of these 0 196. An organic compound 'X' on treatment with pyridinium
187. When compound 'X' isoxidised by acidified potassium chlorochromate in dichloromethane gives compound' Y'.
dichromate, compound 'Y' is formed. Compound 'Y' on Compound 'Y', reacts with Iz and alkali to form
reduction with LiAlH4 gives 'X'. 'X' and 'Y' respectively tri-iodomethane. The compound' X' is:
are: [EAMCET (Engg.) 2006) (EAMCET (Engg.) 2007; AIIMS2008J
(a) C2H sOH,CH3COOH 0 (a) C2 H sOH 0 (b) CH3CHO. 0
(b) CH3COCH3 , CH3COOH ·0 (c) CH3COCH3 0 (d) CH3COOH 0
(c) C2H sOH, CH3COCH3 0 197. Methyl alcohol when reacted with carbon monoxide using
(d) CH3CHO, CH3COCH3 0 cobalt or rhodium as catalyst, compound 'A' is formed. 'A'
on heating with HI in the presence of red phosphorus as
. 188. CH3CH20H~CH3CHO~CI3CCHO
Step 1 Step 2 catalyst 'B' is formed. Identify 'B':
In the above reaction, the role of Cl 2 in step I and step. 2 IEAMCET (Med.) 2007; CPMT 20081
respectively is: IEAMCET (Engg.) 2006] (a) CH 3COOH 0 (b) CH3CHO 0
(a) oxidation, chlorination 0 (c) CH3CH21 0 (d) CH3CH3 0
H3 )CH-OH P + Br2 ) ~ (X),
(b) reduction, chlorination 0 C
198.
(c) oxidation, addition 0 H3 C
(d) reduction, substitution 0
(X) is: (AMU (Engg.) 20071
189. Starch is converted to ethanol by fermentation, the sequence
CH3
ofenzymes used is: (DPMT 2006]
(a) amylase, maltase, zymase 0 I
(a) CH3 -CH-CH2CH3 o
(b) diastase, maltase, zymase 0 CH3 ·
(c) amylase, invertase, zymase 0
0
I .
(d) amylase, zymase, maltase (b) CH3-C-CH3 o
190. Ethylene oxide whtm treated With Grignardreagent yields: . I
[CBSE (Med.) 2006] CH3
(a) cyclopropyl alcohol 0 (b) primary alcohol 0 H 3C " /CH3
(c) secondary' alcohol 0 (d) tertiary alcohol 0 (c) .. /CH-CH" o
191. Tert. butylalcoholis: (CPMT 2006] H3C CH3
(a) 2-methyl propan-2-o1 0 CH3
(b) 2-methyl propan-l-ol 0 I
(c) 3-methyl butan-I-ol 0 (d) CH3 -CH-CH2CH2CH3 o
(d) 3-methyl butan-2-01 0 LiAIH .
192. Which of the following is dihydric alcohol? 199. CH3COOH 4 ) (A),
(PMT (Haryana) 2006; Ludbiana CMC (Med.) 2008] H 0+ .
(a) Glycerol 0 (b) Ethylene glycol 0 (A)+CH 3COOH 3 ) (B)+H 2 0
(c) Catechol· 0 (d) Resorcinol 0 hl the above reaction 'A' and 'B' respectively are:
193. An organic compound 'A' containing C, H and 0 has a (EAMCET (Engg.) 20071
pleasant odour with boiling point 78"C. On boiling 'A' with (a) CH3COOC2HS, C2HSOH o
cone. H 2S04, a colourless gas is produced which (b) CH3CHO,C 2H s OH o
decolourlses bromine water and alkaline KMn04' The (c) C2H sOH, CH3CHO o
organie liquid' A' is: (d) C2HsOH,CH3COOC2Hs o
(GGS (Indraprastha Univ.) EE 20061
G.R.B. Organic Chemistry for Competitions
200. Which among the following compounds will give. a 209. The strongest acid is: (BHU (Screening) 2008]
secondary alcohol on reacting with Grignard reagent (a) HC=Cij 0 (b) C6H6 0
followed by acid hydrolysis? [PMT (Kerala) 2007)' (c) C 2H 6 0 (d) CHJOH 0
(i) HCHO 0 (ii) C2HSCHO 0 210. An organic compound' X' is oxidised by using acidified
(iii) CH3COCH3 0 (iv) HCOOC2Hs 0 l(2Cr207' The product obtained reacts with phenyl
Select the correct answer using the codes given below: hydrazine but does not answer silver mirror test. The
(a) (ii) only ',0 (b) (iii) only· 0 possible structure of' X' is: (CET (Karnataka) 2009)
(c) (i) and (iv) 0 (d) (ii) and (iii) 0 (a) CH 3COCH3 0 (b) (CH3 hCHOH· 0
(e) (ii)and(iv) 0 (c) CH 3 CHO 0 (d) CH3CH20H . 0
20i. The most suitable reagent for the conversion· of primary \ 211. A liquid 'Yas rriixed with ethanol and a drop of concentrated
alcohol into aldehyde with the same number of carbon is: H 2S0 4 was added. A compound with a fruitysmeU'was
. [PET (Kerala) 2007] formed. The liquid was:' (AIEEE 2009)
(a) acidified K2Cr207 0 (a) CH30H. 0 (b) HCHO 0
(b) acidillcdKMn04 0 (c) .CH3COCH3 0 (d) CH3COOH 0
(c) alkaline KMn0 4 0 . 212. The reaction involved in the oil of winter Green test is
(d) pyridinium chlorochromate 0
salicylic acid 'X', A ) product. The product is treated
'(e) Cr03 ,0 . Cone. H2,SO 4
202. In the following reaction, .
with Na2C03 solution. The missing reagent' X' in the
. . . Hio above reaction is: [CET (Karnataka) 2009]
C2HsMgBr + H2~H2.~ 'A' ,
(a) NaOH 0 (b) ethanol 0
o ' (c) methanol 0 (d) phenol 0
'A' is: [AFMC 2007) 213. The function of ZnCl 2 in Lucas test for alcohols is:
(a), C2HsCH2CHO 0 (b) C2HsCH2CH20H 0 [DCE2009)
(c) C2H5CH20H 0 (d) C 2H sCHO 0 (a) to act as an acid catalyst and react with HCI to form
203. When H2C=CH-C09H is reduced with LiAlH4' the H 2 zflCl 4 0
compound obtained will be: '[UPSEE (Engg.) 2007] (b) to act as a base catalyst and react with NaOH to form
(a); CH3CH2COOH 0 ~j H2C=CHCH20H.· 0 , Na2Zn(OH)4 0
{c) CH3CH2CH20H .0 (d) CH3CH2CHO' 0 (c) to act as an amphoteric catalyst 0
204. Catalytic dehydrogenation of primary alcohol gives a: (d) to act as a neutral catalyst 0
., [CET (Karnataka) 2008) 214. What are X and Y in the following reaction sequence:
(a) ketone ' 0 (b) ester . D Cl Cl
'(c) secondary alcohol 0 (d)atdehyde 0 . C2HsOH~(X)~Y
205. The compound on dehydrogenation gives a ke,tone: The . [EAMCET (Engg.) 2009]
original compound is: [CET (Karnataka) 2008) (a) C2HSCI, CH3CHO D.
(a) tertiary ,alcohol 0 (b) secondary alcohol 0 (b) CH3CHO,CH3C02H o
(c) primary alcohol 0 (d) carboxylic acid . 0 (c) CH3CHO,CCl3CHO o
206. RCH 2CH 20Hcan be converted to RCH 2CH:!COOHby the (d) C 2H s Cl,CCI 3CHO o
following sequence of steps: (JEE (WB) 2008) Set II: This set conta~s tbe questions witb two or more correet
(a) PBr3, KCN, H30+ 0 (b) PBr3, KCN, H21P+ 0 .answers.
(c) KCN. H;O+ , 0 (d) HCN, PBr3, H30+ 0 215. Grignard reagents give alkane, on reaction with:
207. Which of·the following will produce only ope product on (a) phenol 0 (b) ether 0
(c) alcohol 0 (d) water 0
reduction with LiAlH4? [JEE (WB) 2008)
216. Isobutyl alcohol cannot be obtained by the reaction
(a) CH3COOCH 2CH3 . 0
between:
(b) CH3CH20COCH2CH3 0 '(a) . C2HsMgBr and CH3CHO 0
(c) CH 3 CH 20COCH3 0
(b) CH3MgBrandCH3CH2CHO 0
(d) CH3CH20C;OCfl2CH2CH3 0
. (c) (CH3hCHMgBrandHCHO 0
208. 'The hydrolysis of 2-bromo-3-methyl ,butane by S N1
(d) CH3MgBrandCH3COCH3 0
mechani~m giv~s mainly: , (PMT (Kerala) 2008) 211. Alcohols act as:
(a) 3-methyl-2-butanol 0 (a)' oxidising agent 0 (b) reduci~gag~~t 0
(b) 2-methyl-7-butanol 0 (c) Lewis-base 0 (d) Broflsted aGid 0
{c} 2. '2-dimethyl-2-propanol n 21ft Glycerol can be converted to acrolein by dehydration in
.(d) 2-methyl-I-butanol 0 presence of:
.(e) l-pentanol D
Alcohols or Alkanols . -" .
(a) conc. H 2S04 0 (b) anhydrous ZnCl 2 O· 222. Which of the following compounds will give iodoform test?
(c) KHS0 4 0 (d) anhydrous CaCl 2 O. o 0
219. Which of the following chemicals are used for the· I I o
denatUration of ethyl alcohol? (a) CH3-C-H 0 (b) CH3-C-CH3
(a) CH 30H . 0 (b) Pyridine· IJ ,0 0
(c) Anhydrous CaCl 2 0 (d) Naphtha o I I
220. Which of the following compounds will give yellow (c) CH3-C-CI 0 (d) CH3-C-NH2 o
precipitate with iodine and alkali? 223. Alcohol can be prepared by which of the following.
(a) 2-Hydroxy propane 0 (b) Acetophenone 0 methods?
(c) Methyl acetate 0 (d) Acetamide 0 (a) By hydration of alkene 0
221. Ethanol can be converted to propane nitrile (CH 3CH 2CN) - . (b) By reduction o'f carbonyl compounds ' 0
by the following reaction(s): (c) ,By:reaction of primary aliphatic amines· with nitrous'
·.''acid . 0
(a) CH 3CH 2CH 20H + KCN ~ IJ (d) 'By hydroly~is of esters 0
224. 1°, 2° 'and '3° alfohols can be distinguished by: ,
(b) CH3CH20H+HCN~ o "(a) CuJ57JK 0 (b) VictorMeyer'stest 0
(c) CH3CH20H TsCl ~ CH CH OTs KCN) o ,,(c) cone. HCVZnCh 0 (d) Br2 water 0
Pyridine 3 2
~25. Alcoholic group' .,::an be replaced by -CI group by the
pelS following reagents:
(d) CH3CH20H . ) CH 3CH 2CI
-POC!3' -HC! (a) Cl.2 ' o
'(b) SOCl 2 o
(c) PCls o
(d) HCI and ZnCl 2 o
NaCN.
-Nat!
)CH}CH 2CN. o
, . glycols.
(d) If (A) is incorrect but (R) is correct.
'. (R) Only i,2-glycols form cyclic 'esters which subsequently
1. (A) Solubility of n-alcohols in water decreases with
undergo cleavage to form carbonyl compounds,
increase in molecular weight.
8. (A) 3° Alcohols show turbidity within 5 minutes, when
(R) The' relative proportion of the hydrocarbon part .in
treated with Lucas reagent.
alcohol increases with increasing molecu'larweight
(R) Conc .. HCI 'and anhydrous' ZnCl 2 in I : 1 mixture· is
which permits enhanced hydrogen bond wi.th water .• e,
. called Lucas reagent.. .. .
2. (A) Di-tert. butyl ether cannot be prepared by WilliamsOn's
9; (A) Grignardreagent reacts with aldehydes·and ketones to
ether synthesis.
, forin alcohol. .
{R) Tert. butyl bromide on n:eatment with sodium tert.
-(R} Alcohbls have acidic liydrogen.
butoxide preferentially undergoes elimination to form
10..(A) Glycerol does not react with HI.
isobutylene and tert. butyl alcohol.
(R) 2-Iodopropane can be produced by treatment of
3. (A) The boiling point of ethanol is much higher than that·of
f~~~J' ethyle~e.
diethyl ether. .
(R) IIi ethanol, the molecules are associated due to inter-
U. (A) : : : ( ' reacts with HI to give
molecular hydrogen bonding, whereas in diethyl ether CH 20H ,
it is not p~ssible.
4. (A) The acidity of alcohols follows the order 1° > 2° > 3°. (R) Initially .ethylene di-iodide .is formed which b.:ing
(R) The +1 effect of alkyl groups (3° > 2° > 1°) favours the unstable loses a molecule ofI2 and forms ethylene.
dissociation of --O-H group.
518 G.R.B. Organic Chemistry for Competitions
: ANSWERS I
OBJECTIVE QUESTIONS
1. (c) 2. (a) 3. (b) 4. (d) 5. (c) 6. (b) 7. (a) 8. (c)' 9. (d) 10., (d)
H. (b) 12. (a) 13. (b) 14. (a) 15. (c) 16. (d) 17. (a)' U. (c) 19. (d) 20. (b)
21. (d) 22. (b) 23. (e) 24. (a) 25. (b) 26. (b) 27. (e) 28. (b) . 29. '(e) 30. (b)
31. (b) 32. (d) 33. (e) 34. (a) 35. (d) 36. (b) 37. (a) 38. (d) 39. (e) 40. (e)
41. (b) 42. (b) 43. (c) 44. (b) 45. (a) 46. (a) 47. (b) 48. (a) 49. (d) 50. (d)
51. (d) 52. (d) 53. (a) . 54. (a) 55. (a) 56. (d) 57. (b) 58. (c) 59. (a) 60. (b)
61. (e) 62. (a) 63. (e) 64. (d) 65. (c) 66. (d) 67. (c) 68. (b) 69. (a) 70. (e)
71. (a) 72. (d) 73. (b) 74. (e) 75. (b) 76. (a) 77. (d) 78. (d) 79. (a) 80. (c)
81. (e) 82. (a) 83. (d) 84. (d) 85•. (a) 86. (e) 87. (a) . 88. (b) 89. (b) 90. (d)
91. (e) 92. (b) 93. (a) 94. (e) 95. (d) 96. (a) 97. (b) 98. (d) 99. (a) 100. (e)
101. (a) 102. (c) 103. (a) 104. (b) 105. (d) 106. (c) 107. (d) 108. (d) 109. (a) 110. (c)
HI. (b) 112. (c) 113. (b) 114. (a) 115. (b) 116. (d) 117. (c) 118. (a) 119. (d) 120. (e)
. 121. (d) 122. (c) 12~. (b). 124. (c) 125. (b) 126. (d) 127. (e) 128. (a) 129. (a) 130. (b)
131. (d) 132. (e) 133. (b) 134. (e) 135. (c) 136. (c) 137. (d) 138. (a) 139. (e) 140. (a)
141. (c) 142. (c) 143. (d) 144. (b) 145. (e) 146. (a) 147. (d) 148. (a) 149. (d) 150. (b)
,
151. (a) 152. (d) 153. (a) 154. (a) 155. (b) 156. (b) 157. (a) 158. (e) 159. (e) 160. (e)
161. (a) 162. (d) 163. (a) 164. (c) 165. (c) 166. (a) 167. (a) 168. (d) 169. (d) 170. (b)
171 •. (a) 172. (b) 173. (d) 174. (b) 175. (c) 176. (d) 177. (b) 178. (c) 179. (d) 180. (b)
181. (a) 182. (d) 183. (b) , 1~. (c) 185. (d) 186. (b) 187. (a) 188. (a) 189. (b) .90. (b)
191. (a) 192. (b) 193. (e) 194. '(d) 195. (e) 196. (a) . 197. (d) 198. (e) 199: (d) 200. (e)
201. (d) . 202. (b) 203. (b) 204. (d) 205. (b) 206. (a) 207. (a) 208.' (b) 209. (d) 210. (b)
211. (d) 212. (c) 213. (a) 214. (c) 215. (a,c,d) 216. (a,b,d) 217. (c,d) 218. (a,b,c) 219. (a,b) 220. (a,b)
221. (c,d) 222. (a,b) 223. (a,b,c,d) 224. (a,b,c)' 225.. (b,c,d)
1. (e) 2. (a) 3. (a) 4. (c) 5. (d) 6. (b) . 7. (a) 8. Jd) 9. (a) 10. (d)
11. (a)
Alcohols or Alkanols 519
(iv)
..
C3H6(CH3-CH=CH2J~?
D0 2
CH 3
(Hint: (i) C}( OH
. (iii) CH3-yH-CHzD
OH
(iV)CH3 -r-CH ZD (vi) OCHzOH]
OD
2. Write down proliuct ofhydroboration oxidation of the following alkenes:
(i)
cr
~
I
CH=CH2
(ii)
CH3 0
I I
(iii) CH3 -CH-C-OCH3 + 2C2 HsMgBr HOH)?
HCI
[Hidt: (i) Reaction involves two steps:
o
C6Hs-C-CI+
Benzoyl
chloride
I
o-Mga---+II
---+ -cD
C6Hs
OMgCI
I .
HOWHO, o-t-O+MgQ,·OH
6 C6li5
(Tertiary alcohol)
i>
(ii)
, . CH'3 0
1 II . . 1 .
: CH3 Ol\;1gBr
I 1 II1
r
. Mg('Br ) . CH3 0 .
1 "OCH
(iii) CH3-CH-C-OCH3 + 2CiH MgBr---t CH3-CH-C-OCH3 _"'--_ _....:3"""-+) CH -CH-C-C2H
s 3 S
I
. CzHs
CH3 0 CH3 OMgBr CH3 OH
I II.'
CH 3 -CH-C-CzH s + CzHsMgBr---t CH3-CH-C..,.-CzH s
I I HOH/Hel I
) CH3-CH-C-C2HS ]
I
, .". .' I I
CzHs CzH s
4. Arrange the following compounds in decreasing order of solubility and boiling point:
(i) CH3CH20H,CH3CH2CH20H, CH3CH2CH2CH20H
.. 'CH
I 3
> CH3-C-OH (Boiling point) ]
I .
CH 3
.'
S. Write down the dehydration products of the following:
H 3C"", /CFh
LOR
U~
(i) (ii) (iii) .
(i)
c5c5
(Major) (Minor)
. (ii)
ac5eS
(Major) (Minor) (Trace)
(iii)
(Major) (Minor)
. ,
Alconols or Alkanols
HCl/ZnC1 2
)
(b) +cr
H
Lj-CH-CH3 (LeSs stable)
.! Hydride shift
Cr03 "
(C) ~ (D) HOHIHC1) (E)
AcOH
CI MgC1
(Hilit: (A) = V
rY (B) rY
=V
522 G.R.B. Organic Chemistry for Competitions
~()U
.. (D)
HOHlHCI !II
if-o
H
(E)
.
+ Mg(
Cl
OH
]
C2 HS C2Hs . C2 HS
I I C2HSBr I
(i) H-C-O-H Na ) H-C-ONa + ---'=-=----+,) H-C-OC2HS+ NaBr
I -II2H2 t I I .
CH3 CH3 CH3
(A)
o
I
Here, Ts ~ Tosyl group CH3 -@-s-
II.
o
(Hint: In (i) reaction, - 0 -H bond of alcohol is broken and the configuration of product around chiral carbon is retained. In (ii) reaction, first '
. step involves decomposition of -O-H bond, in the second step -C-O- bond is broken. In this reaction, inversion of
configuration takes place. Tosyl group is better leaving group hence (C-O) bond is broken.]
10. Arrange the following alcohols in the increasing order of tendency towards esterification:
CH20H
6-CH3
[Hint: (a)
> '6~'CH'OH
, .
>
.
11. Complete the following reaction and give its mechanism in short:
CH3 0
I . I W
CH3-C-OH + CH3 -C-Cl-:.::-+A + B
I' .
C2Hs
Alcohols or Alkanois S23
In this reaction, first of all, an ester is fonned which undergoes decomposition in presence of dil. HCJ.]
12. Give the reagents for following oxidation products:
o
(Xl • 6 (Y).
)LOH
V-OH
. ~CHOH
13. Give the products when L-J. 2 is oxidised using following reagents:
15. Which of the following compounds will give positive iodoform test?
(c)
R,
(i) )C=O Mg )? Mg )?
RV Dil.HCl Dil.HCl
OH
-(iii)
6 Conc. H 2S04 t
abOve4I3 K
(A)
IH~
Alk. KMn°4 •
('ifT---OH
~OH
(Cis)
(B)
OH OH
[Hint: (i)
°I °I
R-C+2[H] + C-R
Mg/HCl I I
>R-C--C-R
I
j(
I
j(
I j(I
j(
(Pinacol reduction)
(ii) +2[H] +
0L:J MglHCl t
(pinacol reduction)
(iii)(A)~ 0 (B) =
.
(!t 0:.
OH
H
+ Enatiomer ]
17. Identify (A), (B), (C) and (D) in the following reactions:
o
CH20H
I
.
.
,---C_H..::.
20_H__ (B) - LiAlH4 t (C) HOHlHCl t (D)
OH
OH
°
(ii) (A) =
~CH20H (B)~ l CH"
/O-CHl
O-CH2
I
Alcohols or Alkanols '
OH (b) CH 3 -C-CH=CH-CH 3 o
I I
(c) CH3 -C-CH2 --CH3 o CH3
I CH 3
CH3
I
(d) None ofthe above 0 (c) CH3~C-CH2-CH CH2 o
19. In which of the following reactions, alcohol will be formed I '
CH3
as final Product?
(d) none of the above 0
(a) (CH 3-CH2-CHi)3 B H20 2 + NaOH) 0
13. When ~OH undergoes debydration reaction in
Cli3 -CH-CH2]2+
(b) , "'-./ (CH3 COO-}z H20) NaBH4) 0 presence of concentrated H 2S04 then what will be the
[ Hg , major product?
(c)~ D(d)~ o
o
CH)
10. When neopentyl alcohol is treated with H 2S04 , a mixture of I H+ -H2<)
two alkenes (85 : 15) is formed. Which statement(s) is/are (Hint: CH 3-C-CH 2-CH2-CH2-GH ' )
correct about these alkenes? I '
CH3
(a) Both give same major products on treatment with HBrD
CH3
(b) Both give different major products on treatment with
HBr in presence ofperoxide 0 CH 3-6-CH 2-CH2-CH 2 1, 2, W shift )
(c) The alkene which is formed in 85% concentration has I ' .' .
higher heat of hydrogenation than other alkene 0 CH)
(d) Both alkenes, on ozonolysis give same product 0 CH3
11. Arrange the following alcohols in order of reactivity I
CH3-C-CH2-CH-CH3
+
I, 2, W shift )
towards gaseous HBr: I .
F CH 3
·~·~0·~OH· OH OH OH
+
CH)
I H+
CH3-C-CH-CH2-CH3~
I
I n m IV CH)
24. Which of the following is the most acidic alcohol? 30. The substance(s) which is/are added to make liquor
(a) CH30H 0 (b) CF3 -CH2 -OH o poisonous is/are:
0 (b) pyridine 0
(c) A
CF3
0 (d)
C t ' XCF3
"""",..., o
(a) methanol
(c) CuS04 0 (d) formaldehyde 0
31. Which of the following compounds on· reaction with
F3C OH F3C OH
CH3MgBrwill give a tertiary alcohol?
25. Which of the following is the most acidic alcohol? (a) C2 H sCHO o
(a) ~OH o (b) ~OH o (b) C2H s COOCH3 o
o
o
o
<
26. In the reaction,
)-MgBr + CH2-CH2 H20 )(A)
(Hint: CH3-C
y H-CH3 + CH3MgBr ----7
J
CH3-CH~CH-CH3
""-/
o I
0-
.
the compound (A) is: + +
:. 22400 mL C14 at STP will be formed by 38. Ethyl alcohol can be manufactured from starch by the
0.037 x 22400gROH process of fermentation. Which enzymes stepwise complete
11.2
the fermentation reaction?
=74gROH
(a) Diastase, invertase, zymase 0
:. Molar mass of ROH 74]
(b) Maltase, zymase, invertase 0
35. Which of the following reactions will yield propan-2-ol?
(c) Diastase, maltase, zymase 0
(a) H2C=CH-:-CH3 + HOH~ o (d) Diastase, zymase and lactase 0.
39. If, ethanol dissolves in water, then which of the following
(b) CH -CHO CH3MgBr)
3 HOH
o would be happened?
(a) Absorption of heat and decrease in volume 0
(c) . CH 0 (i) C2HSMgI ) o (b) Emission of heat and decrease in volume 0
2 (ii)HOH
(c) Absorption of heat and increase in volume 0
(d) H 2C=CH-CH3 Neutral KMn04 ) . o (d) Emission of heat and increase in volume 0
(Hint : When' alcohol is dissolved in water then the solution
36. Ethanol is dehydrated as, shows the positive deviation from Raoult's law.
... MI = + ve endothermic, heat absorbed
(A) (major product)
AV = +ve increase in volume]
40. Aliphatic primary amines on reaction with NaN02/HCI
(B) (major product) give:
(a) only primary alcohol 0
Cone. H2SOJ (C)(majorproduct)
443K (b) only secondary alcohol 0
Major products (A), (B) and (C) are respectively: (c) only tertiary alcohol 0
(A) (B) (C) (d) primary, secondary and tertiary alcohol 0
41. Which of the following alcohols will be oxidised by
'(a) C2H s HS0 4 C2H s OC2H S C 2H 4 0
Br2/KOH?
(b) C2H 4 C2H sOC 2H S C2H s HS04 0 (a) CH30H 0
(c) C2H sHS04 C2H 4 C2HsO~H5 0
(d) C2H 4 C2Hs HS0 4 C2 H sOC2 H S 0 (b) HOA~CH3 0
37. Which of the following will be the major product when
~2
(c) Q - c H20H o
OH
is treated with dil. H 2S04 in the presence of HgS04 ?
(d) oH3 o
(a)
Q<oH o (b) CXOH
. o 42. Which of the following 'gem' diols is stable?
.. CH CH3 OH
3
I
OH OH o
C0
(a) CH3-C-H
. I
~3
OH
(c)
o (d) o
. CH3 OH
OH 0 . I
(b) CBr3-C-H o
I
C01
(Hint:
~H2
Dil.H2S04
>
OH
<
HgS04
CH3
OH 0
(ketO-enol tautomerism)
G.R.B. Organic Chemistry/or Competitions
'OH ~~~ 0
I (d) mixture of mono and disalt 0
(c) CF3-
r
OH
-H o IHiot: Primary alcoholic groups of glycerol form salt with
sodium metal.
CH20H CH~-Na+
. OH
I I· I
CHOH CHOH
(d) C6HS-C-C6HS o I I
I . CHzOH CHlOH
OH GIY"fOI . MollOsodiwn
- salt
H
[Hint:
f 4
F-f--y-H is stabilised by intramolecular
45. Surgical spirit IS:
(a) absolute alcohol 0
(b) rectified spirit 0
FH-O (c) 95% rectified spirit and 5% methyl alcohol 0
hydrogen bonding. (d) 90% rectified spirit and l()o~ methyl alcohol 0
11- 11+ 46. The reaction of glycerol with Hl04 gives:
F----H-O
I . I (a) formaldehyde 0
F-C C-H] (b) formic acid 0
I I (c) ioilic acid 0
F----H-O
8- 11+
(d) oxalic acid 0
43. Which of the following compounds undergo periodate 47. Which of the follOWing will result in the formation of an
oxidation? ether?
(a) (1l1)3CO-Na+ +C2HSBr-+ 0
(a) (yOCH3 o (b) (CH3)3CBr+ C 2H sO-Na+ --+ 0
YOH (c) C6H s O-Na+ +CH3Br~ 0
OH o
IHint: Tertiary halide and aromatic halide do not give
~) Hh
Williamson's ether synthesis.]
o 48. How many isomers of CsHtt OH wi!: be primary alcohols?
(a) Four 0
. (b) Five 0
OH (c) Three 0
. (d) Two ·0
OH OH 49. Final product (D) in the sequence of reactions is:
r
(HInt: All these compounds have -l b-b-j
OH OH1
I I glycolic "
.
HOf;l)D
u+
(a) CH 3 -CH-OH
. I
o
groups, hence, they are oxidised by periodic acid (Hl04 ).] CH3
44. Glycerol fonus salt with sodium metal at 110"C. The sodium (b) CH3 -CH-CH2-CH2Br o
salt is: I
(a) monosalt 0 CH3
OOili~ 0 (c) CH3 -CH-CH2-CH20H o
I
CH3
Alcohols or Alkanols 529
CH3 -C=CH.....,..CH3 + CH 3 -CH-CH=CH2 4. Which among the following sequences' of reactivity for ,
'I ',I ' ," dehydration is'incorrect? ' ,
CH 3 ,CH3 J o ",' ,'"
2-Methylbut-2-ene
(Major product)
Answer the following questions:
3-Methyl but+ene
(Minor product)
(a) o-OH ,
< ~f~ ~H
,'0,
1. Which among the following alcohols will' be the 'most
(b) CH 3 CH 2 CH 2 CH2 0H <CH3"'-:':CH-CH2~CH3 < ,
reactive for dehydration? , ,;, '1 "'", ;';:
OH OR ...:,
I , CH
(a) CH 3 -CH-CH2 -N0 2 I 3
OH
I
" CH3 -f-:- OH
OH OR N(j2
~N02 )JV
(A) (B}~.'
If.
o R-C-O-H~' R-C-O-
I
(b) O-CH20H
I I
R R
} ..
I
, .
10
ETHERS
10.1 INTRODUCTION For example, the net dipole moment of dimethyl ether is
Ethers are a class of compounds which contain one divalent 1.30 D and that of diethyl ether is 1.18 D.
oxygen atom bonded to two monovalent alkyl groups (same or [Besides the open chain saturated homologous series,
different). When both the alkyl groups are same, they are Cn H 2n+ 2 0, there are numerous organic compounds in which
designated as simple or symmetrical ethers and when both - 0 - functional group is present. These compounds are also
are different, they are called mixed or uusymmetrical ethers. termed ethers.]
. "",""~.,,.;H2C CH2
R-O-R R-O-R'
CH 30CH=CH 2; CH2-CH2; . I I;
Methyl vinyl ether
(Unsaturated)
y fI 2 C",
)H2
C2HS-O--C2HS C2 H S-O-C3H 7 Ethylene oxide 0 .
Symmetrical Unsymmetrical (Cyclic) Tetrahydrofuran
or or (THF)
Simple ethers Mixed ethers
Ethers form a homologous series with the general formula
CnH2n+20(same as monohydric alcohols), where the value of
'n' is always more than l. The functional group of ethers is C6HSOCH3 C6 H SOC 2Hs
(C-O-C), Anisole Phenetole
(Methyl phenyl ether). (Ethylphenyl ether)
Ethers may be regarded as anhydrides of alcohols as they
may be obtained by elimination of a water molecule from two
alcohol molecules.
r------- 10.2 NOMENCLATURE
R-O~I~L:!:Jj9J-R ~ R-O-R + H20 There are two systems for naming ethers:
Alcohol Alcohol Ether
1. Common names: In this system, ethers are natt1ed
Just as alcohols are considered as monoalkyl derivatives of after the alkyl groups attached to oxygen atom and adding the
water, ethers may be considered as dialkyl derivatives ofwater. word ether. When both the alkyl groups are same, the prefix di-
H-O-H . R-O-H R-O-R is used. In case of unsymmetrical 'ethers two alkyl groups are
Water . Alcohol Ether
named in alphabetical order.
StrUcture : The oxygen atom in ethers is sp3_
CH 30CH 3 ; C2H sOC2Hs ; CH30C2Hs ;
hybridized. Two of the hybrid orbitals overlap with hybrid Dimethyl ether Diethylether~ Ethyl methyl ether '.'
orbitals (one each) of two carbon atoms to form sigma bonds
C2H sOC3 H 7 CH3 -0-C(CH 3h;
(~C..Q:..O..Q:..C<). The bond angle is 1100, :~owhile
;
Ethyl propyl ether Methyl tert. butyl ether
CH 3CH 2 CH 2-O-CH(CH3h ;
H-O-H bond angle is I 04.so, This is because of greater size Isopropyl II-propyl ether
of alkyl groups resulting in greater forces of repulsion.
ThUs, ethers have a bent structure and are dipolar in
Q-a-Q; (CH 3 )2 CH -a-Q
nature. Diphenyl ether Isopropyl phenyl ether
534 G.R.B. Organic Chemistryfor Competitions
LJ' , il'
HSC2 0 CH3
Oxol;me Furan 2-Ethyl-S-methyI furan
(Tetrahydrofuran)
o o
orTHF
" 0
,Pyran
cjo 10~4 GeNERAL METHODS OF PREPARATION
Oxane , l,4-Dioxan
(Tetrahydropyran) (Diethylene dioxide) 1. Dehydration of alcohols : When an excess of
alcohol is heated at 140°C in presence ofprotic acids, (H 2SO4 ,
4 1
H2 C--O H 3P0 4 , i.e., concentrated sulphuric acid or phosphoric acid)
~ 1 12 two molecules of alcohol eliminate one molecule of water to
HC--CH CH2-CH-CH2CI form symmetrical ether. LOwer ethers are prepared
I I' ""/ industriaUy by this method.
CH 3 C~3 o (a) Acidcatalysed dehydration
2,3-DirnethYI 2-Chloromethyl oxirane
(3-Chloro-l,2-epoxy propane 'f'..H+HOR H2S04(conc,)
oxetane Rv - - - - - ' - '~) ROR + H20
or Epichlorohydrin) 2 Moiecul~s of alcohol l40"C Ether
Note: In case of sqnple 'ethers common names' are also accepted in
'lUPAC system, "
l
Ethers. 535
Mechanism
2·Methylpropan -2.(11 '
Acid catalysed dehydration of 1° alcohol to ether is a (30)
nucleophilic bimo1el:ular substitution (SN2) .reaction Thus, inthe formation of ethers, the dehydration of alcohols is in
involving the attack of alcohol molecule on protonated a . the order:
alcohol, as shown below in three steps: ' Primary> Secondary> Tertiary
Step 1. Protonation ofalcohol to form oxonium salt. . (b) Catalytic dehydration
. ·H Dehydration of a primary alcohol is also affected by
.~+ ,',. ,+1 passing vapours over alumina or thoria at 250°C under
..
CH 3 CH 2-O-H + H --+CH 3CH 2 -O-H
. .. pressure.
Ethatiol (Base) Acid Protonated ethanol
Al 20 3
Step 2. Nucleophilic attack by unprotonated alcohol on 2ROH --~~ R-O-R + H 2 0
protonated alcobol to form protonated ethoxyethane with the Alcohol .~50°C. Dialkylether
elimination of a water molecule, / (Excess)
Limitations: The reactivity of primary (1 0 ) alkyl halides (iii) PhenoUc ethers (alkyl aryl ethers) can.aiso be prepared ina
is in the order, CH3 >CH3CH2 >CH3CH2CH2 and the similar way by treating sodium phenoxide with alkyl halides. For
example, .. '. .
tendency of alkyl halides to undergo elimination is 30 > 20> 10.
···~.n
Hence, for better yield, the alkyl halide should be primary
and aIkoxide should be secondary or tertiary.
~
Ij+' ~- ~I
C2Hs--Br+Na~--CH3
CH3
Heat) C H S __
I
2 . O-C-CH 3
CH3
B
.19 +CH~
SodiUm
Methyl'
bromide
-
SN'-
•
Methyl pbenylether
+NaBr
Bf\
.l9.. . +C,Hjl
Ethyl iodide
Heat
. +N.I
~) H
.~ .. r'!
... CH3
CH3--C--Br +CH3CH20Na
- + d
~CH3--C+CH3CH20H
I
.I
CH 3
Sodium ethoxide I
CH2
. B.. .
19 + HzC=CH...:....cHz-I
Allyl iodide
. Heat
S,;.
..
Tert. butyl bromide 2-Metbyl propene Allyl pbenylether
Sodium
(30 Alkyl halide) pbenoxide or Allyl pbenol
+.NaBr
.Due to steric hindrance, secondary· alkyl halides also ·2C6HS OH +(C
2H5)2SO
4 H··OC
. . • .'2C6
2NaOH (aq.)
S2S
H
prefer to undergo elimination rather than substitution. For Phenol Diethyl sulphate ~ Pbenetole .
--r
2-Bromopropane
Sr . .
(2" Alkyl halide)
f CH 3 H-O-C 2 H s
CH3
2-Ethoxypropane
(20010)
© + Na+O-'-CH3 .~.'. Noreaction
Sod.metboXide .
Bromobenz:::.e:=n,-=-C_ _ _....:..-____....,-....:..-__.:......:...-'--__'-'--:....
<}--cH'Cl Na9-QNo'"I . .
and para-positions are present then reaction takes place, e.g.,
.. . < )-CH20 - {
(Dry) .
Heat) C z H sOC2H s'+2AgI
HBF4 . H2 S04
C 2H s OH + CH 2N 2 -~> C 2H s OCH 3 +N2 H2C=CH2 + HOR. . >CH 3 -CH 2 -OR
Ethyl alcohol Diazomethane ~ Ethyl methyl.ether Alcohol Ether
OC 2 H S
. HBF4 ' .
(CH3hCHOH +CH2N2~(CH3hCH-O-CH3+N2
~ .. CH3 -C=CH 2 + HOC 2H s
H 2 S0 4
-=---~)
.
CH 3 - C -CH3
I
Isopropyl alcohol 2-Methoxy propane
Mechanism: In this reaction, HBF4 acts as a strong acid I I
CH 3 CH 3
and protonates to diazomethane. 2-Methylpropene 2-Ethoxy -2-methyl propane
+ (Tert. butyl ethyl ether)
CH 2N 2 +HBFc-~CH3N2 +BF4 The intermediate is carbocation.
. (\ + +
H2C=CH2 +H ~ CH 3CH 2
+~
R-O-H+CH 3
+ SN 2
>R-O-CH3 +H
+ CH3CH2 +HOR Slow) CH 3CH 2 -O-R
5. Reaction of lower halogenated ethers with Grignard I
H
reagents: Higher members can be prepared by the action of
Grignard reagents on lower halogenated ethers.
ROCH 2X + XMgR' ~ ROCH 2R' + MgX2
Halogenated Grignard Higher
ether reagents ether This method is very useful for preparing mixed ethers.
CH 3
Dry /1
CH3OCH2Cl + IMgCH3 >CH 3OCH 2CH 3 + Mg,
CH 3 -C:-CH 2 + HOCH 3
H 2 S0 4
-=----'--» CH 3- C -OCH3
I.
Monochloromethyl Ether Ethyl methyl ether 'Cl
ether . I I
6. Alkoxy mercuration-demercuration: " CH 3 CH 3
2-Methyl propene 2-Methoxy:2-~thyl propane
". /.
/C=C" + R -OH + Hg(OOCCF3 h
I I
-+ - C-C- + H2 S04 , + EtOH
An alkene Mercuric trifluoro- I I Me2C=CH2 + H < Me3C<
acetate OR HgOOCCF3 Alkene Tert. carbocation
NaBH4 I I
-----+> -C-C-
(Reduction) I I
OR H Me 3C-OEt
Ether
Ether
Alkenes readily react with mercuric trifluoroacetate in In higher cases, there can· be 1,2 hydride or 1,2-methyl
presence of an alcohol to give alkoxy mercuric compounds shift to form more stable carbocation.
which on reduction with NaBH4 in alkaline medium yield CH3 .. CH3
ethers and it is in accordance with Markownikoff's (indirect) IH+ I
~ CH3-C-CH2CH3
CH3 -CH-CH=CH2+ HOC2HS
addition of alcohols toalkenes.
3-Methyl but-I-ene I
CH 3CH=CH 2 +CzHsOH + Hg(OOCCF3h ~ OC2H S
Propene Mercuric 2-Ethoxy -2-methyl butane
trifluoroacetate
NaBH4 . 10.5 GENERAL CHARACTERISTICS OF ETHERS
CH3 -CH--CH2 ---4) CH3 -CH-CH3
I I OH- I Physical properties : (i) Dimethyl ether and ethyl
OC2HS HgOOCCF3 OC 2 H S methyl ether are gases. All ethers are colourless liquids with
2-Ethoxypropane characteristic ether smell. Diethyl ether has boiling point 34SC.
7. Addition of alcohols to alkenes": Ethers may be (ii) They are lighter than water. Lower ethers are highly
prepared by the direct addition of alcohols to· alkenes in the volatile andvery inflammable.
presence of acid, e.g., (iii) They are sparingly soluble in water but readily
soluble in organic solvents. Solubility of ethers in water in
G.R.B. Organic Chemistry for Competitions
(ii) Salt formation: Due to the presence of lone pair of DiL H 2S04
electrons on oxygen atom, ether behaves as Bronsted-Lowry C2HsOC2HS + H 20 ) 2C 2 H s OH
Diethyl ether Heat Ethanol
base or Lewis base and forms stable oxonium salts with
concentrated mineral acids at low temperature. (ii) Action of cone. H 2 S0 4 When warmed with cdn-
:
~
. H centrated sulphuric acid, ethers form alcohol and alkyl
. I hydrogen sulphate. The fmal product is alkyl hydrogen
273K)
..
(C 2 H s hO+CI-
Diethyl oxonium chloride
sulphate. .
or
C2HsOC2Hs+2H2S04 Heat) 2C2HsHS04 + H20 ~.::',
Diethyl ether Ethyl hydrogen sulphate'
C2H s OC 2 H S + H2S04 ~ (C2HS hO+ HS0 4 ' The secondary and tertiary ethers, however, form alkene's
Diethyl ether • I with conc. H 2 S0 4 .
H
Diethyl oxonium hydiogen sulphate CH 3 CH 3
<
reaction.
O-O-R+HI~
4. Ethers can form coordination complexes with Lewis acids
like BF3 , AlCI 3, RMgX, etc. As the ether (having lone pair of )-oH+RI
electrons) are Lewis bases, they easily coordinate to form Alkoxy benzene Phenol
complexes known as etberate!h
Note: The same reactionsare'observed with HBr and HC!. The order of
~Hs OC2HS + BF3 ~ (C2 HS h 0 ~ BF3 reactivity ofhalogen acids is HI > HBr> HCI.
• " L e w i s acid .Boron trifluoride
etherate . (b) When heated with excess of HI, only alkyl iodides are
R",,-- ~(C2Hsh formed.
2C2HsOC 2Hs + RMgX ~ . /Mg ....... Heat
Grignard (C2HshO -.......x C2HsOC2HS + 2HI - ) 2C2HSI + H 20
reagent Excess lOO·C Ethyl iodide
It is for this reason that ethers are used as solvents for
Grignard reagents. That is why Grignard reagents are usually R-0-R'+2HI Heat)RI+R'I+H20
pre]pan~din ethers. Similarly, cyclic ethers are readily cleaved by HBr or HI to
3. Reactions Involving Cleavage of Carbon-Oxygen Bond form dihaloalkanes.
. (i) Hydrolysis: When heated with dilute sulphuric acid H 2C - -CH2
under pressure ethers are hydrolysed to the corresponding
alcohols.
Q + 2HBr IOO·C)
(excess)
I
Br-CH2 CH 2 -Br
I + Il.+O
ct.:;
Tetrahydrofuran 1,4-Dibromobutane .
(THF)
'';''
(a) SN2 mechanism: the product is controlled by the formation of more stable
(i) The ether molecule getsprotonated by the hydrogen of intermediate tertiary carbocation from the protonated ether.
the acid to form protonated ether or oxonium salt. (c) In case of alkyl aryl ethers (phenolic ethers), the
HX ~ H+ +X- products formed are always phenol and an alkyl halide and not
the aryl halide and an alcohol.
+
~H3
R-O-R+H+ Protonation) R-O-R OH
©
.~
Ether I
H
Protonated ether +HI
lOO"C
.. + CH3I
(ii) The protonated ether undergoes nucleophilic attack by Methyl iodide
Methyl phenyl ether. Phenol
halide ion (X-) and forms alkyl alcohol and alkyl halide. (Anisole)
~n/R . .
This is due to the steric hindrance oflarger alkyl group, the
X- +R-O, ~.[X--R-O-R]~R-X +R-OH
• • 'H I Alkyl Alcohol halide ion attackS the smaller alkyl group.
. H halide Diphenyl ethers are not cleaved by HI even at high
Transition stage temperature.
The reactivity through this mechanism is controlled by The importance of this reaction (action of HI with ethers)
.sterleJactors. forms the basis of Zeisel method for the estimation of alkoxy
groups (-OR) such as methoxy (-OCH3) and ethoxy
(b) SN 1 mechanism:
(-OC 2H s ) groups in ethers.
+ .. R-O-R +2HI ----* 2Rl + H 20
...
(i) R-O-R +H+ Protonation) R-O-R
Ether I The alkyl iodide so formed is absorbed in ethanolic silver
H nitrate solution to form silver iodide. From the weight of silver
Protonated ether • jodide formed, the number of alkoxy groups can be
+ determined.
(ii) R-O-R----* R+ +R-O: (iv) Action of PCls : On heating with PCI s • alkyl
I Carhocation I chlorides are formed. There is no reaction in cold.
H H
(iii) R+ + X- ----* R-X R-O-R + PCIs Heat) 2RCI + POCl 3
The reactivity through this mechanism iscontrol1ed by the
stability ojintermediate carbocation. C2HsOC2HS + PCIs Heat) 2C2HsCl + POCl3
Diethyl ether Ethyl chloride
Site of cleavage: In case of unsymmetrical ethers, the
site of cleavage depends on the nature of alkyl groups. For (v) Reaction with acetyi chloride: Ethers when heated
example, with acetyl chloride in the presence of anhydrous zinc chloride
or AlCl3 to form alkyl halide and ester.
(a)C 2H S-·'O-CH 3 +HI 373K) CH 3I + C2H sOH c-------- ZnCl 2
Ethyl methyl ether Methyl iodide Ethyl alcohol CH3CO~1__t:~1!!.SJOC2Hs ) C 2H sCI
Acetyl chloride Diethyl ether Heat Ethyl chloride
The alkyl halide is always formed from the smaller alkyl
group (primary or secondary). +CH3COOC2Hs
Ethyl acetate
CHr:-O-CH(CH3h+ HI 373K) CH31 +(CH3hCHOH With acid anhydride, esters are formed in presence of
Methyl isopropyl ether Methyl Isopropyl ZnC1 2 • .
iodide alcohol
The cleavage of such ethers occurs bYSN 2 mechanism and
---------------
CH 3CO·:OOCCH 3+C 2H s' :OC
2Hs
ZnCI
2) 2CH3COOC2Hs
the fQrmation of the product is controlled by steric factors. Acetic ~dride- - - - - Olcthyl ether Heat Ethyl acetate
'(b) CH 3-0-C(CH 3h+HI 373K) (CH3hC-I (vi) Dehydration:. When ether vapours are passed over
Ten. butyl methyl ether Tert. butyl iodide heated alumina, dehydration of ethers occur to form alkenes.
+ CH 30H Al 20 3
Methyl alcohol C2HSOC2HS ) 2H2C=CH2 + H20
300"C
The alkyl halide is formed from the tertiary alkyl group
(vii) Reaction with carbon monoxide: Under suitable
and the cleavage of such ethers occlJ!S by SN 1 mechanism as
conditions ethers react with carbon monoxide to fOlln esters.
Ethers 541
or
+ 0
. .
CH3 .
+- /""\ C\ . (Minor) p-Methylanisole
(Major)
LiCH3 + H~CH2-0-CH2 -CH3----+
~
CH4 + H 2C=CH 2 + LiOC2 HS
Ring substitution in aromatic ethers
Like phenols, the alkoxy group (-OR) in aromatic ethers
is ortho and para directing and activates the ring towards
l8J
Anisole
+CH3COCI
Acetyl
chloride
electrophilic substitution reactions. acetophenone COCH3
(Minor) p-Methoxy-
acetophenone
(Major) ,
It may, however,. be noted that aromatic ethers are
relatively less reactive towards electrophilic ring substitution
than phenols.
Resonating structures of alkoxybenzene 10.6 OIETHVL ETHER OR ETHOXV ETHANE
(C 2 H sOC 2 H S)
Examples are:
Diethyl ether is the most important and useful member of ether
(i) Halogenation:
series. It is simply known as ether. It is technically called as
~H3
sulphuric ether. It can be prepared by the application of first.
three general methods of preparation of ethers.
Laboratory preparation: The ether is prepared in the
+
laboratory by heating excess of ethanol with concentrated
Anisole o-Bromoanisole . sulphuric acid at 140"C. The reaction proceed~ in two steps.
(Methyl phenyl ether) (Methyl 2-bromo Br 1l0°C .. •
phenyl ether) p-Bromoanisole C2HSOH + H 2S0 4 ) C2HSHS04 + H 20
(Methyl 4-bromo Ethyl alcohol (cone.) Ethyl hydrogen
phenyl ether) sulphate
~H3
C2HSHS04 +C2 HSOH 140°C) C2H s OC2Hs + H 2S04 .
Diethyl ether
II The sulphuric acid acts as a catalyst and is 'not used llp in
acetic acid the reaction. Thus, theoretically a small amount of sulphu,ric
Anisole acid should be sufficient for the conversion oflarge amounts of
Br alcohol to ether.
p-Bromo-
This method. is termed as continuous. etberiticatlon
anisole (90%)
process and the pure ether collected at 34-35OC is called
(ii) Nitration: absolute ether.
~H3
3 Uses: (i) Diethyl ether is used as an excellent solvent in
(iv) It is used as an inhalation anae~thetic because it 7. Action of Forms ethyl acetate No action in cold. On
produces unconsciousness without affecting lungs and heart. C~3COCl (Sweet fiuity smelling heating forms a mixture
liquid). of ethyl acetate and
More recently, Ethrane (F-CH-CF2-O-CHF2)'
ethyl chloride.
I .
CI 8. Action .of air No action. Forms peroxide.
9. Oxidation Forms acetaldehyde Not easily oxidised. It
isoflurane (F3C4H-O-CHF2 ) , and halothane
and acetic acid can also fonn aceta-
CI ldehyde and acetic acid
with strong oxidising
(CF3CHClBr) has largely replaced ether as they. are less agents.
hazardous and more rapid in action.
10. Action ofstrong Ethylsalts are fonned. Oxonium salts are
(v) The mixture of alcohol and ether is used as a substitute acids fonned.
of petrol under the trade name nataDte. .
1L Action ofm Forms ethyl iodide in Forms ethyl iodide and
(vi) It is used as a refrigerant as on evaporation it produces
cold. ethyl alcohol in cold.
cooling. A mixture of ether and dry ice (solid CO 2) gives a On heating forms only
temperature as low as -110°C. ethyl iodide.
(vii) It is used in the production ·of smokeless powders. It 12. Iodine + NaOH Forms yellow crystals Does not respond to
is also used in perfumery. (Iodoform test) ofiodofonn (Cm3). iodofonn test.
Nete: The ether containing the impurity of ether peroxide cannot be
':, .
used as an anaesthetic. The presence of ether peroxide can be Note: L The above tests (except test No. 12) can also be used to
tested with the help of potassium iodide. Iodine is liberated when compare alcohols with ethers.
potassium iodide is added to ether containing peroxide impurity. 2. Test No.3, 4, 5, 6 and 12 may be used for distinguishing ethyl
Pure ether does not liberate iodine from potassium iodide. alcohol from diethyl ether.
The presence of peroxide in ether can also be detected by the
development of red colour when ether is shaken with a.mixture of SOME SOLVED PROBLEMS
ferrous ammonium sulphate and potassium thiocyanate (KCNS).
Fe2+ + Ether peroxide ~ Fe3+ + ether Problem 1. Write the structural formulae ofall possible
ethers having the molecularformula, C 4 H IO Oand name them.
lsCN- Solution: There are three isomeric ethers of moleeul.ar
Fe(SCNhred colour formula, C4HIOO.
CH3CH20CH2CH3. CH30CH2CH2CH3
Cdmparison of Ethyl Alcohol and Diethyl Ether Diethyl ether Methyl propyl ether
Both ethyl alcohol and diethyl ether are typical members (Ethoxy ethane) (l-Methoxypropane)
oftlIeir series. Ethyl alcohol has -OHgroup which is reactive CH 3
~,,' .
+ +
••
CH3CH2 +CH3CH20H~ CH3CH2-0-CH2CH3
.• . I
H" Ag20
Oxonium ion CH3CH2CI (Dry) ) CH3CH2-0-CH2CH3
4. Oxonium ion loses a proton to yield diethyl ether.
+ Na. ICH3
•• ••. + (f)CH3CH20H~CH3CH20Na ) CH 3CH 20CH 3
CH3CH2-0-CH2CHr-~ CH3CH2-O-CH2CH3 + H
.. I .• Problem 5. Explain the Jollowing:
H (a) Dimethyl ether has a lower boiling point (-24°C) than
Problem 3•. How will you synthesise an ether from a ethyl alcohpl (78°C) although both have same molecular
primary alcohol? masses.
(b) Ethers have low solubility in water but high solubility
Solution: (i) ROH + Na ---7 RONa
Alkoxide in conc. H2 S0 4 .
(ii) R'OH+HBr~ R'Br +H 2 0 Solution ':. (a) Ethyl alcohol has intermolecular
Alkyl bromide hydrogen bonding whereas no hydrogen bonding is present in
(iii) RONa + BrR' ~ ROR'+ NaBr dimethyl ether.
Ether (b) The oxygen atom in ethers has two unshared electron
Problem 4. How will you synthesise? pairs and therefore, the oxonium salts are formed with acids.
(a) Divinyl ether from ethylene. This behaviour is not observed in the case of water. Ethers,
(b) n-Butyl alcoholJrom ethylene. therefore, have high solubility in cone. H 2S0 4 and low
(c) Diethyl ether from ethyl iodide. solubility in water.
(d) Ethyl methyl ether from methyl iodide. Problem 6. An ether, (A)" having molecular Jormula,
(e) Diethyl ether from dimethyl ether. C6H140, when treated with excess oj HI produced two alkyl
(j) Ethyl methyl etherJrom ethyl alcohol. iodides which on hytlrolysis yield compounds (B) and (C).
Solution: Oxidation oj (B) gives an acid (D), whereas oxidation oj (C)
(a) fl2 C=CH 2 HOCl) CICH2·CH20H results in the Jormation oj a mixed ketone, (E). Give graphic
Ethylene representation oj (A) to (E). -
H 2S0 .
Solution: Both the alkyl halides on hydrolysis form
4
2CICH2CH20H - - - - - 7 ) CICH 2CH 20CH 2CH2CI alcohols. The alcohol (B) is a primary alcohol as it gives an
140"C
acid on oxidation while alcohol (C) is a secondary alcohol as it
"
Alc.KOH
) H 2C=CH-O-CH=CH2 gives mixed ketone on oxidation. The ether can be thus
Heat Divinyl ether formulated as CH3CH20CH(CH3 )C2HS'
. .ill /CH 3
(b) H2C=CH2 (i) HBr ) CH CH MgBr ' CH3CH20CH(CH3 )C2HS ~ CH3CH21 + IRC"
(ii) Mg 3 2
(A) 1H 20
1 H20
2H
C S
(CH3CH20CHCH2CH3 )
I CH 3CH 20H CH3CijOHC2Hs
2-Ethoxy~~e(A) (l/J) (e )
Oxid. Oxid.
l
CH3COOH CH 3COC 2H s
Acetic acid Mixed ketone
CH3CH2CH2CH20H + Mg(OH)Br . (D) (E)
Solution: The compound does not react with sodium, (iii) By treatment of ethylene chlorohydrin with NaOH.
thus it is not an alcohoL The compound is saturated as it does
not add bromine. It does not react with Schitr s reagent, thus it H 2C===-GH2 HOCI) CICH2 -CH 20H NaOH) CH2-'-CH 2
is not an aldehyde. Ethylene chlorohydrin .." /
. 0
The compound with excess of HI fonns only iodide. Thus,
the compoimd is Symmetrical ether. . Properties: It is a poisohous,fiammable gas. It boils at
ROR + 2HI ) 2RI + H20 14°C: It is a very reactive compound because of its strained
(Y) configuration. Likeotber ethers, an epoxide is converted by an
acid into protonated epoxide which can then undergo attack by
RI ( P+I2 ROH
1 Hydrolysis
O'da'
Xl tlon) Acid
any nucleophilic reagent.
I I. H+ I I I
.
. R'COOH=R'+12+32+1=60; R'=lS=CH 3 H
(Protonated epOxide)
The ltCid is. acetic acid. It is obtained by oxidation of (Z),
So, it has the tendency. to open up the ring, the oxygen
thus (Z] is C2HsOH(ethyl alcohol) and (Y)isC2HSI(etbyl combines with the reactive hydrogen of various compounds
iodid~). The compOund (X) is, therefore,CzHsOC2Hs
fonning a hydroxy compound.
(diethyl ether). . .
CH2-'-CH2+HA----+ HOCH2-CH2A
CiH sOC2 H S -.!!4 CiHs 1 HydroIYSi~C2HsOH Oxid,) '(/ .. Addition product
o .
.. ..... CH 3COOH
Some of the important reactions ate listed below:
ISLI PPLEMENTARY .·READING II .. HOH
HOCH2CH2OH
H+ orOH-
10.7 EPOXIDES (OXIRANES) . '. . ~ ' .
Ethylene glycol
,/\t, are,ringispresent.
Epoxides
.. /
cyclic ethers. in which athre
. emembered, HCl
CICH2CHiOH ..
Ethylene (:h1orollydrin
o . CH 2 -CH 2
NH3
HOCH2CH2NH2
"'(/ 2-Amioo ethanol
CH 2 -·CH2· CH 3-.CH-
... CI:I2 0
EthyieDe oude
"-./
o ""-/
·0 ..
CH 3CH 2OH
H+
HOCH2CH 2OCH2CH3
2-Ethoxy ethanol
1,2-Epoxyethane 1.2-EpOxy propane
(Ethylene oxide) . . (Propylene oxide) CH 0H
3
'-----"----+ HOCH 2CH 20CH 3
Ethylene oxide (oxirane) is the most important member of . . 2·Methoxy ethanol
this class. It may be prepared, . .. . .
Grignard reagents fonn an addition product which on acid
(i) By oxidation Of ethylene with oxygen in presence of .
silver catalyst. . ... . hydrolysis forms a primary alcohol.
CH2-'-CH2+CH3MgI ----+ CH3CH2CH20MgI
2HzC=CH :i+Oz· . Ag)2CH 2 ~H2
"'-/
. . . . . . . . . . ..
It is used (a) in the manufacture of ethylene glycol, (b) in Crown ethers have the ability of forming complexes with
the manufacture of Dacron, (c) in the manufacture ofa solvent, positive ions like Na + ,K+ and Li+ . By this property, ionic
ethoxyethanol used in varnishes and enamels for quick drying. compoUnds can be made to dissolve in non-polar organic
solvents having some crown ether.
10.8 CROWN ETHERS
In this reaction, the crown ether is the 'host' and the
The crown ethers are heterocyclic polyethers usually with . species it binds is the 'guest' complex (known as Inclusion
at least four oxygen atoms. These are called crown ethers compound) •.
because they have a crown-like shape. Their names consist of
is
two numbers, the first of the two numbers the total number of
.. o·~.
atoms in the ring and the second is number of oxygen atoms. O 0\.....·.CI9Jo
\, · .
.
C... 6 \0
/1
. oC
~
·
\Ni
".0···.•.·
..~
15-Crown-5 Crown ether-sodium
Crown ether. .metal ion complex
(Host) (Inclusion compound) .
12-Q0wn.4 18-Cr0wn-6
(12 atoms including" oxygen) (18 atoms including 6 oxygen)
546 G.R.B. Organic Chemistry for Competitions
CJ Action with strong acid (Salt formation): Due to the .' alkyl ~odides are formed. Similarly, cyclic ethers are readily
presence of lone pair (jf electrons on oxygen atom (basic m:
cleaved byHBr or to form dihaloaIkanes.
nature of etheral oxygen), ether behaves as Lewis base and ClActlon of PCI.s: On heating ethers with pels, alkyl
form stable. oxonium salts with cold conc. HCI and conc. chlorides are formed.
H2 S04' CJ Dehydration: On heating ether vapou.rs over Al203 at
CJ Ether also forms coordination complexes with BF3 (Lewis 3000c, dehydration occurs to form aIkenes.
acId), Grignard reagent and AICl3 etc. CJ Reaction with CH 3COCI or (CH3COh 0: On.heating
Reactions due to cleavage of c-o bond ethers with CH 3COCI or (CH 3 COhO in presence of
CJ Hydrolysis: Ethers are hydrolysed to alcohols when anhyd. ZnCI 2 , esters are formed.
heated with dil. H 2 S04 under pressure. CJ Reaction with carbon monoxide: Ethers react with CO
CJ Action ofconc. H2S04: On heatingwithconc. H 2 S04 , in presence of catalyst BF3 at 150°C u:nder pressure forms
ethers form alcohol and finally alkyl hydrogen sulphate. ester.
Cl Action of HI (or HBr): Etherallinkage is broken by HI Cl Uses: Diethyl ether is used as an excellent solvent for
(or HBr) in cold to give RI and R-OH. In case of mixed oils, fats, resins and plastic etc. It is also. used, as an
ethers, the halogen atom attaches to a smaller and less anaesthetic. The mixture of alcohol and ether is used as a
complex alkyl group. When heated with excess of HI, only substitute of petrol under the name natalite.
, ", ~
G.R.B. Organic Chemistryfor Competitions
iii i
(e) Methyl ethers can be formed by the action of (b) Ether is soluble in water.
diazomethane on ...•••...... in presence of a catalyst (c) Ethers are not affected by atmosphere.
boron trifluoride. (d) Metatnerism is shown by ethers.
(f) Ethyl alcohol is isomeric to ........... . (e) Ethyl alCohol and dimethyl ether are functional
(g) Aliphatic ethers are purified by shaking with a.solution isomers.
of ferrous salt to remove ............which are formed on (f) Diethyl ether gives iodoform test.
prolonged standing in contact with air. (g) Dimethyl ether and ethyl alcohol haye same boiling
(h) Ethers form ............ salts with concentrated acids at points as both have same molecular masses. .
low temperature. (h) Ethers can be obtained by dehydration of alcobols.
(i) Diethyl ether when refluxed with excess of HI gives (i) The presence of peroxide in ether can be tested by
two molecules of.: ......... . development of red colour when ether is shaken by a
(j) Ethers act as Lewis bases due to the presence of mixture of ferrous anunonium sulphate and KCNS.
............ on oxygen atom" (j) Pure ether liberates iodine from potassium iodide.
(k) Ether ~n treatment with excess of chlorine in presence (k) Diethyl ether in presence of BF3 combines with CO at
of sunlight forms............ . 150°C and.500 atmospheric pressure and forms ethyl
(I) The mixture of alcohol and 'ether is used as a substitute propionate.
of petrol under the trade name ........... . (1) C2Hs OC2Hs is a linear molecule having zero dipole
(m) Ethers should never be evaporated to............ becaU$e moment.
it may cause explosion. (m) Diethyl ether and l-butanol have the same solubility in
(n) Ethers can form ............ compounds with Lewis acids water.
. . like BF3 , AlCl3, RMgX, etc. . (n) Ethers form oxonium salts when treated with acids.
.... (0) E~yleneoxideonreduction withLiAlH4 forms ........ . (0) Dioxane is an example of cyclic ethers.
(P) The derivatives having three membered cyclic ring,
>'\1< ' are called ........... .
(P) Ethers are less volatile than alcohols.
(q) Ethylene oxide is highly reactive because of its strained
configuration.
o (r) 2-Aininoethanol is formed when ethylene oxide
(q) With pas, ethers form ........... .
combines with anunonia.
(r) When mixed ethers are treated with HI, the iodine atom
(s) Ethers are insoluble in conc. H2S04 while alkanes are
goes to .. : ......... alkyl group. ,
soluble.
(s) Ethers on hydrolysis with dilute sulphuric acid give
(t) Williamson's synthesis of ethers is an example of
nucleophilic substitution reaction.
(t) The IUPAC name of diethylether is .......... ..
"
I.
(u) The reactivity ofhalogen acids with ethers follow the
(u) Coordination complexes of ethers with Lewis acids are
called etherates..
order HI ............ J{Br........ :; .. IICh
. (v) Ethers are more polar than the isomeric alcohols.
. .' (v) Etbtml ivhen treated with strong· oxidising· agents are
3. Match the following:
.converted into.~ ..•.......
(1) Diethyl ether (A) Epoxide
(w) Williamson's. synthesis is· a............ substitution
(2) Williamson's synthesis (B) Unsymmetrical ether
. reaction.. '.
(3) Zeisel's method (C) Anaesthetic
(x) ... ~ ..... ; .. is uSed as inert medium in the preparation of
(4) ROR' (D) Mixture of alcohol
Grignard reagents ..
and ether
Ethers
(5) CH3-CH-CH2
,,/ o
(E) Ether + solid C02 (Ans. (A) HOCI; (8) ctCH2CH2OCH2CH2CI;
(C) H2C=CHOCH:--CH21
(ii) CH3CHBrCH 3 Ale. KOH, (A) HBr )
(6) Natalite (F) Ethoxyethane Peroxide
(7) Halothane (G) Estimation ofalkoxy group
(B) CHj)Na) (e)
(8) Cooling material (H) C2Hs ONa + C2HSBr
(9) Phenetole (I) Coordinate complexes (Ans. (A) CH3CH=CH2; (8) CH3CH2CH2Br;
(l0) Etherates (J) Ethoxy benzene (C) CH3CH 2CH2OCH3J
4. Give the common and IUPAC names of the following (iii) Me3CBr Ak. KOH) (A) HOC!) (B) NaOH) (e)
ethers:
(Ans. (A) M~C=CH2; (8) M~C(0H}-CH2CI;
(i) (CH3 h CHOCH(CH 3)eH2CH3
(ii) CICH2CH2OCH3
(iii) CH]OCH=CH2
A
(C) M~C-CH2]
(iv) P-N02C6HsOC2Hs . (vi) H2 C=CH (i) HBr ) (A) (i) (B) )
5. What happens when? 2
(ii) Mg (il) H20/H+
(a) Ethyl bromide reacts with sodium ethoxide.
(b) Ethyl alcohol is heated with conc. H 2S04 at 140"C. CH3CH2CH2CH20H-ill!4 (e)
(c) Thevapours of ethyl alcohol are passed over anhydroUs
H2C"
alumina at 25O"C. (Ans. (A) CH3CH2MgBr; (8) I /0;
(d) Diethyl ether is heated with phosphorus pentachloride. H2C .
(e) Ethyl iodide is heated with dry silver oxide. . (C) CHjCH2CH2CH2Br]
(t) Ether is heated with hydroiodic acid.
(v) CH3CH=CH2 H 20, (A) (B))(e) CH3 (CH2h Br )
(g) Ether is heated with conc. H 2S04 , H2SO4
[See the prepamtion and properties of diethyl ether.]
CH3CH2CH2CH2OCH(CH3 h
.. Short Answer Type (Ans. (A)CH3CHOHCH3; (8) Na; (C) (CH3)2CHONa) ..
6. How will you distinguish between?
(i) Diethyl ether and n-butane(alkane).
[Hint: Diethyl ether dissolves in concentrated H 2S04 fonning
oxoniwn salt,
H
r I 1
~HSOC2Hs ~ l~Hs-?-C2HsJ ~04
. Oxoniwn salt
ncButane does not react with H2 S04 and thus, two distinct
layers are fonned when H 2 S04 is added to n-butane.]
(ii) Diethyl ether and but-l-ene (an alkene).
[Hint: But-I-ene decolourises alkaline potassiwn pennanganate
solution,
CH3CH2CH=CH2 + H20 + [O]~ CH3CH2CHOHCH20H
But-I_ ButaJ1e..I,2-iliol
Diethyl ether does not decolourise KMn04 solution.]
(iii) Diethyl ether and alcohol (primary).
[Hint: Ethyl alcohol produces hydrogen (bubbles) when reacted
with sodium. Ether does not react with sodiwn.)
(iv) An ether and alkyl bromide.
[Hint: The ether dissolves in cone. H 2S04, the halide does not.
Alkyl bromide fonns a light yellow precipitate of AgBr
when treated with alcoholic AgN03' This test is not given
by ether.]
7. Supply structural formulae for missing compounds.
[Hint: Water is a'stronger base than ether and removes the proton [Hint: The oxiranering is cleaved via SN2 mechanism.
. fromR20lF
+
R20H + H20~ R20+ H3 0
+ 1
J H)C" . H+ H3C, . [H3C, 1 J
C-CH2 .~ "C---CH2 HOH) "C-CH 2
(vii) Why is diethyl ether used as a solvent for (i) BF3 and
(ii) RMgBr?
[Hint: Diethyl ether acts as a Lewis base due to presence of lone
H3 C/ \ /
o
H3C/ \ /
0+
'. H3C/ :
H
I OH2 0H . 1 .
I
(viii) Sometimes explosion occurs during distillation of an (xiii) Write the equations of the reaction of hydrogen iodide
w~ ,
ether sample.
[Hint: Ethers form peroxide with oxygen. The boiling point of (i) I-Propoxypropane (ii) Methoxybenzene
peroxide is higher than that of ether. It is, thus, left as . (iii) Benzyl ethyl ether
residue in the distillation of ether which is very unstable [Hint: (i) CH3CH2CH2-0-CH2CH2CH3 ~
and decomposes violently on heating.] I-Propoxypropane 373K
(ioc) Wohy [(eH3 hCh 0 cannot be prepared either by CH 3CH 2CH20H + CH3CH2CH2I
Willialnson's reaction or by dehydration of tertiary Propan-l-oJ' l-Iodopropane
3~IK'
butylalcohol?
(Hint: The product in both the cases is isobutylene as the tert. (ii) I(5\-OCH3 . 1(5\-0H + CH31
butyl carbocation eliminates an H+. The reaction between ~ ~ Iodomethane
+ . Methoxybenzene Phenol
(CH 3hC on (CH 3hCOH to give an ether is sterically
hindered.' .
The instability of di-, tert.-butyl ether in sulphuric acid
may also be due to steric crowding ofCH3 groups.]
(x) Why ArO-R ethers are cleaved with HI to give RI
and ArOH rather than ArI and R-OH? . 11. Answer the following:
[Hint: ( )-O-R + HI~ < )-OH + R+
(i) What is the synthetic utility of the reaction RMgX or
. RLi with ethylene oxide?
(More stable) (Hint: It is a good method for extending R group of organo-
<)-±-
SN1 attack on a carbon of benzene ring does not occur, nor' [Hint: 2Me3C-Cl . ) MCJC-u-"!""CMCJ
However, yield is poor due to sterichindrance.]
does the b:gh energy (phenyl) form by SN1
(iii) What product. is formed when,
reaction. Hence, Arl cannot be formed. ] HOCH 2 CH 2 CH2·CH2 0H is heated with cone.
(xi) Which of the following is the correct method for H 2 S04 ?
synthesising methyl tert. butyl ether and why? r .. . . .
CH 2 -CH2 1
(a) (CH 3 hC-Bi' + NaOMe --+ 'lHint: Tetrahydrofuran is formed. II J
. CH2 CH2
(b) CH3Br+NaO-t-Bu~
[Hint: The ether formation involves nucleophilic substitution of . "-/
o
alkoxide ion for halide ion.
(iv) The following reaction gives two products. Write the
(J
[(O-+R-X
0- 0-
Slow) [(O-uR_uX·~[(-o-R+X- structures of the products.
-......J . (CH hCH--O-CH3 ill (excess»
3° lllkyl halide can also involve elimination ofHX to give alkene in 3
Heat .
the presence of a base. So, it is better to start with 3° alkoxide and [Hint: The two products obtained are (CH 3)2 CH-I and CH3L
t" alkyl halide, i.e., equation (b)]
In the presence of excess of HI, the initially formed.
CH3Br + NaOC(CH3)3 ~ CH 3 -0-C(CH3)3 -f NaBr alcohol is also converted to iodide.]
Sodiwn tert. butoxide Methyl tert. butyl ether
(xii) 2,2-Dimethyl oxirane can be cleaved by acid (H+).
(v) What would be the major product in the following .
reaction?
Write mechanism. [lIT 1997)
552 G.R.B. OrganIc Chemistry {Or Co';'petitions
[Hint:
I
The product is CH3-C-CH2CH3
I
..
[Hint: The C-O-Cbond in ethers is very strong. The addition
of acid forms protonated ether which is attacked by
OC2 HS nucleophiles (Br - or r) on the less hindered alkyl groups
(Ethyl tert. pentyl ether) to bring the cleavage of ethers to form alkyl halide and an
as the reaction proceeds via SN I mechanism with alcohol.
rearrangement of neopentyl carbocation to tert. pentyl +
carbocation. ] CH3CH 2-O-CH3 + H+ ~ CH3CH2-O-CH3 Br-~
(vi) Sodium metal can be used for drying diethyl ether but •• I
H
not ethanol. Protonated ether
[Hint: Sodium metal reacts with, ethanol to form sodium
CH3Br + CH3CH20H
ethoxide. On the contrary, ethers do not have replaceable --.
hydrogen atom and therefore, do not react with sodium.] Ethers themselves are Lewis bases and are not attacked by
(vii) What products are obtained when: strong bases.]
(xi) Predict the product of the following reaction:
@-O-CH2- @ is treated with HI? . F
@-OH+ ICH2-@] [Hint: As the nitro group is highly deactivating in nature, it will
make the cleavage of C- F bond very easy, i. e. ,F- ions
Phenol Benzyl iodide
(viii) Dh tert.butyl ether cannot be obtained by Williamson's can be replaced by -OCH3 ion.
©
synthesis. F OCH 3
[Hint: To prepare di-tert.butyl ether, the reagents to be ~sed are
~
tert.butyl bromide and sodium tert.butoxide. Since, the
tertiary bromide (30) prefers to undergo elimination
(rather than substitution), therefore, the major product
N0 2
+ NaOCH3 Heat
© +NaF]
,4-Nitrofluorobenzene 4-Nitroanisole
obtained is isobutylene and not di-, tert.butyl ether.
CH3 CH3 (xii) The following is not an appropriate reaction for the
I + _ I . preparation of tert. butyl ethyl ether.
CH3-C-Br + NaO-t- CH3 (-NaBr)~ CH 3 CH 3
I I I I
CH3 CH3
Tert. butyl bromide ' Sodiwn lert. butoxide CH3-C-CI+NaOC2Hs ~CH3-C-OC2Hs
(3°) I I
CH3 CH3 CH3 ·CH3
I I (a) What would be the major product of this reaction?
CH3-C= CH2 + CH3-C-OH ]
Isobutylene I (b) Write a suitable reaction for the preparation of tert.
CH 3 butyl ethyl ether.
[Hint: (a) The major product of the given' reaction is
'(ix) A mixture of ethyl alcohol and n-propyl alcohol on
2-methylprop-l ~ene. It is because sodium ethoxide is a
treatment with conc. H 2S04 gives a mixture of three strong nucleophile as well as a strong base. Thus,
ethers. elimination reaction predominates over sl,lbstitution
[Hint: The 1° alcohols, i.e., ethyl alcohol and n-propyl alcohol reaction.
(both) yields equally stable carbocations and each one of (b)
which can be attacked either by ethyl or n-propyl alcohol CH 3 CH 3
to give a mixture of three etherS. . I _ + I
CH3-C-ONa + CICH2CH3 ~ CH3-C-O-CH2CH3]
I Ethyl chloride . I
CH3 CH3
Sod. lert. butoxide Tert. butyl ethyl ether
Ethers 553
(xiii) How is l.propoxypropane synthesized from 14. Compound (A), C4HIOQ is found to be soluble in sulphuric
propan·l-ol? Write mechanism of this reaction. acid. (A) does not react with sodium or potassium
(Hint: The following two methods can be used: permanganate. When (A)' is heated with excess of HI, it is
(a) WlDiamson's synthesis converted into a single alkyl halide. What is (A)?
. (i) 3CH3CH2CH2011 + PBrr~ 3CH3CH 2CH2Br+ H3P03 (Ans. C2HSOC2HS)
Propan-I-ol I-Bromopropane
(il) 2CH3CH2CH20H + 2Na~ 2CH 3CH2cH20Na + H2 15. A neutral compound (A) having C, H and 0, on refluxing
Propan -1-01 Sodiwn propoxide with m yields methyl iodide and an alkyl iodide (B), which
~~
contains 74.6 per cent iodine. (B) when treated with moist
CH 3CH 2CHi>Na+ + CH3CH 2cH 2.idr Dryelher)
Heat Ag 20 produces a product which undergoes the haloform
CH3CH2CHr-0-CH2CH2CH3 + NaBr reaction. Characterize (A), what would have been produced
I-Propoxy propane if (B) were treated with dry Ag 2O?
(b) By debydration ofpropan-t.ol with eone. B~04 at 413 K. (Bint: (A) is neutral and produces alkyl halides on refluxing with
HI, hence, it should be an ether.
,
CH 3CH2CH 20H + H+ ---+. CH3CH,2CH
+<H
r -0 . 127 x)OO
Molecular mass of (B) = 74.6 = 170
Propan-I-ol . . H
, Protonated propan-I-ol RI=170
CH CH,CH
3 2 2..
~ ~H £1./"
3 2 2 ~
Heat,4I3K)
-H 0. H'
R + 127 = 170
R = 170:-127 = 43 = C3H7
2 Thus, the alkyl iodide, (B), should be isopropyl iodide as the
Propan -J-ol Protooated propan -1-01 '
hydrolysis product, (i.e., isopropyl alcohol) undergoes the
CH3CH2CH2-O-CH2CH2( 'II, . halofonn reaction. (A) is methyl isopropyl ether. '
J-Propoxy propane The reaction of (B) with Ag20 is,
12. How would you bring the following conversions? H 3C,,-
(i) Ethyl alcohol to diethyl ether. ' . 2 . )CHI + Ag20~ (CH3)2CH-O-HC(CH3h + 2Agl ]
H3C / Di-isopropyl ether
, [Hint: Heat ethyl alcohol aod conc. H2S04 at 140"C,
Na . . ANSWERS
or C2HsOH~ ~,"'sON~" 1
C2HsOC2 Hs J 1. (a) Dialkyl; (b) Williamson's; (c) drying; (d) three; methyl propyl
~HsOH --!!!k.., C2HSBr ether, methyl isOpropyl ether; (e) alcohol; (t) dnnethyl ether;
(g) peroxide; (h) oxonium; (i) ethyl iodide; (j) lone pairs of
(ii) Diethyl ether to ethyl alcohol. electron; (k) C2Cl sOCIsC2, perchlorodiethyl ether; (I) natalite;
• ,HI ' . NaOH(aq.) ] (m) dryness; (n) coordination; (0) ethyl alcohol; (P) epoxides; (q)
[ Hmt: ~HSOC2Hs ~
Heat .
2C2HsI ) 2C2H sOH
alkyl chloride; (r) smaller; (s) alcohols; (t) ethoxy ethaoe; (u) >, >;
(v) aldehydes; (w) nucleophilic; (x) diethyl ether;
(iii) Ethyl iodide to diethyl ether.
(y) CH 3HC=CH 2• CH3-CH-CH2, CH3-CH-CH2;
[Hint: ~HsI NaOH(~q.» ~HsOH~ C2HSONa C:iHsJ) . "-/ I I .
o OH OH
~HsOC2Hs] (z) alkyl halide.
. (iv) Diethyl ether to ethyl iodide. 2.' (a) True; (b) Fa1se-insoluble in water; (c) False-aIl ethers that
. . ill' 1 have been exposed to atmosphere for aoy length oftime invariably
[ Hmt : ~HSOC2Hs ~ 2C2HsIJ contain peroxides; (d) True; (e) True; (t) FalSC'-it does not give
iodofonn test; (g) False-both have different hoiling points;
(v) Methyl iodide to methyl ethyl ether. (h) True; (i) True; (j) False-does not liberate iodine; (k) True;
[Hint: . (I) FalSC'-the molecule is not linear, bond angle about llO°.1t has
dipole moment; (m) False-Butanol-l has higher solubility as it
CH31 NaOH) CH30H~ CH30Na . cao fonn hydrogen bonds with water; (n) True; (0) True;
~CH3OCH2CH3]
(P) FalSC'-more volatile thao alcohols; (q) True; (r) True;
.1N'<"""l . CI 2
(s) False-ethers are soluble in conc. H2S04 while alkanes are
insoluble; (t) True; (u) True; (v) True.
3. (I-F); (2-H); (3-0); (~B); (S-A); (6-D); (7-C); (8-E);
CH 3-CH3 ~ CH 3CH 2CI .
hv . (9-J); (10-1).
13. Two compounds (A) and (B) have molecular formula, 4. Common names IUPACnames
C2H60. On reacting with m. (A) gives alkyl iodide and (i) Sec. butyl isopropyl ether 2-Isopropoxy butane
water while (B) gives alkyl iodide and alcohol. What are (A) (ii) j}-Chloroethyl methyl ether 2-Chloro-l ~methoxy ethaoe
and (B)? Write their structures. (iii) Methyl vinyl ether Methoxy ethene
(Ans. (A) C2HsOH; (B) CH3OCH3] (iv) Ethyl p"nitrophenyl ether 4-Ethoxy nitrobenzene
554 a.R.B. Organic Chemistryfor Competitions
OBJECTIVE OUESTIONS
. >
Set I: This set contains questions with single correct answer: 13. Ethers are obtained by reacting alkyl halides with:
1. Ethers are isomeric with monohydric alcohols. Both have (a) dry Ag20 0 (b) moist Ag 2 0 0
the general formula: . (e) dry ZnO 0 (d) moist ZnO 0
(a) Cn H 2n +20 o (b) Cn H 2n O o 14. Indicate the incorrect statement:
(c) Cn H 2n +4 0 o (d) CnH2n-20 o (a) Diethylether is used as anaesthetic 0
2. Ether is: (b) Diethyl ether is used as a fuel 0
R (c) Diethyl ether is an inert compound 0
(a) )C=O o (d) Diethyl ether is insoluble in water 0
H
15. Ethers are riot distilled to dryness for fear of explosion. This
(c) R)O o is due to formation of:
(a) _oxides 0 (bj peroxides 0
R
(c) alcohols 0 (d) ketones 0
3. The IUPAC name ofCH3 0C2H s is:
16. Diethyl ether combines wiL: CO under specific conditions
(a) ethoxy methane 0 (b) methoxyethane 0 to form:
(c) ethyl methyl ether 0 (d) methyl ethyl ether 0 (a) ethyl propanoate 0 ('-) "eeric acid 0
4. An isomer of ethanol is: (c) carb•.m dioxide 0 (d) acetone 0
(a) methanol 0 (b) diethyl ether 0 17.. According to Lewis concept'of acids and bases, ethers are: .
(c) acetone 0 (d) dimethyl ether 0 (a) neutral 0 (b) acidic 0
5. C4H lO O is the molecular formula of diethyl ether. The (c) basic 0 (d) amphoteric 0
metamers represented by this formula is/are: . 18. The mixture of ethanol and sulphuric acid is heated in a
(a) I 0 (b) 2 0 closed flask at 140"C. The flask would then contain:
~3 0W4 0 (a) H2S04 and C2HsOC2HS only 0
6. Diethyl ether may be regarded as an anhydride of: (b) H 20, H 2S04 and C2HSHS04 only 0
(a) C2H s OH 0 (b) C2HsCOOH 0 (c) H2O,C2HsHS04, C2HsOC2HS and H 2S04 only . 0
(c) C2HSCHO 0 (d) C2HsCOOC2HS ·0 (d) H 2O, C2HSOC2HS, C2HsHS04, H 2S04 andC 2H s OH
7. Heating together sodium ethoxide and ethyl chloride wilt . 0
give: 19. Diethyl ether does not react with:
(a) ether o (b) ethyl alcohol o (a) sulphuric acid 0 (b) hydrochloric acid 0
(c) acetaldehyde o (d) acetic acid o (c) hydroiodic acid 0 (d) acetic ::,:::id 0
8. The reaction, 20. Oxygen atom of ether is:
C 2H s ONa + C2HSI ~ C2H sOC2Hs + NaI (a) very active 0 (b) replaceable 0
is called: [KCET 2006; CET (Pb) Engg. 2007} (c) active 0 (d) comparatively inert 0
(a) Wurtz reaction 0 21. The compound which has lowest boiling point among the
(b) Kolbe's reaction 0 following is:
(c) Williamson's synthesis 0 (a) diethyl ether 0 (b) ethanol 0
(d) Grignard synthesis 0 (c) methanol 0 (d) water 0
9. Diethyl ether can be decomposed by heating with: 22. Ethers in contact with air for a long time form peroxides.
(a) water 0 (b) HI 0 The presence of peroxide can be tested by adding Fe 2t ions,
(c) NaOH 0 (d) KMn04 0 followed by the addition of:
to. Diethyl ether on heating with conc. m gives two moles of: (a) KCNS 0 (b) SnCl 2 0
(a) ethanol o (b) iodoform 0 (c) HgCl2 0 (d) KI 0
(c) ethyl iodide 0 (d) methyliodide 0 23. When diethyl ether is treated with chlorine in presence of
11. The compound which has the lowest boiling point is: sunlight, it forms:
(a) H 20 0 (b) C2Hs OH 0 (a) C2HSCI 0 (b) C2H6 0
(c) CH 3 0H 0 (d) C2HsOC2HS 0 (c) CH3COCI 0 (d) (C 2CI s hO 0
12. The product (D) in the following sequence of reactions is: 24. When diethyl ether is heated with excess of sulphuric acid, it
forms:
C2~ ~ (A) NaOH(aq.) (B)~ (C) CH3I) (D)
(a) propionic acid 0
(a) butane 0 (b) ethane 0 (b) acetic acid 0
(c) propane 0 (d) ethyl methyl ether 0 . (c) ethyl hydrogen sulphate 0
(d) ethyl alcohol 0
Ethers 555
25. The hybrid state· of central oxygen atom in diethylether is: (a) dimethyl ether 0 (b) ethyl methyl ether 0
[EAMCET (Engg.) 2007] (c) diethyl ether 0 (d) none of these 0
(a) sp2 0 (b) sp3 0 38. When diethylether is treated with chlorine in dark, it forms:
(c) sp o (d) sp d 3
0 (a) perehloro diethyl ether 0
(b) ethyl chloride 0
26. In ethers, .the C-O-C bond angle is: . (c) acetyl chloride 0
(a) 110° 0 (b) 105° 0 (d) I, l-dichloro ether 0
(c) 1800 o (d) 120°. 0
39. Ether fonn peroxide in contact with air and light and it may
27. Complete combustion of ether gives: cause explosion, since the boiling point of peroxide is:
(a) C2Hs OH 0 (b) CO 2 andHtO 0 (a) equal to ether 0 (b) lower than ether o
(c) C2H4 0 (d) C2H2 0 (c) higher than ether 0 (d) none of these o
28. Intennolecular hydrogen bonding is not present in:
40. Fonnation of peroxide in ether can be prevented by:
(a) CH3COOH· 0 (b) C2H;OH 0 (a) adding small aIriount OfCu20 o
(c) CH30CH 3 0 (d) C2liSNH2 [] (b) shaking with ferrous salt solution o
29. Ethoxy ethane does not react with: (c) distilling with conc. H 2S04 o
. (a) HI 0 (b) conc. H 2S04 0 (d) all of the above o
(c) PCIs 0 (d) Na 0 41. When an ether is treated with P2SS, it gives:
30. Which of the following pairs of reagents will not fonn
ether.?
(a) thioalcohol 0 (b) thioether 0
(c) thioester 0 (d) thioacetal 0
(a) C2HSBr + CH3 COONa 0
42. The boiling point of thioether are ......... than those of
(b) C2H sBr +·C 2HsONa 0
ethers.
(c) C2HSBr + (CH3 h CHONa 0
(d) (CH3hCHBr+ CH30Na 0
(a) higher . . o (b) lower o
31. An equimolar quantities of ethanol and propanol are heated
(c) equal o (d) nearly same o
43. Sulphuric ether is:
with cone. H2S04. The productls fonned is/are:
(a) C2HsOC2HS 0 (b)' C3H70C3H7 0 (a) C2Hs-O-C 2Hs 0 (b) CH3-O-CH3 o
(c) C2HsOC3H7 0 (d) all of these 0 (c) C2Hs-S-C2HS 0 (d) CH3-S-CH3 o
44. Ethanol reacts with diazomethane to produce:
32. Crown ethers are:
(a) cyclic ethers 0 (a) CH3-O-CH3 [] (b) C2H6-'-O-CH3 o
(b) ethers with several other functional groups 0 (c) C2H s -O-C2H s 0 (d) none of these o
(c) mixed ethers 0 45. Which is correct?
(d) not ethers 0 (a) CH 3-O-C2H s +HI~C2HsI+CH30H 0
33. In [18]-crown-6, the number of oxygen atoms is: (b) CH3-O-C2HS + HI~2CH3I+ H20 0
(a) 18 0 (b) 6 0 (c) CH3-O-C2Hs+HI~2C2HsOH+H20 0
(c) 12 0 (d) 24 0 (d) CH 3-O-C2HS + HI ~ CH31 + C2HSOH 0
46. Ether on. heating with acetyl chloride in presence of
34. Epoxides are:
anhydrous ZnCl 2 gives:
(a) unsaturated ethers 0
(b) mixed ethers 0 (a) ethyl alcohol 0
(b) ethyl chloride 0
)c-c(
(c) cyclic ethers with ring 0
(c) ethyLacetate 0
'\/
o (d) ethyl chloride and ethyl acetate 0
(d) not ethers o 47. An 'Organic compound of molecular fonnulaC4 H lO O does
"'/
35. CH2-CH2+LiAlH4
o
~
.
(A), (A) is: not react with sodium. With excess of HI, it gives only one
type of alkyl iodide. The compound is:
(a) ethoxyethane
lEsCRA 2001]
0 (b) 2-methoxy propane 0
(a) CH3CHO o (b) CH3CH20H 0 (c) l-methoxy propane 0 (d) I-butanol 0
(c) H 2C=CH2 0 (d)CH20H-CH20H 0 48. In the following reaction, [PMT 2002]
H 0
2
36. CH3MgI + .......... --=----+ I-Propanol, C 2Hs --O-C2HS + 4H ~p) 2X + H2Q X is:
H+
the missing reagent is: (a) ethane 0 (b) ethylene 0
(a) HCHO !;I (b) C2HSOH 0 (c) butane 0 (d) propane 0
(c) C2H s CI 0 (d) ethylene oxide 0 49. The reagent used for the preparation of higher ethers from
37. When vapours of alcohol are passed under pressure over halogenated ethers is: [CET (Tamilnadu) 2001]
heated Al 20 3 at 250°C, the product obtained is: (a) cone. H 2S04 0 (b) sodiumalkoxide 0
(c) dry silveroxide 0 (d) Grignard reagent 0
·.556 G.R.B. Organic Chemistry (or Competitions
50. Ether which is liquid at room temperature is: (c) OH30H + CH30Na 0
[BV (pune) 2002] (d) C4H9 0Hand C4H 9 0Na 0
(a) C 2H s -O-CH3 0 (b) CHr':"-0-CH3 0 60. The products formed when diethyl ether is reacted with cold
(c) C 2H s -O-C2H s 0 (d) none of these 0 HI are: [EAMCET 20021
51. Ethyl phenyl ether on boiling with conc. HBr gives: (a) C2HSI + C2H s OH 0 (b) 2C2HSI + H 20 0
(a) phenol and ethane 0 (c) 2C 2Hs OH 0 (d) C2Hs-O-O-C2Hs 0
(b) bromobenzene and ethane 0 6L Excess of ethanol when heated witli conc. H2S04 at 14O"C,
(c) phenol and ethyl bromide 0 the compound obtained is: [AFMC 2002]
(d) bromobenzene and ethanol 0 (a) ethene. 0
52. Which of the following will not give anisole? (b) diethyl sulphate , 0
(a) Phenol is reacted with dimethyl sulphate in presence of (c) ethoxy ethane 0
abase I~ (d) ethyl hydrogen sulphate 0
(b) Sodium phenoxide is treat~d with methyl iodide 0 62. Which of the following will be obtained by keeping ether in
(c) Diazomethane is reacted with phenol 0 contact with air for a long time? [PET (Raj) 2003J
(d) Methyl magnesium iodide is treated with phenol 0 (a) C2Hs-O-CH(CH3)---O-OH 0
53. Anisole on treabnent with Br2/CS2 gives: (b)C2Hs-O-CH30H 0
(a) bromobenzene 0 (c) C2Hs-O-C2HsOH 0
(b) methyl-2-bromophenyl ether 0 (d) CH3-O-CH(CH3)---O-OH 0
(c) 0- and p-bromoanisole 0 63. Anisole can be prepared by the action of methyl iodide on
(d) phenol 0 sodium phenolate. The reaction is called:
54. Which of the following is not cleaved by HI even at 525K? [CET (Karnataka) 2008J
(a) C6H s -O-CH3 0 (b) C6Hs-O-C6HS 0 (a) Williamson reaction 0 (b) Fittig reaction 0
'.
G.R.B. Organic Chemistry (or Competitions .
.82. 'A' reacts with CzHsI giving 'B' and NaI. Here 'A' and 'B'
(a)'@-cHzI o (b) @-cH2 0H o
respectively, are: [Punjab PMET (Med.) 2008]
(a) CH3COONa,CH 30CH 3 0
(b) CzHsONa, CzHsOCzH s 0 (c) @ - I o (d) @ - o H o
(c) CzHsOCzHs,CzHsCOOCzHs 0
(d) C2H s OH, C2HsOC2HS 0 89. Which of the following reactions will give good yield of
83. Decreasing order of reactivity in Williamson's ether ether?
synthesis of the fonowing: [DllMET 2010] ~OH (i)Na ~OCzHs .
(I) Me3CCH2Br
(III) HzC=CHCHzCl
(II) CH3CH2CHzBr
(IV) CH3CH2CH2Cl
(a) ~ . (ti) CzHsBr • ~ 0
(a) IIl>II>IV>I 0 (b) I>I1>IV>III 0
(c) I1>III>IV>I 0 (d) I>UI>II>IV 0 (b) (CH ) C-OH (i) Na ) C H -O-C(CH) 0
33 (ii)C SBr 6 S 33
84. In the reaction@-oCH3 ~ ?
6H
(i).Na
(c) (CH3hC-OH )
the products are: (lIT 2010] z z
(li) CH 3CH CH Br
0
Ether.s 559
97. Diethyl ether is obtained by the reaction of: (b) sodium ethoxide with ethyl chloride o
[BHU (Mains)2008] (c) ethanol with red phosphorus o
(a) sodium ethoxide with methyl iodide 0 (d) ethanol with conc. H 2S04 o
J ANSWERS I
OBJECTIVE QUESTIONS
.
1. (a) 2. (c) 3. (b) 4. (d) 5. (c) 6. (a) 7. (a) 8. (c) 9. (b) 10. (c)
11. (d) 12. (d) 13. (a) 14. (b) 15. (b) 16. (a) 17. (c) 18. (d) 19. (d) 20. (d)
21. (a) 22. (a) 23. (d) 24. (c) 25. (b) 26. (a) 27. (b) 28. (c) 29. (d) 30. (a)
31. (d) 32. (a) 33. (b) 34. (c) 35. (b) 36. (d) 37. (c) 38. (d) 39. (c) 40. (d)
41. (b) 42. (a) 43. (a) 44. (b) 45. (d) 46. (d) 47. (a) 48. (a) 49. (d) 50. (c)
51. (c) 52. (d) 53. (c) 54. (b) 55. (e) 56. (d) 57. (c) 58. (b) 59. (a) 60. (a)
61. (c) 62. (a) 63. (a) 64. (d) 65. (d) 66. (c) 67. (a) 68. (b) 69. (c) 70. (c)
71. (b) 72. (a) 73. (c) 74. (c) 75. (b) 76. (a) 77. (c) 78. (c) 79. (d) 80. (c)
81. (a) 82. (b) 83. (c) 84. (a) 85. (a) 86. (b,d) 87. (a,b,c,d) 88. (a,d) 89. (a,c) 90. (a,b)
91. (a,b) 92. (a,c) 93. (b,c,d) 94. (a,c,d) 95. (b,c) 96. (a,c,d) 97. (b,d)
. 1. (a) 2. (a) 3. (b) 4. (b) 5. (d) 6. (c) 7. (b) 8. (a) 9. (c) 10. (b)
G.R.B. Organic Chemistryfor Competitions
~o-I
3. What are (A), (8) and (C) in the following reactions?
CH2'
(a) ' / ,HO+CH30H Cone. H2S04 ) (A)
CH2
CH2'
(b) 1/ '0+ CH~OH CH30Na) (8)
CH2
CH2"
(c) I /0+C6 H 5NH 2 ~(C)
CH2
R-I ]
More stable product
6. (A) C5H120 (ether) on treatment with PCl 5 foons alkyl
chlorides (8) and (C). (8) and (C) both on treatment with aq.
NaOH give alcohols (D) and (E), both (D) and (E) give
iodoform test. What .are (A), (8), (C), (D) and (E) ?
Ethers
, (Ans.
(b) _C...:6;.....;Hs::...C_OOO_H~. (A) CH30H .(B) 11. The ether having best anaesthetic properties is:
(a) diethyl ether 0 (b) dimethyl ether 0
IAns. (c) vinyl ether 0 (d) allyl ether 0
12. When ether is exposed to air for some time, an explOsive
substance produced is:
(a) ether peroxide 0 (b) TNT 0
, (c) ether oxide 0 (d) ether superoxide 0
13. Which of the following is the best procedure to make
isopropyl methyl ether using the Williamson's method?
(a) CH30H+ (CH3hCHOH+ H2S04 --+ 0
(b) CH30H+(CH3hCH-CH20H+H2S04 --+ 0
(c) CH30Na+(CH3hCHBr--+ 0
(d) CH3I+(CH3hCHO-Na+ --+ 0
CJI~COOOHto
.
.C)o CH)OH to ('r-OH
V.
]
OCH3
14. The reactivity of halogen acids with ether follows the order:
(a) HI>HBr>HCI 0 (b) HCI>HBr>HI 0
(c) HBr>HI>HCl 0 (d) HCI>HI>HBr 0
~) (~ 15. Phenetole reacts with HI to produce:
(a) ,C6HSI +CH3CH20H 0
9. Complete the following chain of reactions:
(E) (C6HsMgBr
1
C"""COOOH
(D)
16. Select the incorrect statement among the following:
(a) The C-O-Cbond angle in ether is 1100
,(b) Diethyl ether reacts with excess of HI to form ethyl
0
HOH/HCI iodide 0
G.R.B. Organic Chemistry fOr Competitions
(a)n Br OH
o (b)n
.OH Br
o (b) C6HsCH2Cl and CH3-
?H3
r-0-Na +
CH3
o
(c) 0 o (d)U o
o
o
19. RCH2CH2-0-CH2CH2R on reaction with O 2 gives:
(a) RCH2COOCOCH2R 0
o
(b) RCH2CH-0-CH2CH2R 0 [0)
24. In the reaction R-S-R ---!:..;"':'---4) ,X, the product X
60H is:
KMn04
H2C=CH-CH2-0-CH-CHr-CH3 0
! .A.V·
o
1. Oxane
I
(c) (CH3hCH-0-CH2CH2CH3 +02~
OOH
D·O o
4. Oxetane
HOO-CH2'-....
/CH-0-CH2CH2CHj 0 Codes A B· C D
CH3 . (a) 3 4; 2 1 0
(b) 1 2 3 4 0"
(c) 4 3 2 1 0:
'. (d) 1 4 2 3 0
....
: . "
. -/
"
G.R.B. Organic Chemistry for Competitions
il-oc:1, I}~R.7"O__R'+X'"
'
'Q-o-CU 2 CH3 + NaBr
Thisreaetion isused;m the synthesis .of symmetrical and (b)o-O-Na + + CH)CH2Br ---+
unsymmetrical ethers: ' .
~t may be. noted tbatfor pieparil18UDsynunelrical etherS, the Q - o H + H2C=CH2 + NaBr
halide USed should preferably be primary .because.~ and
tertiary alkyl halides may fOrm alkenes as majorploduet due.to (c) o - B r +.CH)CH 20-Na + ---+
. elimination process. . . .
cn) .' o-O--,CH2~H)'+ NaBr
I . .... + .
CH)-C-Br + Na 0- -C2Hs---+
I (d) o - B r + CH3CH20Na ---+
CH3
Sodium
etboxide
. .0 + CH) CH20H + NaBr ,
CH3
. I . . 4. There are two possibilities for the synthesis of following
CH3-C===CH2+ C2HSOH + NaBr ether:
2-m:JhyI propene . .
Aryl ethers or phenolic ethers can be prepanxl'byusil18
!iodium phenoxide and alkyl halides. However,aryl halides and
sodium alkoxide' cannot be' u~ for preparil18pbenolic' ethers Route 1 o - B r + Na +O--CH2-Q---+
because aryl halides are less. reactive towards nucleophilic
substitution .reactions.· .
Answer the following questions : o - 0 - C H 2- ( )+NaBr
1. Arrange the following halides in decreasing order of
reattivity towards Williamson's ether synthesis: Route2 o-o-Na+ + Br-CH2- Q - - - +
CH3CH2CH2C1; CH)CH2CH2Br;
(u) (v)
(CH3 h C-CH2Br ; H2C=CH-CH2CI
(w) (x)
. Which of the following is correct?
(a) (x»(v»(u»(w) (b) (u»(v»(w»(x) (a) Route 1 gives required ether
(c) (w»(x»(v»(u) (d) (v»(w»(x»(u) (b) Route 2 gives required ether
2. Methyl tertiary butyl ether (MTBE) is added in gasoline to (c) Both route 1 and route 2 give the required ether
improve its octane number.. (d) None of the route is correct
CH3 5. To which of the following mechanisms does the reaction
I (Williamson's ether synthesis) belong?
CH3-C-O-CH3 (a) SN 1 (b) SN 2
I
cn) (c) EI (d) E2
()
I . +HI--+ +CH3I (a) True (b) False
"
(a) True
"
(b) False
11.1 INTRODUCTION H H
Both aldehydes and ketones possess the same general formula 1 1
CH3-C-H-~)CH3-C-O .
C II H 2n O and contain a carbon-oxygen double bond
I. . Acetaldehyde .
()C=O) known as carbonyl group. Thus, aldehydes and H
Ethane
ketones are collectively referred to as carbonyl compounds. ·;H
· . 1·
In aldehydes, the carbonyl group is linked to an alkyl group and
Thus, aldehydes contain the monovalentgroup-. 'C=O
a hydrogen atom, while in ketones it is united with two alkyl
groups which· may be same or different. When both the alkyl (aldehydic or formyl group) linked to a hydrogen atom or an
groups are the same, the ketone is called a simple or alkyl group. Hence, the general formula of thealdebydes is
symmetrical ketone and in case both the alkyl groups are H
different, it is known as a mixed or an unsymmetrical ketone. 1
represented as R-C =0. (R may be H or alkyl group).
R~ R~ j R~ Aldehydes can also be regarded as the.first oxidation ..
../C=O ../ C=O ../C=O
H../ R../ R'''/ products of primary alcohols. "
Aldehyde Same alkyl groups Different alkyl groups
linked to carbonyl group linked to carbonyl group
RCHzOH [O}) RCHO + HiO
Primary alcohol Aldehyde
(Simple) (Mixed)
v Ketones may be considered as derivatives of bydfo-
, Ketones .'.. carbons, in which tlle two. hydrogen atomsofa carbon atom
However, the frrst member of aldehyde series, formal- . present iritli~middie ofc~n cbainbavebeen replaced\it.8.····
H bivalentoxygen.··atom.,· . .. . . .'", c_.· y .• 'f.'·",
I H- 0
dehyde (H-C=O) is an exception to the above definition as
1 -.~. .
it does not have an -alkyl group .. CH 3 - .C-CH 3 -2H )CH 3 -.C-CH3
Aldehydes may be considered as derivatives of I +[0]' Acetone·
hydrocarbons in which two hydrogen atoms of the end carbon H
atom have been replaced by a bivalent oxygen atom. Propane
H H
I
H-C-H -2H) H-C=O
I
1 +[0] Fonnaldehyde
H
Methane
Aldehydes and Ketones
H-C=O
I CH)-C=O,
I
Methanal Ethanal
carbon-carbon double bond. Since, oxygen is more H
electronegative, the electrons of the bond are attracted towards
oxygen. Consequently, oxygen attains a partial negative CH)CH2 -C =O
I
charge and carbon a partial positive charge making the bond Propanat
polar (electronegativity values, C = 2.5 and 0 = 3.5). The high H H
values of dipole moment,
s+ s-
, I , I
CH)-CH-'C-.o ,CH)-CH-CH2-C=O
>C=O I ,I
(2.3-2.8D) cannot be explained only on the basis of CI CH)
inductive effect and thus, it is proposed that carbonyl group 2-Cbloropropanal 3-Metbyl butanal
due to high polar character is a resonance hybrid of the Ketones: There are two systems of naming ketones.
following two structures:
" ,+ -
1. Common system: Common mimes of ketones are
given by simply naming the alkyl groups attached to the
/C=O ~ /C-Q carbonyl group and adding the word-ketone. In case of simple
11.2 NOMENCLATURE or symmetrical ketones, they are named as dialkyl ketones.
However, unsymmetrical or mixed ketones are named by
Aldehydes: There are two systems of naming aldehydes.
naming the two alkyl groups attaChed to, the ketonic group as
1. Common system: Common names of aldehydes are
separate words in ,lphabetical order and adding, the word
derived from the names of corresponding carboxylic acids to
ketone. The common n~e of the first member is given acetone
which they are oxidised. Suffix "ic acid" of the acid is replaced '
by "aldehyde". ' (as obtained by distilling ,calcium acetate). Examples are,
G.R.B. Organic Chemistry for Competitions
ryOH
V
[0] .
PeC inCH2Cl2
, ryo
V
alcohols are dehydrogenated to aldehydes and secondary
alcohols to ketones.
RCH 20H Co) RCHO + H2
Primary alcohol 300"C Aldehyde
Cy<:lohex-2-en-I-ol Cydohex-2-en-l-one
G.R.B. Organic Chemistry fOr Competitions
I
CH3 -C-OH Cu ) CH 3 -C" + H20
I 300"C I
CH3 CH 3
Tert. butyl alcohol W) 2-Methyl propene
CH3 CH3
CH3-C-OH
I Cu
)CH3-C+H20
I
I 300"C 1\
CH2-CH3 CH-CH 3
2-Methyl butan-2-ol 2-Methyl but-2-ene
(iii) Oppenauer oxidation: Secondary alcohols can be oxidised to ketones by aluminium tert. butoxide. [(CH 3h COll At
3 >
The secondary alcohol is refluxed with the reagent and then acetone (or cycIo hexanone or p-benzoquinone. etc.) is added.
+3GH3"'-..C=O~ R"'-..C=O+(H3
C
R"'-..CHO) AI "'-..CHO) AI
( IV" 3
CH3/
. '
R/ H3C/
3
Secondary alcohol oxidises to ketone and acetone reduces to isopropyl alcohol.
R, H 3C, R, H3C~
'CHOH + 'C=O [(CH3)3COhAl) 'C=O + ........CHOH
R'/ H3C/ . R'/ H3C/·
Sec. alcohol Acetone (excess) Ketone Isopropyl alcohol
. (2°)
Unsaturated sec. alcohols can also be oxidised to unsaturated ketones (without affecting the )C=C( double bond) by this
reagent.
OH o
I .,
AIunuruum b'd I .
tert. utOXl e ) CH -C-CH2 -CH=CH
CH 3 -CH-CH2 -CH=CH 2 3 2
Pent-4-en-2-o1 cyc1ohexanone . Pent-4-en-2-one
j)
HoD
Cyclohex-2-en-l-ol
Al[OCH(CH3hh)
Acetone
o
..9
Cyclohex-2-en-l-one
2. From Carboxylic Acids
(i) By dry distillation of calcium salts of fatty acids: When calcium formate is dry distilled alone fo~dehyde is obtained.
(HCOOh Ca A) HCHO + CaC0 3
Calcium formate Formaldehyde Calcium carbonate
AldeJgdes.'Jlnd·Ketones
Other aldehydes. can be prepared by the dry distillation of equimolar mixture of calcium salt of a fatty acid .with calcium
formate.
(RcoohCa + (HCoohCa -42RCHO+2CaC03
(CH3COOhCa+ (HCOOhCa -42CH 3CHO+2CaC03
Calcium acetate .Ca).cium formate Ace~ldehyde
The yield is generally poontue to side reactions. Thus, aldehydes are not prepared by this method.
Symmetrical ketones may be obtained when calcium salts of fatty acids (other than formic acid) are heated at 400°C.
(CH3coohCa -4CH3COCH3 +CaC0 3
Calcium acetate Acetone
Note : The calcium ~ts offatty acids are fonned by heating carboxylic acids with calcium oxide.
The yield of simple ketones can be increased by using barium, thorium or manganese salts in place of calcium salts. If a
mixture of calcium salts of carboxylic acid is 'heated, mixed ketone is obtained. The yield of a mixed ketone is generally poor.
(RCOOh Ca + (R'COOh Ca - 4 2RCOR' + 2CaC93
Mixed ketone
0
CH3COOH+HCOOH Al2 3) CH3CHO +H 20+C02
400"C Acetaldehyde
!he yieldis about 60%.
Symmetrical ketones are also obtained when vapours of a carboxylic acid are passed over under similar conditions.
'2CH 3COOH MnO )CH3COCH3 + H20+C02
Acetic acid 300'C Acetone . .
3. By Hydrolysis of Gem-dihalides
Aldehydes are obtained by alkaline hydrolysis of those gem-dihalides in which two halogen atoms are attached to the terminal
carbon atom. Usually a mild alkali is used for this;purpose.
/CI . AlH
CH3CH/ 2KOH ) CH 3CH / -H2~ CH 3CHO
""-CI . ""-oH Acetaldehyde
Ethylidene chloride UJlStable
Ketones are formed by hydrolysis of1hose gem-dihalides in which the two halogen.atoms are attached to a non-terminal
carbon atom.
H3C, /Cl
C
H3C/ "-CI
lsopropylidem:
chloride
'fhis method is not used much since aldehydes aie affected' by alkali and dihalides are usually prepared from the carbonyl
compounds.
·572 G.R.B. Organic Chemistryfor Competitions
4. From Alkenes
(i) By reductive ozonolysis: Alkenes are dissolved in an organic solvent such as chlorofonn, carbon tetrachloride or glacial
acetic acid and a stream ofozonised oxygen is passed. The ozonide fonned is then decomposed by passing hydrogen in presence of
palladium or zinc dust and water. The product or products fonned depend on the structure of alkene.
. H, 0 I
H, 0
I\ I
I
, \
.
Ketones
CH3CH3
I I 03
CH 3 -C= C-CH3 -------+ Ozorude
. H2
) 2CH 3COCH 3 + H 20
2,3-Dim:lthyl but-2-ene Zn/H2 0 Acetone
(ii) Alkenes can be oxidised to aldehydes by an oxidising agent called Lemieux reagent.
o
NaI04 )0 2R-~-H
Lemieux
reagent
(iii) Alkenes can be oxidised to aldehydes and ketones by an oxidising agent Cr02C12 in CH 2C12'
CH 3 CH 3
2-Methyl pent-l-ene 2-Methyl pentanal
CH 3CH 3 CH3 0
I I I I
CH3 -C=C-CH 3 ) CH3 -C--C-CH3'
2.3-Diroothyl but-2-ene I .
CH3
3,3-Diroothyl butan-2-one
Aldehydes and Ketones
CH)CH=CH 2
, Propene,
~. :~;. (\-CH OH
+
OMethylene
CH
2, • [o-rn1:. • 2
Cycluhcxyl methanol
CsHSNHCr03 cr(PCC)
CH2Cl2
• o-CHO
Cyclohexane
cyclohexane carbaldehyde
5. From Alkynes
(i) By hydration: Hydration of acetylene gives acetaldehyde. Water molecule adds up to acetylene in presence of mercuric
sulphate and dilute sulphuric acid at about 6O"C to form an unstable enol~intermediate. It rearranges to give acetaldehyde.
H- H '
. . HgS04 6O"C I I
HC==CH+HOH, ' )H-C=C-OH~ CH)CHO
;" Acetylene Dil. H2SO4 Unstable Acetaldehyde
Formaldehyde cannot be prepared by this method.
Ketones are formed on hydration of homologues of acetylene under similar conditions. Markownikoff's rule is followed in
water addition.
OH 0
HgS04. 60°C I II
CH 3C==CH + H-OH ) CH3-C=CH2 ~CH3-C-CH)
Propyne Dil. H2 SO4 Unstable (enol) Acetone
o
Hg2+ II
CH3-C==C-CH3 + H-OH , CH3-C-CH2-CH3
But-2-yne Dil. H2 S04 Butan-2-one
(ii) By hydroboration-oxidation: Hydroboration occurs with alkynes and the products formed are oxidised with alkaline
H202' Aldehydes are formed if the triple bond is located at the end of the chain (i.e., non-terminal alkynes), and in all other cases
(i.e., terminal alkynes) ketones are formed.
3CH 3-C=CH BH3. TIIF ) (CH 3CH =CH-hB H202/0W )CH 3-CH=CHOH TautomeriseS )CH) CH 2CHO
Propyne (Enol) Propana\
B H
CH) CH 2CH 2C ==CH R2 - ) CH)CH2CH2CH=CHBR2 H202/0Jr) CH3CH2CH2CH=CHOH~
Pent-I-yne (Enol)
CH)CH2CH2CH2CHO '
Pentanal
R2B-H CH 3CH 2 " / CH 2CH 3 H20 ' /CH2CH 3
,CH)CH2 "
CH3CH2C==CCH2CH3 --~) /C=C, -~-~) /C=C,,'
Hex-3-yne H /' ....... BR2 ' H /' "'OH
~CH3CH2CH2-C-CH2CH3
A
Hexan-3-one
G.R.B: Organic Chemistry (or Competili!)u
o 0
CH3~C==C-CH2CH3
(i) BH3
.. "
THF I "
_ )CH3-C-CH2CH2CH3 +CH3-CHi-C-CH2CH3
Pent-2~yne ~ (11) Hl0 2/0H Pentan-2-one Pei:ttim~3-one
(Major) (Minor)
6. From Grignard Reagents . ".,
(i) On reaction with nltriles: Grignard reagents give aldehydes with hydrogen cyanide (HCN) and ketones with alkyl
cyanides (RCN).
_ + Dry 2H20 ~H
HC==N + RMgI . ) HC=NMgI -.::...+~) RCHO +NH3 +Mg ......
Hydrogen Grignard ether I. H Aldehyde 'I
cyanide reagent R
Addition product
R-C=N
'Alkyl cyanide
+
+RMgI~R-C=NMgI.
I·
2H20 R,
) . /C=O+NH3 +Mg......
W R/ 'I
~H
R ~rone
Addition product
The alkyl radical in the aldehyde comes from the Grignardreagent and incase ofketoneoneofthealk:yl radicals is contributed
by Grignard reagent.
(ii) On reaction with esters: Formic ester is used to prepare aldehyde and all other esters give ketone on treatment with
Grignard reagent.
o OMnY o
I + I &,1
2HOHlH+
H-C-OC2Hs +RMgX ~H-C--OC2Hs ) R-C-H + Mg(X)OC2 Hs
Ethyl formate I' -C2 H SOH Aldehyde "
R
o OMgK o
. II
"
CH3 -C--OC2HS - +
+ RMgX ~CH3 -C-OC 2Hs I 2HOHfH+ )CH -C-R + Mg(X)OC2HS
3
Ethyl acetate· I . -C2 H SOH Ketone
R
(iii) On reaction with acid haUde and acid anbydride : Formyl chloride gives an aldehyde and all other halides give
ketone.
o OM~1 0
II I HOHlH+ . II
H-C-Cl +CH3M~1 ~ H-C-Cl ----'===-~)CH3 -C-H + M~12
Fonnyl chloride I Acetaldehyde
CH 3
o OM~1 0
(iv) On reaction with ortho ester: Ethyl ortho formate gives aldehyde.
----I /OC 2 H s /OC 2H s
CH~ MgI:':__ !I~_~~.£2_1!~, /1 ) CH 3CH"",OC H
, "'OC2HS' /' 2 S
·------Ethyloriho-forrtmte -Mg'oC S
2H
Except ortho formic ester, all other ortho esters on reaction with Grignard reagent give ketones.
Aldehydes
~ R' R .. R'
_/C-c( [0]) 'x=O + )C=O
R' I I . . . .R' R/ . . RI/ .
OH OH Kek.nes
13. Aldehydes from alkyl halides
In this method DMSO (dimethyl sulphoxide) reagent is used. 1° alkyl halides give aldehyde, 2° alkyl halides give ketone, but
3° alkyl halides do not participate in this reaction. .
R-CH 2X +(CH3hSO~RCHO+(CH3hS+HX
10 alkyl halide
R 2 -CHX +(CH3hSO~R2CO+(CH3hS+HX
2°alkyl halide
R3-CX +(CH3)2S0~Noproduct
3°alkyl halide
3° alkyl halides cannot undergo oxidation due to absence of reducing iH~ atom.
14. Aldehydes and ketones from cadmium and lithium salts
Dialkyl cadmium can be synthesized using Grignard reagents.
2RMgX +CdCI2 ~ R 2 Cd + MgC12 + MgX2
R2Cd + R'COCI---+ RCOR' + RCdCI
Similarly, aryl carbonyl compounds can also be synthesized. Lithium salt of carboxylic acid can be used to synthesize
carbonyl compound.
OH OH o
- + I HOH ,. R-C-CH 3
I -H20 I
R-COOLi +CH3Li~R-C-CH3 )R-.C-CH3
. I H+ I . Ketone
OLi (-LiOH) OH"
.•
.~
Physical:. (i) The fust member ofthe aldehyde series, formaldehyde, is a gas while next ten members of the aldehyde series
are colourless volatile liquids at ordinary temperature. Ket0lles up to eleven carbon atoms are also coloUrless volatile liquids. The
higher members of both the series are solids. .
(ii) Lower aldehydes have unpleasant odour but the nigher membeJs have ftuity odour. Ketones possess pleasant smell.
(iii) Lower-members of aldehyde and ketone series are soluble in water, as they can form hydrogen bond withwater. However,
the solubility decreases as the molecular mass increases. The' members having more than five carbon atoms are somewhat
insOluble. These compounds are freely soluble in organic solvents such as alcohol, ether, etc.
(iv) The boiling points of aldehydes and ketones are comparatively higher than alkanes of similar molecular masses due to
appreciable intermolecular attraction (dipole-dipole interaction) as the aldehydes and ketones are polar compounds. However,
their boiling points are lower than corresponding alcohols due to absence of intermolecular hydrogen bonding. Boiling points
increase with increase in molecwar mass.
(v) Density of aldehydes and ketones is less than that of water.
Relative reactivity of aldehydes and ketones'
Aldehydes are more reactive than ketones on account of the following facts:
(3) Aliphatic aldehydes and ketones .
(i) InduCtive effect: . The ~vity of the carbonyl group towards the addition reactions depends upon the magnitude of the
positive charge on the carbonyl carbon atom. Hence, any substituent that. increases the positive charge on the carbonyl carbon must
increase itS I"e3Ctivity towards addition reactions. The introduction of negative group (-1 effect) increases the reactivity while
introduction of alkyl group (+1 effect) decreases the reactivity, therefore~ greater the number of alkyl groups attached to the
carbonyl group and hence, lower is its reactivity towards nucleophilic addition reactions. Thus, the following decreasing order of
reactivity .is observed: . . . .
(::hemical: . Both aldehydes and ketones contain a carbonyl group in their structures and their chemical properties are mainly
governed by this group.
0 0
II I
R C H R C R
Alkyl Carbonyl Hydrogen Alkyl Carbonyl Alkyl
group group
.
An aldehyde
atom group
.
group
A ketone
group
The carbonyl group is a highly reactive polar group due to resonance and permanent -/ effect of the negative oxygen atom, as
the 1t-electrons of the double bond are shifted to the more electronegative oxygen atom.
, 0 ,3+3-
/C=o~ /C-O
The high dipole moments of methanal (2.27D) and acetone (2.85D) are in agreement with the polar nature of )C=O group.
Mechanism of nucleophilic addition reactions .
The carbonyl group has two active centres which can be easily attacked.· The positively charged carbon is readily attacked by
electron rich nucleophiles. The negatively charged oxygen is attacked by electron deficient electrophlles. H~wever, duripg .
addition reaction nucleophilic attack precedes the electrophilic attack because the anion produced is more stable than the
cation. .
B~OII t. -0 bI . I
0-
The mixture is added to the compound, if yellow crystals ofiodofonn (Cm 3) are fonned, it will confinn thaiCH3CO-- group
is present in the compound. This test is known as iodofonn test. The test is given by ethyl alcohol and thoseseeondary alcohols
(CH3 -CHOH-R) which on oxidation give methyl ketones.
(iii) Oxidation by selenium dioxide (SeOz) : Selenium dioxide oxidises the reactive methylene group adjacent to carbonyl
'>
group at the a-carbon to fonn dicarbonyl compounds. For example,
H-CH2 -CHO + Se02 ---+ H-C-C-H +Se + H20
Acetaldehyde > I I
> 0 0
Glyoxal
o
I
HCH2-CCH3 +Se02 ---+H-C-C-CH 3 +Se+H20
, Acetone I I
0,0
Methyl glyoxal
0 0 0 0 0
I I I I I
CH3CCH2CH3 + Se02 ---+ H3C-C-C-CH3 + H-C-C-CH2CH3 + Se + H20
Ethyl methyl ketone Butan-2,3-dione' Ethyl glyoxal .
• (Dimethyl glyoxal) (Major)
(\1inor)
A reactive methylene group adjacent to >C=O group at thea-carbon forming a part of the ring also oxidises to a ketonic
group. For example, >
Ni, Pt or Pd
CH 3CHO + H2 ) CH3CH20H
Acetaldehyde Ethyl alcohol
, d R, ........OH
NI,PtorP
) R' /
'C""""
"'-.. H or
RCHOHR'
Secondary alcohol
Ketone
)C=o
G.R.B.
LWH
H2C=CHCHO 4 ) H2C=CHCH 20H
Acrolein H+ Allyl alcohol
. Unsaturated aldehydes can be reduced to unsaturated alcohols (1") without affecting C=C in presence of reducing agents
LiAlH4 in dry ether or NaBH4 in alcohol. Catalytic hydrogenation however, reduces both C=C and )C=O group
simultaneously.
LiAlH4
.-----+CH3CH=CHCH20H
or NaBH.i But-2-en-I-01
(Crotyl alcohol)
ffi.3CH=CHCHO+H 2
But-2-en-l-al
(Crotonaldebyde)
Hz/Ni
L..--::...--+CH)CH2CH2CH20H
Butan-I-ol
LiAlH
C 6 H s CH=CHCHO +H2 _ _ _4,---+) C6HsCH=CHCH20H
Cinnamaldehyde or NaBH4 Cinnamyl alcohol
/ (3-Pbenylprop:..2-en-I~al) (3-Pbenylprop-2-en-l-ol)
H2INi
300"C
Cyclohex-3-en-I-one Cyclohexanol
.NoH
Ethanol V·
Cyclohex-3-en-l-ol
?H
0I3-CHCH20120120H + C2HSOH
Pentaoe-l,4-diol
(Both )C=O and ester groups are reduced)
~
CH3-C-CH2CH2COOC2Hs
Ethyl4-0xopentanoate
OH
I .
CH3-CHCH2CH2COOC2Hs
. Ethyl 4- hydroxypentanoate
(Only)C=O group is reduced)
Reduction to hydrocarbons: The carbonyl ()C=O) group of aldehydes and ketones can be reduced to methylene
()CH2) group to form hydrocarbons by the following methods.
R~uction» ........ ~H
)C=O /'L 2
Using reducing agents such as:
(i) Zn-HglConc. HCI-Clemmensen's reduction
(ii) HIIRed phosphorus at 150°C
(iii) H2N-NH21K0H at 180-2000C-Wolff~Kishner reduction
Clemmensen's reduction: Aldehydes and ketones are converted into alkanes when treated with amalgamated 'zinc and
concentrated HCI. This reaction i~ known as Clemmensen's reduction.
o
I Zn-Hg
CH3-C-H+4H---~»CH3--CH3 + H20
Acetaldehyde- Cone. HCI Ethane
Zn-Hg
CH)COCH3 + 4H ~ CH)CH2CH3 + H 20
Acetone Cone. HCl .. ' Propane
Clemmensen's reduction is not applicable to keto alcohols (containing acid sensitive -oH group), a-hydroxy ketones,
unsaturated cyclic ketones and high molecular weight substrates in which activated Zn and gaseous HCI in organic solvents (ether
or acetic anhydride) can be used. .
. Clemmensen 's r~duction may also be carried out with Zn-Hg and DCI in D 20 in place of HCI in H 20.
The same conversio~( )C=O ----»)CH 2)·can be. made by heating aldeh)J~s and ketones with red phosphorus and conc.
hydroiodic acid or basic solution ofhydJ;azine..
CH)CHO+ 4HI
Acetaldehyde
R-C=0+NH2NH2 --K!-cOH
--t-)R-CH 2 +N2 +H20 "
. I 200"C I
H ., H
This reaction can be carried with sodium ethoxide or NaOH at bight temperature. Besides hydrazones,phenylhydrazones and
semicarbazones respond to this reaction. .
/C= NNH2 "2 s
" H NNH......... " C H ONa,200°C
/C=O 2 2) ) )CH2 +N2
(-H20) , Hydrazone Glycol M tb I
" . " "e yenegroup
Ketones can also be reduced to secondary alcohors with aluminium isopropoxide in propan-2-01 solution and this is
Meerweili-Ponndorf-Verley (MPV) reduction. The mechanis~ of this reaction is the reverse of oppenauer oxidation.
R R
'-....C=O + 2H [(CH312 CHOh Al ) ~CH-OH
R/" in( CH312CHOH R/
-.c.
Ketone
+2[H] MPVredoctiOO,Hc:r
Cyclobex-2-en-l-one Cyclobex-2-en-l-ol
Bimolecular reduction or Pinacol formation: Two molecules of ketones undergo reduction in the presence ofMglHg to
form pinacol. Upon treatment with mineral acids, pinacol is converted into pinacolone. This transformation involves dehydration
and rearrangement called pinacol-pinacolone rearrangement.
CH) CH 3 CH 3 CH3
1 1
MWHg )CH3~C--CH3 HOH)CH3-1-1-CH) + Mg(OHh
Benzene as 1 I
solvent 0 0 1 I
OH OH
""-../
Mg
2,3-Dimetbyl butane-2,3-diol
(Pinacol)
CH3 CH 3 CH3
I 1 H+/A I
CH3~-CH3--~=-~)CH3--C---C--CH)
1 I -H20 " I II
OH OH CH) 0
Pinacol
- .
~
3,3-Dimetbyl butan -2-one
(Pinacolone)
Mechanism: This reaction involves: ·l-Protonation, 2-deprolonation, 3-alkyl shift and 4-dehydration.
CH 3 CH3 CH) CH 3 CH 3 CH)
1 " 1 H+ 1 I -H2 0 . 1 I"
CH3-C~-CH3 -~) CH3 -C---C-·CH 3 ) CH 3~--CH3
" 1·1
OH OH
Pinacol
1
+OH2
1
OH 1
+ 1
OH
Alkyl Shift
CH3 CH)
. 1 . H+ 1 +
CH3 -C-C-CH3 --=-=--- CH3 --C---C-CH3
+-<
." 1 "" I 1
CH 3 0 CH 3(OH
Pinacolone
Migratory attitude of alkyl group lies in following sequence:
C6HS-" > (CH3hC- > (CH 3hCH- > -C2Hs > -"CH3
(~) Addition of hydrogen cyanide: AMehydes and ketones react with hydrogen cyanide (KCNor NaCN + dil. H2S04) to
form cYanohydrins. This reaction occurs very slowly with pureHCN. Therefore, it is catalysed at a pH 9-10 in presence of a base
(Nucleophilic addition reaction).
Aldehydes and Ketones
Cyanohydrins'
OH
CH 3-, y=::O + HCN pH 9-10 )' CHr-:-y<CN
, H H
Acetaldehyde Acetaldehyde cyanohydrin
HCN is too weak an acid, to add directly to a >C=O group. It requires slightly alkaline reaction conditions such as those
found in NaCN-HCN buffer solution. In this way, the concentration ofCN - ion is increased and the CN - ion thus generated being
a stronger nucleophile readily adds to carbonyl carbon to yield corresponding cyanohydrin..
'/to .'
HO- + H-CN ---+- -:CN + H 0 2
Addition ofCN- is in a slow step (rate determining step) and hence, nucleophilic addition.
Mechanism
Addition of hydrogen cyanide to >C=O group involves the following steps: '
Step 1. The hydrogen cyanide interacts with the base to form nucleophile, i.e., cyanide ion,
.n 0.
HO+ H~ ---+- H20 + CN-
'
Nucleophile
Step 2. The nucleophile attacks the carbonyl carbon to form an anion,
"o~_
/ C ~ +CN
"r _'
) /C-O
Step 3. The proton from the solvent (usually water) combines with the anion to form cyanohydrin (the addition product).
CN CN
In,
>C-O- +H+ ftomH20orHCN »C-OH
i"
Cyanohydrin
Note: All aldehydes fonn cyanohydrins but in ketones, only acetone, butanone, pentan-3-one and pinacolone fonn cyanohydrins.
The cyanohydrins are good synthetic reagents as they can be converted into a.-hydroxy acids and a.-amino acids (Strecker'S
synthesis).
G.R.B. Organic Chemistry jor Competitions
Heat) H 2C=CHCOOH
H2S04 Acrylic acid
a-Hydroxy propionic acid
(Lactic acid)
H 0 /NH2
2 ) CH3CH(
"CooH
Alanine (a-amino propionic acid)
CH 3
H3 C "", /OH H+/H2 0 H 3C"", /OH I
C, ---=~) /C, ) H 2C=C-COOH
H3C/ "CN H3C"""'" COOH Methyl acrylic acid
Acetone cyanohydrin a -Hydroxy -a -methyl
propionic acid
(iii) Addition of sodium bisulphite (NaHS0 3 ): Crystalline solid derivatives are formed when aldehydes and aliphatic
methyl ketones are shaken with saturated aqueous solution of sodium bisulphite.
/OH
Proton> ' C ........
'transfer / ' ""'SOiNa+
Bisulpbite
addition product
. . . S03 Na
CH 3 -C=0+NaHS0 3 ~CHs-C<-'
I Sodium I 'OH
H bisulpbite • H
Acetaldehyde Acetaldehyde bisulpbite
H3C"", . H3C"", /S03 Na
/C=0+NaHS03 ~ ./C,
H3C/ H 3C"""" 'OH
Acetone . Acetone bisulpbite
Note: All ketones do not undergo this reaction. Only methyl ketones form additiQn products with SOdium bisulpbite.
These bisulphite compounds on heating with NaCN yield cyanohydrins.
.. ~.
0+ 0 - ' 0- 0+ ....... /R
. >C VO + R -MgX ---+) /C"'" _ + .
. OMgX
Adduct
FQr c\ample, formaldehyde forms a primary alcohol. .
H . \lI
\ .\ + /OH
H-C=O + RMgI Ether) H-<>:cOMgI HOH, H ) . RCH20H + Mg/ ..
Fonnaldehyde . ,1 '. Primary alcohol ""-I
R·
. I
. 00)
Higher aldehydes give secondary alcohols.
H H "tr
I I + ./OH
R-C=O+ R'MgI Ether)R-C-OMgI HOH,H) RCHOHR' +Mg/
Aldehyde \ Secondary alcohol ""- 1
R' (20)
RCH=O+H 2 NOH
.. H+ >RCH=NOH+H 20 .
Aldehyde Aldoxime
R R
)C=O+H2NOH H+ ) )C=NOH+H 20
R'/ pH=3.5 R'/
Ketone Ketoxime
C)=0+H2NOH.--+ C)=NOH
Cyclohexanone Cyclohexanoneoxime
These oximes can be hydrolysed back to aldehydes and ketones by reaction with acids .
. The reaction ofH 2NOH with a symmetrical ketone, R 2C=O gives one oxime, but the two isomeric oximes may form from the
reaction of an aldehyde or non-symmetrical ketone because the rotation about the pi-bond in >
C= N is not free and therefore,
geometrical isomerism is possible when the two groups on the carbonyl carbon are different. For example,
R OH R
""'-C=N/ and ""'-C= N
H/ •• H/ ~OH
(Z)cis(syD-) (E) trans(anti-)
R ' .. OH
""'-C=N/ and
R
- ..
""'/C=N,
R/ .. R/ 'OH
Oximes are solids having specific melting points, so these are usedfor the separation and identification ofaldehydes and ketones.
Beckmann rearrangement: Ketoximes on treatment with acid catalyst such as conc. H 2S04 , PCls. H 3P0 4 , SOCl 2 or
C6HsS02C~ etc., undergo Beckmann rearrangement to form a substituted amide. For example,
o
H 3C",,- SOCl2 II
/C=NOH--~)CH3-C-NH--CH3
H3C Ether. N -Methyl acetamide
. Acetoxime
Benzophenone oxime
This rearrangement is intramolecular and involves 1,2-shift. It has been demonstrated that it is always the anti -R group that
migrates in the Beckmann rearrangement.
o
II
CH 3CH 2CH= NOH ~ H-C-NHCH2CH3
Propionaldoxime N -Ethyl furmamide
O=N-OH
(YO
Cyclohexanoneoxime . Caprolactum
Aldehydes and [(e,tones
(ii)Reaction with hydrazine (NH 2 NH:2) : Aldehydes and ketones form hydrazones with hydrazine (at pH = 3;5), A water
molecule is eliminated.
H+
(CH 3hC=0+ H2N-NHC 6H S ) (CH3hC=NNHC6Hs + H 20
Acetone Acetone phenylhydrazone
Substituted phenylhydrazines like 2,4-t:iinitrophenylhydrazine (DNP, Brady's reagent) react similarly with carbonyl
compounds to form the corresponding hydrazones. These hydrazones have specific melting points and hence used for the
identification of aldehydes and ketones.
(iv) Reaction with semicarbazide (H:2NNHCONH:2): Aldehydes and ketones combine with semicarbazide to form
crystalline compounds called semicarbazones.
Acetone .
Control of pH during addition of ammonhi'derivatives to aldehydes and ketones.
The reaction of ainmonia derivatives to aldehydes and ketones iscatalysed by acids. In acidic medium, the carbonyl oxygen
gets protonated. Due to the presence of positive charge on the carbonyl carbon, the weak m,icleophiles like ammonia derivatives
attack the carbonyl group very easily.
G.R.B. Organic Chemistry tor Competitions
Mechanism: The addition-elimination reactions with ammonia derivatives (NH 2 -Z) are Carried out in weakly acid.ie
medium (PH = 3-4).
Step 1. In acidic medium, the carbonyl oxygen gets protonated.
"/C=O:
•• + H+ ~. [ "
......C=OH+ +-----+ '-. •• ]
...... C-OH
(From acid} /' •• /'.•
Protonated carbonyl group
Step 2. In ammonia derivative, the nitrogen atom has a lone pair of electrons (Nucleophile) attack the positively charged
carbonyl carbon and results the positive charge on nitrogen atom. .
Step 3. The unstable intermediate loses a proton, H+ and water molecule to form a stable product (imioes).
[ >C<~.~H] ~,Z
V'H
-w) >C<~H N-Z
I·
0
-H2 ) )c=N-·Z
Product
H
+ Now, if the medium is highly aeidie then the ammonia derivatives being basic in nature, may form their respective salts
(NH 3ZX - ) which cannot act as nucleophiles and consequently, the reaction does not occur. However, if the medium is basic, the
protonation of carbonyl group will not occur and hence, the reaction is not favoured. Thus, to carty out such reactions we have to
properly control the pH of the medium. The optimum pH of the medium is around 3.5.
(v) Reaction with thioalcoho~s: Aldehydes and ketones combine with tbioalcohols more rapidly than alcohols and form
thioacetalsand thioketals, respectively. .
:-----li:SC H
2 s
CH 3CH='O 1____+ :
1
Acetaldehyde L_~ SC2Hs
Ethyl thioalcohol
,..-----,
: H:SC2 H S
(CH3hC==: 0 + :
Acetone L ____l!:SC 2H S
Etbanethiol
These sulphur derivatives of carbonyl compounds are used as sedative sulpha drug.
Alkaoe ditbiol reacts with both aldehydes and ketones in presence of BF3 -ether to give corresponding cyclic thioacetals
(ditbianes) and cyclic tbioketals. .
R,,- .
C=O+
HSCH2BR..._ether
I OJ ) /
R,'c,
/SCH 2
I
R/ HSCH2 (-H20) R 'SCH 2
Etbane-l,2-dithiol Cyclic thioketal
(vi) Reaction with phosphorus pentachloride (pels) or thionyl chloride (SOC. z) : Oxygen atom of the carbonyl group
is replaced by two chlorine atoms to form gem-dihalides. For example,
., CI
CH3CH=O + PCIs ----t CH3CH( + POCt 3
Acetaldehyde CI
Ethylidene chloride
Aldehydes and Ketones ••••
Isopropylidene chloride
Ketone Ketimine
Schiff's base is pink in colour and it can be decolourised by passing S02 gas. The colourless solution obtained is known as
S£hiff's reagent. .
(viii) Reaction with secondary amines (R2NH): Aldehydes and ketones that have at least one a-hydrogen reacts with
secondary amines to fonn enamines (a, p..unsaturated tertiary amine).
. /R PTSorH+ /R
H3C-C =0 + HN'R
........ (p-Toluene sulphonic acid)
) H2 C=C-N ' R
........
1 1
CH3 20 Amine (-H20) CH3
Acetone Enamine
In enamines, the double bond is present between carbonyl carbon and a-carbon of carbonyl cQtnpound part.
3. Condensation Reactions
Aldol condensation (Reactions involving a-hydrogen) : It is a chemical reaction in which twoor more molecules of same
or different carbonyl compounds containing a-hydrogen atom unite together in the presence of dilute bases such as NaOH,
Ba(OHh or K2C03, etc., to fonn compounds calledaldols. The tenn aldol is derived from the combination of words aldehyde and
alcohol, the two functional groups present in the product. In such condensation, the hydrogen of one molecule in a-position with
respect to the carbonyl group enters into combination with the oxygen of the .carbonyl group of the other molecule forming a
hydroxy group. So, aldol condensation is an important reaction based on the acidity of a-hydrogens of aldehydes and ketones.
Characteristics of Aldol Condensation
(i) This reaction may take place between (a) same or different aldehydes, (b) an aldehyde and a ketone, and (c) same or
different ketones. The carbonyl compound must contain an a-hydrogen atom which is involved in aldol condensation in presence
of dilute alkali (dU. NaOH, Na2C03 or Ba(OHh, etc.). However, formaldehyde though contains no a-hydrogen atom yet
undergoes abnonnal aldol condensation in presence oflime water.
(ii}New carbon to carbon linkage is fonned (an irreversible process).
(iii) The condensation product, i.e., aldol, loses a molecule of water to fonn unsaturated aldehyde or ketone.
Examples: (i) Acetaldehyde undergoes aldol condensation in presence of dilute caustic alkali or potassium carbonate to
fonn p..hydroxy butyraldehyde or aldol. .
H H
I 0-. . Dil.NaOH I
CH3 -C....:..-O + H-CH2CHO ) CH3-C-CH2CHO
Acetaldehyde Acetaldehyde orK2C03 I .
(Two molecules of etbanal) OH
3-Hydroxy butanal
[Aldol (Acetaldol)]
G.R.B. Organic ChemistryJor Competitions
On heating with dilute acids, aldol loses a molecule of water to give a, J3-unsaturated aldehyde (Crotonaldehyde).
H H
I I Heat,H+ ) CH 3CH=CHCHO
CH3 -C--C-CHO
r~----L-I (-H20) But-2-en-l-al
(Crotonaldehyde)
IOH HI
I _______ .l
H CH3 H CH 3
I f\ I OW pi al
CH3CH2-C=O +H-HC-CHO --..;;;-=---+) CH3CH2 -C-CHCHO
Propanal
(Electrophile)
a
(Nucleophile)
. I
OH
3-Hydroxy -2-methyl pentanal
(p-Hydroxy -a -methyl valeraldehyde)
The aldol condensation of two molecules of same aldehydes or ketones is called self eondensation. It can also takes place
between two different aldehydes or ketones or between one aldehyde· and one ketone is c.alled erossed (mixed) aldol
eondensation.
H H
0-. I OH-
CH3CH2-C=O + H-CH2CHO -~)CH3CH2 -C-CH2CHO
I
Propanal Etbanal I·
(Electrophile) (Nucleophile) OH
3-Hydroxy pentanal
In presence of base, the a-hydrogen atom in lower aldehyde is more acidic and so migrates, while in presence of an acid, the
a-hydrogen atom in higher aldehyde is more basic. .
H CH 3 H CH3
I 0-. I H+ ~ al
CH 3-C=O +H-CH-CHO ) Clh-C-·CH-CHO
Ethanal a I .
(ElecoopJiile) Propanal OH
(Nucleophile)
3-Hydroxy -2-methyl butanal
(p-Hydroxy -a -methyl butyraldehyde)
These J3-hydroxy aldehydes or ketones are collectively called aldols and the reaction is known as aldol eondensation.
Generally with two different aldehydes, all possible condensation products are obtained; but by using different catalysts, one
product may be made to predominate in the mixture.
A common method used to obtained a single aldol product is to use LDA. to remove the a-hydrogen when creating the enolate.
Because LDA is a strong base, all. the carbonyl compounds will be converted into an enolate, so there will be no carbonyl
compound left with which to react. Addition will occur when the second carbonyl compound is added slowly to the reaction
mixture. This aldol reaction is known as directed aldol addition.
' .
CH ~O
3.
LDA) CH -CHO
(B)
ase
2
100% yield
\
(i) CH3CH2CHO ) CH CH
("") HOH
1l
.
3 2
4 HCH 2CHO
. OH
(ii) Acetone undergoes aldol condensation in the p~esence of Ba(OHh to form diacetone alcohol.
OH
0-. I
(CH 3hC=O+ HCH 2COCH 3 Ba(OHh) (CH3hC-CH2COCH3
Acetone Acetone 4-Hydroxy -4-methyl pentan-2-one
(Two molecules) (Diacetone alcohol) (Aldol)
Diacetone alcohol loses a water molecule on heating in presence of little iodine and forms mesityl oxide.
fOH--iI:
-1----1-
( CH 3 )2 C-.-CHCOCH3 12,Heat) (CH ) C=CHCOCH
. (-H20) 3 2 3
4-~ethylpent-3-en-2-one
(~esityl oxide)
A~l:::d=eh~}1,-=d=es~a~nd=.::K.,-=e~to"""nae",,-s _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _""":""-"59S
....'=Jt '· · ·
(iii) Formaldehyde undergoes abnormal repeated aldol type condensatil}n in presence of Ba(OHh or Ca(OHh to fonn
formose sugar. '
H H H H H H H H H H HH H
I I I I I I I I I I I I I
With rrKke
H-C=O + H-C=O ----1> H-C-C=O HCHO. H_C-C_C=O---:H,--C,-H_O~) H-C-C-C-C-C-C=O
Fonnaldehyde Formaldehyde I Ba(OHh I I Ba(OHh·1 I I I I
OH OH OH OH OH OH OH OH
Glycollic aldehyde Formose (a mixture of sugars)
(iv) Acetaldehyde reacts with benzaldehyde (which has no a-hydrogen) in the presence of a base to fonn an aldol which on
heating yields cinnamaldehyde.
H
I 0""
C6 H sC. +HCH 2CHO OH- ) Heat, H+ ) C H CH=CHCHO
( H 0)' 6 5
Benzaldehyde Acetaldehyde - 2 . 3-Phenylprop-2-en-l-01
(Cinnamaldehyde)
(v) When aldehyde condensed with ketone, it is the a-hydrogen atom of the ketone which is involved in the condensation
(crossed aldol condensation), e.g.,
H 0 H 0
I ~ I OH- I /I
CH 3 -C=O + HH2C-C-CH3 -~) CH3 -C-CH2 -C-CH3
Acetaldehyde Acetone I
OH
4 - Hydroxy pentan -2 -one
(Low yield, 25%)
Mechanism of aldol condensation (Acidity of a-hydrogen) : Aldol condensation involves th~ following steps through the
formation of carbanion or the enolate ion which is stabilized by resonance in Step 1:
Step 1. The base (OH-) ion removes one of the a-hydrogen atom (which is somewhat acidic) from aldehydes and ketones to
form a carbanion or the enolate ion.
~
H-C-C=O + OH
_ Slow
~,=='''''~>
Y Yn.
H20+ H-C::-C=O ~H2C=C"
/~:.
, I
H
·U· H
Acetaldehyde Enolateion
o 0 ~
/I e II I
CH3 -C-R + Base ----1> CH2 -C-R ~ H2C=C-R
Ketone Carbon nucleophile Enolate ion
The acidity of a-hydrogen is due to resonance stabilization of enolate anion.
Step 2. The enolate ion (nucleophile) attacks the carbonyl carbon of another aldehyde molecule to form the anion.
•• 3-
cy~ ./0 Fast :,:- Y
CH 3 -C-H + :CH r (........ :;;=,,==~> CH 3 -CHCH2 C-H
3+ ,'H Anion
Acetaldehyde Enolate ion
(Electrophile) (Nucleophile)
Step 3. A proton from water is accepted by anion to form aldol and the OH- ion is regenerated.
aR.B. Organic Chemistry for Competitions
[ Ag20+4NH40H.--..+2[A,g(NH3h]OH +3H 20
, ToUens' reagent ,
RCHO +2Cu0-4RCOOH + Cu 2 0
Aldehyde Qlue Cuprous oxide (Red ppt.)
[RCHO+2Cu 2+ +30H- ~RCOO- + 2Cu+ +2H20]
, Redppt.
Reduction of Benedict's solution : It is solution of copper sulphate, sodium citrate and sodium carbonate. When heated
with an aldehyde, a reddish brown precipitate appears: So, all the organic compounds which give positive test with Fehling's
solution, also give same testwith Ben.edict's solution [CuO or.Cu(0H)2]'
Solution,I ~Alkaline solution of potassium or sodium citrate.
Solution' U ~CuS04 I)
CUS0 4 +2NaOH--1> Cu(OH)2 + Na2S04
CH2~ONa CH 2COONa
I I .
Cu(OH)2 + HO-C-COONa --1> HO-Cu-O-·C-COONa
. I I
CH2 -COONa CH 2COONa
Blue coloured complex
Note: Benzaldehyde does not respond to Fehling's or Benedlcttests due' to alkaline nature of these reagents. Ketones.aIso do not reduce Tollens'
. reagent, Fehllng'ssolution and Benedict's solution. Hence, these reagents can be used to distinguish between aldehydes and ketones.
Oxidation of ketones: Unlike aldehydes, ketones do not have any hydrogen atom attached to >C=O group. and hence,
they cannot be oxidised by weak oxidising agents such as Tollens' reagent or Fehling's solution.
Ketones are, however, oxidised by strong oxidising agents like acidified dichromate, acidified or alkaline KMn04, .hot
concentrated HN0 3, etc., to a mixture of carboxylic acids with lesser number of carbon atoms. .
CH 3COCH3 K2Cr207/H2S04) CH COOH +C0 + H 0
3 2 2
Acetone +4[0] Acetic acid
[RCOOR' . H+ )RCOOH+R'OH]
R2CO + R' COOOH --1> RCOOR' + R.cOOH
Ketone Per acid Ester Acid
(0) Schiff's test of aldehydes: Schiffs reagent is a dilute solution ofpara-rosaniline hydrochloride whose red colour has
been discharged by passing sulphur dioxide gas. Aldehydes when treated with Schiff s reagent (magenta solution in sulphuro~s
acid, H2S03) restore its pink colour.
Ketones do not give this test. . \
G.R.B. Organic Chemistry (Or Competitions
(iii) Reaction with ammonia: Except formaldehyde, other aldehydes form addition products with an etheral solution of
ammonia. These addition compounds on heating with dilute acids regenerate the aldehyde.
H H
I
R-C=O + HNH2
. Ether I
. ) R-C-NH2
Aldehyde I
OH
Aldehyde aminonia
H H
I I
CH 3 -C=O + HNH2 ---7 CH 3 -C-NH2
Acetaldehyde I
OH
Acetaldehyde ammonia (Adduct)
This addition product on warming with water, decomposes to give imines.
3C":'3 COCH 3 + NH 3
Acetone
'~. (3 molecules).
Triacetone amine
(iv) Reaction with alkaU: Aldehydes having a-hydrogen atom on heating with concentrated alkali (except formaldehyde)
give a brown resinous, mass of characteristic odour. The aldehyde-resin is formed (resinification) probably through a series of
condensation reactions.
CCHO
2CH 3CHO Conc.NaOH) CH 3CH-CH 2CHO Heat) CH3CH=CHCHO HH2 ) CH3CH=CH-CH-CH2CHO
. I (-H20) Crotonaldehyde I
OH. OH
CCHO
Heat) CH3CH=CH-CH=CHCHO (i) HH2 ) CH3CH-CH-CH=CH-CH=CHCHO
(-H20) ... (ii) Heat, -H20
Repeated .
-----=---~) Brownresmous mass
Ketones do not give this,reaction.
Formaldehyde, benzaldehyde and other aldehydes containing no a-hydrogen atoms on heating with concentrated alkali
solution (50%}undergo Cannizzaro's reaction. In this reaction, one molecule is oxidised to carboxylic acid at th~expense of
. other vyhich is reduced to 1° alcohol, e.g.,formaldehyde undergoes disproportionation (oxidation-reduction), i.e.,
i -
.; 2HCHO :+ NaOli ---+ HCOONa + CH 30H'
Fonnaldehyde (50%) Sodium fonnate Methyl alcohol
Some other examples of Cannizzaro's reactions are:
Aldehydes and Ketones
~10
H
1If'
(F"') +
H
(F"') l-If'
I
H-C-OH H-C=O
I I
0-
H
(Alcohol) (Salt of an acid)
Cannizzaro's reaction involves same or different aldehydes having no a.-hydrogen atoms and is proton (H+ )-hydride (H-)
transfer reaction. .
C6HSCHO + NaOH+ HCRO ~C6HsCH20H+ HCOONa
Benzaldehyde Formaldehyde Benzyl alcohol Sodium formate
This reaction is called crossed Cannizzaro'S r e a c t i o n . ,
In compounds containing two carbonyl groups, the intramolecular or internal Cannizzaro's reaction takes place, where
one-half part of the molecule is reduced and the other half part (of the same molecule) is oxidised.
CHO CH20H CH 20H
I +NaOH(conc.)~ I DiI.HCI) I
CHO COONa COOH
Glyoxal Glycollic acid
CH3 -C-C-H + NaOH ~ CH 3 -CH-COONa
\I \I I
.0 0 OR
Methyl glyoxal Sodium lactate
C6 H S
I
C6Hs -C-C-C6HS + NaOH(conc.) ~ C6HS -C-COONa
1\
o O·
I I
·OH
Diphenyl glyoxal Sodium benziUate
"'i",i· · ,J~; ,; ,!i........._.__"--________~---------------G-.R-.-B-._O....rg...a_n_ic_C_he_m_'_·s_try"-'ll..fo_r_C_o_m.....!P-.e_t'_·ti_·o_ns
Exception:. Certain aliphatic monoalkylated aldehydes (havinga-hydrogen atoms) may undergo Cannizzaro's reaction
(quantitative disprop0rtionation) when heated with aqueous NaOH. For example,
CH 3 CH 3 CH3
I .
CH3 -CH-. CHO+NaOH
170-200"C I
)CH3 -CH-CH 20H+CH 3 -CH-COONa
I
2-Methyl propanal 2-Methylpropan-I-ol Sod. 2-methyl propanoate
'- This exceptional behaviour is probably due to +1 effect of the two alkyl groups.
,(v) Tischenko's reaction: This is a modified form of Cannizzaro's reaction. All aldehydes with or without a-hydrogen
'atoms undergo Cannizzaro's reaction in presence of aluminium ethoxide. The acid (by oxidation) and the alcohol (by reduction)
formed react together to give the ester.
Al
" .
2CH 3CHO (C2Hs Oh ) [CH3COOH +C2HsOH]~CH3COOC2Hs
Acetaldehyde Ethyl acetate
(C2 HSOh Al
2CH3CH2CHO ) [CH3CH2COOH +C3H70H]~C2HsCOOC3H7
Propionaldehyde . Propyl propionate
H Al
H 2C=CHCHO (C2 SOh ) H 2C=CHCOOCH 2CH=CH 2
Acrolein Allyl acrylate
(vi) Reaction with alcohols: Aldehydes combine with alcohols in presence of dry hydrogen chloride gas forming first
hemi-acetals (unstable) and then the acetals (dialkoxy alkanes). The acid catalyst in most of the cases is p-toluene sulphonic acid
(Ts-:-OH).
H H H
I Dry HCI I HO~H5 I
R-C=0+H-OC 2Hs < > R-C-OC2HS < > R-C-OC 2HS
Aldehyde Ethyl alcohol I DryHCI I
OH OC2HS
(Hemi-acetal) Acetal
The reaction is reversible and therefore, the acetal formed can be decomposed by dilute mineral acids to give back to original
. aldehyde.
C
H3 " " /OC 2H s H+ H3C"".
C + HOH ') H /C=O +2C 2H s OH
. H / ""'OC 2H s
Acetal Acetaldehyde
A large excess of alcohol is used to shift the equilibrium in favour of acetal formation. Ketones do not readily react with
monohydric alcohols.
R......... . Dry HCI R......... /OH R'OH
/ R/C=O + R'-OH <' 'R/C""'OR 1 < ~lhO '
(Hemi-ketal) Ketal
Ketals may however, be prepared by treating the ketone with ethyl ortho fonnate.
R""
R
/C=O + HC(OC2HSh ----10
. Ethyl ortho formate R/
/C"'"
OC2HS
R"" /OC 2 Hs .
+ HCOOC 2H s
.
However, On treatment with ethylene glycol, cyclic acetal and cyclic ketal (1,3-dioxolans) are formed.
R......... HO-CH . " R O-CH
.........C=O + . I 2 p-Toluene sulphoruc aCId (PTS» ""C/ I2
H/ HQ-CH2 Reflux H / ""'O-CH2
Aldehyde Ethylene glycol Cyclic acetal
A'idehwles and Ketones
~ N~~ ~
(Reduction Without protection of
• carbonyl group)
~CHO' ~CH20H
~ >ROH ~ /OR
~CHO • VCH'OR ~. N~~
.
(Protected aldehydic group) ..'
2ROH + .,J:,
~CHO
. HOHnICI
.
,J:,
~CH'OR
/OR
(Thus, this method can be used for preferential reduction of ketonic group.)
(vii) Polymerisation: The lower aldehydes show a marked tendency to polymerise forming compounds in which several ,.,.
molecules are linked together through oxygen. [For details see formaldehyde and acetaldehyde]. Ketones do not form polymers.
(viii) Condensation with chloroform: Ketones condense with chloroformlbromoform in presence of caustic potash to
form chlorohydroxy compounds (chlo~tonelbrometone) respectively.
CH 3"", . . CH 3"", /OH
........C=O + CHCl3 KOH) ........C,
CH3/' CH3/' 'C0 3
Acetone 1,1,1-Trichloro-2-methyl propan -2-01 .'-<
(Chloretone)
Aldehydes do not respond to this reaction.
(ix) Formation of sodio-derivatives: Ketones yield sodio-derivatives when treated with sodium or sodarnide in ether
solution.
Ether .
CH3COCH3 + NaNH2 - ) CH3COCH2Na + NH3 .
Acetone Sodamide Sodio-derivative
These sodio-derivatives can be treated with alkyl halides to produce higher methyl alkyl ketones.
Aldehydes do not respond to this reaction.
(x) Reaction with nitrous acid: Ketones when treated with nitrous acid form isonitroso derivatives.
CH3COCHH2 +O=N-OH CH3 COCH = NOH +H20
Acetone lsonitrosoacetone (Oximino acetone)
This reaction is used for detecting the presence of -COCH2 - group and not observed in aldehydes.
(xi) Reduction in neutral or alkaline medium: When ketones are reduced with Mg-Hg and water, pinacols are the main
product which on heating with dit. H2S04 give pinacolone. This reaction is,called as Pinaeel-Pinacolone rearrange.ent.
G_.R_.B_._O_r..='g:..,.Q_nl_'c_c_'h_e_m_is_try~fo_r_C_o_m...4;p_e__ti_ti_on_s
;·«;'6:::;;..·00.:.;.;.;,.;;.···.·.•..:...'_--.;.._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
(xii) Reformatsky reaction: This reaction involves the treatment of aldehydes or ketones with a-bromo acid ester in
presence of metallic zinc to form j3-hydroxy ester, which can be easily dehydrated into a, j3-unsaturated ester.
(a) BrCH2COOC2Hs + Zn (Benzene) Br-Zn-CH 2COOC2H s
a-Bromoetbyl acetate Organo zinc compound
(b) Addition to carbonyl group,
H
I _____ ,
~ /OOH
CH 3 -C==0+H2 IC , _ A ) CH 3CH=CHCooH
Acetaldehyde - -- - _I 'CooH - C02 Crotonic acid
Malonic acid
A ) C6 H SCH=CHCooH
-CO2 Cinnamic acid
(xvii) Schmidt reaction:. This is a reaction between a carbonyl compound and hydrazoic acid in presence of conc. H2S04.
'K.(ltones
l. With Schiff's reagent Give pink colour. No colour.
2. With Fehling's solution Give red precipitate. No precipitate is fonned.
3. With Tollen's reagent Black precipitate ofsilver or silver mirror is fonned. No black precipitate or silver mirror is formed.
4. With saturated sodium bisulphite Crystalline compound (colourless) is fonned. Crystalline compound (colourless) is fonned
solution in water
5. With 2,4-dinitrophenylhydrazine Orange-yellow or red well defined crystals with Orange-yellow or red well defmed crystals with
melting points characteristic of individual melting points characteristic of individual ketones.
aldehydes.
6. With sodium hydroxide Give brown resinous mass (FonnaJdehyde does not No reaction.
give this test).
7. With sodium nitroprusside and few A deep red colour (Fonnaldehyde does not respond Red colour which changes to orange.
. drops of sodium hydr!>xide to this test).
co + H2 Elec.;~scbar~ HCHO
~
- ': I rFonnaldebyde
Water gas
. ..
Formaldehyde is manufactured by oxidation of methyl alcohol and also by dehydrogenation of methyl alcohol in presence of
copper or silver catalyst at 300-4000C. .
Laboratory preparation: Formaldehyde is prepared in laboratory by catalytic oxidation of methyl alcohol.
Excess of methyl alcohol is removed by fractional distillation. The.tesultingmixture is called formalin which contains 40%
formaldehyde, 8% methyl alcohol and 52% water.
Physical properties: (i) It is a colourless, pungent smelling gas and is extremely soluble in water. Its solubility in water may
be due to hydrogen bonding between water molecules and its hydrate.
(ii) It can easily be condensed into liquid. Theliquid formaldehyde boils at -21°C.
(iii) It causes irritation to skin, eyes, nose and throat. .
(iv) Its solution acts as antiseptic and disinfectant.
Chemical properties: Formaldehyde is structurally different from other aldehydes as it contains no alkyl group in the
molecule. Though, it shows general properties of aldehydes, it differs in certain respects. The abnormal properties offormaldehyde
.are given below:
(i) Reaction with ammonia: Like other aldehydes, formaldehyde does not form addition product with ammonia but a
crystalline compound, hexamethylene tetramine (Urotropine). .
6HCHO +4NH3
Fonnaldehyde Hexamethylene tetramine
(Urotropine)
The reaction may be given as,
CH 20H
I
H, ..... .
/C=O+NH 3 .
H... . HOH2C-N
CH2
I
/N""
. CH2
I
N-CH20H
Fonna\debyde
. ""CH/
CH2.
~I~
CH2 . CH2
'NH I
_--=-3-+) .........N '-..
/CH2 CH2
N/ 'N
~/
. CH 2
Hexamethylene tetramine (Urotropine)
Fig. 11.1 . Urotropine
Hexamethylene tetraminehas a cyclic structure. It is used as medicine in case of urinary troubles under the name of
Urotropine or hexamine. Nitration of urotropine under controlled conditions gives an explosive RDX (Research and
Development Explosive).
(ii) Reaction with sodium hydroxide (Cannizzaro'sreaction)~
(iii) Aldol condensation: Formation offormose (hexose).
(iv) Condensation with phenol: Formaldehyde condenses with phenol to give a synthetic plastic, bakelite. The
condensation occurs in presence of dilute sodium hydroxide or ammonia at 80-90°C. Bakelite is used for preparing electrical.
insulators, electric switches and toys, etc.
Aldehydes and Ketones
When phenol is treated with 40% formaldehyde in presence of dilute acid or alkali,amixture of ortho and para-hydroxy
benzyl alcohol is formed, This reaction is called Lederer Manase's reaction.
OR
6 ¢ 6-
OR OR
CH20H
+ ilCHO N.OH +
Cross linking of these compounds result into Bakelite. Overall equation can be represented as:
OH OH
OH
{r CH2
.y . -O-CH,-&.
y .
6Phenol
II
+H-C-H
o
.Fonnaldehyde
Base
·-¢-
., CH2.. .
......
OH.·
.,
-¢-CH2
.. .
OH . .. OH
Fig. 11.2 Bakelite (Three dimensional product)
(v) Condensation with urea: Formaldehyde also condenses with urea in acidic solution to form a plastic like product,
I
. CH 2
I I
-.CH 2 ",- . /CH 2 -N-· CO-N-.
.mH 2NCONH 2 + nCH 20 --'---+ /N-CO-N, .
Urea Fonnaldehyde -CH2 . . . 'CH2-N-CO-N-
. I I
CH 2
I .
Formaldehyde-Urea plastic
(vi) Reaction with alcohol :. Formaldehyde reacts with methyl alcohol in presence of dry hydrogen chloride or fused
calcium chloride forming methylal which is used as soporific.
-------ii:
OCH 3 .A)CH 3 .
H 2C O + =r
. ---~I
: +.
H10CH
. Dry) H C/
2'.
. + H 0
2
Fonnaldehyde • ____ 1 3 Hel · · 'OCH 3
Methyl alcohol DimethoXy methane
(Methylal)
(vU) Polymerisation: Formaldehyde readily undergoes polymerisation.
(a) Para-formaldehyde: When an aqueous solution of formaldehyde (formalin) is evaporated to dryness, a white
crystalline solid with fishy odour is obtained. It is a long chain polymer..
nHCHO ~ (CH20)n or +CH 20-CH 20-CH20-1n' (n=6t050)
(Aq. solution) Para-fonnaldehyde
On rapid heating, it gives back gaseous formaldehyde.
When a formaldehyde solution is treated with conc. H2S04, a white solid, poiyoxy methylene ( CH 2 0 ) n ,H20 is formed,
Cone. H 2 S04
nHCHO " > (CH20 )n,H20 n>lOO
Heat Polyoxy methylene
G.R.B. Organic Chemistry for Competitions
(viii) Reaction with Grignard reagent: Fonnaldehyde forms primary alcohol with Grignard reagent.
R
I
Ether) H--C-OMgI HOH )RCH20H+Mg~~
H-. C=O+RMgI
I I H+ Primary
alcohol
'-....1
H H
Formaldehyde does not react with chlorine and phosphorus pentachloride. It does not give iodoform test.
Uses: (i) The 40% solution of formaldehyde in water (fonnalin) is used as disinfectant, germicide and antiseptic. It is used
for the preservation of biological specimens.
(ii) It is used in the preparation of hex amethylene tetramine (urotropine) which is used as an antiseptic and germicide.
(iii) It is used in silvering of mirror and decolouring vat dyes. .
(iv) It is employed in the manufacture of synthetic dyes such as para-rosaniline, indigo, etc.
(v) It is used in the manufacture offormamint (by mixing formaldehyde with lactose)-a throat lozenge.
(vi) It is used for making synthetic plastics like bakelite, urea-formaldehyde resin, etc.
(vii) Rongalite-a product obtained by reducing formaldehyde sodium bisulphite derivative with zinc dust and ammonia and
is used as a reducing agent in vat dyeing.
(viii) As a methylating agent for primary and secondary amines, e.g., .
C2HSNH2 +2HCHO >C2HsNH-CH3 +HCOOH
Acetaldehyde occurs in certain fruits and was first prepared by Scheele in 1774 by oxidation of ethyl alcohol.
Itmay be prepared by any of the general methods already dealt in section 1104.
Laboratory preparation: Acetaldehyde is prepafed in the laboratory by oxidation of ethyl alcohol with acidified
potassium dichromate or acidified sodium dichromate.
Manufacture: Acetaldehyde can be manufactUred by one of the following methods:
(i) By air oxidation of ethyl alcohol.
(ii) By dehydrogenation of alcohol.
(iii) By hydration of acetylene.
(iv) From ethylene (Wacker process).
Physical properties: (i) Acetaldehyde is a colourless volatile liquid, b.pt is 21°C and has a characteristic pungent smell.
(ii) It is soluble in water, chloroform, ethyl alcohol and ether. Its aqueous solution has a pleasant odour. In water, it is hydrated
to a considerable extent to formethylidene glycol.
CH3CHO+ H20~CH3CH(OHh
Chemical properties: It gives all characteristic reactions of aldehydes (already discussed in section 11.5). Besides general
reactions, acetaldehyde shows the following reactions also:
(i) Haloform reaction: It responds to iodoform reaction due to the presence ofCH 3 CO group.
(ii) Polymerisation: Acetaldehyde undergoes polymerisation forming different products under different conditions.
(a) Paraldehyde: It is formed, when anhydrous acetaldehyde is treated with a few drops of conc. sulphuric acid.
,
Aldehydes and Ketones
CH3
I
CH
0/ '0
3CH3CHO ~ (CH3CHOh I I
""/
Acetaldehyde Paraldehyde, (trimer) CH 3 --CH CH--CH3
o
Paraldehyde
(A cyclic trimer)
It is a pleasant smelling liquid (b.pt. 124°C). It has cyclic structure and when heated with dilute sulphuric acid, it changes again
into acetaldehyde. It is used in the medicine as a hypnotic and soporific (sleep producing).
(b) Metaldehyde: Acetaldehyde on treatment with dry hydrogen chloride gas or a few drops of conc. H2S04 is converted
into metaldehyde (CH3CHO)4' It is a white solid (m.pt. 246°C). On heating it sublimes but changes again into acetaldehyde when
distilled with dilute sulphuric acid. It is used as a solid fuel. .
CH 3--CH ~ CH--CH 3 CH3~a~--CH--CH3
A) I
o
I
Ii} I
0
I
CH3 --C-H 0 CH--CH3
Acetaldehyde (4 mol)
CH3--CH~--CH--CH3
Metaldehyde (A cyclic tetramer)
CH OH Cu ) HCHO
3 300"C Formaldehyde
(ii) CH 3CHO K2 Cr20 7) CH 3COOH NaOH) CH3COONa Sodalime) CH4 _CI-=-i~) CH3CI AgOH)
Acetaldehyde H2 S04 Acetic acid Sod acetate Heat Methane hv
Cu ) HCHO
300"C Formaldehyde
3. Acetone or PropaJione, CH 3 COCH 3 or Dimethyl Ketone
It is a symmetrical (simple) ketone and is the first member ofthe homologous series of ketones. In traces, it is present in blood
and urine. It may be prepared by any of the general methods already dealt in section 11.4.
Laboratory preparation: Acetone is prepared in laboratory by heating anhydrous calcium acetate.
Manufacture: Acetone is manufactured by following methods:
(i) By air-oxidation of isopropyl alcohol. .
(ii) By dehydrogenation of isopropyl alcohol.
(iii) From propene: (a) Wacker's process.
(b) Propene is absorbed in concentrated sulphuric acid and the resulting product is boiled'With water when isopropyl alcohol is
formed. Isopropyl alcohol on dehydrogenation yields acetone.
. HCI ) (CH3hC=CHCOCH3
-H2 0 Mesityl oxide .
Uses: (i) As a solvent for cellulose acetate, cellulose nitrate, celluloid, lacquers, resins, etc.
(ii) For storing acetylene.
(iii) In the manufacture of cordite-a smokeless powder explosive.
(iv) In the preparation of chloroform, iodoform, sulphonal and chloretone.
(v) As a nail polish remover.
(vi) In the preparation ofan artificial scent (ionone), plexiglas (a tough transparent plastic) and synthetic rubber.
Tests: (i) Legal's test: When a few drops of freshly prepared sodium nitroprusside and sodium hydroxide solution are
added to an aqueous solution of acetone, a wine colour is obtained which changes to yellow on standing.
(ii) Indigo test: A small amount of ortho-nitrobenzaldehyde is added to about 2 mL ofacetone and it is diluted with KOH
solution and stirred. A blue colour of indigotin is produced.
(iii) Iodoform test: Acetone gives iodoform test with iodine and sodium hydroxide or iodine and ammonium hydroxide.
G.R.B. Organic Chemistry fOr Competitions
Problem 3. Both )C=Oand )C=C( bonds undergo addition reactions, give the basic difference in their nature.
Solutiou: The )C=O grouping undergoes nucleophilic addition while )C=C( undergoes electrophilic addition
reactions. The difference is due to the fact that C of )C=O grouping is more electrophilic than C of )C=C(grouping since
oxygen is more electronegative than carbon. Thus, carbon of )C=O reacts with nucleophiles. The )c=c( grouping is
nucleophile and hence reacts with electrophiles.
Problem 4. Explain why aldehydes are more reactive than ketones.
Solution: The carbonyl group IS polar in nature.
Lower positive charge on the carbon of carbonyl group makes the aldehyde or ketone less reactive towards nucleophiles. In .
ketones, the positive charge on the carbonyl carbon is lowered by high +1 effect of two alkyl groups in comparison to aldehydes in
which one alkyl group is present. Further increase in the number of alkyl groups also increases the sterlc hindrance making it less
reactive. Thus, in general, aldehydes are more reactive than ketones. <
Problem 5. Under what circumstances may an aldehyde be prepared by oxidation ofprimary alcohol, ROH, with acid
dichromate? . .
Solution: If the aldehyde product is more volatile than the reactant alcohol and H 2 0, it may be removed from the reaction
mixture by distillation as it is formed. For example, acetaldehyde (b.pt. 21°C) can be prepared from ethyl alcohol (b.pt. 78°C) by
this method. "
Problem 6. RCOCI fails to give ketone when treated with R-Mg-". X but with R 2 Cd, a ketone is obtained easily. Explain.
Solution : " No doubt, Grignard reagent reacts with acid halide to form a ketone but Grignard reagent further reacts with
ketone readily and ultimately forms a tertiary alcohol.
R R ",'
RCOCI RMgX') )C=O .RMgX' )~~C-OMgX
" R
R2Cd reacts with RCOCI andforms ketone easily as Cd of R2Cd is sufficiently electrophilic to initiate the reaction.
- +
RCOCI + R2Cd ~ [R 2CdCl +RC=O] ~ RCOR + RCdCl
•
Problem 7. Accountfor the boiling points_of2-propanol, propanone and 2-methyl propene (the molecular masses are
approximat~lythe same) are 82°(" 5~C and - ~C respectively.
Solution: The high boiling point of alcohol is due to hydrogen bonding.
R--O-H---O-R
I
H
The dipole-dipole attractive forces of carbonyl compounds cause them to have higher boiling points than alkenes.
61.0 G.R.B. Organic Chemistry for Competitions
Cr PO' CH3CH2CO,
(ii) CH 3CH 2CHO K2 207) CH3CH2COOH 2 S) ""0
Propionaldehyde S0
H2 4) Propionic acid Heat CH3CH2CO/
Propionic anhydride
o
II
LDA ) (A) (i) CH 3- C- CH\ (B)
Problem 9. Complete the following reactions: (i) CH3CHO
(ii)HOH
o
\I
o
(ii)CH3-C-CH3 LDA) (A) (iii)6
"
NaOH ) (A)
SOC
Heat) (B)
o
II'
(V)C6 H S _' C-CH 3 OH-) (A) Heat) (8)
o 0 OH
I
Solution:' (i)CH3-C-H (Base»CH2-CHO
LDA - (i) CH3 ~~-CH3
--=----~)CH3-C-CH2CHO
I"
(A) (ii) HOH' I
CH3
(B)
o 0 0 0 OH
.I LDA I - '(i)CH3-~-H
(ii) CH3-C-CH3 -~)CH3-' C-'CH2 -....:--=-----+) CH3-C-CH2-CH-CH3
'II I
(Base) " (A) (ii) HOH , (B)
o~t o ' -. OH' 0
A+1J'O::,' ' O~ . "'06'~'
.(iDle) i
+ '. ' ". 'soc
.
6 -,0, "'
," "
fl
.
(-H20)
-
, ' Cyclohexanone ~-Hydroxy ketone (A) (B)
(A)
Aldehydes and Ketones 611.
4 .'.. .. '
(~H2<?) ) ,C~H~CH2C~!T~~0
. . ' .. ' , . ' 'C6 H S .
" " , .(IJ) , .,
i
.0 OH. ,. ·0
a+ .. a- I ow I .. II
+ H:-CH z -C-C6 H S ":-,,---+>C6":S-Y-.-'-.CH2-.C-,C 6 Hs
I ' .
CH3
(A)
Problem io. An f,llhne, C6H12,ajter ozonolysis yielded two products. One ofthese gave a positive iodoform reaction but a
negative Tal/ens' test. The othet: product gave a positive Tollens' test but a negative iodoform reaction. What is the structure and
name of the alkene? .
Solution: One product is methyl ketone as it gives positive iodoform test while other product is an aldehyde: The aldehyde
does not have methyl group as it does not respond to iodoform test. Hence, the products of ozonolysis are,
GH3COCH3 and CH 3CH 2 CHO
CH3"- .' . .
Therefore, the alkene is, .. ./'C=CHCH 2CH 3
CH3./' '
. 2-Methyl pent-2-ene
. Problem 11. Co;"pound (A), C s HlOO, forms a phenylhydrazone, gives' negative Tol/ens' and iodoform tes(s and is reduced
to pentane. What is the compQund?
Solution: (A) fonns a hydrazone, it is a carbonyl compound. It is a ketone as it does not reduce Tollens' reagent. The ketone-does
no.t have methyl group as~t does not respond ,to iodoform test. Thus, the compound is: ' .
o
CH3CH2--.C-CH2CH3
"
Pl!i1tan - 3 - o n e , .
Problem 12. Explain why the additiofl ofhydrogen cyanide to carbonyl compounds is accelerate<lby bases and retarded by
acids. . . ' [lIT 2003]
Solution: . The addition ofRCN to)C=OcornpoUndsproceeds as f~ilows:.
Oa- 0- OH
SUPPLEMENTARY READING
11.9 ACROLEIN, ACRALDEHYDE OR PROP-2-EN-1-AL (H2C=CHCHO)
It is obtained by dehydration of glycerol. Dehydration is donewith the help ofKHS0 4 or P20S or conc. H2S04'
CH 20H CH2 CH2
~HOH KHS04) ~ lsomerises) ~H
I Heat III
CH20H -2H20 CHOH CHO
Glycerol Unstable Acrolein
Commercially, it is prepared by passing a mixture of ethanal and methanal vapours over sodium silicate (catalyst).
':!
Aldehydes and Ketones t$13
>
H
C 2H s.......
~C=O >
CH 3 ,
' C2 H S,
.."...C=O
reduces RCOCI mto RCHO. ' '. CH3_ C2 H S
[JS~di~m.aitiininium hydride, NaAlH4 also reduces esters Thus, +1 effect of alkyl group decreases the reactivity
into~~ld.ehYde. . whereas the introduction of negative group (-I effect) ,
[J' Ketbnes can
be'prepared,by the. action of dialkyl cadmium increases the reactivity, e.g., chloral
on aCidchloricles. ' (trichloroacetaldehyde) is more reactive than acetaldehyde
[J Stephen's reduction: The reduction. ~f alkyl cyanide by as the chlorine atoms increase the positive charge on the
SnCl2 and conc. Hel followed by aCid hydrolysis to give carbonyl carbon. '
aldehyde is known as Stephen's reaction. The a-H atoms of aldehydes and ketones are reactive
[J From acetoacetic ester: Ketones are prepared by the (acidic in nature). This is due to the fact that the anion
hydrolysis of acetoacetic ester or its alkyl derivative with resulting from removal ofa-H atom by base gets stabilized
dilute aqueous acid or dilute alcoholic solution of alkali. .. by resonanee.
[J Fronl1,2-glycols: By oxidation with lead tema-acetate, Reactions common to aldehydes and ketones
(CH3COO)4Pb or periodic acid, m04' [J Substitution reactions: The a-H atom of alkyl group of
[J From alkyl halides': On treatment with dimethyl >C=O ~ompounds can be replaced by halogen atoms
sulphoxide (DMSO), the 1° alkyl halides give aldehyde and
(C12 .or Br2) even at room temperature. Acetaldehyde on
2° alkyl halides give ketone., '
halogenation (chlorination). gives trichloroacetaldehyde
a Physical properties: Except HCHO (it is a gas), all (chloral) and acetone yields trichloroaceton~. The excess of
other aldehydes and ketones are volatile liquids at ordinary
alkali ,decomposes the tribalogen compounds to ,give
temperature. U~wer aldehydes have unpleasant odour
haloform (CHX3 ) •.
while ,ketones possess pleasant smell.' The carbonyl
compounds are strongly polar in. nature which results in [J Acetaldehyde, acetone and methyl ketones (-COCH 3)
appreciable· intermolecular attraction. Therefore, their undergohaloform (Iodoform) reaction with X2 (12) and ,
boiling PQints'are higher than those ofnon-polar substances 'NaOH.
of comparable molecular weightS. However, their boiling [J Oxidation by Se02: Seleniwn dioxide oxidises the
points are lower than corresponding alcohols. due to 1;he reactive methylene gr.oup adjacent to carbonyl group at the
absence pf intermolecular hydrogen bonding. a-caibon to form dicarbonyl compounds. Forexampte,
q Chemical properties :' Both aldehydes and ketones
, contain a >
C '0 group which is ,highly polar' due to
n:sonance mid permanent -I effect of the negative oxygen
acetaldehyde gives glyoxal and acetone yields methyl
glyoxal.
Reactions of carbonyl group (Addition reactions)
atom. ' [J Addition of hydrogen: Different products are obtained
, '" 0' ,
/c=o~/c-~.,
,+ ;::./ depending on the nature of reducing agents.
[J Molecular hydrogen in presence of metallic catalyst (such
as Ni, Pt and Pd) reduces aldehydes'and ketones into 10 and
The p6~jtivelycharged carbon is readily attacked by the
2° alcohols respectively.
electron'rich nucleophiles, while the negatively charged
[J. With nascent hydrogen produced (such as Zn + CH3COOH,
oxygen is attacked by electron cleficient electrophiles.
Na +C 2H s OH, Na + H 20, Zn + alc. NaOH, etc.) gives ]0
[J Relative reactivity of aldehydes and ketones'
and 2° alcohols (reduction to alcohols).
The reactivity of)C '. 0 gr()up for nucleophilic addition [J With LiAlH 4 , NaBH4 or LiBH4 (complex metallic
depends mainly on: , , hydrides), aldehydes give 1° alcohol while ketones give 20
(i) ability of carbonyl oxygen to carry a negative charge, alcohol.
(ii) inductive effect of the groupSa~hed to the carbonyl [J' Unsaturated aldehydes can be reduced to unsaturated
, carbon atom and " alcohols (1°) without affecting C=C in ,presence .of.
of
(iii) siz~ substituent group (sterlc '(actor). reducing agents LiAlH4 in dry ether or NaBH4 in alcohol.
[J Clemmensen's reduction: Aldehydes and ketones are
The decreasing order ofreactiyity of >C=O group is as
follows:. converted into alkanes, (i.e., )C=O group is reduced to
>CH 2 grou~) when treated with Zn-Hg and conc. HCl.
This reaction is known as Clemmensen's reduction.
Aldehydes and Ketones 615
a The same conversion ( )C=Ointo )CH 2) can be made a Reaction with H2NNHC6HS: Aldehydes and ketones
by heating aldehydes and ketones with red P and conc. m. ,react with phenylhydrazine (H2NNHC6HS) to form
a Wolff-Kishner reduction: Aldehydes and ketones are phenylhydrazones ()C=NNHC6Hs).
conveniently reduced to hydrocarbons in presence of a Reaction_ with - 2,4-dinitrophenylhydrazine (DNP,
excess ofhydrazine (H 2N-, NH2) and strong base (NaOH Brady's reagent): DNP reacts similarly with carbonyl'
orC2HsONa) on heating. compounds to form corresponding 2,4-dinitrophenyl-
""-C 0 ""-C-NNH C2HsONa
hydrazone.
/ = 0 + H 2NNH 2 -H2 )0/ - 2-----+-) D Reaction with H 2NNHCONH 2 .: Aldehydes and
(Hydrazone) ~, 200"C
ketones combine with semicarbazide (H2NNHCONH2) to
>CH 2 +N2
a Meerwein-PonndorfVerley (MPV) reduction: Ketones form semicarbazone ( )C=NNHCONHz).
can be reduced to sec. (2°) alcohols with aluminium .a Reaction with H 28 -: Carbonyl compounds react with
isopropoxide [(CH 3hCHOh Al in propan-2-01. H 2S to form tbioaldehydes and tbioketones respectively
a Bimolecular reduction (Pinacol formation) : . Two
moles of ketone undergo reduC'tion in presence of ()C=S).
Mg-HglHOH to pinacol which on heating with mineral Condensation re~ctions
acids, converted into pinacolone (pinacol-pinacolone D Aldol condensation (Reactions involving a-hydrogen) :
rearrangement). It is a chemical reaction in which two or mQre molecules of
a Addition of HCN: Both aldehydes and ketones add same or different carbonyl compounds containing a-H
HCN (KCN + dil. H 2S0 4) in presence of basic catalyst to atoms unite together in the presence of a dilute base such as
fonn: cyanohydrins. NaOH, Ba(OHh or K2C0 3 etc., to form a new product
a Cyanohydrins are good synthetic reagents and can be which combines the properties of alcohol and aldehyde or
converted into a-hydroxy acids, esters and amino acids, ketone, is called aldol condensation.
a Addition of NaH803 : Aldehydes and ketones on a Characterbtics of aldol condensation
shaking with a saturated solution ofNaHS0 3 gives a solid (i) This reaction may take place between (a) same or
derivative of sodium bisulphite compound. different aldehydes, (b) an aldehyde and a ketone, (c) same
D These bisulphite compounds on heating with NaCN yield - or different ketones.
cyanohydrins. (ii) The carbonyl compound must contain hydrogen atom at
a Addition of Grignard reagents: The >C=O group a-carbon to the )C=O group which is involved in aldol
adds onto Grignard reagent and the addition product on condensation. However, formaldehyde though contains no
. hydrolysis decomposes to yield 1°, 2° or 3° alcohol a-H atom yet undergoes abnormal aldol condensation in
depending on the nature of carbonyl compound. For' presence of lime water. '
example, HCHO forms 10 alcohol, higher aldehydes (iii) New C-C linkage is formed (an irreversible process).
(RCHO) give 20 alcohols and ketones give 3° alcohol. (iv) The condensation product (i.e., aldol) loses a molecule
D Reaction with alcohols : Aldehydes and ketones of water to 'give a, p..unsaturated )C=O compounds.
combine with alcohols and form acetals andketals Reactions in which aldehydes and ketones differ
respectively and can be easily hydrolysed by acids. a Oxidation of aldehydes: Aldehydes are easily oxidised
.a Reaction with thioalcohols: Thioalcohols react more to corresponding carboxylic acids and thus acts as strong
rapidly than alcohols and form thioacetals and thioketals. reducing agents. Oxidising agents may be strong (such as
Replacement of carbonyl oxygen (Condensation acidified K2Cr207 or acidified' Na2Cr207 or acidified
reactions) KMn04 or hot conc. RN03) or mild (such as Tollens'
a Reaction with NH 20H: Aldehydes and ketones react reagent or Fehling's solution or Benedict's solution).
with hydroxylamine (NH 20H) to form. oximes a Reduction of Tollens' reagent : It is ammoniacal
AgN03. Aldehydes reduce weak (mild) oxidising agents
(>t=NOH). '
rike ammoniacal AgN03 (Tollens' reagent) to metallic
a Beckmann rearrangement: Ketoximes on treatment silver which deposits as mirror (Reducing character of
with acid catalyst (conc. H2S04, H 3 P04 , SOCl2 or PCIs aldehydes). This reaction is known as silver mirror test.
etc.) undergo Beckmann rearrangement to form a a Reduction of Fehling's solution : It is an alkaline
substituted amide (RCONH-R). solution of cupric ion complexed with sodium potassium
a Reaction with NH 2NH 2 : Aldehydes and ketones form . tartrate. Aldehydes on heating with Fehling's solution give
, hydrazones ()C . NNH 2) with hydrazine. a ~eddish brown precipitate of cuprous oxide (Cu 20).
G.R.B. Organic Chemistryfor Competitions
a Reduction of Benedict's solution: It is· a solution of aluminium ethoxide (C2HSO) 3Al The acid and alcohol so
~pper sulphate, sodium citrate and sodium carbonate. formed react together to give an ester. This is known as
When heated witlJ. an aldehyde, a reddish brown precipitate Tischenko's reaction (a modified Cannizzaro's reaction).
ofCu 20'appears (similar to Fehling's test). a Formation of sodio derivative :. Ketones yield sodio
~ a Ketones do not reduce Tollens' reagent, Fehling's solution derivatives when treated with sodium or sodamide
and Benedict's solution (Distinction between aldehydes (NaNH 2) in ether solution. Aldehydes do not yield sodio
and ketones)~ . derivatives.
o Oxidation of ketones : Ketones are oxidised with a Reaction with HN0 2 : Ketones when treated with
difficulty. They are oxidised only on heating with a strong nitrous acid (HN0 2) form isonitroso derivative. This
oxidising agent to a mixture of carboxylic acids with lesser reaction is not observed in aldehydes. ,
number of carbon atoms. a Reduction in neutral or alkaline medium: When
a Oxidation of mixed ketones is governed by Popoff's rule ketones are reduced with Mg-Hg and water, pinacols
according to which, the
smaller alkyl group.
> c=o group remains with the (dihydric alcohols) are the main product which on heating
with dil: H2S04 give pinacolone.· It is called
Pinacol-pinacolone rearrangement.
a Baeyer-Villiger oxidation: Aliphatic ketones undergo
a Reformatsky reaction : This' reaction involves the
oxidation with per acids such as Caro's acid (H 2SO S) or
treatment of carbonyl compounds with a-bromo acid ester
per benzoic acid (C 6 H s C0 3H) or per acetic acid
in presence of metallic zinc to form J3-hydroxy ester, which
(CH3C03H), etc., to form esters or their hydrolysed
can be easily dehydrat~d into a, J3-unsaturated ester.
products (carboxylic acids and alcohols).
.a SchiWs test of aldehydes: Schiff's reagent is a dilute
a Claisen-Schmidt reaction (Claisen reaction) : This
condensation reaction is between an aliphatic aldehyde or
solution of p-rosaniline hydrochloride whose pink (red)
ketone containing a-hydrogen with benzaldehyde in
colour has been discharged by passing S02 gas. Aldehydes
presence of dilute alkali to form an a,J3-unsaturated
when treated with Schiff's reagent (magenta solution in
compound (similar to aldol condensation).
H 2S0 3) restore its pink colour. Ketones do not give this
test.'
a Reaction .with diazo methane (CH2N2) : In this
a Reaction with NH3 :. Except formaldehyde, other reaction, aldehydes can be converted to ketones and lower
ketones can be converted to higher ketones.
aldehydes form addition product with NH3 (aldehyde
ammonia). . . a Pyrolysis of ketones: PyrolYSIS of ketones at 700"C
gives ketene (CH2 =C=O).
a Formaldehyde on reaction with NH3 gives hexamethylene
a Knoevenagel reaction: A reaction between aldehydes
tetramine (urotropine) which is used as an urinary
and compounds with active methylene group (such as
antiseptic.
malonic ester, acetoacetic ester and cyanoethyl acetate,
a Ketones on treatment with NH 3 form complex ketonic
etc.) in presence of a base (pyridine) catalyst to give (1,
amine.
J3-unsaturated acid is called Knoevenagel reaetlon.
a Reaction with alkali: Aldehydes having a-hydrogen
atom on heating with conc. alkali (except HCHO) gives a a Schmidt reaction: .This is a 'reaction between a carbonyl
brown resinous mass (resinification). Ketones do not give compound and hydrazoic acid (N 3 H) on heating in
this reaction. . . presence of conc. H2S04 to form N-alkyl acidamide.
a Cannizzaro's reaction: HCHO, C6HSCHO and other a Condensation with CHCI 3 : Acetone condenses with
aldehydes containing no a-hydrogen atoms on heatiDg CHC13ICHBr3 in presence of KOH to forDi
with conc. alkali solution undergo oxidation reduction chloretonelbrometone respectively.
reaction. In this reaction, one molecule of aldehyde is a Condensation with aniline: Aldehyde condenses with
.oxidised to carboxylic acid and the other is reduced to 10 aniline and forms Schiff's base.
alcohol (disproportionation). This is known as
RCHO+H2NC6HS ~RCH=NC6Hs +H20
Cannizzaro's reaction. (Schiff's base)
a When an aldehyde (baving no a-H atom) is treated with
a Polymerisation : Lower aldehydes show {l marked
HCHO and aqueous base, it is the formaldehyde that
tendency to polymerise forming compounds in which
imdergo oxidation (rather than other aldehyde) and this
several molecules· are linked together through oxygen.
reaction is knoWn as crossed Cannizzaro's reaction.
a Compounds cOntaining two carbonyl groups undergo
a Para-formaldehyde : When' an aqueous solution of
formaldehyde (formalin) is evaporated to dryness, it
intramolecular or internal Cannizzaro's reaction. '
polymerises . to a white crystalline solid,' ,
a Tischenko's reaction: All aldehydes (with or without
para-formaldehyde (HCHO)n where n= 6 to 50. It is a long ,
a-H atoms) undergo Cannizzaro's reaction in presence of
chain polymer.
Aldehydes and Ketones
OH OH
Aldehydes and Ketones 619
"
3. Match the following:
(i) (A) Formaldehyde (1) Iodofunn test .
(B) Acetone . (2) Test of aldehydes
(C) 'Acetaldehyde (3) Ammoniacal silver nitrate
(D) Halofonil reaction (4) Polymer of phenol and formaldehyde
(E) Schiff's reagent (5) Calcium acetate
(F) Clemmensen's reduction (6) Urotropine
(G) Bakelite (7) Boiling point 210C
(H) Tollens' reagent (8) Zinc amalgam and conc. HCI
(ii) (A) Cannizzaro's reaction (1) H2C=CH2 + PdCI 2· + H20 CuC1 2 ) CH3CHO+ Pd + 2HCl
OH .
Ba(0H)2 I
(B) Rosenmund's reaction (2) (CH3)2CO+ H'CH2COCH3 ---==-+) (CH3)2-C-CH2COCH3
(C) Oxo process (3) ZoIHg + Conc. HCI
(D) Wacker process (4) 2HCHO NaOH, HCOONa+ CH30H
(E) Clemmensen's reduction (5) H2/Pd-BaS04
(F) Aldol condensation (6) (C2HSOhAl
C02 (CO)8
(G) Tischenko's reaction (7) Alkene + CO + H2 . ) Aldehyde
(H) Fehling's solution .(8) Red ppt. of Cu 20
4. Complete the following equations and write down the names of the products:
(vii) CH3COCH3 12 ) ?
NaOH
(viii) CH3CHO + NaHS0 3 -----. ?
(ix) CH3CHO+Ag20-----.?
(x) CH3CHO + HiNOH -----. ? PdC1 2 , CuC1 2
(xx) H2C=CHZ +02 )?
Pd-BaS°4 ) ? H 20
(xi) R-COCI + Hz
o (xxi) CH3COCH3 + CH3MgBr NH4a)?
1\
HOH
(i) Mg-Hg/HOH ) ?
(xii) CH3-C-CH3
(ii) H+. ~ • (xxii) CH3CH2CHCl 2 Boil, alkali) ?
5. Jdentify the (A), (B), (C) and (D) in the following reactions sequence:
(i) HC==CH H2S04(dil.» (A) CH3Mg~r) (B) K2Cr20 7 ) (C)
Hg2+ H20IH H2S04
H2 CH 3Mgar , D
Pd/BaS04 ) (C) H 0/H+) (, ,,)
2
o
II
(xii) CH3 -C-CH3 +CH 3CH2CHO 011 HA)~(B) , NaBH4 ) (C)
(Roorkee 2000)
(xvii) CH3-CH-CH3 KCN(ale.» (A) (i)SnCI 2/HCI ) (B)
I (ii) H20, OH, H20 2
I
(xviii) CH3CH2G5.CH N~NH2 in ) (A) CH3Br) (B) H2S04 ) (C)
Llq. NH3 HgS04 ,333K
o
(xxi) 2CH3-~-CH3 Olr) (A) NaHS04 ) (B)
Heat
(Roorkee 2000]
[
Hint: (CH3)2C=O + HCN ~ (CH 3hC <OH H20) (CH 3)2C(OH)COOH ]
CN a-Methyl lactic acid
(v) Fonnaldehyde is treated with methyl magnesium bromide and the product is then hydrolysed.
(vi) Ammonia reacts with fonnaldehyde.
(vii) Ammonia reacts with acetone.
(viii) Chloral is heated with aqueous sodium hydroxide.
[Hint: CCl3CHO + NaOH ~ CHCl 3 + HCOONa]
(ix) Acetaldehyde reacts with Fehling's solution.
[Hint: CH 3CHO+ 2CuO~ CH 3COOH + Cu20 (Red ppt»)
(x) Acetone is distilled with conc. H2S04'
+ShorflnswerType· .
7. (i) Give an industrial preparation of (a) fonnaldehyde, (b) acetaldehyde and (c) acetone.
(Hint: (a) CH30H + 026OO"C ) HCHO
Cu
(ii) Give the methods by which ethyl alcohol may be converted into acetaldehyde.
[Hint: (a) By oxidation with acidified K2Cr207 or acidified KMn04.
(b) By catalyticdehydrogenation-vapours are passed over heated copper at 300°C.)
(iii) How is an aldehyde obtained from an acid chloride?
[Hint: By Rosenmund'sreduction, RCOCI + H2 Pd/BaS°4 ) RCHO + HCl)
(iv) Write an equation for making aldehydes by the oxo process.
[ Hint: R-CH=CH2 + CO+ H2 C02 (CO)8) RCH2CH2CHO ]
[
Hint: CH3CHO+ NH3 ~ CH 3CH(OH)NH2 H:zS04) CH3CHO+ ~HS04 ]
Impure Pure
(vi) How is impure acetone purified?
[
Hint: (CH3)2.CO + NaHS03 ~ (CH 3)2C(OH)S020Na Na2C03) (CH3)2CO ]
. Impure . Pure
8. (a) Write the structuralfonnulae and give the IUPAC names for all the aldehydes and ketones of molecular fonnula, CsHlOo.
CH3 CH 3
I I
[
Hint: Aldehydes: (i) CH3CH2CH2CH2C~O (ii) CH3-CH-CH2CHO (iii) CH3CH2CH-CHO (iv) (CH3)3GCHO
Pentanal 3-Methyl butanal 2-Methyl butanal 2,2-Dimelhyl propanal
. . . CH3
I .
Ketones: (i) CH3CH 2CH 2COC.H3 Oi) CH3CH2COCH2CH3 (iii) CH3-CH-CO-CH3 ]
PenIlm-2-one Pentan-3-one 3-Methyl butan-2-one
(b) Write the functional isomers ofCsHIOO, that can give Cannizzaro's reaction.
[Hint: (CH3)3 C-CHO (2;2-Dimethyl propanal»)
622 G.R.B. Organic Chemistry for Competitions
(c) A keto ester, C6HIO03 that forms oxime and by iodofonn test (with 12 andNaOH) forms CH2 (COONah and em). Give its
structure.
0.
. ~ .
[Hint: CH3-C-CH2COOC2Hs (Ethyl-3-ketobutanoate)]
9. How will you differentiate between?
(i) Acetaldehyde and acetone.
[Hint: AcetaJdehyde responds to following tests while acetone does not give any of them:
(a) Acetaldehyde + Schiff's reagent solution ~ Pjnk colour.
(b) AcetaJdehyde + ToHens' reagent ~ Silver mirror.
(c) AcetaJdehyde + Fehling's solution ~ Red precipitate.
(d) Acetaldehyde + Sodium hydroxide (cone.) ~ Brown resinous mass.]
(ii) Aldehydes and ketones with (i) Tollens' reagent (ii) Fehling's solution.
tHint : Same tests as in (i)] .
(iii) Acetone and diethyl ether.
[Hint: Acetone forms yellow coloured iodoform when heated with 12 and NaDH, i.e., it gives iodoform test. Diethyl ether does not give this test.]
(iv) Fonnaldehyde and acetaldehyde.
[Hint: Acetaldehyde forms yellow precipitate of iodoform with an alkaline solution of iodine, i.e., gives iodoform test. Formaldehyde does. not
give this test.] ,
(v) Ethyl alcohol and acetone.
(Hint: Ethyl alcohol gives pink colour with eerie ammonium nitrate while'acetone does not Acetone gives pink colour with an alkaline solution
. of sodium nitroprusside while ethyl alcohol does not.] .
(vi) Formaldehyde and ethyl alcohoL
(Hint: Formaldehyde resPonds to following tests while ethyl alcohol does not give any them: of
(a) HCHo.+,Schiff's reagent ~ Pink colour
(b) HCHD + Tollens' reagent ~ Silver mirror
(c) HCHD + Fehling's solution ~ Red precipitate
Ethyl alcohol gives iodoform test while HCHD does not.]
(vii) Pentan·2-one and pentan-3.one.·. .
[Hint: Pentan-2-one having -COCH3 group forms a yellow precipitate ofiodof~ with an alkaline solution ofiodine, i. e. ,gives iodoform test
while pentan-3-Olle does not.]
10. How would you bring the following conversions?
(a) Acetone from acetaldehyde.
Hint: CH 3CHD. . [0] + ) CH3COOH' Ca(OHh) (CH 3CDDhCa Heat ') CH3COC.H3 ]
[ Acetaldehyde K2Cr2071H Acetic acid Calcium acetate , . Acetone
(b) Methanal to ethanal (not more than ~ steps).
Hint: HCHD CH 3MgBr) CH3CH 2DMgBr H 20 ) CH 3CH 2DH [0]' +) CH3CHD ]
[ . Addition product Ethyl alcohol K2Cr2~/H Ethanal
[
Hint: CH4 ~ CH 3CI Na . ) CH3-CH) ~ CH3,CH2Cl NaOH(aq.) )' CH)CH20H, then fo1l9W (g) J
hv Methyl cbloride Wurtz reactton Ethane hv Ethyl cbloride Ethyl alcohol
(i) Butan-2-one from ethyl alcohol.
CH 3 '
'H OfH+
2 )
I
C2HS -CHQH
[ Sod. silicate, ,
' H0
-Hint: CHlCHQ ' HC~? ) CH 3CHQHCHQ =--4 H2C=CHCHQ HCN) H2C=CHCH(QH)CN
" " 'H O/H+
2, ) H2C=CHCH(QH)COOH
' ' ,
' 1
. . ' . ,,'
(I) Propanal to propyne.,
• S PCl '
, Hmt:CH 3 CH2 CHQ ~ CH3CH2CHCl2
[
CH 3 . . CH 3
. . I
[ Hint: CH3-CH-CHO + H-C-CHO Oil. NaOH) CH3-CH-CH-~-CHO ]
I . I . I I I
CH 3 · CH3 CH3 OH CH3
2-Methyl propanal 3-Hydroxy-2,2,4-trimethyI pentaDal
(r)· Ethanal to 3-hydroxy butanal to butan-} ,3-diol.
(Hint:. CH3CH=O + HH2CCHO ·Dil. NaOH ) CH3CHCH2CHO
. Ethanal (Aldol condensation) I
OH
3-Hydroxy butanal
(s) Ethyne or propyne to pent~3-yn-2-o1. .
11. Acetaldehyde undergoes a reac~on to form a product which (b) Acetone, acetic acid and methyl alcohol.
exhibits properties of aldehyde~ and alcohols. (c) Ethyl alcohol,propanone and acetic acid.
(i) Name the reaction and give equation. 15. Explain the following with one example:
(ii) Write the structural formul. of the product formed. (a) Aldol condensation
(iii) What are the reagents other than acetaldehyde required (b) Cannizzaro's reaction
. for the reaction to take place? . (c) Wolff-Kishner reduction
12. Which of the following compounds would undergo aldol (d) Rosenmund's reduction
condensation, which the Cannizzaro's reaction and which (e) Clemmensen'sreduction
neither? Write the structures of the expected products of (t) Polymerisation
aldol condensation and Canni~ro's reaction. (g) HaIoform reaction
(i) Methanal (ii) 2-Methylpentanal (h) Tischenko's reaction
(iii) Benzaldehyde (iv) Benzophenone (i) Beckmann rearrangement
(v) Cyclohexanone (vi) I-Phenylpropanone 0) Meerwein-Ponndorf-Verley reduction
(vii)Phenyl ethanal (viii) Butan-I-ol (k) Pinacol-Pinacolone rearrangement
(ix) 2,2-Dimethyl butanal (I) Refonnatsky reaction
13~ (a) Four different bottles containing methyl alcohol, ethyl (m) Oppenauer oxidation
alcohol, acetic acid and acetone have lost their labels. (n) Claisen-Schmidt reaction
What chemical tests would be performed to identify 16. How do you account for the following?
them? (a) Boiling points of aldehydes lie between parent alkanes
(b) Four different bottles containing isopropyl iodide, and corresponding alcohols.
acetone, propionaldehyde and heptane have lost their (b) Aldehydes and ketones have high dipole moments.
labels. What· chemical tests would be performed to (c) NaHS03 is used for the purification of aldehydes and
identify them? ketones.
14. How will you obtain the pure products from the following (d) Iodoform is obtained by the reaction of acetone with
mixtures? hypoiodite but not with iodide.
(a) Acetaldehyde and ethyl alcohol.
:.: A;: :ld: :;e~h~y: : ;de:; :;s;. ;a;: :.n: : ;d:. :IG;.:.e; ;t; ;:.o;.; .ne:; :;s:. .-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _.....;.,'...:,6::··~=·;';;~··C·.•
(e) Hydrazones of aldehydes and 'ketones are not prepared (iv) Chloral hydrate is a stablec.ompound even it is a
in highly acidic medium. gem-diol.
[Hint: (a) Alkanes have low boiling points as no hydrogen [Solution: In chloral, the -/ effect of three chlorine
bonding and no dipole-dipole attractive forces are present. atoms destabilise the> c=o structure .as it puts 0+
Alcohols have high boiling. points as intermolecular
hydrogen bonding is present. In aldehydes, dipole-dipole 5"
charge on the carbon adjacent to the carbonyl C In the
forces are present due to polar nature of carbonyl group ..
Thus, boiling points of aldehydes lie between alkanes and chloral hydrate, adjacent ,positive charges are not
alcohols. present. As a result,' wea~ nucleophiies like water
(b) The large dipole moment is due tothe large contribution" readily add to the >C=O group forming chlorill
of the polar structure (resonance) to the hybrid. .< '
........... ........... + - hydrate there by shifting the equilibrium almost entirely
/C=O~ /C-O· towards right. Besides this, the' intramolecular
(c) Aldehydes and ketones form insoluble crystalline H-bonding betWeen CI and H atoms of the -OH group
compound with NaHS0 3 whic~ can be filtered. These on further -StabilIses the chloral hydrate molecule. The
distillation with saturated solution of Na2C03 again give hydrog~n bonding in the molecule also increases its
the aldehyde or ketone. stability. .
. OH
........... . ........... / Na2C03 ""- . Cl'
/C=O+ NaHS0 3 ----'> /C"'-- ----"-----"-~) /C=O
S03 Na
CI OH
.' '+0+ 0.+ 0"-
(d) The reaction is initiated by the replacement of methyl
CI---+-C-C=O.
I I ,]
protons (H+) by 1". CI-,-,-,OH
CH 3COCH 3 + 310- ----'> CI 3COCH 3 + 30W
(e) In highly acidic medium, the protonation ofhydrazine
t ~
-cI
CI H
Chloral hydrate
decreases its nucleophilic character.J Chlonil
17. Explain the following with proper reasoning: (v) Formation of oximes and other ammonia derivatives
(i) Why do halogen acids which are easily added to from carbonyl compounds require slightly acidic media
)C=C <grouping, fail to give addition products for maximum r. a t e . ' .. /
[Solution: In weakly acidic medium, carbonyl group
with )C=O grouping? is protonated,
........... + +
(Solution Halogen' acids readily combine to the r /C=O+H~ >C-OH
polarised )C=O bond. This facilitates the addition of Lewis bases. However,
. . OH in strongly acidic media, the nitrogen of the reagent is
........... ~ ........... + x- . . . . . . /"
/ C=O+ H+ ...--- /C-O-H~ /C ............... protonated through the unshared pair of electrons imd
X thus the reagtmt cannot attack the carbonyl group. In
The addition product being similar to gem-dihydroxyl basic media, there is no protonation of carbonyl group. ]
compound decomposes into the original substance. 18. Arrange the following:
eX ~ >C=O+HX]
H (i) -CHO, -COCH3 ,-COOH, :"-tOCI,
c(:!7 -CONH~, -COOCH3, -COO- in decreasing
order of nucleophilic addition.
(ii) Pure HCN fails to react with aldehydes. (ii) CH3CHO, CH3COCH3 , HCHO, C2H 5COCH3 in
[Solution: HCN is a covalent compound and does decreasing order of nucleophilic addition.
not furnish CN- ions. However, in the presence of (iii) CH3COCH2CHO, c. CH3COCH3, 'CH 3CHQ
bases, it furnishes sufficient concentration of CN- ions CH3COCH2COCH3 in increasing order of expected
and the reaction proceeds. enol content. . .
HCN+OH- ~H20+~] (iv) CH 3CHO, C6f15CHO, (CH 3 hCO, FCH 2CHO jn
(iii) Why only RCHO, RCOCH3 and cyclic ketones react decreasing order of reactivity.
<Vl!.d.6.6
with NaHS0 3?
[Solution: S0:3-:- is a large ion. Its addition is
possible only under the condition that ) C .0
grouping is not sterically hindered as is the case for in decreasing order of reactivity;
RCHQ RCOCH3 and cyclic ketones.]
, .
. '"'7
..
Aldeh des and Ketones
(Hint:
CH 3 CH3 CH 3
\ H+ \ -H 20 \+
CH3-C-CH20H~ CH3-C-CH20H ---=--+ CH 3-C-CH20H
\ (l") If
OH
D
OHi
(3 )
1"
3lY A"A"77)
"""" T
8
Olt ) (A) Heat) (B) LiA1H4) (C)
o
(Hint: Di-ketone can undergo internal aldol condensation reaction to form (A).
o , 0, o ,
~
4 '~'
~
3
,58"OW
7 • 3
4 68
57 _ '4
3 6,',8"
57 ,---+-
1 / (-H20) 1, - , " ;) 1 ~+',
(a-c) 0 ',' 0 0-
0 0 0 OH
~ ~.
0 ~J
H+ Heat • liAIH.t
1 7
• •
5
-0 8 ' HO ; (C) ,
'(8)
(A)
r ..
'20. Write the structural formulae and names of the four possible (j) m:esitylene; (k) aldol; (I) carboxylic acids;
aldol condensation products from propanal and butanal.In , (m) CH 3-C=CH-C-CH3; (n)sp2; (0) nUCleOphilic;
, ',\ 1\, ,"', , '
each case indicate which aldehyde acts as nucleophile and " O-H---O,
which as electrophile. CH3
21. (a) Give two typical reactions of an aldehyde. \
(b) Give two typical reactions of a ketone. CH
(c) What is the productformed when acetaldehyde acts as a '/",
reducing agent? ?' ? " ~j,' ' \
(d) Give one use of the following reagents: (P) CH3.,---'-~/CH-CH3; (~ CH 3CP-;, (r) Il~es"
(i) Schiff's reagent, (ii) Tollens' reagent, (iii) Fehling'-s -__ '0- '
solution, (iv) 2,4-dinitrophenylbydrazine. ' , ,(paraldehyde)
(e) What product is obtained when acetone is distilled with , Wolff-KisJuier reduction; (s) do not possess; (t) CuS04 solution"
conc. H2 S04 ? sOdium potaSsium tartrate or Rochelle salt, red-brown; {u)silver
(~How is meta-formaldehyde, obtained from mirror; (v) phenol; (w) H 2/Pd - BaS04 ; (x) alcohols,alkanes; (y)
formaldehyde? acetone; (z) iodoform test. ' '
2. (a) False-gives tertiary' alcohol; (b) True; (c) True; (d) True;
ANSWERS (e) True; (f) False---only aldehydes reduceTollens' reagent;
(g) FalStl-'-ODly by thosewmch have a-hydrogen a~m; ,
1. (a) aldehyde (except HCHO); (b) formalin; (c) biological and (h) False-only by those which do not have a-hydrogen;
anatomical; (d) HCHO, NH3; (e) CnH2nO; (f) condensation; (i) True; (j) False-both give iodoform test; (k) True; (I) True;
(g) Rosenmund's reaction; (h) Clemmensen's IJ!3ction; (i) pink; (m)True; (n)"True; (oiFalse-shows,tautomerism; .
(p}False-:-gives formaldehyde; (q) True; (r) False-metameI1!; (s)
G.R.B. Organic Chemistry (or Competitions
FaIse-do not restore pink colo.ur; (t) False-act as reducing (viii) (A) CH3CH=CH 2; (B) CH 3CHBr-CH 2Br;
ageiltssince tbey theD)selves can be oxidised; (u) True; (v) False; (C) CH 3C==CH; (D) CH 3COCH 3 _
(w) True; (x) True; (y) Fals~hloral is -more reactive than (ix) (A) (CH3hC(OH)CN; (E) (CH 3hC(OH)COOH;
acetaldehyde; (z) False-converts into CH 3CH=CJ:ICOOR (C) H1C=C-COOH; (D) HOCH1-CHCOOH '
3. (i) (A-6); (B-5); (C-7); (I}-'--l); (B-2); (F-'---8); (0-4); (B-3). 1 1
(ii) (A-4); (B-5); (C-7); ~l); (E-3); (F-2); (G--6); CH3 CH 3
(H-3) -
(x) (A) CHlCH2CHiCH-CH2COOC2Hs;
4. (i) (CH 3CHOh, Paraldehyde; (ii) HCOOH; Formic acid;
1
(iii) HCOONa (sodium foimate)and CH30H (methyl alcohol); OH
(iv) (C~)6N4' Hexamethylene tetramine; (v) C6H3(CH3h, (E) CH3CH2CH1COCH2COOC1Hs;
Mesitylene; (vi) (CH3hC(NHz)CH2COCH3. diacetone amine;
(C) CH3 CH2CH Z CH2COOC2H S ;
(vii) CHI3 (iodoform), CH 3COONa (sodium acetate);' ,-'
(viii) CH)CH(OH)OS02Na, bisulphite addition compound of . ""-/
aWUlldehyde; (ix) CH3COOH (acetic acid) and Ag (silver);
(x) CH3CH=NOH, oxime;. (xi) R-CH() + HCI;
/c"b
o - . A 1
H2C--CH2
II
(xii) (CH3l3C;-C-CH3; (D) CH 3CH 2CH z CH 2CH 20H ;
(xiii) H2C=CH- -CH3; ~(xiv) CH3CH2CHiCHO;
rr ""-c/
0' :
(xv) CH3CH z ?H-CHO;
.
- /"0
1 ' 1
H 2C--CH2
D
OD
(E) CH3CHzCH2C-CHzCH20H
~
(xi) (A) CH3COOH; (E) CH3COCI; (C)CHlCHO;
(D) CH l CHOHCH 3
0
3
- OH
, I, ' , (xiv) , (A) Conc. H2 S0 4 ; (E) (Mesitylene)
'(v), (A) CH 3CHz?H-;-Ca-CN ; H3~CH3
, CH 3
. , OH' '. "
or (A) Dry HCI; (E) (CH3)zC=CH-C-CH=C(CH3h
~
_ (B) CH3~H2?H~ b~~CHZ~2 (Pborone)
. CHO
(xvii) (A) CH3 -CH-CN; (B) CH 3 -CH-CHO .
I I ~ .", . I..fN.. 'DiI.NaOH
CH 3 · CH 3 (vii) -Qr-CH2----SH=O + H-HC~ II
(v)b>d>~>o
OH CH3 .
~L~~H-C~·
~15 II~ [Hint: More is the angle strain in cyclic ketones, more is its
CH2CH3 0
3-Hydroxy-2-methyl-l,3- diphenyl pentan-I-one . reactivity for nucleophilic addition reactions.]· .
G.R.B.
)'" CH 3
. ~ I· OW· 5 4. 3 2 I
20. (1) CH3CH2CHO + HHC'-CHO ~ CH3 CH 2-CH-ZH-CHO
Propanal Propanal ,I,
(Electropbile) . (Nucleopbilej . ,OH . H3
3 -Hydroxy -2-methylpentanal
Propanal acts both aselectrophile as well as nucleophile. ,
(il) cH3CH2CH&:"HH(:---':"CHO OH-) tH3 tH2-~H-tH-tHO
Propanal I '. I I
(EI~pbile)' CH 2CH 3 ' OH CH2CH3
~~I 2-Ethyl~3-hydroxypentanal
, (Nucleopbile) , ,
Propanai as electrophile and butanal as nucleophile.
,.~ 6 5 4 3 2 '1
(iii) CH3CH2CH2CHO+ HHC-CHO CH3 CH2 CH2-ZH-CH-CHO
Butanal I , ' I
(Electropbile) CH3 fI CH3
Propanal 3-Hydroxy-2-methylhexanal
(Nucleopbile)
Butanal as electrophile and propanal as nucleophile.
, ~ OH- 6 5 4 3 2· 1
(iv) CH3CH2CH2CHO'+HijC-CHO ~ CH3CII2CH2-ZH-CH-CHO
Butanal I " I,
(Electropbile) . CH2CH3 H. CH2CH3
'Butanal 2-Ethyl-3-hydroxybeXanal
(Nucleopbile) ,
Butanal acts both as electrophile as well as nucleophile.
. ~ .
(E) CH 3CHiCH(OH)COOH; (F) CH3-:-CH(COOH)·CH20H]
. .
{Ans. (A) CH3CH2CHO; (8) H2C=CH·CH20H; (C) CH3 CH 2CH(OH)CN; (D) CH3 -CH(CN)CH20H;
! Oxidation ! Oxidation
CH3CH2CH2COOH (CH3hCHCOOH
! NaOH/CaO ,! NaOH/CaO
CH3CH2CH3 CH3CH2CH3 ] , ,
7. An organic compound having molecular formula CsH100exists in two chain. isomers, (A) and (B). ISomer
, .
(A) Undergoes
-,
the ,
Cannizzaro's reaction to give 2,2-dimethyl propanoic acid and2,2-dimethylpropan-l-oI.Compound (B) in the presence of dilute
alkali undergoes aldol condensation to form 3-Iiydroxy-2-propyl heptanal. Give graphic representations of (A) aDd (B).
[ Hint: Isomers have, f~nnula C4H~HO. -
(A) undergoes Cannizzaro's reaction, thus it does not have a-hydrogen. The structure of (A) is (CH3):iCCHO.
CH)
COa(CO)g I
CH3-CH2-CH=CH2 + C() + H2 )'CH3CH2Cl~ifH2CHO + CH3~6CHlCHO
H2 ' H2
CH3CH2CH2CH2CH20H CH)CH2CHCH20H ]
PenhIn -1-01 I '
~
CH)
2-MetbyI buIIm-l-ol
9. An organic COM()Ound (A) having molecular formula CSHIOO can show various properties depending on structures. Draw them if
it:
(a) shows CannizzAro's reaction.
(b) gives iodoform test and converted into isobutyric acid.
(c) reacts with Na and deeolourises Br2 water. It can also show geometrical isomerism. '
(d) reduces Tollens' reagent and has chiral carbon.
(e) is obtained by ozonolysis of3,4-diethyl-3-hexene.
, 0 OHH,," QH
, " ,I I ' , ,I '
I Ans. (a) (CH)hC-CHO; (b) CH3-C-CH(CH3h; (c) CH) -C=C.,-CH2CH3; or CH3CH2 -C=CH-CH);
H
I
(d)CH3-,-CH2CH); (e) CH3CH2-y, y- CH2CH3]
CHO C2HSC2HS '
G.R.B. Organic Chemistry@r Competitions
OBJECTIVE OUESTIOMS
SET I: This set contains ,questions 'with: single correct answer. (a) Cannizzaro's reaction 0
. 1. The general formula of both aldehydes and ketones is: (b) Rosenmund' s reaction 0
(a) Cn H 2n +2 0 0 (b) Cn H 2n O .0 (c) Haloform reaction 0
(c) Cn H 2n - 2 0 0 (d) Cn H2n+40 . 0 (d) Clemmensen's reaction 0
14. At room temperature, formaldehyde is:
2. The grouping )CO is Rresent in:
(a) a gas 0 (b) a liquid D
(a) ethers 0 (b) alcohols 0 (c) a solid 0 (d) not known D
(c) ketones 0 (d) rione of these 0 15. Formalin is the commercial name of:
3. Aldehydic group can occur: '[MHCET (Med.) 2007]
(a) anywhere in the carbon chain 0 (a) formic ac~d D
(b) in the middle of carbon chain 0 (b) fluoroform D
(c) only at the second carbon atom of the chain 0 (c) 40% aqueous solution of methanal D
(d) only at-the end carbon atomofthe carbon chain O. (d) paraformaldehyde D
4. The carbon atom of the carbonyl group is: 16. The reagent with which both acetaldehyde and acetone react
(a) sp-hybridizedO (b) sp2 -hybridized 0 eaSily is: . - '
(c) sp3-hybridized 0 (d) dsp2_hybridized 0 (a) Fehling's solution 0 (b) Grignardreagent 0
5. When acetylene is passed through .diL H2S0 4 in the (c) Schiff's reagent 0 (d) Tollens'reagent D
17. A compound that gives a positive iodoform test is:
presence of HgSO,., the compound formed is:
(a) pentan-I-ol 0 (b) pentan-2-one D
(a) C2Hse:f:l 0 (b) acetone 0,
(c) pentan-3-one 0 (d) pentanal D
'(c) CH 3CHO 0 (d) carbide'ofHg 0
18. 2HCHO + NaOH -----7 CH30H + HCOONa
6. Aldehydes are frrst oxidation products of:
(a)' primary alcohols 0 (b) secondary alcohols 0 The abpve reaction is ,known as:
, (c) tertiary alcohols 0 (d) monohydric alcohols D' (a) Wurtz reaction 0 (b). Rosenmund's reaction D
7. Isopropyl alcohol on oxidation fohns: (c) Frankland reaction 0 (d) CannizZaro'S reaction D
(a) acetone 0 (b) ether 0 19. An aldehyde on oxidation gives:
, (c) acetaldehyde 0 (d) ethylene 0 ' (a) analcohol 0 (b) an· acetone D'
8. Dry heating of calcium acetate will give: ' - (c) an ether 0 (d) an acid D
, -[AFMC 2097; CMC Ludbiana (Meel.) 2008) 20. The compound that will not give iodoform test on treatment
(a) CH3COOH 0 (b) CH3CHO 0 with alkali and iodine, is:
(c) C2H6 . 0 (d) 'CH3COCH3 0 (a) acetone . 0 (b) ethanol. D
9. When a mixtUre of calcium acetate and calcium formate is (6) diethyl ketone 0 (d) isopropyl alcohol D
heated. It yields: 21. Main product(s) of the reaction is/are:
(a) acetone 0 (b) acetaldehyde 0 H 3 C",,- H
(c) formic acid .0 (d) acetic acid 0 /C=O~?
H3 C/ Pd
10. When propyne is treated with aqueous sulphuric acid in
, presence of mercuric sulphate, the major product is: (a) CH 3COOH+ H2 0 (b) CH3CH2COOH D
(a)propanal 0 (c) CH3 CH(OH)CH 3 , 0 (d) CH3CH20H . D
(b) propyl hydrogen s u l p h a t e D 22. Tollens' reagent is:
(c) propanol' 0 (a) alkaline mercuric chloride D
(d) acetone D (b) alkaline potassium permanganate D
11. Which of the following compounds, is oxidised to prepare (c) ammoniacal silver nitrate D
ethyl methyl ketone? (d) ,ammonium citrate 0
(a), Propan-2-o1 0 (b) Butan-I-ol 0 23. When dihydroxy acetone reacts with mo4 , the product
(c), Butan-2-o1 '_"'_ 0 (d) Tert. butyl alcohol 0
is/are: 'InPMER (Med.) 2008)
12. When but-2-yne is treated with dil. H2S04/HgS04, the
(a) HCHO 0 (b) HCHO and HCOOH D
product formed "is: (c) HCHO and C02 0 (d) HCOOH 0
. (a) butan-I-ol o (b) butan-2-o1 o 24. Schiff's reagent is:
(c) acetone o (d) butanone o
13. ~he reaction, (a) magenta solution decolourlsed with sulphurous acid 0
(b) magenta solution decolourised with chlorine D
RCOCI + H2 - - - - ' - - \ > RCHO + HCI (c) ammoniacal cobalt chloride solution 0
iscaJled: (d) ammoniacal manganese sulphate solution 0
Aldehydes and Ketones
(a) acetalde,hyde o (b) isopropyl alcohol o (a) ethyl iodide 0 (b) ethyl alcohol 0
(c) acetone o (d) ethyl alcohol o (c) methyl alcohol 0 (d) methyl iodide 0
48. In the following sequence of reactions, the end product is: 59. Paraldehyde is formed by the polymerisation of:
[CPMT2004]
CH 3CHO HCN) (A) H 20 ) (B) (a) ,CH3CHO 0 (b) HCHO 0
(c) CH30H 0 (d) (CH3 hCO 0
(a) CH3COOH 0 (b) CH3CHOHCOOH 0
60. Which of the following is used as a hypnotic? [AFMC 2005]
(c) CH3CH2NH2 .0 (d) CH3CONH2 0
(a) Paraldehyde 0 (b) Metaldehyde 0
49. In the following sequence of reactions, the end product is: .
(c) Acetaldehyde 0 (d) Formaldehyde 0
CH CHO Condensation) (A) Dehydrating agent) (B) 61. The enolic form of acetone contains:
3 Mild alkali Heat
(a) 9 sigma bonds, I pi bond and 2 lone pairs 0
(a) aldol o
(b) crotonaldehyde . 0 (b) 8 sigma bonds, 2 pi bonds and 2 lone pairs 0
(c) paraldehyde 0 (d) metaldehyde' 0 (c) 10 sigma bonds"1 pi bond and I lone pair 0
is
50. Which of the following an example of aldol condensa- (d) 9 sigma bonds, 2 pi bonds and I lone pair 0
tion?
62. The formation of cyanohydrin from a ketone is an example
(a) 2CH 3CHO NaOH(dil.» CH3CHOHCH2CHO 0 of: [CET (J&K) 2007; JEE (WB) 2008]
(b) HCHO ~aOH(dil.» CH30H 0 (a) electrophilic addition 0
(b) nucleophilic addition 0
(c) C6HSCHO+ HCHO NaOH(dil.» C6HsCH20H 0 (c) nucleophilic substitution 0
(d) electrophilic substitution 0
(d) C~HsCHO NaOH(conc.» C6HsCH20H . 0
63•. Paraldehyde is used as a:
51. Formaldehyde can be distinguished from acetaldehyde by
the use of: [UPSEAT 2004]
(a) medicine 0 (b) poison 0
(c) polymer 0 (d) dye 0
(a) Schiff's reagent 0
(b) Tollens'reagent 0 64. A compound (A) has molecul8l' fonriula C2C130H. It
(c) Fehling's solution 0 reduces Fehling's solution and on oxidation gives a
(d) Iodine in presence of base 0 monocarboxylic acid. (A) is obtained by the action ofCl 2 on
52. Which compound does not react with PCI s ? ethyl alcohol. The compound (A) is:
(a) CH3CHO 0 (b) CH3COCH3 0 (a) chloroform . 0 (b) chloral 0
(c) HCHO 0 (d) C2HSOH 0 (c) trichloro ethanol 0 (d) . trichloroacetic acid 0
53. Diacetone alcohol is obtained from acetone by the use of: 3 3
. (a) conc. H2S04 0 (b) Ba(OHh 0 65. Thecompound H C©CH
. . is a condensation' product. It
(c) dil. H 2S04 . o (d) dil. NaOH 0
54. Which of the following reactions is a condensation CH 3
reaction? . is obtained either by treating 3 molecules of acetone witti
(a) HCHO ---4 Paraformaldehyde 0 . conc. H 2S04 or passingpropyne thr~)Ugh a red-hot tube.
(b) CH3CH0---4Paraldehyde 0 Theproduct is:
(c) CH3COCH3 ---4 Mesityl oxide 0 (a) phorone 0 (b) . diacetonyl alcohol 0
(d) H2C=CH2---4Polyethylene 0 (c) mesityloxide 0 (d) t;nesitylene 0
55. Which of the following would undergo aldol condensation? 66. A compound (A), CsHlOo, forms a phenyl hydrazone and
(a) CH3CHO 0 (b) CCl 3CHO 0
gives negative Tollens'. and iodoform testS. The compound
(c) HCHO 0 (d) (CH 3hCCHO 0
on reduction gives n~penflm:e. The compound (A) is:
56. Methyl ketones are characterized through the:
[AMU2002]
(a) ToIiens'reagent 0 (b) iodoform test 0
(c) Schiff's test 0 (d) Benedict'sreagent 0 (a)' pentanal o (b) pentan-2-oneO
57.· Treatment of propionaldehyde with dB. NaOH gives: (c) pentan-3-one o (d) amyl alcohol 0
(a) CH3CH2COOCH2CH2CH3 0 67. The product Z in the series is:
(b) CH3CH2CHOHCH2CH2CHO 0 . . H'-'-l' Na CO
H2 C = CH2 ~X ywvyslS >Y 2 3 )Z
(c) CH3CH2CHOHCH(CH3)CHO 0 12 (excess)
(d)CH3CH2COCH2CH2CHO .0
. (a) C2HsI 0 (b) C2HsOH 0
58. Formaldehyde gives an additive product with methyl
(c) CHI3 0 (d) CH3CHO 0
magnesium iodide which on aqueous hydrolysis yields:
68. Ifformaldehyde and KOH are treated together, we get:
[BHU2005]
(a) methane o
(b) methanol . 0
(c) ethyl acetate 0 (d) acetylene [j
Aldehydes and Ketones
89. A natural compound (X), C4HS02, reduces Fehling's 99. If pentan-2-one is reacted with NaBH4, followed by
solution, liberates hydrogen when treated with sodium metal hydrolysis with D 20, the product will be :
and gives a positive iodoform test. The structure of (X) is: (a) CH3CD(OD)CH2CH2CH3 0
(a) CH3CHOHCH 2CHO 0 (b) CH)CD(OH)CH2CH2CH3 0
(b) HOCH2CH2CHO 0 (c) CH3CH(OH)CH2CH2CH3 0
(c) CH3COCH2CHO 0 (d) CH3CH(OD)CH2CH2CH3 0 "
(d) CH3COCH 2CH 20H 0 100. Aldol condensation between. following compounds,.
/OR followed by dehydration gives methyl vinyl ketone:
90. Compounds of general fontmla, ")C, are called: (a) fOrfnaldehyde and acetone . 0
. '" "OR
(b) formaldehyde and acetaldehyde 0
(a) diesters o (b) acid anhydrides o (c) two molecules of acetaldehyde 0
(c) hemiacetals o (d) acetals o . (d) two molecules of acetone 0
91. In the reaction, 101. Aldol condensation will not take place in:
(CH3 h C~O + X ~ ( CH3 h C(OC2H S h + HCOOC 2H s, (a) HCHO 0 (b) CH 3CH2CHO 0
Xis: (c) CH3CHO 0 (d) CH3COCH3 0
(a) ethyl oxalate 0 (b) propan-2-01 0 102. In the reaction, CH3CHO+ HCN-----+CH3CHOHCN, a
(c) ethylorthoformate 0 (d) none of these . [J
chiral centre is produced. The product is:.
92. Major product obtained when acetone is reduced with
(a) meso compound O,(b) laevorotatory 0
MglHg, H+ in neutral or alkaline solution: (c) dextrorotatory o (d) racemic mixture:O
(PET (Raj.) 2003]
103. Which of the given compounds will give positive test with
o Tollens' reagent?
(a) Acetamide 0 (b) Acetaldehyde 0
(c) Acetic acid 0 (d) Acetone 0
(b) CH3CH2CH3 o 104. The haloform reaction of acetone with sodium hypobromite·
(c) CH3CHOHCH3 o yields:
Cd) (CH3hC-CH2COCH3 o (a) acetic acid 0 (b) propio~ic acid o
I (c) acetaldehyde 0 (d) isopropyl alcohol o
OH 105. Which is the best solvent?
93. During reduction of aldehydes with hydrazine and potas- (a) HCHO 0 (b) CH3CHO o
sium hydroxide, the first is the formation of:· (c) CH3COCH3 0 (d) CH3COOH o
(CBSE (Med.) 2002] 106. When formaldehyde is treated with ethylamine, it gives:
(a) RCH-NNH 2 0 (b) RCONH2 0 (a) ethyl alcohol 0 (b) propionaldehyde 0
(c) RCH NH 0 Cd) R-C=N 0 (c) dimethylamine 0 (d) ethyl methylamine 0
94. Acetaldehyde' and ethyl alcohol reacts in presence of dry 107. When formaldehyde is treated with methanol in presence of
HCl gas. The product obtained is: dry HCI gas or fused CaCI 2, it yields: .
(a) CH3CH 2CH20H 0 (a) acetaldehyde. 0 (b) mercaptal o
(b) CH 3 -CH(OH}-CH 3 0 (c) methylal 0 (d) dimethyl ether o
(c)CH3 -CH(OH}-C2HS 0 108. Formaldehyde is used:
(d) CH 3CH(OC2H s h 0 (a) as antiseptic and germicide D·
95. A bad smelling yellow insoluble resin is obtain.ed by boiling (b) for making synthetic plastics and resins o
NaOH solution with: . '(c) for the preservation of biological specimens o
(a) HCHO 0 (b) CH3CHO 0 (d) all of the above o
(c) CH 3COCfl3 0 (d) C2H s COCH3 0 109. Polarization of electrons in acrolein may be written as:
96. Acetals are: . [CBSE (Med.) 2002)
(a) aldehydes 0 (b) ketones 0 8- 8+
(c) diethers 0 (d) hydroxy aldehydes ' 0 (a) H 2 C=CH-CH=O o
97. Which of the following compounds give a ketone with - 8+ .s-
Grignard reagent? (b) H2 C=CH-CH 0 o
(a) HCHO 0 (b) CH3CH20H 0
.s- .s+
(c) CH3CN 0 (d) CH31 0
(c) H 2 C=CH-CH:-O o
.s- .s+
98. Reduction of acetonitrile in presence of SnCI 2IHCI, (d) H2 C=CH-CH=O o
followed by hydrolysis gives: 110. Acetoacetic ester on hydrolysis by boiling with dil. acid
(a) HCHO 0 (b) CH3CHO 0 yields:
(c) CH3CH2CHO 0 (d) CH 3 COCH 3 0
Aldehydes and Ketones 631"
(a) acetic acid 0 (b) acetaldehyde 0 121. In the Cannizzaro's reaction given below,
(c) propanal 0 (d) propanone 0 2Ph-CHO~ PhCH20H + PhCOO-
111. Grignard reagent reacts with (X) to give aldehyde, (X) may
the slowest step is: , [AIEEE 2009]
be:
(a) acetyl chloride 0 (b) acetic anhydride 0 (a) the attack ofOH- at the carbonyl group 0
(c) ethyl formate 0 (d) water 0 (b) the transfer of hydride to the carbonyl group 0
112. Acetone on condensation gives: (c) the abstraction of proton from the carboxylic acid 0
. (a) mesitylene 0 (b) phorone 0 (d) the deprotonation ofPh-CH 20 H ' 0
122. In the following sequence of reactions, the alkene affords
(c) mesityloxide 0 (d) all of these 0
113. A carbonyl compound with molecular weight 86, does not the compoundB. The compound 'B' is: [AIEEE 2008]
reduce Fehling's solution but forms crystalline bisulphite CH3CH=CHCH3
.
~A~B
Zn
derivatives and gives iodoform test. The possible compound
can be: (a) CH3CHO 0 (b) CH3CH2CHO 0
, (a) pentan-2-one and pentan-3-one 0 (c) CH3COCH3 0 (d) CH3CH2COCH3 0
(b) pentan-2-one and methyl butan-2-one 0 123. Among the following compounds, which will react .with
(c) pentanone and pentanal 0 acetone to give a product containing >C=N-?
(d) pentan-3-one and 3-methyl butan-2-one 0 (a) C6HSNH2 0 (b) (CH 3 hN 0
114. Which has minimum reactivity towards nucleophiles? (c) C6HSNHC6HS 0 (d) C6HsNHNH2 0
(a) Butanone 0 (b) Propanone 0 124. In a Cannizzaro's reaction, the intermediate that will be the
(c) Ethanal 0 (d) Methanal 0 best hydride donor is:
oi 0+
115. CH3CH=CHCHO is oxidised to CH 3·-CH=CHCOOH, H H
using oxidising agen~ as:
(a) alkaline KMn0 4 0 (a) o- o (b) 0
- o
(b) K2Cr207/conc. H 2S04 0
(c) ammoniacal AgN03 0
D+o- D+o-
(d) dilute HN0 3 0 H H
116. Propanal on aldol condensation with aqueous K 2C03 gives
mainly: (e) 0 (d) o
(a) 3-hydroxy butanal 0
(b) 3-hydroxy-2-methyl pentanal 0 MeO 02N
(c) 3-hydroxy propanal 0 125. The reagent of choice for the selective reduction of a ketone
(d) 4-hydroxy-4-methyl pentan-2-one . 0 in the presence of an ester is:
117. Which will give a yellow precipitate with iodine and alkali? (a) LiAlH4 0 (b) NaBH4 0
(a) Ethyl methyl ketone 0 (b) Acetophenone 0 (c) H2/Pd-C 0 (d) Na-C 2H s OH 0
(c) 2-Hydroxy propane 0 (d) AU of these 0 126. The 'enol' form of acetone aftertreatrnent withD2O, gives:
118. The product(s) obtained via oxymercuration [PET (Kerala) 2006]
(iIgS04 + H 2S0 4 )of but-I-yne would be: OD 0
(a) CH3CH2CH2CHO 0 I I
(b) CH3CH2COCH3 0 (a) CH3-C=CH2 0 (b) CD3-C-CD3 0
(c) CH3CH2CHO+ HCHO 0 OH OD
(d) CH3CH 2COOH + HCOOH 0 I I
(c) H 2C=C-CH2D 0 (d) D 2C=C-CD3 0
o
I 127. Oxidation of acetaldehyde with selenium dioxide produces:
119. Ketones R-C-R'. Where, R=R'=alkyl group can be (a) ethanoic acid 0 (b) methanoic'acid 0
obtained in one step by: (c) glyoxal 0 (d) oxalic acid 0
(a) oxidation of primary alcohols tJ 128. Which of the following does not give formaldehyde on
(b) hydrolysis of esters o heating or distillation? [PMT (MP) 2000]
(c) oxidation of tertiary alcohols o (a) Formalin 0 (b) Trioxan 0
(d) reduction of acid chloride with alcohol o (e) Paraldehyde 0 (d) Paraformaldehyde 0
120. Among the given compounds, the most-susceptible to 129. The appropriate reagent for the following transformation
nucleophilic attack at the carbonyl group is: [IIT(S) 2000]
(a) MeCOCI 0 (b) MeCHO 0
(c) MeCOOMe 0 (d) MeCOOCOMe 0
. " ~. ::" .
o o OH OH
HO
tr
(a) Zn(Hg), HCI
CHl
o
HO
(b) NH2NH2,OH-
("yCH2CH3 .
,)---J IS:
o
(a)
(c)
/~~
o
II
/CY"
O(b)~
O(d)~
o
.0
o
(c) H2INi o
(d) NaBH4 o OH OR
130. Which of the following has the most acidic hydrogen? '138. A substance C4HlO0 yields on oxidation, a compound
(UT(S) 2000] C4H s O, which gives an oxime and positive iodoform test.
(a) Hexan-3-one 0 (b) Hexan..2,4-dione 0 The original substance on treatment with conc. H2S04
(c) Hexan-2-one 0 (d) Hexan-2,3-dione 0 gives C4HS' The structure of the compound is:
131. Which of the following is correct? [CBSE (Med.) 2001) (SCRA2000]
(a) Reduction ofany aldehyde gives secondary alcohol 0 (a) CH3CH2CH 2CH20H 0
(b) Reduction ofvegetable oil with H2 SO4 gives glycerine OH
,0 I
(b) CH3CHCH2CH3 0
(c) Alcoholiciodine with NaOH gives iodoform 0
(d) Sucrose on reaction with NaCI gives invert sugar 0 (c) (CH3 hC-OH 0
132. Which of the following is the industrial method of (d) CH3CH2-O-CH2CH3
'.,,}
0
preparation of acetaldehyde? , (AMU (PMT) 2009] 139. (CH 3 hCO NaCN )(A) HjO )(D)
HC! t:.
(a) H2C=CH2 + H 20 Pd++) CH3CHO 0 In the above seque~ce of reac~ons, (A) and (D) are:
. [CPMT 2000]
(b) CH3COCI+H2 ~CH3CHO+HCI 0
BaS° 4 (a) (CH3hC(0H)CN, (CH 3 hC(0H)COOH. 0
(b) (CH 3hC(0H)CN, (CH3 hC(0H)2 . 0
SnC! ' H 0+
(c) CH3CN---4CH3CH NH~CH3CHO 0 (c) (CH 3 hC(0H)CN, (CH 3 hCHCOOH 0
HC! (d) (CH3hC(0H)CN, (CH 3 hCO 0
(d) None of the above ' 0 140. Aldol condensation will not be observed in: (GATE 2001]
133. Acetone, formaldehyde and' acetaldehyde can be distin- (a) chloral 0 (b) phenyl acetaldehyde 0
guished when treated with:, [CPMT 20021 (c) hexanal 0 (d) nitromethane 0 '
(a) H2NNH2 0 (b) NH3 0 . 141. The most reactive compound towards formation of
(c) NH20H 0 (d) C6HsNHNH2 0 cyanohydrin on treatment with KCN followed by acidifica-
134. When three molecules of acetone condense in presence of tiotiis: [GATE 2001]
dry HCI, the product formed is: [MGIMS (Wardha) 20031 (a) benzaldehyde 0
(a) mesityloxide 0 (b) glyoxal 0 (b) p-mtrobenzaldehyde 0
(c) mesitylene 0 (d) phorone 0 (c) phenyl acetaldehyde 0
135. Ozonolysis of C1H l 4 gave 2':'methyl pentan-3-0~e. The (d) p-hydroxy benzaldehyde 0
alkene is: (DPMT 2000] 142. A mixtur~ of benzaldehyde and formaldehyde on heating
(a). 2-ethyl-3-methyl but-I-ene 0 . withaqueousNaOHgives:. [lIT (S) 2001]
(b) 2-methyl-3-ethyl but-3-ene 0 (a) benzyl alcohol and sodium fonnate . 0
(c) 2,5-dimethyl-3,4-diethyl h e x - 3 - e n e O (b) sodium benzoate and methyl alcohol 0
(d) 2-methyl-3-ethyl but-I-ene 0 . (c) sodium benzoate and sodium formate 0
136. In th~ reaction, (d) benzyl alcohol and methyl aloohol 0
CH3CHO+HCN~CH3CH(0H)CN HOH)
143. Which of the following reacts with NaOH to produce an
acid and an alcohol? [MGIMS (Wardha) 2001]
. CH3CH(0H)COOH
(a) HCHO 0 (b) CH3 COOH 0
an asymmetric centre is generated. The acid obtained will
(c) CH 3 CH2COOH 0 (d) C 6H s COOH 0
be~ [UPSEE (Engg.) 2007; JCECE (Med.) 20081
144. Which of the following is not correctly matched?,.
(a) (L)-isomer 0 [SCRA2001]
(b) (D)-isomer 0
(c) 20% (D) + 80%(L)-isomer 0 Clemmensen's )""-CH
Reduction ,/ 2
o
(d) 50% (D) + 50% (L)-isomer 0
137. Which of the following will be most easily dehydrated in Wolff-Kishner )""-CHOH
Reduction ,/
o
aCidic conditions? . (llT (S)2000]
Aldehydes and Ketones 639.
149.
addition product with sodium bisulphite solution?
(a) CH20
(c) C6Hs CHO 0 (d) CH3CHO
[CET (J&K) 2009]
0 (b) C6HsCOCH3
(a) 3° alcohol o
(b) 2° alcohol
o (d) no reaction
(AFMC2004]
0 ~OH o
(c) ether 0 (d)Ll (e) o
150. The correct order ofreactivity of PhMgBr with, CH3
o 0 0
158. The increasing order. of the rate of HCN addition to
II II II compoundsA-Dis: [AIEEE2006]
Ph-C-Ph CH3-C-H CH3-C-CH3 is:
(I) (II) (III) (A) HCHO (B) CH3COCH3 (C) PhCOCH3 (D) PhCOPh
(lIT 2004] (a) A<B<C<D 0 (b). D<B<C<A 0
(a) I>II>ill o
(b) ill> II> I o 00 D<C<B<A O~ C<D<B<~ 0
(c) II>ill>I o
(d) I>ill>II o 159. Which of the following. compounds is obtained when
151. Which one of the following can be oxidised to the acetone is reacted with HCN? • [CET (Gujarat) 2006]
corresponding carbonyl compounds? [CBSE (Med.) 2004] (a) (CH 3 hC(OH)NC 0 (b) CH3CH2 CH-CN 0
(a) 2-Hydroxy propane 0 . I,
(b) Ortho nitrophenol 0 OH
G.R.B. Organic Chemistry for Competitions
°I
(c) CH3CHzCH2-C-CH3 0
(a) FeCl 3
[DeE (Engg.) 2007)
0 (b) Tollens'reagent 0
(c) NaHS0 3 0 (d). 2,4-DNP 0
(d) (CH3hC=O 0 174. On reaction with hydroxylamine, aldehydes produce:
166. The smallest ketone and its next homologue are reacted with [CET (J & K) 2007)
NH20B to fOnn oxime: [UT 2006] . (a) ketoxime 0 (b) hydrazone 0
(a) two different oximes are formed 0 (c) semicarbazone 0 (d) aldoxime .0
(b) three different oximes arefonrted 0 175. Aldehyde with NH2' NH 2 forms: [BCECE (Med.) 2008]
(c) .two oxime!! are optically active 0
(a) aniline' 0 (b) hydrazones 0
(d) all oximes are optically active 0
(c) nitrobenzene 0 (d) none of these 0
167. The product formed in aldol condensation is:
[CBSE (Med.) 20071
Aldehydes and Ketones
176. The most suitable reagent f~r the conversion of primary (a) alkane 0 (b) alkene 0
al(X)hol into aldehyde with the same number of carbon is: (c) alkyne 0 (d)' ketone, ' . ci
" .[PET (Kerala) 2007] 183. Which of the following pathways produ~es 2-hexanone?
(a) acidifiedK2Cr207 0 , , [PMT (Kerala) 2008]
(b) acidified KMn04 0 (i) I-Hexyne is treated with H 2S04, HgS04 and water
(c) alkaline KMn04 0 (ii) 3-Methyl-2-heptene is treated with 0 3 followed by
(d) pyridinipm chlorochromate 0 , hydrolysis .
(e) cr0 3 0 (iii) n-Butyl magnesium brorriide reactS .with acetaldehyde
177. Which of the products is formed when acetone is reacted followed by hydrolysis and then chtomic acid oxidation
with barium hydroxide solution? [AFMC 2008] (iv) Hydroboration oxidation of l-hexyne
o CH3 (a) (i), (ii) and (iii), 0 (b) (i) and (iQ only 0
I I (c) (i) and (iii) only '. 0 (d) (i), (ii) and (ivf 0
(a) CH3-C~CH2-C-CH3 0 . (e) . all the four methods ', 0
, I 184. In a reaction RCHO is reduced to RCH 3 using amalgamated
OH
zinc and concentrated-Hel and warming the solution. 1(he
reaction is known as: [nCE 2009]
o (a) Meerwein-Ponndorfreaction 0
. (b). Clemmensen's reduction 0
, (c) Wolff-Kishner reduction .0
. (d) S~hif'f's reaction 0
o LiAIH '. '. -
I o 18S. CH 3 COOH 4 ) (X) Cu )'(Y) dilute >(Z),
(c) CH3-C-CH-CH-CH3 . . 300"C . NaOl:l .
I I In the above reaction; (Z}is: [CET (Karnataka) 2009]
OH CH3 (a) aldol; . 0 (b) ketol 0
OH oil, (c) 'acetol 0 (d)lmtanol " . ' 0
I I 186. The synthesis of crotonaldehyde from acetal~hyde is an
(d) CH3-C--C-CH3 o example of .... ;. reaction: [EAMCET 2009]
I I .
CH 3 CH3
(a) nucleophilic addition 0
(b) elimination 0
1.78. CH3CH2C==N --4 CH 3CH 2CHO (c) electrophilic addition 0
the compound Xis: [AIIMS 2008] (d) nucleophilic addition elimination. ' 0
(a) H21Pd-BaS04 IJ (b) SnCI 2IHClIH20,boil 0 187. In which of the following reactions n~w ~bon-carbon
bond is not formed? [JEE (WB) 2009]
(c) LiAlH4/ether 0 (d) NaBH4/etherIH30+ 0
(a) Canilizzaro reaction 0 (b) Wurtz reaction 0
179. Reduction of aldehydes and ketones into hydrocarbons
(c) Aldol condensation 0 (d) Friedel-Ctaf\s reactio~ ci
using hydrazine and sodiuni ethoxide is called:
188. Compound (A) undergoes Cannizzaro reaction : and (B)
. [BHU (Mains) 2008]
uildergoes positive iodofonn test. Therefore, [DPMT 2009]
(a) Clemmensen reduction 0 (a) A = Acetaldehyde; B = l-Pentanal. .' 0
(b) Cope reduction 0
(b) A = C6HsCH2CHO; B = 3-Pentanone 0
(c) Dow reduction 0 (c) A = Fomialdehyde; B== 2-PentanoIk . '. 0
. (4) Wolff-Kishner reduction 0
(d) A =;;-Propiona.Idehyde; B=Fp'entanol 0
i80. 3 ..Hydroxy butanal is formed when X reacts with Yin dilute .
189. The compound which is not formed duritig the dry
. Z solution. What are X, Yand Z?·· [AIIMS 2008] .
distillation ofa mixture of calcium fonnate arid-calcium
X Y Z acetate is: . '.' [CET(Karnataka) 2009]
(a) CH3CHO (CH3 hCO NaOH 0'
(it) propanal ' 0 (b) propanone . 0
(b) CH3CHO CH3CHO NaCI 0
(c) ethanal. 0 (d)' methanal '. 0
(c) (CH3hCO' (CH3 hCO HCI 0 190. Aldol condensation does not occur b¢tween: .[DPMT 2009]
(d) CH3CHO CH3CHO NaOH 0 .' (a) two·different aldehydes' , I . ' ,., . - 0
1~1. A Wittig reaction with an aldehyde gives: [VITEEE 2008]
(0) two different ketones 0
(a) ketone 0 (b) a long chain fatty acid 0
(c) aD aldehyde and ketone 0
(c) olefin compound 0 (d) epoxide .0
(d) an aldehyde and an ester '0 '
182. A strong base can abstr.act an a-hydrogen from:
, [CBSE (Med.) 2008] 191. Which factor/s will incieas~ the reactivity of>e=Ogroup? :
[AMU(Engg.) 2009]
G.R.B. Organic Chemistry fOr Competitions
(i) Presence of a group with positive inductive effect (c) Both can be reduced into alcohols 0.
\. (ii). Presence of a gtoup with negative inductive effect (d) Both undergo aldol condensation 0.
(iii) Presence oflarge alkyl group 200. Which are mixed ketones?
(a) only (i) . 0. (b) only(ii) 0. (a) Propan-2-one 0. (b) Butan-2-one 0.
(c) (i) and W) 0. (d) (ii) and (iii) 0. (c) Pentan-3-one' 0. (d) Pentan-2-one 0.
192. The major oi:ganic product fonned from the followiitg 201. CH2Cl2 on heating with NaOH solution gives:
reaction . (a) CH30H 0 (b) HCOONa o
0. (i) CH3NH 2 ' //0
'r-(. .
(ii) LiAlH4 (iii) H20
) (c) HCHO 0 (d) CHz,
........OH
0.
(c)
K
NHCH3
OH
0.
.
(d)
OH
X·
. NHCH 3
o
(a) alkenes .
( c) ketones
0. (b) aldehydes
0 (d) 'alkynes
204. Which of the following compounds win give positive
0.
d
193. Which· of the following reaction will· not result in the iodofonn test?
formation of carbon-carbon bonds? .. (a) C61:1sCOCH3 0. (b)CFhmC2HS 0
[CBSE (Med.) Prelims] 2010 . (c) CH3CHOHC 2H s 0 (d) CH3COOCOCH3 0.
(a) Reimer-Tiemann reaction' 0. i05. Grignard reagent can give aldehyde with:
(b) Cannizzaro reactic;)fi 0. (a) ethyl formate . 0. (b) ethyl 0t:tho formate 0.
(c) Wurtz reaction 0 (c) methylcyanide 0. (d) hydrogen cyanide 0.
(d) Friedel-Crafts acylation 0 206. Which of the following reagents react in a same manner
194. Which of the following statements is not correct? with HCHO and C 6H s CHO?
(a) NaOH 0. (b) NH3 0.
[DUMET 2010]
(c) HCN 0 (d) Fehling's solution 0.
(a) Aldehydes and ketonescontain polar carbonyl group 0 . ·207. The names of the compound, CH3CH2CH2CH2CHOare:
(b) Aldehydes and ketonesuridergo nucleophilic .addition
. 0. (a) butyraldehyde 0. (b) 4-methyl butanal 0
(c) valerilldehyde 0 (d) pentanal 0
(c) Aldehydes and ketones undergo electrophilic
208. Which of the following methods can be used to prepare
. substitution 0
aldehydes?
(d) Lower members of aldehydes and ketones are soluble
(a)' By the reduction of acid chlorides in presence ofPd or
in water due to hydrogen bonding 0 / ~ 0.
SET n: This set contains. the questions. with· .two or more correct (b) By passing the vapours of fatty acids with formic acid.
answers. '0.
195•. Which compounds undergo Cannizzaro's reaction? (c) By interaction of formic ester with Grignard reagent 0.
(a) Methanal 0 (b).Ethanal 0. (d) By the reduction of alkyl cyanide with SnCl2IHCI and
(c) Propanone 0 (d) Benzaldehyde 0 hydrolysis 0.
196. Reaction of Grignard reagent with ...... gives alcohol. . 209; Ketones can be prepared by:
(a) carbon dioxide 0 (b) formaldehyde· 0. ·(a). heating calcium propionate with calcium formate 0.
(c) acetaldehyde 0. (d) acetone 0 (b) dry distillation of fused calcium acetate 0.
. 197. Which Rf the following reagents react in a same manner (c) hydrolysis ofpropyJidene chloride with alkali 0.
with HCHo~ CH3CHO and CH3COCH3? . (d) action of dialkyl cadmium on acid chloride 0
~a) HCN O.'(b) NH20H . 0. 210. Which of the following compounds will give Fehling's
.. t(c) Schiff's reagent o (d) NH3 0. solution test?
198. ~ plastic bakelite is obtained from:
.' (a) Acetone 0. (b) Benzaldehyde 0
(a) benzene' 0. (b) fOrmaldehyde 0. (c) Acetaldehyde 0 (d) Propanal 0
(c) ammonia . 0 (d) phenol O.'
. 1~9. Which ~tateineDts are correct in the case ofacetaldehyde and 2U; Which of the following compounds will undergo aldol
, acetone? condensation?
(a) Both react with NaHS0 3 0. (a) Acetaldehyde 0
. (b) Both give io,dofonn test 0 (P) Benzaldehyde 0.
:---.,......----------------""'-='=',····~j:»L{
A:..:.l=:::a:!::eh::;.Yt:::d~e~'S~and~Kt~et:lo::o~ne:::.'S:..·_ _- - - - - - _ -_ _ _ _ _
Following questions consist of an Assertion (A) and the 4. (A) Fehling's reagentis a test for all aliphatic aldehydes.
. Reason (R). Use, the following keys to choose the (R) Aliphatic aidehydescan be easiiy oxidised even with
appropriate answer: mild OXidising agents. .
(a) Ifboth (A) and (R) ~e correct and (R) is tb,e correct 5. (A), 2-Metbyl propanalundergoes Canniziaro's reaction.
explanation of (A), ' (R) It has an a-hydrogen atom. '
(b) Ifboth (A) and (R)are correct but (R)is not the correct , 6. (A) Formaldehyde is a planar molecule.
explanation of (A). . , (R) Carbort ato~ in formaldehyde is sp2 -hybnm:zed. '
(c) If (A) is correct but (R) is incorrect. 7; (A) Nitromeibane can give aldol cond.eIlsation.,
(d) If (A) is incorrect but (R) is correct. (R) a-hydrogen of nitromethane is acidic.' ,
1. (A) Carbonyl compounds take part in nucleophiliC addition 8. (A) Chloral hy~te i~ stable." "
reactions. , (R) It is stable due to its high molecular weight., .
(R) These reactions are initiated by nucleophilic attack' at 9. (A) Acetaldehyde does not show aldol condensation.
the electron deficient carbon atom. (R) CompoundS havingatleast ()ne a-hydrogen give aldol
2. (A) Primai-Y alcohols can be easilyoxidisedto aldeh~es. " condensation. . .
(R) Aldehydes are prone to further oxidation to carboxylic 10., (A) Loweraldehydes and ketones are solubleiQ water'but
acids, the' solubility. decreases as, the . molecular mass
3. (A) The addition of ammonia derivatives on carbonyl
increases. . ' ,.' j . ,
compounds is carried in weakly acidic medium. (R) Distincti5)D .between aldehydes and ketones can be
(R) hi weakly acidic medium, attacking nucleophile-is also fuade qy'Toilens' reagent;
protonated. ' '
G.RJ,J. Organic Chemistry (ot Competitions
;
, ,
,~ .
Aldehydes and Ketones
(iv) (CH3hCCH2-C-CH3
i (i) Br2, NaOH" (CH3hCCH2COOH +' CHBr3
(ii) H+ 3,3-Dimethyl butanoic acid Bromofonn .
(v)
°
Q~,c . ., • +HCI]
o
2-Benzyl cyclohexane-l,3-dione
/-. '
OH 'CH20H CH20H
, , Pent8 erydaitol
3. Complete the following reaCtions:
o 6
Cl
.
'
•
;' ~~.",,',:' .T:':::s~{,~:,;~:t~:,,'. :;';
i§~~~~~~~~~~.__________~--------------~-------------------G-.R-.-B-.O-~~a-nl-c-C-h-e.m-i-sby~fi_or_C_o_m~w_e_nn_o __
m
~~J15 0
Caprol\lCtum
, Nylon-6]
. .
4. Compldte the folloWing reactions: ."
o
(Ans•. (A) OBr, .
6. Complete the followingteactionsi ..
. . 0
. . I .
(b) @-CHO+ CH3 -C~ -""=-+ (B)
. . . ' . - ~ o
;-;:::\\ II . ;-;:::\\
(Ans. (a) (A) @ - C H CH-C7~H3; . (b) (9) ~CH . CH-C~]
..,. Identify (A), (B), (C), (D) and (E) it) the following reactions:
. '( (b) <0 >-CH 2CHO '. NaO» .) (C). A, NaHS04 ) (D) H2/Ni) (E) .
[An,.
.
(b)(C) 0-'
.--''. 'CH2-CH-CH
.
I I
OH CHO
-- -o' ;
.' ;' OH .' OH "
(D) (}-CHz-CH=f-<
CHO'
) ; (E) 0-'
--. CH2-CH2--'--CfI -o']
1--
CH20H
Aldehydes and Ketones ·647
. ~ .'1 (F)
Cl 0 H
lAns. (A)
6 CH3·
(B) 0 (C) 25 , . (D) c5
I
(E)
/
CH2
I
CH
c=o
2
CHO
I
.CH 2
(F)
210B
9. Provide a detailed reaction mechanism for the following;..
Using (i) 1 equivalent of1I2 with Pt, (ii)H2 with Raney Ni, (iii) NaBH4/CH30H?
(Hint: See the text for reduction. ]
11. In the reaction,
, NaNH 2
H-C=:C-H . )A
12. Match the List I with List II and select the correct answer
from the given codes: o
List I List II
(Reaction) . (Reagent/catalyst) .
• -- A. Cannizzaro reaction (i) SnChlHCI . .
B. Stephen's reaction' '(ii) NaOH
C. Clemmensen reduction (iii) ZnlHg-conc. HCI ,.
, D. ' Rosenmund's method (iv)P~!BaS~4 ' 15. What is the product formed when cyclohexanone undergoes
, Bm mg xy ene aldol ~ondensationfollowed by heating?
Codes:
(a)
(b)
(c)
A
(i)
(ii)
(iv)
B
(ii)
(i)
(iii)
C
(iii)
(iii)
(ii)
D
(iv)
(iv)
(i)
o
o
o
(a).qD. ~(b)O=p
o
o
o
O(d)W
(d) (i) (iv) (ii) , (iii) OH
'" .~
13. Which bf the following reactions is not correct?
se02 '<'>--r)' o
(a) CH3-CHO ) CHO- cao (glyoxal) o (c) " - ( "--./
(b)cr 0
Se02
~
C( o Plint:
OH
o °
~
0
Cyc1ohexan-I,2-dione
Ill-H
20
, '0,
O=pl
o
16. A carbonyl compoU)ld 'A' reacts with hydrogen cyanide to
form a cyanohydrin 'B' which on hydrolysis gives an
optically active alpha hydroxy acid 'C. 'C gives positive
iodoform test. A,B and C respectively are given by the set:
. H"", ~H H""'cC°H 0
if
(a) HCHO, H',/C""'CN' H/ "COOH
~H5' /OH'
if
(c) C1I3CH2CHo, JC,
R ...r - "CN'
o
o
(c) cr; ,0
~.o
~
.........,. . .. o
o
Aldehydes and Ketones
17. Acetone + A ---+ mrime ofacetone 21. Methyl-n-propyl ketone on oxidation with K2Cr207 and
Acetone + B ---+ diacetone amine . H2S04 gives mainly:
Acetone + C ---+ mesitylene (a) CH3CH2CooH + CH3COOH 0
Acetone + D ---+ isopropylidene chloride (b) CH3CH2CH2COOH + HCooH 0
A,B,C aridDare: (c) CH3COOH + HCooH 0
(a) NH20H,NH3,Conc.H2S04, SOCh 0 (d) CH3CH2CooH + CO 2 + H20 0
(bJ HN02,NH3,Conc.H2S04,PCls 0 22. Structure ofCsHsCl2, which on aqueous alkali hydrolysis
(c) HN02,NH3,Conc.H2S04,Ch 0 gives a product which does not give positive iodoform test,
(d) NH20H,NH3,H2S04,CI2 0 but gives silver mirror test, is:
18. Which of the following is/are example(s) of aldol CI . Cl
condensation? . I I
. OH (a)~.C-C2HS o (b) C6HS-C-CH3 o
LJ -·1 . I.
(a) 2CH3CHO Dil. NaOH) CH3-6H-CH2-CHO 0 CI Cl
CH2Cl
V
(b) 2CH3~C-CH3 Oil. NaOH)
OH
III
0
CH3-C-CH2-C-CH3D
(e) 0
YCI
o
I . CH3
CH3
NaOH(aq.) /OH -H 20
. plint: C6 HsCH2CHCI 2 ) C6HsCH2CH, ---=--i'
(c) 2HCHO I)iI.NaOH)CH30H+HCOOH 0 'OH
(d)C6Hs CHO+HCHO DiI.NaOH)C6Hs CH20H 0 C6HsC1I2CHO
Final product will give silver mirror test but not iodoform
19.. Select the incotrectly matched options: test]
. Zn/Hg 23. Which one ~f the following reagents is used to get spl -
(a) R-CO-CH3 )R-:--CH2-CH3 0
Cone.HCI hybridised carbon atom from-sp2 -hybridised carbon atom?
(Clemmensen reduction) (a) Zn/Hg and Conc. HCI 0
COOH Pyridi (b) Red PIHI 0
/
(b) R"-CHO+CHT-.. ne )
. - 'CooH -H20, -CO2 (c) NH2-NH2/KOH 0
(d) All of the above 0
R-CH-:-CH-CooH (Knoevenagelreaction) 0 24. Aldehyde
(c) R-CHO+N H Cone. H2S04 ) . • A' (C4 HSO) AI-t~rl.-butoxide). B' (ester) HOWH+,
,3 . (330 _ 340 K)
Tlschenko
R - CN+ RNHCHO+N 2 (Schmidt reaction) 0 H3C , , - · H3 C,,-
. / . CH-COOH+ /CH-CH20H
(d) BrCH2COOC2 HS + Zn Dry ether) H3C . . H3C
BrZn -. CH2COOC2Hs (perkin reaction) 0 • A.' and • B' are :
CHO . '.-, H3<\ . H3C" jCH3
20. I· + NaOH -4 Product(s) (a) /'CH-CHO, . /CH-CooCH 2CH, .
CooH H3 C H3 C ~H3
. IdentitY the product(s):
H3C,,- .. . /CH3
o
. CooNa CH20H (b) /CH-CHO,CH3CHCOOCH2CH, 0
(a) I o (b) I o ~C . CH3
CooNa COONa
(c) both (a) and (b) are correct 0
CHO (d) none is correct . 0
(c) both (a) and (b) . o (d) I o 25. An alkene (A) on ozonolysis gives (B) as one of the product,
COONa
(B) can perform Cannizzaro reaction. (A) is :
[Hint : This ~ction involved Cannizzaro reaction hence, two
(a) but-2-ene 0
products are obtained,
CHO COONa CHzOH (b) isobutene 0
1 + NaOH-.-.+ I + I] (c) (CH3hC=C(CH3)2 0
COOH COONa COONa (d) C6HsCH2CH=CH-CH3 .0
G.R.B. Organic Chemistryfor Competitions
..
26. One mole of a hydrocarbon (A) on ozonolysis gives two O-H Q
moles of dicarbonyl compound (A) is : I+ II. +
<a) 0 o (b) 0 0
o
II YT+ I +HOH .
H-C
I
O-H
OH
~H-C-OH+H
(c) f:J o
32. (I)
H-C-H+n ~H-C-H~CH30H+OW]
+
Pd_',.....Ba_S_O--'-4~) R -CHO
R _COCI _ _
Boiling xylene
27. Which of the following alkanes cannot be prepared by the (II) R -CN SnCI 2!HCI) R -CHO
Clemmensen reduction of ketone? HOH
(a) Neopentane 0 (b) Neohexane 0 Reaction (I) and (11) are ...... and ...... respectively.
(c) Both of these 0 (d) None of these 0 (a) Oxo-process, Wacker's process 0
.28. Reaction of acetaldehyde with NH20H will be fastest at (b) Rosenmund's reaction, Stephen's reaction 0
which of the following pH ? (c) Gattermann's synthesis, Stephen's reaction 0
(a) I 0 (b) 7 0 (d) Reimer-Tiemann's reaction, Wacker's process 0
(c) 8 0 (d) 6 0 33. Consider two aldehydes containing a-hydrogens,
. . CHO CHO (I) CH3CH2CHO
< ) (:)
19. Tischenko reaction of gives
(II) H 2C=CH-CHO
The correct statement(s) is/are :
<o~<o> (oQ6>
forms a phenyl hydrazone and gives negative Tollens' and
iodoform test. Compound (A) on reduction gives n-pentane.
Compound (A) is :
(c) o (d) o (a) pentanal 0 (b) 2-methoxy hexanone 0
(c) pentan-3-one 0 (d) amyl alcohol . 0
35. The fmal product' B' in the following sequence of chemical
30. In the reactions : reaction is: .
Zn/Hg CH OH Cn ) A NaOH) B+CH30H
A 3 300.C
Cone.HeI
NH2-NH2 (a) an alkene 0
)C. 0 KOH
B (b) a carboxylic acid 0
(c) an aldehyde 0
Red P/HI
C (d) sodium salt of carboxylic acid 0
423K
36. The fmal product (III) obtained in the reaction,
(a) A is an aldehyde; B is ketone andC is an alkene 0 CHj
(b) A ,B and C are alkenes 0
(c) A,B and C are alkanes 0 I
CH3-C-CHO+ CH3CH2CHO~(I)
OH-
W y-
(Hint: H-C-H+OW-4H-C-H~
I
OH
Aldehydes and Ketones
CH3 (c) 3 2 4 o
I (d) 2 3 4 o
(b) CH3-C-CH=C-CH20H o
I' I
CH3 CH3
CH3
I
(c) CH3-C-CH2-CH-CH20H o
. 1 I
CH3 CH 3 o
. CH3
I o
(d) CH3-C-CH2CH2CH20H o
I .
CH3
37. Which of the following four hydrogens is most acidic? o
0,
_ . (ii) I \ (d) all of the above 0
.
Q J
(i) H
CH2-C-CH2-CH3
.
(iii) (iv)
40. In acidic medium, in presence of conc.
acetaldehyde will give :
OH
H2 S04 ,
I
(a) ( i ) - 0 (b) (ii) 0 (a) CH3-CH-CH2CHO 0
(c) (iii) 0 (d) (iv) 0 (b) CH3-CH-:-CH-CijO 0
(Hint> Hydrogen (ii) will be most acidic because'it is attached to
CH3>C~'C<H
two electron withdrawing groups, i.e., phenyl group and
carbonyl group.] ,
38. Match the List I with List IT and Select the correct answer (c) H b. ) CH
3
.0
from the codes given below the lists:
List I (Reaction) ""C
A. CH3CH=CHCHO~CH3CH=CHCOOH eH0H
B. CH3CH=CHCHO ~ CH3CH CHCH20H CH3 H
C. R-COOH~R~CH20H I I
D. CH3CH2Coa ~CH3CH2CHO 1I-C-0-C-CH3
List IT (Re!lgeni) . I . I .
1. LiAlH4 · . (d) o .0 o
2. NaB~,Li~ I I
3. Ammoniacal AgN03 CH3-C - 0- C- H
4. H 2 ; PdlBaS04 I I·
H CH3
Codes: A B C D
(a) 4 3 2 I 0
(b) 2 3 4 0
11. (c) ·12. (b) 13. (d) 14. (a) 15. (b) 16. (b) 17. (a) 18. (a,b) 19. (b) , 20. (c)
21. (a) , 22. (d) 23. (d) 24. (a) 25. (b) 26. (d) 27. (a) 28. (d) 29. (d) 30. (c)
31. (b) 32. (b) 33. (c) 34. (c) 35. (d) 36. (b) 37. (b) 38. (c) 39. (b,c) 40. (c,d)
G.R.B. Organic Chemistry (or Competitions
polar?
H SC 2 ,,-
~) NaHS03
(d) a1lofthese
3. Which among the following carbonyl co~unds is most 3. The product of given reactio.,n 6 [0]
KMn04 /(H+)
)? is:
(a) /C=O,
H3 C
H3C,
(c)H/C=O
(a) CH3-CH2-CH2-CH2-C-H
°II CH3
I
(d) CH3-CH-CH2-CH2-CH2-COOH
~) CHr-..,CH2-CH2-C-CH3
°II 5. Which of the following is most reactive towards oxidation?
(a) HCHO ~) CH 3 CHO
o o
, II
(c) CH3-CH2-C-CH2,..-CH3 (c) CH3-~-CH3
(d) All are equally reactive
Passage 3
Passage 2 Aldehydes witli atlelistone a~hydiOgenUriaergoaldol
Carbonyl compounds give different oxiW¢on products with condensation. Two molecules of same or different aldehydes take
•different reagents. Several oxidising agents can be used to oxidise part in such condensation. One of the two aldehyde molecules
carbonyl compounds.' . AmmQniacal silver nitrate (Tollens' must have an a-hydrogen. Ketones under similar condition' give
Aldehydes and Ketones
.,
.0(
'IQIO"'Nabii')'r'Y;~~Q\lc; .
Bit.(OHh ... Intramolecular .aldol .• contiensati()n )is . given .. by
dialdehydes, diketones or keto ald~hydes.TI,le.,tlilceWriesshoUld
;.~ <.~COONa··
.. ··clIb·· • . .•
,be. 2,5; 2,6;. 2,7 and 2,8..mk:etones.Intr.ltildlecwaraldol . Answer the folJowing questions:
. cOndensation is the bestiliethOd for Prepant'ti6h of five and .six 1. The aldehyde which shows CanniZzaro's reaction is:
membered ring. For example: .' (a) HCHO (b) C6H5CHO
o O. (c) CCl3-CHO (d) all of these
..11 ..II'i
N'""O"H' (:.alp -2; The aldehyde having a-hydrogen which gives Cannizzaro's
CH 3-C--..,H+CH-C---'H
. .... "~"'.
3 h.?-'~-'< . reaction is:
OR (a) CH3-CH2-CHO (b) CH3-CH-CHO
I . I
.... ' . I
.CH3'::...."C+"CH2CHO CH3
(b) False
CH 20H
(a) I
CH20H
COONa
(c) I
COONa
(d) all of these
. 3. When mixture of ethanal and propanal is treated with
aqueous NaOH, the product contains 4 aldols. 4. Mixture of C6H5CHO and HCHO is treated with NaOH
(a) True (b) .False then Cannizzaro's reaction involves:
4. In the reaction, (a) oxidation ofHCHO
~O
(b) reduction of HCHO
(c) oxidation ofC6H 5CHO
. 0 0
II NOH HO
1\
(d) reduction ofC6H5CHO
CH3-CCH2CH2C-CH3 ~ ,. 5. Which of the following' compounds gives internal crossed
CH Cannizzaro's reaction?
the product formed is due to' intramolecular ketol o . 0
condensation. II
(a) C6HS-CH2-C-H(b) C6Hs-C-CHO
I
(a) True' (b) False
5. Mixture of HCHO and CH3CHO will not give aldol
condensation.-,
, (a) True (b) False
Passage 4
(c)
a
~,
I
CHO
CHO
(d)
Passage 5
CHO
I
CH2-CHO
fH 3
'H3 C
CN
I
(b) H3C-CH-C-Hand H-C-H (d) >C-CH-OH
, t t' H3 C .\
. . bH 3 . ~ , ~ [Hint:p+Q
K ZC03(aq,)
, )R~S
HCN
bH 3 ~ t
Aldehydes and Ketones 655
CH 3
or CH 3CH3 [0])CH 3CH zOH. [0]) CH 3CHO . [0]'1
Ethane . Ethyl alcohol Acetaldehyde.
I \
(CH 3hCHCH zCOOH CH 3 -C-'cOOH
CH 3COOH
Acetic acid
Isopropy~ acetic acid . I
,CH 3
Trimethyl acetic acid
H-CH 3 [0]) HCHzOH [0]) HCHO [0]) HC~OI~
Methane Methyl alcohol Formaldehyde Fortnlc aCid
3. IUPAC system: Acids are muiied as alkanoic acids
(Alkane '7 e + oie acid), The name is derived by replacing 'e' of
So, saturated monoearboxylie acids are the first oxidation the corresponding alkane by -oic acid.
products of aldehydes or second oxidation products of primary
HCOOH Methanoic acid (Methane e + oie acid)
alcohols. ,
[MonoearboxyIic acids may also be regarded as the CH 3COOH Ethanoie acid (Ethane - e + oie acid) . ,
derivatives of carbonic acid in which .one -OH group has CzHsCOOH Propanoic acid (propruie e + oie acid)
been replaced by an alkyl group. In case of substituted acids, the longest chain including the
HO' HO carboxyl group is selected and numbering is done from the side
"C=O -OH) "C=O] of carboxyl group, i. e., carbon atom of the carboxyl group is'
HO/ +R . R/ numbered as 1.
Carbonic acid Monocarboxylic acid s 4 3 Z I
C-C-C-C-COQH
Monocarboxylic acids are represented by the general
formula, RCOOH, where R may be either a hydrogen atom or For example,
Br
an alkyl group. RCOOH are also called monoprotic acids
because they give one proton in the solution.
S 4 3 Z I .4 31 z 1
CH 3 -CH-CH-CHzCOOH; CH 3 -CH-CH-COOH
12.2 NOMENCLATURE I 1 I
CH 3 CH 3 CH 3
The monoearboxylic acids are named according to the 3,4~Dimethyl pentanoic acid 3-Bromo-2-methyl bUf!'U1oic acid
following systems:
1. Common or trivial names: The names of lower 12.3 ISOMERISM
members are derived from the Latin or Greek words that Monocarboxylic acids show chain and functional isomerism.
indicate the source of the particular acid. The common names 1. Chain isomerism: This is due to the difference in ~e
, . have ending -ic acid. structure of carbon chain.
Formula Source Common name CH 3
HCOOH Red ant (Latin; Ant Formica) Formic acid I,
CH 3COOH Vinegar (Latin; Vinegar Acetum) Acetic acid CH3CHzCHzCOOH ;. CH 3 -CHCOOH
Butanoic acid . 2~Methyl propanoIc acid
C2H sCOOH Proton-pion (Greek; Proton"" First, Propionic acid
Pion = Fat) 2. Functional isomerism: Monocarboxylic acids show
functional isomerism with the esters of the acids,hy<1r?xy
C3H 7COOH Butter (Latin; Butter Butyrum) Butyric acid
carbonyl compounds and )lydroxy oxiranes.
C4 H 9COOH' RoOt of Valerian plant Valeric acid
(C Z H 4 0 Z ) : CH3COOH; HCOOCH 3 ;
The higher members are named on the basis of number of Acetic acid 'Methyl formate
carbon atoms. Incase of substituted acids, the position of the
CHzOH ' CH z """':'<':;H-OH
substituent is indicated by Gre(,':k letters a, ~, 'Y, 8, etc.
y P a a
1
CHO
; ""-/
.,
". 0
CH 3 -CH-.CHz-COOH CH3-CH-COOH Glycolaldehyde . Hydroxy ethylene oxide
1 1
CH 3 CH 3 (C3H60Z): CH 3CH zCOOH; CHz-CH~HzOH;
~-Methyl butyric acid a-Methyl propionic acid Propionic acid '~/ .
3. Optical isomerism: Monocarboxylic acids having atleast one chiral atom exhibit optical isomerism.
CH3CH2, * /H
'cc 2 - Methyl butanoic acid
H3 C/ . 'COOH (Activevaleric acid)
[0] ) CH 3COOH
Acetic acid
. K2Cr207
CH3COCH2CH3 ) 2CH 3 COOH
Eth)(l methyl ketone H2S04 Acetic acid
Methyl ketones can also be converted to carboxylic acids through the haloform reaetion~
o 0
II (i) X 2INaOH I
R-C-CH3 >R-C-OH+ CHX3
Methyl ketones (ii) H20 Halofonn
o o
II II
R-C-CH3 +312 +4NaOH Heat ) R-C~Na +CHI 3 + 3NaI + 3H20
o
I
CH3CH2CH2-C-CH3 + 3NaOI --+CH3CH2CH2COONa+CHI3 +2NaOH
Pentan-2-one Sod. hypoiodite Sodium butanoate
The sodium salts of carboxylic acids (containing one carbon atom less) on acidification give the corresponding acids.
- +' Hydrolysis
CH3CH2CH2COONa + HCI ) CH3CH2CH2COOH + NaCI
Butanoieacid
2. Hydrolysis of alkyl cyanides or nitriles: When an alkyl cyanide' or nitrile is hydrolysed with hydrochloric acid or
sulphuric acid mixed with an equal volume of water, the .-CN group is hydrolysed to a carboxyl group. This is a very useful
method for the synthesis of acids.
(ii) Alkyl halides are actually used, CH3Br NaCN) ,CH3CN _H....;.p=--~) CH 3COOH + NH3
MethyJbromide or KCN Methyl cyanide H+' A Acetic acid
The acid fonned by this .method contains one carbon atom more than the original alkyl halide. With 2 alkyl halide the yield of nitrile is very
0
poor, however, in case of3° alkyl halide, elimination takes place at the place of nucleophilic substitution.
. 13 11 2 '
3. Hydrolysis of terminal tribalogen derivatives ~f alkanes: Trihalogen derivatives of alkanes in which all the three
halogen atoms are attached to the tenninal carbon atom, ~n hydrolysis with aqueous alkali solution, form monocarboxylic acids.
R
~x
~/§ +3NaOH
(aq.)
.
-3NaX
: )[R-.:c~g~]
OH ......
-H 0)
2
1
RCOOH :3NaX
NaOH '.
Unstable .
RCOONa
CHCl3 +3NaOH -~) HCOOH + 3NaCI
Chloroform (aq.) Formic acid
1NaOH
HCOONa
Sodium formate
CH3CCl3 +3,KOH(aq.) . )CH 3C(OHh ~CH3COOH+H20
l,I,I-TrichlorOethane /:-3KCI. Unstable Acetic acid
4. From Grignard reagents and carbon dioxide (carbonation of Grignard reagents): When carbon dioxide is passed
through an ethereal solution of Grignard reagents, an addition product is formed which on hydrolysis with a mineral acid yields a
fatty acid. .
Dry H 2O /x
O=C=O. + RMgK --'--~)O=C-OMgX ) RCOOH + Mg """
H+
Carbon dioxide ether
I OH
R
Addition product
. OH
~.f) Dry H 2O
CH3 -MgBr +O=C=O )O=C-OMgBr )CH 3COOH+Mg(
ether. I. . H(;:l Acetic acid Br
. CH3
This synthesis of carboxylic acids is applicable to primary, secondary and tertiary (allyl, benzyl and aryl) halides, provided
they have no groups inconsistent with, a. Grignard reaction.
. .
Mg (i)C0 2
(CH3hC-C1 )(CH 3hCMgCI ..... ) (CH3hC-COOH
Tmt. butyl chloride . (Ether) (11) HOH 2 ,2_Dimethyl propionic acid
~l
QMgCI+ C0 2 ---+)o-~-OMgCI HOH
(HCI)
)Q-C-OH+Mg,
CyclohexyJ magnesium 0 oII .. . "OH
chloride
M nCO'
R-CH2 -x g ) RCH2MgX ..~ 2) RCH2COOH
. .(Diethyl ether) . (11) HOH Higher acid
! Note:. The acid for:tnedhas one carbon atom more than the alkyl group present in ·the Grignaid reagents. .
5. Hydrolysis of esters: Esters ,on hydrolysis with mineral aci4s or alkali form fatty acids. So, e~ters not only undergo acid
hydrolysis, but they also undergo a base-prolnoted hydrolysis.
RCOOR' +.H 2 0 HCI ) RCOOH+ R' OH
"8.
RCOOR' + NaOH '----+) RCOONa + R' OH
Est~ . 8. Sodium carboxylate
. .' WorOH-
CH3COOC2HS + fl20 . . ) CH3COOH + C 2H sOH
. . Ethyl acetate. i 8. Acetic acid Ethyl alcohol
Hydrolysis in acidic medium is reversible but in basic medium it is irreversible. Mechanism Of ester hydrolysis in basic and
acidic Dledium may be given as, . .
..
Carboxylic Acids
o ,OH 0
I .' H+ I '/tStIJ- OH- II. :
(Acidic medium) R-C-OR' )R-C-OR"~R-C {$ ---+)R-C-OR'+H10
Protonation + " \----
'OR' .
o 0- 0
I OH- I. I
(Basic medium) R-C-OR'---+) R-C-OR'~R-C-O-' +R'OH
I
OH
This method is particularly useful for the preparation of higher fatty acids from oils. ~d fats which are triesters of glycerol.
When oils and fats are heated with an alkali, they.;ire hydrolysed forming salt (soap) and glycerol. The process is known as
saponification.
CH2ooCC17H35 CHzOH·
I. I
CHOOCC17H35+3NaOH ) CHOH +3C 17 H 35 CooNa
I I Sodium stearate
CHZOOCC17H3S CHzOH (soap)
Tristearin (fut) Glycerol
o. Action of heat on gem c!icarboxylic acids: Th~icarboxylic acids of malonic acid series,
iti which two carboxylic
groups are linked with the same carbon atom, on heating eliminate a molecule of carbon dioxide giving fatty acids.
, /COOH Heat
CHZ'- ) CH 3COOH
'-COOH -C02 Acetic acid
Malonic acid
/COOH
R-CH, Heat) R-CH1COOH
"COOH -C02 Monocarboxylic acid
Substituted malonic acid
The reaction is actually carried out between an alkyl halide and the sodium'derivative of diethyl malonate. The substituted
malonic ester formed is hydrolysed and then heated to get the monocarboxylic acid.
CooH
R-X + NaCH/COOC2Hs -NaX) R_CH/COOC2Hs H2 0) RCH/ ' Heat) RCH1CooH
Alkyl halide ",",COOC2HS "'"'COOCzH s H+ . "'"'CooH -C02 MonocarboxyIicacid
Sodium diethyl malottate
The acid obtained contains two more carbon atoms than the starting alkyl halide.
7. Carbonylation of alkenes (Koch reaction): When a mixture of an alkene, carbon monoxide and steam is heated under
'pressure at 350°C in presence of phosphoric acid (H 3 P0 4 ), monocarboxylic acid is formed. '
H PO
HzC=CHz +CO+ HzO 3 4 . )CH 3 -CH1CooH
. Ethene . Steam Pressure, 350"C . Propionic acid
H PO
CH3CH=CH2 +CO+ H 20 3 4 ) CH 3 -CH-CooH
Propeile Steam Pressure, 350°C . I
CH 3
'2-Methyl propanoic acid
This is a recent method of making carboxylic acids and this acid-catalysed hydrocarboxylation of alkenes is calledKocb
reaction.
8. Heating sodium alkoxide with carbon monoxide:· By the action of carbon monoxide on heating with sodium alkoxide
under pressure, a sodium salt of the carboxylic acid is obtained
. which
.
9n treatment with an acid yields carboxylic acid. ,
RONa +CO Heat,160"C) RCooNa En) RCOOH
Sod. alkoxide Under presSure Sod. salt Acid
O
CH2-CH2-COOH
RCONH2 + HN02
Amide Nitrous acid
~RCOOH+N2 +H 20 I [0]) I
Hot alkaline KMn04 CH2 -CH 2 -COOH
CH3CONH2 +HN02 ~CH3COOH+N2 +H20 Cyclohexene . Adipic acid
Acetamide Acetic acid
Alternatively, ozonides can be subjeCted to oxidation with
Acyl chlorides and anhydrides are easily hydrolysed with
H 20 2 to give carboxylic acids. Alkynes on ozonolysis also
water or alkalies.
give carboxylic acids.
RCOCI + HOH ~ RCOOH + HCl
Acid chloride Carboxylic acid KMnO/H+
R-,C=C-R' + 3[0] + H 20 4 ) RCOOH
o 0 Alkyne
I I
CH3-,C-=-CI+NaOH(aq.)~CH3-C-ONa+HCI
+R'COOH
+ RCH 2COOH +C 2H 50H Ether, alcohol and acid having same molecular mass have
12. Oxidation of alkenes and alkynes: Alkenes can be boiling points in following sequence:
oxidised to carboxylic acids with acidified or hot alkaline CH3CH2 -O-CH3 < CH3CH2CH20H < CH3COOH
KMn0 4 or K2Cr207' M,ethoxy ethane , Propanol Ethanoic acid
II
Increasing hydrogen bond strength and boiling point.
Carboxylic Acids
~: 0·-
.. 10-4-IO-s(pKa =4-5). ThepKa of water is about 16 and
the apparent pKa ofH2C03 is about 7. These relative acidities
R-C'<!.O-H R-C/··· - mean that the carboxylic acids react readily with aqueous
'o-H solutions ofNaOH and NaHC03. to form soluble sodium salts.
II Table--Ionisation constant of some CarboxyJic acids
From these structures, it is clear that the carbonyl part of
the carboXylic group is electrically neutral (compare it with . Name of A.~; .;:·.\..'..,. . .,:.M..•"·. 0.·. 1:eeularFonn~.:·
. ···.,~}'}~tteD
,,;,;,!stutK..
aldehydes and ketones in which only one structure is Trichloroacetic CCl 3COOH .. 23200 x 10-s
electrically neutral) and does not have a double bond character acid
but a reduced double bond character. Thus, carboxylic acid Dichl()f08l;:etic Cl 2CHCOOH 5530~10-5
does not give the reactions of the carbonyl group. acid
The stability of carboxylate ion can also be explained in Oxalic acid COOH 5400 x lO-s(Kal )
terms of delocalization of n-electron density. As the carbonyl I for first ionisation
COOH
carbon involves sp2 -hybridization leaving one unhybridized
Fluoroacetic acid FCH2COOH 260 x 10-s
n-orbital, therefore, this n-orbital can overlap sidewise with
either of the n-orbitals of oxygen atom forming n-bond[as Malonic acjd CH 2(COOH)2 140xlO-$(Kal )
shown below in the figures (a) and (b)]. The resulting n-orbital for first ionisation
cloud is spread over both oxygen atoms and carbon atom. 2-Chlorobutanoic CH3CH2CHCOOH 139xlO-s
aCid I"
. CI
I .
Chloroacetic acid CICH2COPH 136xl0-~ .
Bromoacetic acid BrCH2COOH' 125 x 10-$
Iodoacetic acid~ ICH2COOH 67 xl 0-5
Formic acid HCOOH 17.9xl0-s
(a) Acetic acid CH 3COOH 175xlO-S '
(Delocalized n-closed in carboxylate ion) Propanoic acid CH3CH2COOH 140 x 10-$
n-Butyricacid CH 3CH 2CH2COOH 132 x 10-$
This delocalization gives stability to.the carboxylate ion.
G.R.B. Organic Chemistryjor Competitions
Cause of acidic nature: The molecule of the carboxylic Hence, the following sequences are observed.
acid can be represented as a resonance hybrid of the following HCOOH > C 6 H s COOH > CH 3COOH > C2HsCOOH
forms: pKa 3,77 4.17 . 4.71 4.88
. orKa (l7.7xlO-5 ) (6.3 x 10-5 ) (1.75 x 10-5 ) (1.30 x 10-5 )
C:? .
I
R-C-O-H
n· ~
:0:-
I +
R-C=Q-.:....-.-H
COOH
I
COOH
> CH 2
"'-COOH
/COOH
CH 2COOH
>
CH 2COOH
I
I II [Alkyl group is electron releasing group and decreases
Due to electron deficiency on o~ygen atom of the hydroxyl acidity as size increases.]
. group (structure II), there is displacement of electron pair of the
CH3 <CH3CH2-«CH3hCH-«CH3hC-,
0 -H bond towards the oxygen atom. This helps in release of
[Chlorine is electron withdrawing group_ The acidity of
hydrogen as proton. The. resulting ,carboxylate ion is also
the acid increases as the number of chlorine atoms increases in
stabilised by resonance as resonance energy ofthe carboxylate
the a.-position.]
ion is mucn'higher than that ofundissodated acid.
CI 3CCOOH> Cl 2CHCOOH> CICH2COOH > CH 3 COOH
R---C~_
pKa 0.64 . 1.48 2.85 4.71 .
[Electron withdrawing nature of halogens decreases from
Resonance forms of
fluorine to iodine, i. e., F > CI > Br > I]
carboxylate ion FCH2COOH>CICH2COOH> BrCH 2COOH> ICH2COOH
Thus, the acidity of the carboxylic acid is due to powerful [Inductive effect is stronger at a.-position than j3-positio,n.
resonance stabilization of the anion. Similarly, at j3-position it is more stronger than at y-position.]
[Resonance is confrrmed' by measUring bond leJigth in y ~ a y~ a
CH 3CH 2CHCICOOH>CH 3CHCICH 2COOH>
formic acid and sodium formate] , ,
/ 1.23 A ,1.\A _
pKa 2.86 4.05
y ~ a
H~ [H-c~~l
CH2CICH2CH2COOH
Na+ 4.52
, , / ' Q-,-H I OJ ·Relative acid-strength:
1.36 A . . 1.27 A (a) RH< NH3 <HC=eCR<R-OH<H-OH
F011lllC aCl,d Sodimn formate < Ar-OH <R-COOH
Atkoxideanion from alcohol does not show resoitance and (b) CH3CH2COOH< HCHicOOH <C 6 H s CH2COOH <
is not stabilized since, the alkyl group has.electron repelling pKa 4.87 4.76 4.31
inductive effect. This lack of stabiliZation is respoJisible for a HOCH 2COOH <CICH 2COOH
. very weak aciditY of alcohols.. pKa' 3:87 287
, R-O-H J(-O- +H+ 'Relative basic-strength (of conjugate bases):
Alcohol' No resonance . RCOO- < HO- < RO- < HC=C- < NH:2 < R
hybrid
Effect of substituents on acidity : ... Any factor that 12.7 GENERAL CHEMICAL CHARACTERISTICS
stabilizes the ariion more than it stabilizes the acid should OF FATTY ACID~
increase, the, acidity and any factor that makes the anion less
A molecule of a monocarboxylic acid is composed of (i) car-
stable should decrease the acidity of the carboxyiic acid.
boxylic group; the functional group and- (ii) an alkyl group.
An electron withdrawing group, EWG (having -1 effect) . Hence, the chemical properties of monocarboxylic acids are
stabilises the anion by dispersing the negative charge and due to these groups. The chemical reactions, in general, may be
therefore. increases the acidity. On the other hand, electron- discussed under following heads:
donating group, EDG (+1 ,effect) intensify the negative charge o
on the' anion resulting in the decrease of stability and thus
decreases the acidity of the acid.
I
1. Due to carboxyl group (-C-OH)
'.~c/f':'0J-
'G G ---7 c/·~,]
(i) Reactions involving proton (removal of hydrogen of
.the -OH group). _
, "-'cr "'0' (ii) Reactions involving hydroxyl group (-OH).
G-electron withdrawing G-electron releasing (iii) Reactions involving carbonyl group ( )C=O).
group, acidity increases . group, acidity decreases (iv) Reactions involving carboxyl group as a whole.
2. Reactions due to alkyl group.
Carboxylic Acids
1. Reactions due to Carboxyl Group most of these salts are insoluble and precipitate in the reaction
(i) Reactions Involving Proton: mixture, no reaction occurs with additional quantities of
(a) Reaction "ith strongly electropositive metals : Grignard reagents. '
Monocarboxylic acids react with strongly electropositive
metals (such as Na, K, Ca, Zn, etc.) evolving hydrogen and R'CH 2MgBr + RCOOH Ether) R'CH 3 + RCOOMgBr
forming corresponding salts (acidic character). However, lithium alkyls react to give lithium salts which
R-COOH RCOO- +H+ are often soluble and further react to form a dilithium salt
+ which gives a ketone with acid.
R-COOH+H20 RCOO- +H30
RCOOH +CH3Li ---+CH4 + RCOOLi
They exhibit acidic character due to their ability to ionise
to give proton (H+ ). .
RCOOLi +CH3Li ---+ RC(OLih --='--+ RCOCH 3
2HCOOH +2Na ---+ 2HCOONa +:H2
Formic acid Sodium formate . I
CH3
2CH3COOH + 2K ---+ 2CH3COOK + H2
Acetic acid Potassium acetate (ii) Reactions Involving Hydroxyl Group:
2CH3COOH + Zn ---+ (CH3COOh Zn + H2 (a) Formation of esters (Reaction with alcohols) :
Acetic acid Zinc acetate When carboxylic acids are heated with alcohols in presence of
(b) Reaction with alkalies: Monocarboxylic acids dehydrating agents like conc. H 2S04 or dry HCI gas, esters are
neutralise hydroxides to form corresponding salts and water. formed.
CH 3COOH + NaOH ---+ CH 3COONa + H 20 R-COOH + HOR' RCOOR' + H 20
Cone. H2S04 Ester
CH 3COOH + NH 40H ---+ CH3COONH4 + H 20 CH3COOH + HOC 2Hs ... '> CH 3COOC 2H s + H 2 0
Acetic acid Ammonium acetate Acetic acid Ethyl alcohol Ethyl acetate
Carboxylic acids can be regenerated by treating these salts This reaction is termed esteritication. It is a reversible and
with dilute mineral acids. slow reaction, but is speeded up by the presence of small
CH 3COONa + HCl---+ CH 3COOH + NaCI amount of inorganic acids as catalyst, e.g.,
Sodium acetate Acetic acid
Cone.
(c) Reaction with carbonates and bicarbonates R-COOH + HOR' ---=-~ R-COOR' + H20
Monocarboxylic acids react with weaker bases such as
Sin<;:e, esterification is an equilibrium reactio!l, therefore,
carbonates and bicarbonates forming corresponding salts with
to shift the equilibrium in the forward direction, water is
evolution of carbon dioxide (effervescences). It is a
removed as soon as it is formed and either carboxylic acid or
laboratory test of -.-COOH group.
the alcohol is used in excess. The rate at which a carboxylic
CH3COOH + NaHC0 3 ---+ CH3COONa + C02 + H 20 acid is esterified depends primarily upon the stearic hindrance
2CH 3COOH + Na2C03 ---+2CH3COONa +C0 2 + H 20 in the alcohol and the carboxylic acid. .
2CH3COOH +CaC0 3 ---+ (CH3COOhCa + CO 2 + H 20 :The reactivity of alcohols towards esterification increases
Calcium acetate as:
During the reaction of carboxylic acids with N~C03 or Tertiary (R3C...,--QH) < Secondary (R 2 CH-OH)
Na2C03, the CO 2 evolved comes from NaHC03 orNa2C03 < Primary (R-CH2 0H) < CH 30P
and not from the carboxylic group as shown below: Similarly, reactivity of carboxylic acids increases as:
0 0 0 R3C-COOH< R2CH-COOH < RCH 2 COOH
II(\~II 11_+ < CH 3COOH< HCOOH
R-C-O-H+ NaO-C-OH ---+R-C-O-Na
Acid Sodium bicarbonate (Mechanism of esterification 1''' ~arboxync acids See
Problem 8 on page 675-676.)
o (b) Formation of acid chlorides (Reaction mth
~IID
+ H-O-C..!-Q-H ---+ CO 2 + H 20 phosphorus halides or thionyl chlorides): Acid chlorides
Carbonic acid are formed when :;nonocarboxylic acids are heated with
This reaction can be used to distinguish carboxylic acids phosphorus chlorides or thionyl chlorides in pyridine. Similar
from phenols (because phenols do not give effervescence with reactions are observed with phosphorus bromides.
aqueous solution of NaHC03 ).
(d) Reaction with organo-metallic reagents: Carbo- CH 3COOH + PCIs Pyridine) CH3COCI + POCl 3 + HCI
Acetic acid A . Acetyl chloride
xylic acids react with Grignard reagents extremely rapidly to
give hydrocarbons and the magnesium salts of the acids. As 3CH3COOH + PCl3 ~3CH3COCI + H 3P0 3
G.R.B. Organic Chemistry (or Competitions
o 0
2CH 3COOK + 2H20 Electrolysis) CH 3 - CH 3
~ ~ Potassium acetate Ethane
R-C-CH 2COOH A) R-'C-CH3 +C02
[3-Keto acid Ketone , +2C0 2 +2KOH + H2
(d) Formation of aikyJ halides (Hunsdiecker's
/>:Keto acids are unstable acids. These readily undergo
reaction) : An alkyl halide is formed when the silver salt of
decarboxylation through a cyclic transition state.
monocarboxylic acid is heated with halogen.
R-C-CH2-C=0 ~ R-C-Q-C=O '
CH 3COOAg + Br2
CCI
4) CH3Br + AgBr + CO2t
I I ellOH+ I~ Silver acetate Heat Methyl bromide
o H-O O-}
'--./ ' A carboxyl radical is produced in a two-steps process as
R-C-CH3 follows:
o '0
! (enol)
I
(i) R-C-OAg + Br2
CCI
4 )
I
R-C-OBr + AgBr
Similarly, if unsaturation is present at p and y-positions o 0
then again decarboxylation takes place simply on heating. I I . .
y f3 (l Heat' (ii) R-C-OBr + Br2 ----+ R-C-O + Br
H2C =CH-CH2 -COOH ----+ H2C=CH-CH 3 +C0 2t o
(b) Dry distillation of calcium salts of carboxylic acids: II. .
R-C-O ----+ R + C02
When calcium salts of fatty acids other than calcium formate
are heated, ketones are fonned. . .
R + Br ----+ R-Br
(RCOOhCa Dry) RCOR +Cac0 3 (e) Formation of amines (Action of N 3 H): Primary
Calcium salt distiL Ketone
amines containing one carbon atom less than the parent acid
Dry are formed when monocarboxylic acids react with hydrazoic
(CH 3COOhCa .. ) CH 3COCH 3 +Cac0 3
Calcium acetate distIl. Acetone acid (N 3 H) in presence of concentrated sulphuric acid.
When calcium formate is heated, formaldehyde is eVolved. H2 S04 (conc.)
RCOOH+ N3H ---=--~--~) RNH2 +C02 +N2
Acid Hydrazoic Primary
(HCOOh Ca Heat) HCHO + Cac03
acid anIine
. Formaldehyde
. H2S04 (conc.) .
However, when a mixture of calcium salt of a fatty acid CH3COOH+N3H ) CH3NH2 + C02 +N2
(other than formic acid) and calcium formate is heated, an Acetic acid Methylamine
aldehyde is formed. This reaction is call~d Schmidt reaction.
(CH 3COOhCa+ (HCOOhCa Heat) 2CH 3CHO + Caco 3 (t) Reaction with CH 2 N 2 : Diazomethane undergoes
Calcium acetate Calcium formate Acetaldehyde condensation with carboxylic acid to give an ester.
Note: Instead of calcium salts, vapours offatty acids can be passed over
R-COOH+CH2N2 ~R-COOCH3 +N2t
manganous oxide at 300"C orA1 20 3 at 400°C when similar
aldehydes and ketones are obtained. (g) Reaction with ketene: Forms acid anhydride.
(c) Electrolysis of sodium or potassium salts of CH 3COOH + CH 2CO ----+ CH 3CO· o· COCH 3
Acetic acid Ketene Acetic anhydride
carboxylic acids (Kolbe's synthesis) : Electrolysis of
sodium or potassium salts (concentrated aqueous solution) of (h) Reduction to alkanes: On heating with conc. HI
fatty acids yields alkanes. and red P at 2000C or by catalytic reduction, the --COOH
RCOONa ~ RCOO- + Na + converts into -CH 3 to form an alkane.
At anode 2RCOO- ----+R-R +2C0 2 +2e- RCH2COOH +6Hl RedP) RCH 2CH 3 +2H 20+31 2
200°C Alkane
+ 2H20 '
At cathode 2Na + 2e- ----+ 2Na ) 2NaOH + H 2 RCOOH+3H 2 ~RCH3 +2H 20
A
.li68. G.R.B. Organic Chemistry (or Competitions
Laboratory preparation: Formic acid is conveniently (i) Acidic properties: It is a monobasic acid. Its disso-
prepared in the laboratory by heating glycerol with oxalic acid ciation constant value is 18 x 10-5 .at 25°C. Its acidic properties
at 100-120°C. are due to its ionisation in an aqueous solution.
HCOOH ~ HCOO- +H+
Formic acid Fonnate ion
670; G.R.B. Organic Chemistry (or Competitions
(ii) Action of heat: When heated above 160"C, it (c}Itreduces ammoniacal silver nitrate (ToUens' reagent).
- decomposes to give carbon dioxide and hydrogen.
HCOOH + Ag 20 Heat) 2Ag + CO 2 + H2 0
HCOOH~C02 +H2 Silver mirror
(iii) Dehydration: When fonnic acid is warmed with (d) It reduces Fehling's solution, i.e., gi~es red precipitate
conc. H 2SO 4 it decomposes to give carbon monoxide and of cuprous oxide.
water. HCOOH+2CuO~ Cu20 +C0 2 +H 20
H SO Red ppt.
HCOOH 2 4) CO+ H2 0
Uses: Fonnic acid is used,
Note: L Formic acid does not fonn an anhydride.
(i) in the labomtory for preparation of carbon
2. The above reaction is used for the preparation of CO in the
monoxide.
laboratory.
(ii) in the preservation of fruits.
(iv) Action of heat on formates: (a) When sodium
(iii) in textile dyeing and finishing.
formate is heated to 360°C, it decomposes to form sodium
(iv) in leather tanning.
oxalate and hydrogen.
COONa (v) as a coagulating agent for rubber latex.
(vi) as an antiseptic and in the treatment of gout.
2HCOONa Heat)
Sodium formate 360·C
+ H2 I (vii) in the manufacture of plastics and water proofing
COONa
Sodium oxalate compounds.
(b) It does not form a hydrocarbon when sodium formate is (viii) in electroplating to give proper deposits of metals.
heat ~d with soda lime or its aqueous solution is electrolysed (ix) in the preparation of nickel formate which is used as
but hydrogen is evolved. a catalyst in the hydrogenation of oils.
(x) asa reducing agent.
HCOONa + NaOH CaO) Na2C03 + H2 (xi) in the manufacture of oxalic acid.
l!. .
(xii) as a strong irritant.
(c) Formaldehyde is formed when dry calcium formate is
heated. . Tests of Formic Acid
(HCOOhCa ~ HCHO + CaC0 3 (i) It tiuns blue litmus red.
Drycalcium funnate Fonnaldehyile (ii) .Its aqueous solution gives effervescences with
(d) Formamide is formed when ammonium formate is sodium bicarbonate.
heated. (iii) Its neutral solution gives red precipitate with
HCOONH4 ~ HCONH 2 + H20 Fehling's solution.
Amm funnate Formamide (iv) Its neutral solution with Tollens' reagent gives silver
(v) Reducing properties: Like aldehydes, fonnic acid mirror or a black precipitate.
behaves as a reducing agent. It is oxidised to an unstable acid, (v) It giv~ white precipitate with mercuric chloride
carbonic acid? whichdecomposes into CO 2 and H20. which changes to grey.
o 0 , HgCl2 ~ Hg2Cl2 ~ Hg
lI2,+N.oH
. CHI3 ~ HC==CH
500'+'
CICH2CH = CH2
Iodoform Acetylene Allyl cbIoride
CH)COCI L . -_ _ C-=-2H--,fJ~H
_ _---+ CH3m~H5
CH 2COOH
I CH20HCOOH
CH2COOH a-Hydroxy acetic acid
Succinic acid
.Carboxylic Acids
[O])CH COOH
.' 3
Acetic acid
.,', ",',.:
HCHO H2/Ni
. ) CH 3O~' Hl )CH
3I KCN(Alc,} ) CH 3CN . H 20) CH3COOH
Formaldehyde Methyl M;e$yl ; Methyl H+ Acetic acid
.. alcohol .. Iodide . cyanjde
Arndt-Eistert homologation: Thi~ isa con~e~i,ent Im~thQd qfco~v~rting an acid, RCOOH into its n~xt higher h~mologue,
RCH 2COOH.
SOCl 2 CH2N2 . EtOH Hydrolysis,
RCOOH . ) RCOCI ) RCOCHN2' ) RCH 2COOEt . ) RCH 2COOH
,--_ _ _ _ _.,--_ _------'1 Ag20
o
'. Ag20,6. HO [ . . B+ B~. <.OH] .
Tautomenses) 'II
R-CH2-.-,C-OH
.. . )R-CHCO.. 2 ) R-..CH=C ..OH
(Wolff rearrangement) Ketene" Higher acid
NH 3 · H t Br2/KOH I
CH 3 COOH )CH 3COONH 4 ea) CH 3CONH2 . . ) CH3NH2
.Acetic acid Amm. acetate Acetamide Methylamine
AgOH )CH 3CH 2 ()H [0]) CH 3CHO [0] ') CH COOH .'
3 , '
", R-C~,
/ Co·• ( ) R-C~
'0'-
.----!- •
. C·..
O · -H ..
+O-H
, (I) (II)
,(II) Resonance structure suggests that there is some double bond character in C-O bond of the acid. This is
responsible for the shorter bond length ofC-O bond in RCOQH
(c) Acetic acid undergoes intennolecular hydrogen bonding and exists as a dimer.
. -,O---H-O"
CH3-C'~ /C-CH3
O-H---O
Thus, the molecular mass of acetic acid is 120 in vapour state.
Probl~m 4..
Explain: (a) Acetic acid isa stronger acid than ethyl alcohol. (b) Trichloro acetic acid is a stronger acid than
acetic acid. '
Solution: ,(a) Acetic acid is a stronger acid than ethyl ~lcohol because the acetate ion fonned by ionIsation is stabilized by
resonance while, the ethoxide ion has no resonance. The negative charge in acetate ion is delocalized over two oxygen atoms while
the negative charge in ethoxide ion is localized on the single oxygen atom.
H
I
CH3-C-0:-
I ••
H
Ethoxide ion
Acetate ion
, f, (No resonance is present)
(Resonance structure)
, Hence, CH 3coO- ion is more stable and aweaker base than CH 3CH 20- ion. As a weaker base has a stronger conjugate acid,
CH 3COOH isa stronger acid than CH 3 ClhOH.
(b) ElectroQ withdrawing 'substituents decrease the negative charge on the carboxylate ion and stabilise it, i.e., loss of proton
becom~s relatively easy. Three chlorine atoms are electron withdrawing substituents in trichloro acetic acid' and thus, it is a
stronger acid than acetic acid.
Problem 5~ How will you obtain?
(a) Butanoic acid from 'l-bromoprojJane, (b) Propanoic acid/rom ethyne,
(c) 2-Midhylbutanoic 'acidfrom butan':'2-01, (d) Butanoic acid/rom ethyl bromide.
,. .'~. KCN H3 0 + ,
SolutIOn: (a) CH3CH2CH2Br )CH3CH 2CH 2CN >CH3CH2CH2COOH
Mg CO 2 + '
, . or CH~CH2CH2Br >CH3CH2CH2MgBr >CH3CH2CH2COOMgBr H ) CH3CH 2CH 2COOH
Ether
(b) HCs=G,H :;;~) H2 C=CHCI Mg) H2 C =CHMgcl CO 2 ) H2 C =CHCOOMgCl H+) HiC=CHCOOH H2/Pd)
Ether
Carboxylic Acids 675
C~JH2
(d) CH3CH2Br +\Mg ~CH3CH2MgBr --0-=--~)CH3CH2CH2CH20MgBr
H 0+'
3
, " ,)
) CH3CH2CH2CH20H-, -I
CH 3CH2CH2COOH «-<_--=-[0...;;]_---'. '
KMn°4 /H 2 S0 4
O[~
(iii) CICH 2COOH, CI2CHCOOH, CI3CCOOH.
(iv) CICH 2COOH, CH3CH2COOH, CICH 2CH 2COOH, .~ T Proton
O[H2
(CH 3hCHCOOH, CH 3COOH R-C-O-R' " ' R-C-O-R'
(v) CH 3COOH, CI2CHCOOH, CH3CH2COOH, I, + Transfer' I
CI3CCOOH, CICH2COOH OH OH
(vi) HCIO, HCI0 2 , HCI03, HCI04. 'lIlT 2001) (III)
Solution: (i) CH3COOH < HCOOH <CICH2COOH Stcp IV. Loss afwater molecule.
(ii) (CH3hCCOOH«CH3hCHCOOH<CH3COOH The intermediate (HI) loses a molecu'Ie of water to afford
(iii) CICH 2COOH < Cl 2CHCOOH < C13CCOOH protonated ester (IV).
(iv) (CH 3hCHCOOH<CH 3CH 2COOH<CH 3COOH
~I
+
OH 2
< CICH 2CHiCOOH <CICH2COOH
(v) CH3CH2COOH <CH 3COOH <CICH 2COOH < -H 20
R-C-O-R' '~ R-C-O-R'
Cl 2CHCOOH <CI3CCOOH
I II'
(vi) HCIO<HCI02 < HCI03 < HCI0 4 ·
Problem 8. Explain the mechanism of esterification of
COH •
:OH
+
(III) Protonated ester
carboxylic acids.
(IV)
-';"?"':::.
'i.;4~~':rtJ:!:/:6~::;...'______...,....-____________________~G.:.:.R,!:. B: : :.:. .O~rg:a:a: :.:n: :.:ic:. .C: : :'h:.:;:e:;:;m: :.:i~stry: . &. t.: .to:.:. r. .:C:;.:o: :.:m: .t.p;.;:e;:;.:ti.:.:ti; ;.:on.:;: s
oI H+, 18 18
°II
CH3-'C-OH+CH3-0-H'~ CH3-C-OCH3 + H20
Acetic acid Methyl alcohol Methyl acetate (Ester)
( 18 0-labelled) (18 0-labelled)
oII 18 H+
°I 18
C6HS-C-OH+H-O-C2HS ~C6H5-C-OC2Hs+H20
Benzoic acid Ethyl benzoate
( 18 0:labelled)
9. Which of the following is an unsaturated fatty acid? 10. Which type of organic compound is most resistant to
(a) Lauric acid (b) Linolic acid oxidation bY,acidified potassium dichromate? '
(c) Stearic acid (d) Palmitic acid (a) Alkene (b) Alcohol
(Ans. (b)] (c) Aldehyde ' (d) Acid
(Ans. (d)J
COOH COOH
I I
H-'CI-OH Alk.KMn0 H-C-COOH H-C-Br
4 Br2 water
( II
H-C-OH (Syn-addition) H-C-COOH (Anti-addition)
) I
Br-C-H
'.'. I Maleic acid r
COOH (Cis) COOH
Tartaric acid (Racemic mixture)
(Meso)
COOH COOH
I I
H-CI-OH H-C-COOH H-C-Br
(
Alk. KMn0
4 , I Br2 water) I
HO-C-H (Syn-addition) HOOC-C-H (Anti-addition) H-C-Br
I Fumaric acid
(Trans)
I
COOH COOH-
Tartaric acid (Meso)
(Racemic mixture)
(ii) Formic acid forms a white precipitate with HgCI2 solution. Acetic acid does not respond to this test. .
(b) ,(i) Oxalic acid when heated decomposes and evolves C02. The gas when passed through lime water forms a white
precipitate. ' ,~,
,COOH
I ~ HCOOH +C02
COOH Formic acid .'
Oxalic acid
CO 2 +Ca(OHh -----+CaC0 3 + H20
Acetic acid does not give this test.
(ii) Oxalic acid acts as a reducing agent. The decolourisation of acidified KMnO 4 solution occurs when oxalic acid is added to
it and the solution is warmed. This test is also not given by acetic acid.
2KMn0 4 +3H2S04-+K2S04 +2MnS0 4 +3H20+50
COOH
I +[O]-+2C02 +H 20
COOH
',iii) Oxalic acid in solid while acetic acid is a liquid with characteristic odour.
(c) Both the chemical tests used in part (b) of this question can also be employed to make distinction between oxalic acid and
succinic acid. .
Problem 10.' Compare the products/ormed on heating the/ollowing dicarboxylic acids:
(a) Oxalic acid, (b) Malonic acid, (c) Succinic acid, (d)Adipic acid. '
Solution! (a) Oxalic acid on heating loses a molecule of COl and is converted into formic acid.
COOH
I HCOOH +C02
COOH Formic acid
,(b) Malonic acid, on heating undergoes decarboxylation.
/COOH'
CH2~ Heat) CH3COOH + C0 2
COOH Acetic acid
Malonic acid
Carboxylic Acids
FCH 2COOH>CICH 2COOH> BrCH2COOH> ICH 2COOH When sodium fonnate is heated with sodalime, hydrogen is
(because F > CI > Br > I). evolved.
(J Inductive effect is stronger at a -position than j3-position and (J By dry distillation of calcium salts of monocarboxylic
than y-position. acids : Calciunl. acetate gives acetone and calcium
(J Electron releasing group (+1 effect) destabilises the anion fonnate gives fonnaldehyde. However, when a mixture of
and so decreases the acidity. i.e .• calcium acetate and calcium formate is heated, acetaldehyde
HCOOH > CH3COOH>CH3CH2COOH> is fonned.
(CH3hCH-COOH> (CH 3hC-COOH (J By passing the vapours of fatty acids over MoO at 300°C or
Al 20 3 at 400°C similar aldehydes and ketones are obtained.
Chemical properties
(J By Kolbe's electrolytic reaction: Electrolysis of Na or
o K salts (concentrated aqueous solution) offatty acids yields
II alkanes.
(1) Reactions due to -C-OH group
(J By Borodine Hunsdiecker reaction: An alkyl halide is
(a) Reactions involving proton (removal of H-atom of
. fonned when the silver salt of monocarboxylic acid is
-OHgroup) :
heated with halogens.
(J Salt formation: Monocarboxylic acids react with Na. K,
(J By Schmidt reaction: Monocarboxylic acids react with
NaOH. NaHC0 3 or Na2C03. etc .• with the evolution of
hydrazoic acid (N 3H) in presence of conc. H2S04 to give a
hydrogen and fonn corresponding salt.
primary amine containing one C-atom less than the parent
(J Reaction with organometallic reagents: RCOOH reacts
acid.
with R'MgX (GR) rapidly to give an alkane (R'H)
(J Reaction with diazomethane (CH 2N 2 ): Diazomethane
corresponding to the alkyl group of Grignard reagent.
(b) Reactions involving -OH group: undergoes condensation with fa~ acids to give methyl ester
. (J Ester formation: RCOOH reacts with ROH in presence with the evolution ofN 2.
of dehydrating agents like cone. H 2SO 4 or dry HCI gas,. to (J Reaction with ketene (CH 2C=O) : Fonns acid
fonn esters. anhydride.
(J Formation of acid chlorides: By the action of PCl s • r.J Reduction to alkanes: On heating with conc. HI and red
PCI3. SOCl 2/pyridine or C1 2/Br2 in presence of red P on P at 200°C or catalytic reduction. the -coon converts
carboxylic acids. acid halides are fonned. into -CH3 to fonn an alkane.
(J Formation of acid anhydrides: Dehydration of mono- (J Arndt-Eistert reaction: This reaction is a method for
carboxylic acids on heating with P20 S gives acid anhydride converting an acid RCOOH to a homologous series,
or when sodium salt of acid is heated with acid chloride, RCH 2COOH and its derivatives such as esters and amides.
acid anhydrides are fonned. In this reaction, R-'COCI from R-COOH is converted to
(J Formation of amides and nitriles: Monocarboxylic RCH 2COOH (by hydrolysis), RCH 2COOR' (by reacting
acids on treatment with NH 3 fonn ammonium salts which with R'OHlAg 20) and RCH 2CONHR (by reacting with
on heating lose a molecule of water to fonn corresponding R' NH21Ag 2 0). .;
amides. (2) Reactions due to R (alkyl) group
(J The acid amide (RCONH2) on heating with P20S loses one (J Halogenation :. The a-hydrogen atoms are highly
reactive due to the presence of electronegative -COOH
. more water molecule forming a cyanide (RCN) or nitrile.
group. On halogenation (C1 2 or Br2) hi presence of a
o catalyst (red P or Fe, etc.,), the a-H atoms are replaced by
(c) Reactions involving -~- (carbonyl) group: chlorine or bromine atoms. The reaction occurs in presence
of sunlight or on boiling.· This reaction is known as
(J Reduction· to alcohols: Reduction products depend on
the nature of reducing agent. By using LiAlH4 (LAH) in HeD-Volhard-Zelinsky (HVZ) reaction.
ether solution or ruthenium (Ru) and carbon as catalyst, the (J Direct iodination can be done in presence of an oxidising
-COOH group is reduced to -CH 20H (10 alcohol). agent like HI03 or HgO.
BH 3ITHF or H 2 in presence of copper chromite (J Oxidation : Carboxylic acids having at least one
(CUO +Cr203) also reduces -COOH into -CH 20R j3-hydrogen convert into P-hydroxy carboxylic acids on
(d} Reactions involving -COOH group as a whole: oxidation with H 20 2. Oxidation of a-methylene group
(J Decarboxylation: On heating anhydrous salt of acid with takes place by Se02 to give a-keto acid.
sodalime. forms an alKane with the elimination of CO 2 .
Carboxylic Acids 683.
.:. Very Short Answer Type (z) Ammonium salts of carboxylic acids on heating form
1. Fill in the blanks:
(a) Formic acid when heated with conc. H 2S04 produces
2. State whether the following statements are True or False:
(a) Monocarboxylic acids are called fatty acids.
(b) The lUPAC name of acetic acid is methanoic acid.
(b) Formic acid is ............ acid than acetic acid. (c) Formic acid is not the typical acid of the mono-
(c) Formic acid ............ Tollens' reagent. carboxylic acids series.
(d) Ka value of chloroacetic acid is ............ than the Ka (d) Acetic acid like formic acid shows reducing properties.
value Ji acetic acid. (e) Oxalic acid is non-poisonous in nature.
(e) O",allc acid when heated with glycerol at 110°C forms (f) Calcium oxalate is soluble in acetic acid.
(g) Hydrolysis of an ester in presence of a dilute acid is
(f) Oxalic acid is a ............ carboxylic acid. known as saponification.
(g) ............ acetic acid is called glacial acetic acid. . (h) When some insect like honey-bee bites, irritation is felt
(h) ............ is formed when acetic acid is heated with due to formic acid.
phosphorus pentoxide. (i) Formic acid undergoes halogenation.
(i) Sucrose on heating with concentrated nitric acid forms G) Methyl fonnate is the isomer of acetic acid.
(k) Oxalic· acid is used for the removal of ink and rust
G) When carbon monoxide is passed on NaOH under stains.
pressure, the compound formed is ........... . (I) I-Iell-Volhard-Zelinsky reaction is given by those acids
(k) Sodium formate when heated, forms ........... . which have a-hydrogen atoms. .
(1) Neutral solution of acetic acid gives ............ colour (m) The boiling point of propionic acid is less than that of
with neutral ferric chloride. n-butyl alcohol, an alcohol of comparable molecular
(m) LiA1~ reduces acetic acid to ........... . mass.
(n) Electrolysis of an aqueous solution of sodium (n) Acetyl chloride on heating with anhydrous sodium
propionate will form ............ .. acetate forms acetic anhydride.
(0) Ethanoicacid when reacted with sodium carbonate (0) A carboxylic acid shows the reactions of carbonyl
liberates ........... . group also.
(P) . Propionic acid and ethyl fonnate are ........... . (P) Acetic acid exists as a dimer in vapour state.
isomers. (q) 2-Chloropropanoic acid is weaker than 3-chloro-
(q) Acid hydrolysis of alkyl nitriles gives ........... . propanoic acid.
(r) The reaction in which an alkene is converted to (r) Formic acid is decomposed into carbon monoxide and
monocarboxylic acid with CO and steam in presence of
H20 when treated with cone. H2S04'
H 3 P04 is called ............ . (s) Formic acid when heated with P20 S forms an anhy-
(s) Substitution of chlorine in the alkyl group of a . dride.
carboxylic acid ............ the strength of the acid. (t) Formic acid is the only acid which gives reactions of a
(t) Monocarboxylic acids have higher boiling points than carboxylic acid as well as an aldehyde.
the corresponding alcohols due to ........ , .. . (u) Acetate ion is a stronger base than methoxide ion.
(u) Carboxylic acids can be obtained from the reaction of (v) All the C-O bond lengths in carboxylate ions are
carbon dioxide and ........... . identical.
(v) Malonic acid on heating yields ........... . (w) Formic acid acts as a reducing agent while acetic acid
(w) The formula ofthe main product obtained when PCIs does not show this property.
reacts with acetic acid is ........... . (x) Lower carboxylic acids are highly soluble in water.
(x) Kolbe's electrolysis of ............ produces n-hexane on (y) Highly branched carboxylic acids are more acidic than .
anoM unbranched acids.
(y) In Hell-Volhard-Zelinsky reaction the carboxylic acids (z) The reaction between an acid and alcohol is termed
are halogenated at the ...... : ..... position by using saponification.
. ; ........... and .......... ..
3. Match the following:
(A) Acetic acid (1) Soda lime (M) CICH 2COOH
(B) Formic acid (2)· Poisonous (N) . Dicarboxylic acid
(C) Decarboxylation (3) Phosphorus (0) Soap ..
(0) Hell-Volhard-Zelinsky reaction (4) Kolbe's synthesis (P) Fermentation of sugar
(E) Oxalic acid (5) Saponification (Q) Carbon monoxide
. (F) Electrolysis ofCH3COOK . (6) Vmegar ' (R) Alkane
(G) CH3COOC zH s + NaOH (7) Dehydration (S) Reducing acid
(H) Formic acid + conc. H ZS04 (8) Red ants (T) Ethane
C Pd/BaSO , K CO
(x) CH 3COCI 4) (A) 2 3) (B) Heat) (e)
II
o (xi) CH CH COOH P/Br2) (A) (i)A1c. KOH(excess» (B)
CH2CH 2COOH 3 2 (ii) H+
(xvii) \ (CH 3CO)20 )
, CHz CH 2COOH (xii) (A)-~.LHB) LWH4) (e) HBr/H 2S04 ) (D)
., /CH2COOH Na· .
(CH 3CO)20 ~ CH3CH2CHzCH3
(xviii) CH3CH, ' ) Ether
, ","CH2COOH
Carboxylic Acids
(xv) ~Hydroxy propionic acid from ethylene oxide. (Ans. The solubility of RCOOH in water is due to hydrogen
(xvi) Tartaric acid from ethylene. bonding of -COOH group and water. R-portion being
(xvii) Malonic acid from acetic acid. lyophobic resists solubility. As R gets large, this factor
prevails over the first factor and thus, higher acids become
(xviii) Lactic acid from acetic acid.
insoluble.) '. .
16. How are the following conversions made?
(b) Highly branched carboxylic acids are less acidic than
(i) -COOH to H
unbranched acids.
(ii) -CN to -COOH (Ans. The -COOHgroup of the branched acid is shielded from
(iii) -CONH2 to -NH2 solvent molecules and cannot be stabilized by solvation as
17. What is the action of heat on the following? effectively as unbranched acid like the acetate anion.]
(i) Oxalic acid, (ii) Ammonium oxalate, (c) Acetic acid can be halogenated in presence of phos-
(iii) Calcium fonnate, (iv) Calcium acetate, phorus and chlorine but fonnic acid cannot be
(v) Sodium fonnate, (vi) Malonic acid, halogenated in the same way.
(vii) Adipic acid, (viii) Succinic acid. (An'S. This is HVZ reaction. It occurs only in those carboxylic
18. Arrange the following in order of increasing acidity: acids which have a-hydrogen atoms. Acetic acid
(i) Propanoic acid, chloroethanoic acid, 3-bromo- possesses three a-hydrogen atoms but formic acid does
propanoic acid and trichloroacetic acid. not have even a single a-hydrogen atom. Thus, formic
(ii) 2-Fluorobutanoic acid, 2-iodobutanoic acid, acid does not undergo this reaction.]'
2-bromobutanoic acid and butanoic acid. (d) Carbon-oxygen bond lengths in formic acid are 1.23 A
(iii) Acetic acid, 2-methyl propanoic acid, 2,2-dimethyl and 1.36 A but in sodium fonnate both carbon-oxygen
propanoic acid. bonds have same value, i. e., 1.27 A.
(Ans. The formate ion present in sodium formate is a resonance
(iv) Oxalic acid, malonic acid, succinic acid, glutaric acid.
hybrid of the following two structures:
19. Write short notes on the following:
H-C-O- ~ H-C=O
(i) Decarboxylation of fatty acids.
(ii) Kolbe's synthesis. on I
0-
(iii) Relative strength of the acids. Thus, in resonance hybrid the bond length of C-O are
(iv) Koch reaction. id~tical. In formic acid, no such resonance exists and
(v) Schmidt reaction. thus, the bond lengths are different.]
(vi) Hunsdiecker'sreaction. (e) Formic acid is stronger than acetic acid.
20. Answer the following: (Ans. In acetic acid, methyl group is present which exerts +1
(i) Why 100% pure acetic acid is named glacial acetic effect and thus increases negative charge on the
acid? . carboxylate ion and destabilise it. The loss of proton
(Ans. The melting point of pure anhydrous acetic acid is 17°C. It becomes comparatively difficult in comparison to formic
is solid below this temperature and looks like 'icy', i. e., acid. Hence, acetic acid is a weaker acid than formic acid..]
glacial.] . (f) Fluoroacetic acid is stronger than chloroacetic acid.
(ii) What is vinegar and how is it made? (Ans. Both fluorine and chlorine are electron withdrawing
(Ans. Vinegar is 5% aqueous solution of acetic acid. It is fonned substituents. However, the capacity of fluorine is more
by fermentation of sugars and starch. Ethanol is the than chlorine as it is more electronegative than chlorine.
intermediate product.] The fluoroacetate ion is more stabilised and thus,
(iii) Why the bond length of c=o in carboxylic acids is a fluoroacetic acid has higher tendency to lose its proton.
Hence, it is a stronger acid than chloroacetic acid.]
bit longer than in aldehydes?
(g) Formic acid shows reducing properties.
(Ans.
..0:-
Due to resonance, there is considerable contribution of the
.
(Ans. Formic acid is easily oxidised to carbon dioxide and water
and thus acts as a reducing agent.
resonance form, R-C<' to the hybrid form, HCOOH + [0] ~ H 20 + CO 2
+~-H It reduces Tollens' reagent, Fehling's solution and
i.e., there is some single bond character in c=o bond mercuric chloride solution.]
which makes it somewhat longer than in aldehydes.] (h) ~Keto acids undergo decarboxylation easily.
(iv) Why the C=O in RCOOH is less reactive towards (Ans. j3-Keto acids are unstable acids. These readily undergo
nuc1eophiles than in aldehydes and ketones? decarboxylation through a cyclic transition state.
(Ans. In RCOOH, there is less positive charge on carbon atom of R-C-CH2-C=0
the c=o group. Thus, this carbon is less electrophilic in I I
RCOOH in comparison to aldehydes and ketones and so is o H-O
less reactive towards nucleophiles.] '-./ .
21. Account for the fOllowing:
(a) Carboxylic acids with five or fewer carbon atoms are
water soluble but, higher ones are insoluble.
Carboxylic Acids ;i687
?i
(iii) (A) CH3-C-OMgBr;(B)CH3COOH;(C)CH3CH20H iOOH + 0 ~ 2COz + H2 0 ] x5
[ COOH ..
(iv) (A) CH 3CHO; (B) CH 3CooH; (C) CH 3COCI
(v) (A)· CH3CHO;(B)CH3COOH; (C) CH 3COONa; (D) CH4 COOH
(vi) (A) (CH 3COOhCa; (B) CH 3COCH3; (ix) I Heat ) H~OOH + CO2
(C) (CH 3 hC(0H)CN;(D) (CH 3 hC(0H)COOH COOH
(vii) (A) CICH2COOH; (B) NCCH2COOH; . CHCooH CHCO ........
(C) CH2(COOH)2 (Malonic acid) (x) II ~II )0
CHCOOH CHCO/
(viii) (A) BrCH2-CH 2Br; (B) NCCH2-CH2CN;
(C) HooCCH2-CH2COOH(Succinic acid) LiAlH . .
(xi) RCOOH + 4[H) 4 ) RCHzOH + H2 0
(ix) (A)CH 3CH(OH)CN; (B) CH3CHOHCooH;
(C) CH 3COCOOH(Pyruvic acid)
G.R.B. Organic Chemistry for Competitiol1S
. H O/H+
15. (i) CH31 + KCN ~ CH 3CN 2 ) CH3COOH
CH 3CHO ~ CH 3COOH
(v) CH 3CH2COOH LiAlH4) CH3CH2CH20H~ CH3CHzCH2CI KCN) CH 3CH zCH 2CN Reduction) CH3CH2CHzCH2NHZ
(xii) C2HSBr ~ CH3CH2MgBr (~~ co2 +) CH3CH 2COOH ~ CH3CH-C;OOH NaOH) CH3CHOHCOONa !HCI
(11) Hp/H (P) 1
Br
(xviii) CH3COOH PCl s ) CH3COCI . H 2/Pd ) CH3CHO .HCN )CH3CHCN HPIH+) CH3CHCOOH
BaS°4 I I
OH OH
16. (i) Decarboxylation with soda lime, (ii) Hydrolysis in presence of acid, (iii) Hofinann bromide reaction with Br2 and NaOH.
17. (i) HCOOH + CO 2, (ii) Oxamide + 2H20, (iii) HCHO + CaC03• (iv) CH3CHO + CaC03, (v) (COO)2Na2 + H2, (vi) CH 3COOH + CO2,
. . CH2CO,
(vii) Cyclopentanone + CO2 + H20, (viii) 1 / 0 + H20
.CH2CO
18.· (i) CH3CH2COOH < BrCH2CH2COOH < CICH 2COOH < Cl3CCOOH
(ii) CH3CH2CH2COOH < CH3cH2CmCOOH < CH3CH 2CHBrCOOH < CH3CH2CHFCOOH
(iii) (CH 3hOCOOH < (CH3hCHCOOH < CH3COOH
(iv) HOOCCH2CH2CH2COOH < HOOCCH 2CH2COOH < HOOCCH2COOH < HOOC-COOH
CH 3
I
(B) CzHs-C-COOH or
I
H
One asymmetric carbon atom is present.]
2. An unsaturated dicarboxylic acid (A), C6Hg04 loses C02 on heating and gives another unsaturated acid (B), CSHg02. Upon
catalytic reduction (B) affords pentanoic acid. Assign structures to (A) and (B).
I Ans. (A)CH3CH=CH·CH(COOHh; (B)CH 3CH=CH·CH2COOH]
G.R.B.
3. An organic acid (A), CSHIO02 reacts with Brz in the presence of phosphorus to give (B). Compound (B) contains an asymmetric
carbon atom and yi~lds(C) on dehydrobromination. Compound (C) does not show geometric isomerism and on decarboxylation
gives an alkene (D) which on ozonolysis gives (E) and (F). Compound (E) gives a positive Schiff's test but (F) does not. Give the
structures of (A) to (F) with reasons.
P and Br2 •
[ADS. R-CH 2COOH ----'=--+) RCHBrCOOH, where R is C3H7
(A) (B)
lozonolysis
(CH3hCO + HCHO]
Acetone Formaldehyde
(F) (E)
does not give Schiff's test gives Schiff's test
4. An acidic compound (A), C4 Hs 0 3 loses its optical activity on strong heating yielding (B), C4 H60 2 which reacts readily with
KMn04 . (B) forms a derivative (C) with SOCI2, which on reaction with (CH3 h NHgives (D). The compound (A) on oxidation with
dilute chromic acid gives an unstable compound (E) which decarboxylates readily to give (F), C3H60. The compound (F) gives a
hydrocarbon (G) on treatment with amalgamated Zn and HCl. Give the structures of (A) to (G) with proper reasoning.
[Ans. Compound (A) is a hydroxy compound and is optically active.
H
. I
CH 3 -C-CH2COOH. On heating it gives an unsaturated compound which reacts with KMn04'
. I .
OH
NH
CH3CH=CHCOOH SOCI 2) CH 3CH=CHCOCI (CH 3)2 ) CH 3CH=CHCON(CH3h
~ ~ ~
5. An acid (A) contains carbon 40.7%, hydrogen = 5.1 % and its silver salt contains 65.1 % silver. The ethyl ester of (A) has V.D. of
87. What structure (A) may have? How would you distinguish between isomers?
CH2COOH ]
[ Ans. (A) may have two structures. I ; CH3CH(COOHh
CH2 COOH
6~ Give the structures of the four optically active structural isomers of C4Hs 0 3 (A to D) and evolve C02 with aq. NaHC0 3. Find the
structure of (A), the isomer that reacts with LiAlH4 to give an achiral product and (B) gives an iodoform lest.
[ Ans. (A)CH3-CH-COOH; (B)CH 3 -CH-CH2 COOH; (G)CH 3CH2 CHCOOH; (D)CH 3 -CHCOOH]
L
CH 0 H '
I
OH
I
OH
I
OCH3
2
9. A mixture of an acid anhydride (A) and a monobasic acid (B) on heating produces an.other m.on.obasic acid (C) .of equivalent weight
74 and an anhydride (D). The acids and anhydrides remain in equilibrium. The anhydride (D) c.ontains tw.o identical fluor.o alkyl
groups. The acid (B) contains a trifluoro methyl group and has an equivalent weight .of 128. Give the structures .of (A) to (D) with
pr.oper reasoning (At.omic weight of fluorine 19).
Solution: Acid anhydride (A) + M.onobasic acid (B) ;;:--"" Mon.obasic acid (C) + Anhydride (D)
(CF3 group) (Two CF3 gr.oUps)
Eq. wt. = 128 Eq. wt. = 74
Pr.obable formula .of acid (B) = CF3 (CH 2 )n COOH
. . M.olecular weight
EqUIvalent weIght of (B) == .. •
BaSlcIty .
128= 57+ 12+ l4n + 12+ 32+ 1
1
n=l
(B) = CF3 CH 2COOHand (D) = (CF3 CH2COhO
Similarly, molecular f.ormula .of acid (C) can be calculated t.o be CH3 CH 2COOH The reaction, theref.ore, can be given as,
(CH 3CH 2COhO+ F3 CCH2COOH ~ CH3CH2COOH + (F3CCH2COhO
(A) (B) (C) (D)
10. An .organic comp.ound (A) C 6 H 12 0 3 on treatment with c.oncentrated H2S04 gives CO, H 20 and (B). Comp.ound (B) can be
prepared by passing vap.ours .of 1-pentan.ol .over heated copper at 570 K. C.omp.ound (A) .on heating gives (C), C12H2004' Give.the
structures .of (A) to (C) with proper reas.oning.
Solution: C.ompound (B) must be ~entan.ol because it is prepared by passing vap.ours .of 1-pentan.o1 .over heated copper.
(-2H20) /O-CO,,--
~ CH3(CH2 hCB,,- ....... CH(CH 2 hCH 3
Heat '-CO-O""'-
(Lactide)
._ 11. An organic compound (A) CSHS03 on heating with soda lime gives (B), which reacts with HCN to give (G). The compound (G)
reacts with thionyl chloride to produce (D) which on reaction with KCN gives compound (E). Alkaline hydrolysis of(E) gives a salt
(F), which on heating with soda lime produces n-butane. Careful oxidation of (A) with dichromate gives acetic acid and malonic
I
acid. Give the structures of (A) to (F) with proper reasoning.
1--_ _ _ _ _ _0xi=·dat~io~n'__+CH3COOH + CH
2
<
.........COOH
NaOHlCaO) CH3
Heat
-L (8)
CH2CH3 HCN) CH3-b-CH2 CH 3
I
CN
(C)
1 SOO,
COONa CN Cl
I . HOH I I
CH3- C -CH2CH3 (. + CH3 ~C-CH2CH3 ( KCN CH3- G-CH2CH3
! Na OIl I -KCI
I
COONa CN CN
~) ~ (D)
I N.oHlCaO.
Heat
CH,-CH,-CH,~CH,
n-Butane
o
II /COOH
CH3-C-CH2-CH2-COOH C:ue~) CH3-COOH+ CH2"'"
(A) OXIdation Acetic acid COOH
Malonic acid
Carboxylic Acids
OBJECTIVE OUESTIONS
Set I: This set contains the questions with a single correct answer. 13. Formic acid is not a representative member of the carboxylic
1. Which of the following is not a fatty acid? acids because:
(a) Stearic acid 0 (b) Palmitic acid 0 (a) it is the ftrst member of the series 0
(c) Propionic acid 0 (d) Phenyl acetic acid 0 (b) it does not contain an alkyl group 0
2. Lemon is sour due to: (MHCET 2007] (c) itisagas 0
(a) citric acid 0 (b) tartaric acid 0 (d) it contains an aldehydic group while the other acids do
(c) oxalic acid 0 (d) acetic acid .0 . not have the aldehydic group 0
3. Which of the following acids is present in vinegar? 14. Which of the following will not undergo HVZ reaction?
(a) Hydrochloric acid 0 (b) Acetic acid o (a) 2,2-Dimethyl propanoic acid ' 0
(c) Tartaric acid 0 (d) Citric acid o (b) Propanoic acid 0
4. The general formula Cn H2n 02 could be for open chain: (c) Acetic acid 0
[AIEEE2003] (d) 2-Methyl propanoic acid 0
(a) diols 0 (b) diketones 0 IS. The ruPAC name of caproic acid is:
(c) carboxylic acids 0 (d) dialdehydes. 0 (a) pentanoic acid 0 (b) hexanoic acid 0
S. Monocarboxylic acids (saturated) are regarded as ........... . (c) heptanoic acid 0 (d) octanoic acid 0
oxidation products of paraffins. 16. The reaction of CH3MgBr on dry ice followed by acid
(a) ftrst 0 (b) second .0 hydrolysis gives:
(c) third 0 (d) fourth o (a) acetic acid 0 (b) formic acid 0
6. Monocarboxylic acids show functional isomerism with: (c) acetone 0 (d) aCetaldehyde 0
(a) esters 0 (b) alcohols o 17. The acidic character of fatty acids ............ with an increase
(c) ethers 0 (d) aldehydes o in molecular mass. ,
7. Acetic acid is obtained when: (a) sometimes increases sometil'i:ies decreases 0 .
(a) methyl alcohol is oxidised with KMn04 0 (b) decreases 0
(c) increases 0
(b) calcium acetate is distilled in presence of calcium
(d) none of the above 0
formate IJ 18. Malonic acid on heating gives acetic acid while succinic _...
(c) acetaldehyde is oxidised with K2Cr207 and H2S04 0 acid on heating gives:
(d) glycerol is heated with H2S04 0
(a) butyric acid 0 (b) propionic acid. 0
8. Formic acid is obtained when: , (c) succinic anhydride 0 (d) oxalic acid 0
(a) calcium acetate is heated with conc. H2S04 0
19. Which of the following best represents the structure of the
(b) glycerol is heated with oxalic acid 0
carboxylate ion?
(c) acetaldehyde is oxidised with K2Cr207 and H2S04 0
(d) calcium formate is heated with calcium acetate 0 /P.
(a) R-C ""'-"'_ o
9. Which of the following is isobutyric acid? . 0 0
(a) CH3CH2CH2COOH o
(b) (CH 3 hCHCOOH
(c) CH3CH2CH2CH2COOH o
o
(c) R-C
/P.
").-0 o (d) None of these o
CH3~
(d) /,",HCOOH o 20. Some carboxylic acids and their ruPAC names are given
C2 HS below. Which of the following is not correctly matched ?
10. The higher boiling points of carboxylic acids are due to: [PMT (Kerabi) 2010]
(a) their acidic nature 0 (a) Formic acid Methanoic acid 0
(b) intermolecular hydrogen bonding 0 (b) Acetic acid - Ethanoic acid 0
(c) theirdimerisation 0 (c) Iso-butyric acid - 2-Methyl butanoic acid .0
(d) both (b) and (c) 0 (d) n-Butyric acid - Butanoic acid 0
11. Carboxylic acids do not give the characteristic properties of: (e) Malonic acid - Propanedioic acid 0
(a) >C=Ogroup 0 (b) -COOHgroup 0 21. Formic acid and formaldehyde can be distinguished by
(c) alkyl group 0 (d) none of these 0 treating with:
12. The acidic nature of the carboxylic acids is due to: (a) Benedict's solution 0 (b) Tollens'reagent . 0
(a) high degree of ionisation of the acid 0 (c) Fehling's solution 0 (d) NaHC03 0
(b) greater resonance stabilization of the acid 0 22. Which of the following has the highest boiling point?
(c) greater resonance stabilization of the carboxylate ionO (a) CH3OCH2CH3 0 (b) CH3CH2CH20H 0
(d) all of the above 0 (c) CH3COOH 0 Cd) CH3CH2CH2CH3 0
·<cD; ~;l; i ;·Ils:=: .)I; ;.· .· · _· _ _ _ _ _ _ _ _ _ _ _,...-_ _ _ _ _ _ _ _ _ _ _ _ _ _ ~G~.R~.:E.B~.~O~rg,~a~n!!ie~C:!!.h£!em~is!!.try1.l:.(o~r~C~o~m!!1p~e:!:tl~·tl~·o'E§.ns
23 .. Amongst the acids (a) HC==CCOOH, (b) HzC=CHCOOH 34. Which of the following reduces carboxylic acid directly to
and (c) CH3CHzCOOH, the acid strength follows the primary alcohols?
sequence: (a) LiAlH4 o
(b) Na + C2H50H o
(a) (a) > (b) > (c) 0 (b) (a) < (b) < (c) 0 (e) NaBH4 (d) Hz o o
(c) (a) = (b) (c) 0 (d) (a) = (b) < (e) 0 35. In the reaction,
24. Which of the following compounds is produced when
o.-chloroacetic acid is heated with Ag powder? (A) KCN) (B) Hydrolysis) (C)
(a) Acetic acid 0 (b) Acetone 0 The product (C) is:
(c) Maleic acid 0 (d) Succinic acid 0 (a) acetic acid 0 (b) formic acid o
25. CH3CH zCOOH ~ (A)
Cl
(B)
(c) oxalic acid 0 (d) propionic acid o
Red P 36. Pyroligneous acid contains:
The compound (B) is: [BHU (Mains) 20()8] (a) 2% acetic acid 0 (b) 50% acetic acid 0
(c) 10% acetic acid 0 (d) 20% acetic acid 0
(a) CH 3 CHCOOH o (b) F2CHzCOOH 0
37. When sodium formate is heated at 360"C, main product is:
I
OH OH [JIPMER (Med.) 2008]
(c) H 2C=CHCOOH 0 (d) CICHzCHzCOOH 0 (a) sodium oxalate and H2 o
26. -OH group in alcohol is neutral, while it is acidic in (b) oxalic acid and Hz o
carboxylic acid because: (c) sodium oxalate o
(a) alcohol has alkyl group with +1 effect 0 (d) CO2 and caustic soda o
(b) carboxylic acid is an electrovalent compound [] 38. Sodium acetate + acetyl chloride gives:
(c) alcohol is a covalent compound 0 (a) CH3 COOH 0 (b) sodium formate 0
(d) in carboxylic acid, -OH group is joined to the (c) acetic anhydride 0 (d) acetone 0
electron withdrawing carbonyl group 0 39. Fermentation of ethyl alcohol into acetic acid is done by:
27. Acetic acid exists in a dimer state in benzene due to: (a) zymase 0
(a) condensation reaction 0 (b) diastase 0
(b) hydrogen bonding . 0 (c) maltase 0
(c) presence of carbonyl group 0 (d) Bacterium Mycoderma aceti 0
(d) presence of a-hydrogen 0 40. When sodium formate is heated with soda lime, it forms:
28. Which of the following acids is the strongest? [VITEEE 2008]
[MGIMS (Med.) 2007] (a) H2 0 (b) CO 0
(a) CH3 COOH 0 (b) CHzCICOOH 0 (c) CO 2 0 (d) water vapour 0
(c) CHClzCOOH 0 (d) CCl3COOH 0 41. Methyl magnesium bromide on reaction with SOz followed
29. Which of the following is the strongest acid? by hydrolysis gives: [AMU (Engg.) 2010]
(a) HCOOH (PKa 3.77) 0 (a) methyl sulphonic acid 0
(b) C6H5COOH(PKa 4.22) 0 (b) methane sulphinic acid 0
(c) CH 3 COOH(pKa 4.71) 0 (c) dithio acetic acid 0
(d) CH 3 CH zCOOH(pKa 4.88) 0 (d) ethanethiol 0
30. Which one of the following is a strong reducing agent? 42. In the following reaction,
(a) Ethanoic acid 0 (b) Benzoic acid 0
RCHzCOOH X Excess NH3 ) Y
(c) Methanoic acid 0 (d) Chloroacetic acid 0
31. When sucrose is heated with conc. HN03 in presence of the major amounts of X and Yare: [UPSEE (Engg.) 2008]
V205, the prod,uct formed is: (a) RCHBrCONH 2; RCH(NH2)COOH 0
(a) sucrose nitrate 0 (b) formic acid 0 (b) RCHBrCOOH; RCH2CONH2 0
(c) citric acid 0 (d) oxalic acid 0 (c) RCH2COBr; RCH2COONH4 0
32. The weakest acid among the following is: (d) RCHBrCOOH;RCH(NH2 )COOH 0
43. Which one of the following would be expected to be most
(a) CH3 COOH 0 (b) CICHzCOOH 0
highly ionised in water?
(c) ClzCHCOOH 0 (d) CI3C·COOH 0
(a) CH2CICH z CH zCOOH 0
33. Formic acid:
(b) CH3 CHCICH 2COOH 0
(a) is immiscible with water 0
(c) CH 3CH 2CHCICOOH 0
(b) reduces ammoniacal silver nitrate 0
(d) CH3CH2CCl 2COOH 0
(c) is a weak: acid, nearly three and a half times weaker than
44. Mercuric chloride is reduced to mercurous chloride by:
acetic acid 0
(a) acetic acid 0 (b) carbon tetrachloride 0
(d) is prepared by heating potassium formate 0
(c) formic acid 0 (d) ammonia 0
45. Which is the correct order of acidity from weakest to 55. The carboxylic acid which reduces Tollens' reagent is:'
strongest acid for these compounds : [VMMC2007)
OH I (a) CH 3CH 2CH 2COOHD (b) CH CH 2COOH 0
6 2) 8
3
O"-C/ 0H (c) CH 3 COOIi 0 (d) HCOOH 0
56. What is the main reason for the fact that carboxylic acids can
undergo ionisation?
CF,CH,OH. (a) Absence of alpha-hydrogen 0
(n (b) Resonance stabilization of the carboxylate ion 0
(II) (III) (IV)
(c) High reactivity of alpha-hydrogen 0
[PMT (Kerala) 2010} (d) Hydrogen bonding ,0
(a) I<IV<III<II o (b) IV<I<III<II 0 57. CH3CH2CH2CH2CH2COOH ~
o (d) II < III < I < IV
r
(c) III<IV<I<II 0
(e) II<III<IV<I o 2
46. Which one of the following is used to remove ink and rust CH3 CH 2CH 2CH 2CH-COOH
stains on cloth? the reagents used in the conversion are: [DPMT 2008)
(a) Oxalic acid 0 (b) Alcohol o (a) (i) Red P, Br2/(ii) NH3 (excess) 0
(c) Ether 0 (d) Kerosene o (b) (i) PBr3/(ii) NH3 0
47. Oxalic acid on6:eatment with conc. H 2S04 gives: (c) (i) PBr3, NaCN/(ii) LiAlH4 0
[AFMC2010) (d) none of the above 0
(a) CO only o (b) CO2 only o 58. Between CH 3COOHand HCOOH, the HCOOH will be:
(c) CO2 + H 2 0 o (d) H20+CO+C02 o (a) less acidic 0 (b) equally acidic 0
48. Which of the following is used in synthetic lemonade? (c) more acidic 0 (d) non-acidic 0
(a) Tartaric acid [J (b) Acetic acid 0 59. What are A, B, C in the following reactions?
(c) Citric acid 0 (d) Oxalic acid 0 (i) (CH3C02 hCa ~ A
49. The reaction,
CCI (ii)CH3C02H~B
RCOOAg + Br2 --4 RBr + AgBr + CO2 RedP
is called: (iii) 2CH3C02H -,-P-=-40....:.10"--l» C [EAMCET 2009)
(a) HVZ reaction 0 (b) Hunsdiecker reaction 0
(c) Hofmann's reaction 0 (d) Carbylamine reaction 0 A B C
(a) C2 H 6 CH3COCH3 ( CH3 COhO o
50. RCOOH + N3H H 2S04(Conc.» RNH2 + CO 2 + N2 (b) (CH3COhO C2 H6 CH3COCH3 o
The above reaction is called: (c) CH 3 COCH 3 (CH 3CO hO C2 H 6 o
(a) HVZ reaction o (d) CH3COCH 3 C2H6 (CH 3COhO o
(b) Hunsdiecker reaction o 60; Adipic acid is a:
(c) Schmidt reaction o (a) dibasic acid 0 (b) tribasic acid o
(d) decarboxylation reaction o (c) monobasic acid 0 (d) tetrabasic acid o
51. Acetic acid does not form acetyl chloride with: 61. Hydrated oxalic acid contains:
[AFMC2007) (a) two water molecules 0 (b) three water molecules 0
(a) PCIs 0 (b) PCl 3 o (c) four water moleculesD (d) five water molecules 0
(c) SOC1 2 0 (d) C1 2 o 62. Lactic acid is:
52. The product (C) in the following reactions is: (a) propionic acid 0
(b) a-hydroxy propionic acid 0
NH" H t PO
RCOO.H~(A)~(B)~(C) (c) Jl-hydroxy propionic acid 0
Heat
(d) none ofthe above 0
(a) RNH2 0 (b) RCN o 63. Which of the following compounds does not react with
(c) RNC 0 (d) RCONH 2 o NaOH? (CPMT 2004)
53. The compound insoluble in acetic acid is:
(a) CH3COOH 0 (b) CH 3CONH 2 0
(a) calcium oxide 0 (b) calcium carbonate 0
(c) C 6 H s OH 0 (d) CH3CH20H 0
(c) calcium oxalate 0 (d) calcium hydroxide 0
64. Tamarind contains:
54. Which of the following cannot reduce Fehling's solution?
[BHU (Screening) 2008)
(a) tartaric acid o (b) lactic acid o
(a) Formic acid o (b) Acetic acid. 0
(c) citric acid o (d) succinic acid o
(c) Formaldehyde o
(d) Acetaldehyde 0
if
G.R.B. Organic ChemistryforCompetitions .
(a) fonnic acid 0 (b) acetic acid 0 97. Maleic acid and fumaric acid:
(c) propionic acid 0 (d) oxalic acid 0 (a) have identical melting point 0
86. Cyanogen on hydrolysis with dii. HCI gives: (b) form the same ester with methanol 0
(a) fonnic acid 0 (b) acetic acid 0 (c) have identical solubility in water 0
(c) glycol 0 (d) oxalic acid 0 (d) form the same anhydride on heating 0
87. Maleic acid on catalytic reduction gives: 98. Which of the following is most effective for the hydrolysis
(a) oxalic acid 0 (b) malonic acid 0 of an ester?
(c) succinic acid 0 (d) tartaric acid 0 (a) Dilute alkali 0 (b) Dilute acid 0
88. By the oxidation of benzene with air in presence of V20S (c) Water 0 (d) Acid or alkali 0
catalyst heated to 400-450"C yields: 99. An unsubstituted amide is converted into the acid and
(a) acetic acid 0 (b) succinic acid 0 nitrogen by:.
(c) malic acid 0 (d) maleic anhydride 0 (a) HCI 0 (b) HN02 0
89. Ammonium succinate on strong heating gives: (c) NaOH 0 (d) P4010 0
(a) succinic acid 0 (b) succinic anhydride 0 100. Which of the following reactions is expected to readily give
(c) succinimide 0 (d) tartaric acid 0 a hydrocarbon product in good yield?
90. Acetic acid dissolved in benzene shows a molecular mass (a) RCOOK Electrolysis) o
of:
(Ii) 30 0 (b) 60 0 Br2
(b) RCOOAg~ o
(c) l20 0 (d) 240 0
91. CH3COOH+CH2=C=O~(X) (c) CH3 CH3 ~ 0
frv
(X) is most probably:
(a) (CH3CO)20 0 (b) CH3COOCH2CH3 0 (d) (CH 3 )3C-O C2H50H) 0
(c) CH3CH2COOCH3 0 (d) (COOHh 0 101. Which of the following methods cannot be' used for the
92. An aqueous solution offonnic acid cannot be fractionated to preparation of an ester?
get anhydrous acid because: (a) RCOOH+R'OH+H+ 0
(a) it explodes on wanning 0 (b) RCOO+R'OH+Pyridine 0
(b) its boiling point is about the same as that of water 0
(c) RCOOH+R'OH+OH- 0
(c) it decomposes in aqueous medium 0
(d) it polymerises on wanning 0 (d) (RCO)20+ R'OH+ Pyridine 0
102. Best starting material to synthesize 2-methyl-2-butenoic
93. Action offonnic acid on ToUens' reagent shows:
acid is:
(a) acidic nature offormic acid 0
(b) basic nature of fonnic acid 0
(c) that formic acid is a reducing agent 0
(d) that fonnic acid is an oxidising agent 0
94. Propionic acid when reacted with bromide in the presence of
phosphorus forms: o
(a) CH2{Br)CH2COOHD (b) CH 3CH2COBr 0 I
(c) CH3-CH-CHO 0 (d) CH3CH2-C-CH3 0
(c) CH3CH(Br)COOH 0 (d) CH3CH(Br)COBr 0 I .
95. Fonnic acid can be distinguished from acetic acid by its CH3
reaction with: [BHU 2006)
(a) ToUens' reagent 0 (b) NaHC03 . 0 103. Which of the following carboxylic acids undergoes
(c) NaOH 0 (d) none of these 0 decarboxylation easily?
96. A compound undergoes the following sequence of reactions: (a) C6HsCO-CH2COOH 0
(b) C6H sCOCOOH 0
C3H SN Hydrolysis C H 0 °2 /P (c) C 6Hs-CH-COOH 0
) 3 6 2~
(A) I
NH3 OH
C3HS02CI----"'-7 C3 H1N02 [DCE2000) (d) C6HS -CH-COOH 0
(8) (C)
The compound (C) is:
I
NH2
(a) l-nitropropane o 104. The molecular weight of benzoic acid in benzene as
(b) 2-aminopropionic acid o
(c) 2-nitropropane o determined by depression in freezing point method cor-
(d) 2-hydroxypropanamide ·0 responds to:
;\;' ··~.·.·.!:I"'.!!'I!!9128:,,,'!_-:-________________________G=.R.:;;;.B::::..:..;O:;:::.r:,..::g..:;:a::.:n::;:ic;...;C:;;;;n:.:,:e:.:.;m..:;:is;;.;trY;...<...;A""o.:...r.,.;;;C""o,;;";.m",,p..;;;.eti-..·ti...'o_n=s
(a) ionization of benzoic acid 0 In the above reaction, product 'P' is: [CBSE (Med.) 2002]
(b) dimerisation of benzoic acid 0
6 6
CHO COOH
(c) trimerisation of benzoic acid 0
(d) solvation of benzoic acid 0
105. When propionic acid is treated with aqueous NaHC03, CO 2 (a) 0 (b) o
is liberated. The 'C' of CO 2 comes from:
(a) methyl group 0 (b) carboxylic acid group 0 OH
(c) methylene group
0
(e) 6
113. On vigorous oxidation by permanganate solution,
o
6
117. When H 2C=CH-COOH is reduced with LiAlH4' the
compound obtained will be:
(a) o [AIEEE 2003; JCECE (Med.) 2008]
(a) CH3CH2COOH 0 (b) CH3CH2CHO 0
~ . COOH (c) CH3CH2CH20H 0 (d) H2C=CHCH20H 0
118. Ethyl isocyanide on hydrolysis in acidic medium gives:
(c) HCOOH D(d)U o [AIEEE 2003]
MgBr (a) ethanoic acid and anunonium salt o
(b) propanoic acid and anunonium salt o
o
112·6 (c) ethylamine and methanoic acid
(d) methylamine and ethanoic acid o
Carboxylic Acids
119. The correct order of acidic strength of carboxylic acid is: 125. Identify X and Y in the following sequence of reactions
[DCE2009] respectively:
(a) acetic acid < benzoic acid < formic acid o
(b) formic acid < benzoic acid < acetic acid o CH3CHO HN03 ) X _P4-"-O-"IO~) Y
A
(c) formic acid < acetic acid < benzoic acid o [EAMCET (Med.) 2005]
(d) acetic acid < formic acid < benzoic acid o (a) C 2 H s OHand C2H4 o
120. Which among the following is the strongest acid?
[DPMT2004]
(b) CH3COOHand(CH3COhO o
(a) HOCI 0 (b) HCI0 2 o (c) CH3COOHand CH3COOCH3 o
(c) HCI03 0 (d) HCl04 o (d) C 2 H sOHand CH3COOH o
126. The correct order of increasing acid strength of the
121. When CH3COOHreacts with CH 3 -MgX:
compounds:
[AMU (Med.) 2004]
(A) CH3C02H (B) MeOCH 2C02H (C) CF3C02H
(a) CH3COX is formed 0
Me" .
(b) hydrocarbon is formed 0 (D) /C0 2 H IS: [AIEEE 2006]
(c) acetone is formed 0 Me/
(d) alcohol is formed 0 (a) B<D<A<C o (b) D<A<C<B o
122. Among the following acids, which has the lowest pK a (c) D<A<B<C o (d) A <D< C<B o
value? [AIEEE 200:; I
(a) CH 3COOH 0 (b) HCOOH 0 127. The d (+) lactic acid is obtained from: [CET (Gujarat) 20061
(C)(CH3hCH-COOHD (d) CH3CH 2COOH 0 (a) fermentation of cane sugar 0
123. Products of the following reaction, (b) green vegetables 0
(c) muscles 0
CH3 -C==CCH2CH3 (i) °3 ) ? are: (d) fermentation ofmiIk sugar 0
(ii) Hydrolysis
128. An acid reacts with isotopically labelled methanol to
[CBSE (Med.) 2005]
produce: [PMT (HP) 2006]
(a) CH3COOH + CO 2 o (a) methyl acetate having the labelled oxygen 0
(b) CH3COOH + HOOCCH 2CH 3 o (b) water having all the labelled oxygen 0
(c) CH 3CHO+ CH3CH 2CHO o (c) both methyl acetate and water contain isotopic oxygen 0
(d) CH3COOH + CH3COCH3 o (d) no esterification 0
124. A set of reactions yielded a product (D):
129. Amount of oxalic acid present in a solution can be
CH3COOH SOC\ (A) Benzene determined by its titration with KMn04 solution in the
anhyd. AlC1 3 presence of H 2SO 4. The titration gives unsatisfactory result
when carried out in the presence ofHCI because HCI:
(B) HCN) (C) HOH) (D)
[AIEEE 20081
The structure of (D) would be: [eBSE (Med.) 2005] (a) oxidises oxalic acid to carbon dioxide and water 0
COOH (b) reduces permanganate to Mn 2+ .0
I (c) gets oxidised by oxalic acid to chlorine 0
(a) r(Y-CH2-i-CH3 o
(d) furnishes H+ ions in addition to those from oxalic acid
~ OH o
130. When acetic acid is treated with P20 S, the product is:
[AMU (Med.) 2006]
o (a) ester 0 (b) ether 0
(c) alcohol 0 (d) anhydride 0
131. When acetyl chloride reacts with sodium propionate, the
productformedis: [DPMT20091
(a) acetic propionic anhydride 0
o (b) acetic anhydride 0
(c) n-propyl acetate 0
Cd) pent-2,4-dione 0
132. In the reaction
o CH3CH2COONH4
po
---L4 (A)
H+/HO
2) (B)
CA) and (B) are: [DPMT (Med.) 20071
700· G.R.B. Organic Chemistry for Competitions
JJ
(a) Ifboth (A)and (R)are correct and (R)is the correct but it does not give the test of carbonyl group.
bOnd~O{
explanation of (A).
(b) Ifboth (A) and' (R) are correct but (R) is not correct
explanation of (A). , eR) Due .. resonance ,Jouble,1he
(c) If (A) is correct but (R)is incorrect.
(d) If (A)is incorrect but (R)is correct. group is greatly reduced.
1. (A) Acetic acid does not give halofonn reaction. 7. (A) The pKa value of acetic acid is lower than that of
(R) Acetic acid has no a.-hydrogen. phenol.
2. (A) Acetoacetic .ester CH3COCH2COOC2Hs gives (R) Phenoxide ion is more resonance stabilized.
iodofonn test. [AIIMS 2004]
(R) It has CH3CO- group attached to methylene group. 8. (A) HCI04 is a stronger acid than HCI03.
3. (A) Formic acid reduces mercuric chloride. (R) Oxidation state ofCl in HCI04 is + VII and in HCI03 it
(R) Formic acid has reducing aldehydic group. is+V. [AIIMS2004)
4. (A)(CH 3h C-COOHdoes not give HVZ reaction. 9. (A) The molecular weight of acetic acid determined by
(R) It does not have any a.-hydrogen. depression in freezing point method in benzene and
5. (A) Formic acid is a weaker acid than aCetic acid. water was found to be different.
(R) pKa of formic acid is less than acetic acid. (R) Water is polar and benzene is non-polar. [AIIMS 20051
IANSWERSl
OBJECTIVE QUESTIONS
1. (d) 2. (a) 3. (b) 4. (c) 5. (c) 6. (a) 7. (c) 8. (b) 9. (b) 10. (d)
11. (a) 12. (c) 13. (d) 14. (a) 15. (b) 16. (a) 17. (b) 18. (c) 19. (b) 20. (c)
,21. (d) 22. (c) 23: (a) 24. (d) 25. (c) 26. (d) 27. (b) 28. (d) 29. (a) 30. (c)
31. (d) 32. (a) 33. (b) 34. (a) 35. (d) 36. (c) 37. (a) 38. (c) 39. (d) 40. (a)
41. (b) 42. (d) 43. (d) 44. (c) 45. (b) 46. (a) 47. (d)' 48. (c) 49. (b) 50. (c)
51. (d) 52. (b) 53. (c) 54. (b) 55. (d) 56. (b) 57. (a) 58. (c) 59. (d) 60. (a)
61. (a) 62. (b) 63. (d) 64. (a) 65. (c) 66. (b) 67. (c) 68. (b) 69. (d) 70. (b)
71. (c) 72. (a) 73. (d) 74. (b) 75. (c) 76. (b) 77. (b) 78. (c) 79., (b) 80. (d)
81. (b) 82. (a) 83. (cl 84. (d) 85. (c) 86. (d) 87. (c) 88. (d) 89. (c) 90. (c)
91. (a) 92. (b) 93. (c) 94. (el. 95. (a) 96. (b) 97; '(c) 98. (a) 99. (b) 100. (a)
101. (c) 102. (d) 103. (a) 104. (b) 105. (d) 106. (d) , ' 107. (a) 108. (a) 109. (a) 110. (b)
111. (b) 112. (b) 113., (d) 114. (c) 115. (b) 116. (b) 117. (d) 118. (c) 119. (a) 120. (d)
121. (b) 122. (b) 123. (b) 124. (d) 125. (b) 126. (c) 127. (c) 128. (a) 129. (b) 130. (d)
131. (a) 132. (d) 133. (c) 134. (a) 135. (c) 136. (a) , 137. (c) 138. (b) 139. (a) 140. (d)
141. (a,c) 142. (a,b) 143. (a,c) 144. (b,d) 145. (a,b) 146. (a,b,c) , 147. (a,b,d) 148. (b,c,d) 149. (b,c) 150. (a,b,c,d)
151. (b,c,d)
1. (c) 2. (d) 3. (a) 4.. (a) 5. (d) 6. (a) 7. (b) 8. (b) 9. (a)
t
G.R.B. Organic Chemistry for Competitions
0
whereas compound (B) gives hexa-I,6-dioic acid. What are (A) and (B)?
(Hint: Compound (A) must be an alkyne because it gives mixture of two acids on oxidation. Compound (D) should be cycloalkene because it
gives dioic acid on oxidation.]
2. Complete the following reactions:
o
(Q 0:~C:OH ~ . . . . . . . . . . . . . . . + <Xl,
o
(ii) CH3 -~-OH PCls t (A) Rnse~d's) (B) Dil. NaOH ) (C)
reactIon
0"
0 0
o
(Ans. (i)
6- CH2COOH II
(ii) (A) = CH 3 -C-Cl, (D)= CH3 - C -H,
o
II
(iii)
('r-Br
V
3. Complete the following reactions:
(iv)
6- CH3
0-I H- CH =CH-CH 3
V O-C-R
II
o (SN')
'------~ (B)
Dil. NaOH
Br
I
(vii) CH3 -CH2 -COOH, CH3 -CH-COOH, CH3 -C-COOH
I ·1
Br Br
[Ans. (i) CHzCICOOH, HCOOH, C6H sCOOH, CH 3 COOH, CzHsCOOH, (CH 3)zCHCOOH
(ii) CH 3CH zCHCICOOH, CH3CHCICH 2COOH, CHzCICHzOI.::COOH, CH 3CH2CH 2COOH
(iii) CCI 3COOH, CHCI 2COOH, CH 2CICOOH, CH 3COOH
(iv) FCHzCOOH, CICH 2COOH, BrCHzCOOH, ICHzCOOH
(v) CH 3 -CH-COOH, CH3-CH-COOH, CH 3-CH-COOH, CH 3 CH 2COOH
I I I
NOz CN Cl
Br
I
(vii) CH3-C-COOH, CH3-CH-COOH, CH 3 -CH z -COOH]
~r Ar
7. Complete the following reactions:
(i) ~c==cB
V
_KM-::-n~O-,::-4~) or031H20
(ii)
W Cone. KMn04
.o.,H3O+
(iii)
a CH2
HBr
----t (A) Mg/Etber ) (B)
) (F)
. 704 G.R.B. Organic Chemistry (or Competitions
0
, II
(iv) cr-<>H 2CH3Li
)1
H2O
(V)
C; COOH
t=O
BzI4
H0
2
)?
•
0
(vi)
t>1 U -Cl+H ----+ 1
. [ADs. (i) y C o o H
C1h CH CH
HBr CO2+HjO eyCH!
(iii) Jo
e y Br 3 MgfEtber • e yMgBr
3 Jo CooH
a
1-
(If) (8) (C)
Peroxide
°II °II
(iv) Cr~H 2CH3Li
H~
. CrC-C H
3
(v) ~x 0
BU.
2''{o Jo
H~
~o.
..
I
C=O
CooH CH20H
Carboxylic group is reduced in preference to ester group present in the same molecule.
(v» [>-
.
°
Vl
11
Cone. ill
Excess
-, > ',-.
CH 2 -CH 2 -1
Cone. HI
Excess
)I
CH2-r;H_' Adipieaeid
o Alkaline) (A)
KMn04
~
,OH
cra) HB)
AcilH
HCN )
ceoo
(C) HOH/HCI) (D) Red P ) (E)~
HI
Ng~
(F)
IAns.
O Alkaline
KMn04
..
CX (A)
OH
__
AcOH
J
C_rO_ --II>1I
(8)
HCN
II
~CN
(C)
HOHIHel
(X
(E)
COOH
COOH
., RedP/H(
a. (D)
OH
COOH
OH
COOH
" -CH2
__ CHi....,
CH CH-COOH
IAns. (i) (A): \I I This product is formed as a result of Diels' Alder reaction.
CH CH-COOH
"CH{/'"
a
OH
CH) Cone. H2S04
---=--~) (A) NBS ) (B) NaCN) (C) HOHtHCI) (D)
II (N-Bromosuccinimide)
a
OH
IAns. ,
CH3
Cone. H2S04 II eyCH3
II
' NBS
Allylic
J U CH3
Br
" NaCN II 'U~ CH
3
CN
HOHlHCI .. U CH3
"t 1
+ NH3
COOH .
(A) bromination (8)
Succinimide
Br OH
(c) CH3-CH 2-COOH
RedP I . ow I
) CH3-CH-COOH ~ CH3-CH-COOH + Br-
. Br2,a
o 0
r------· ~
/O!fl ___ lJ!)~-C~ -2Hp /O-C~
~
CH 3 -CH........ ,.:t"------, /CH-CH3 ) CH 3 -CH, /CH~CH3]
. ........C-OH HIO' Il . ........C-O'
II -------~ I
o 0
Lactic acid Lactide
13. Give the star mark to the hydrogen which is most acidic in the following compounds:
o o
II II
(a) CH3-CH2-. C-CH2-CH3 (b) H2C=::=CH-CH2-C-H
o OH 0
II (d) CH3-CH-C-OH
I II
(c) CH3-C-O-CH2-CH 3
(Ans. (a) Hydrogen of methylene group will be most acidic.
o
I .
.
CH 3 -CH2 -C-CH2-CH3 .
(b) In this compound, allylic hydrogen will be most acidic.
~
CH2=CH-CH2-:-C-H .
(c) Hydrogen of methylene group will be most acidic.
o
.11
CH3-C-O-~H2-CH3
14. What happens when malonic acid is heated with urea in presence ofPOCI 3 ?
W r:------
~:.~l!--.!IJ-N>
f
IAns. CH2'1 ~ ___+___ =0
-tOH H.LN
"------, I
o H
Barbituric acid (Malonyl urea)
¢H
15. Complete the following reactions:
(i)
CH(C'CH2
¢
COOH COOH
IAns. (i)
/C,
¢ B2"<. II
H20 fOJr
/CH,
.
CH3 CH2 CH3 CH20H
(D) =
COOH
oH
(E)
(06
COOH
ND3 ) (A) ~ (B) 011) (C) Rearrangement) (D) 2011) (E) + C02
Heat Heat'
COOH
6
(n)
o
II
Heat
) (A) ~ (B) on-) (e) Rearrangement ~ (D) 20n-) (E)
o
II
Heat
0
II
, c,.....,..ND C-N-Br N=C=O
6 6!'
C-ND2
o
(C)=
6 0
(D) =
6 (E)
(5
II II
C-NH '
II
(~~6
C-N-Br N=C=O
6 6~
C-NH2
17. The compound which does not give a crystalline product on CH CH COOH Red P/Br2) (A) KCN) (B) HOH/H\ (C) ,
3 2 ~
reaction with either sodium bisulphite or 2,4-DNP but (a) propanoic acid D (b) malonic acid 0
reduces ammoniacal silver nitrate solution is: (c) acetic acid D (d) a.:-methyl malonic acid 0
(a) C 6 HsCHO D (b) C 6 H sCH 20H D 24. Which of the following has the highest pKa value?
, 0
o 0
~ ,
II N02 II .
(c) H-C-OH D (d) CH 3CHO D
(a) ~OH D, (b) ~"OH D
18. The reaction of tartaric acid wffu Fenton's reagent results in
the formation of: + 0 o
(a) dihydroxy maleic acid
(b) suCcinic acid
D
D (c)
NMe311
~OH O(d)NC~ OH, D
(c) lactic acid D
(d) crotoQic acid D 25. Which ofthe following is the most acidic?
H
o 0
~OH ~OH
19. CH3 -CH 2-COOH ,N3 ) (A)(by reaction Rd
H2S04 (a) 0 (b) 0
1
, A Br2/P
" Br CI
RI -),Schmidt reaction; R2 -)HVZ reaction 26. Consider the following compounds, which of these will
(b) (A) CH3CH 2 CONH 2 , (Ji) CH 3 Clf2 COBr D release COt with 5% NaHC0 3?
R 1 -) HVZ reaction; R2 -) Schmidt reaction o OH
(c) (A) CH3 CH2 NH 2, (B) CH 3 CH 2COBr 0 "r---( /COOH
R, -) HVZ reaction; , R2 -) Schmidt reaction '~' , CH 2"-.COOH
(d) None is comet 0 ' (iii)
o OH (ii)
20. C4 H 6 0 4 ~ C 3 H 6 0 2 S~lirne) C 2 H 6 (i)
(A) , (B) (a) (i), (ii) and (iii) 0 (b) (i) and (iii) o
The compound [A] is: (c) (it) and (iii) 0 (d) (i) and (ii) o
(a) CH3 -CH(COOHh o 27. Which of the following has the lowest pKa value?
CH 2-COOH 0'
(b) I o
, CH2 -COOH (a) CH3 -CH2 -C-OH o
(c) both are correct 0 "
(d) none is correct, 0
(b) CH 2=CH-C-OH
V o
21. Which one of the following undergoes decarboxylation
most readily? o
(a)
o
I
CH 3 CCOOH
(c) 0- 1
II
C-~H o
o
~
~
(d) H-Cs=C-C-OH "
(c) CH3 CCH 2COOH
22. Malonic acid on heating gives ......... while on decarboxy-
y
[Hint: In (H-C-C-C-OH);the carboxylic group is
lation gives .......... ' attached to C]
(a) acetic acid, ethane _ 0 28. The compound X, in the reaction,
"(b) propanoic acid, methane 0
(c) propanoic acid, ethane 0 X CH3MgI) Y Hydrolysis) Mg(OH)I + CH COOH
3
'(d) acetic acid, methane, D is:
23. Predict the product 'c' in'the following chain of the (a) HCHO P (b) CH3CHO o
. ' reactions:
o (c) (CH3)2CO o
(d) CO 2 o
Carboxylic Acids 709
19. The most suitable reagent for laboratory preparation of 36. (A), (B) and (C) are three dicarboxylic acids such that:
acetyl chloride from acetic acid is:
(a) PCls 0 (b) HCI 0 (A) _-=A=---+> carboxylic acid + CO2 t .
(c) SOCh 0 (d) PCl 3 0 (B)· A ) acid anhydride + H20t
(HInt: CH3COOH + SOCl 2 ~ CH~COCI + S02 t + HCI t (C) A ) cyclic ketone + HzO+CO z t
Byproducts in above reaction are in gaseous state hence, then:
they can be separated easily.] (A) (B) (C)
30. When propanoic acid is treated with aqueous NaHC0 3 , (a) adipic acid malonic acid succinic acid 0
CO 2 is liberated. The carbon ofcarbon dioxide comes from: . (b) malonic acid adipic acid succinic acid 0
(a) methyl group 0 (b) carboxylic group 0 (c) adipic acid . succinic acid malonic acid 0
(c) methylene group 0 (d) bicarbonate 0 (d) malcmic acid succinic acid adipic acid 0
. • /COOH
IHint: CH 3-CH2- COOH + NaHC0 3 ~ (Hint: CH2'-. CH3-COOH + CO 2
CH 3-CH2-COONa + H20 + CO2 t '-COOH Carboxylic acid
Thus, carbon of carbon dioxide comes from sodium
bicarbonate. ]
31. Decarboxylation of carboxylic acid takes place:
(a) in soda lime treatment 0
(b) in quick lime treatment 0 . Succinic acid Acid anhydride
(c) in Kolbe's electrolysis 0 o
W~d~~~~ 0 I
..,.......C,
3l. A dibasic organic acid (A) on heating gives (B). The
CH CH2 + CO 2 + H20 ]
compound (B) on soda lime treatment gives the lowest I 2 I
alkane which can be prepared by Wurtz synthesis. The Adipic acid CH z-·-CH 2
compound (A) is: '
Cyclic ketone
/COOH
(a) CH r ..... 0 Conc. H2S04 ) X +Y
......... COOH
CH 2 -COOH 37. HCOOH/ ..
(b) I ,0 . ' \ . Dil. H 2S04 ) Z
CH 2 -COOH
./CH2 -COOH
Products X, Y and Z are respectively:
(c) CH 2-..........:. 0
CHz-COOH COOH CooH
/COOH· (a) CO, H2 O, I 0 (b) I . CO, H 2 0 0
(d) CH 3 -CH....... . 0 COQH COOH
........ COOH COOH CooH
33. 0.759 g of a silver salt of a dib.asic organic acid on ignition (c) COz. H2 • I. 0 (d) I ,C02 • H2 0
left 0.463 g metallic silver. The equivalent weight of acid is: COOH COOH
(a) 70 0 (b) 108 0
(Hint: HCOOH Cone. H:zS°4 ) CO(g)+ H20(g)
(c) 60 0 (d) 50 0 11 .
(Hint: Equivalent weight of acid
Mass Of. silver ~t x 108 _ 107]
Mass of sIlver reSIdue
.' 2HCOOH + [0] nil. H2SO4 )
OOH
COOH
+ H20] f
34. The reagent, which distinguishes formic acid from acetic
acid is: .
38. CH3 CH 2COOH Br2/Red p) (A) Ale. NH3 ) (B)
A
(a) 2,4-dinitrophenyl hydrazine 0 The fmal product (B) in above reaction is:
(b) HgCl2 0 (a) alanine 0 (b) pyruvic acid 0
(c) C2 Hs ONa 0 (c) .citric acid 0. (d) lactic acid 0
(d) Hg 2 Clz 0 Br
35. Which of the following compounds easily undergoes .
Bri/Red P; CH -bH-COOH
decarboxylation? 3
(a) CChCOOH 0 (b) Jl-Keto carboxylic acid 0 A lAlC. NH3
(c) HCooH 0 (d) CH3 C O O H O
(Hint: P-Keto acids are most easily decarboxylated. ,NH2
I
? -C0 2 ~ CH 3-CH-COOH]
CH3-t-CHz-COOH ) CH3-~-CH3] Alanine
710 G.R.B. Organic Chemistry for Competitions
39. Which of the following carboxylic acids undergoes 42. Which of the following intermediate species is/are formed
decarboxylation most easily? in the reaction of acrylic acid with HBr to give
o ~bromopropanoic acid?
I o H 2 C=CH-COOH HBr) BrCH2-CH 2-COOH
(a) 0-0C-CH2-COOH
+
V II
o
, /OH
(a) H 2 C=CH-C ......... o
(b) o-C-COOH ......... OH
/OH
OH (b) H 2 C=CH-C'OH o
I - +
(c) V I CH-COOH o
~ NH2 o
I o
(d) VCH-COOH
o
40. Arrange the following carboxylic acids in order of 43. Which ofthe following will give cyclic products upon being
decreasing acidity: heated or being treated by an acid?
Oxalic acid Malonic acid Succinic acid /COOH
(I) (II) (UI) (a) CH3 -CH 2 -CH 2 -CHz -CH, o
(a) I>II>III 0 (b) III>II>I 0 "OH
(c) II > 1II > I 0 (d) II > I > III 0 OH
41. The intermediate(s) formed during the reaction I
(b) CH3 -CH-CHz-CH 2 -CHz-COOH 0
C6 H5 CH 2COOAg + Br2 CCI 4 ) C6 H 5 CH2Br, OH
is (are): I
(c) CH3 -CH 2-CH-CH 2 -CH2 -COOH 0
OH
o I
(d) CH3 -CH z-CH 2-CH-CHz-COOH 0
44. What types of isomerism are exhibited by hexanoic acid?
o (a) Chain isomerism 0
• (b) Position isomerism 0
(c) C6HS-CH2 o (c) Functional group isomerism 0
(d) Bf o (d) Metamerism 0
R-CH2-CHz-'-OH~R-CH2
< CO"
CO./'"
./'"0
-CH2-COOH
Passage 2 (A) (B)
In above conversion, the reactant (A) follows the sequence
Carboxylic acids having atleast one a-hydrogen react with
of reactions with three reagents.
Cl 2 or Br2 in the presence of phosphorus (or a phosphorus halide)
to give a-halo acids. This reaction is known as
Hell-Volhard-Zelinsky reaction (HVZ reaction), +
(c) HCN,PBr3, KCN (d) H30,KCN,PBr3
Br
R-CH 2-COOH
P/Br2
~
I
) R-CH-COOH
5. CH 3CH 2COOH RedP + Br2 >(A) Ale. -KOH>(B). The
product (B) is:
The HVZ reaction is limited to the formation of a-chloro and' (a) 2-ketopropanoic acid
a-bromo acids and it is sometimes awkward to carry out. The (b) acrylic acid
reagents (X 2 and P) are noxious and the reaction time is often long (c)2-hydroxy propanoic acid
and the conditions of reaction are harsh. (d) 2-amino propanoic acid
Answer the following questions:
712 G.R.B. Organic Chemistryfor Competitions
6
.... (II) 1,4 and 1,5-dibasic acids on heating give cyclic
anhydride.
(III) 1,6 and 1,7 -dibasic acids give cyclic ketones.
Indicate whether the following. reactions are right or wrong:
COOH Adipic acid Cyclohexanone
1. I G
200 C ) CO 2 + CO+ H2 0
(a) Right (b) Wrong
COOH
Oxalic acid CHz-COOH CH2-CO~
(a) Right (b) Wrong 5. I ~I .......0 + H 20
CH 2 -COOH CHz-CO
............... COOH /!,. Succinic acid Succinic anhydride
2. CH2~ ~CH3COOH+C02t'
COOH Acetic acid (a) Right (b) Wrong
Malonic acid
13.1 DERIVATIVES OF CARBOXYLIC ACIDS The relative reactivities of various acyl 'compounds have
The classes of compounds obtained from carboxylic acids by been found to be in the following order:
the replacement of -OH group of the -COOH grOllP with o 0
-X,-NH z• --DOCR or -OR are termed as acid , /C=O>R-C-O-C-R'>R-C
~. ~ (0 >R-C\lo.l
p
derivatives. .x OR' NH z
X_~)
r--..,.._O_H_rep_la_ce_d._b_y _ _ ~
R-C-X
X (el or Br or I) Acid halide Out of acid halides, the acid chlorides are more important
o ones,
-OH replaced by -NH2 \I The overaJI order of reactivity can be accounted for in
fI
R-C-OH-
R-C-NH2
Acid amide
terms of the following 'three factors:
(i) Basicity of the leaving group, (ii) Resonance effect and
Add
o o 0
II (iii) Inductive effect.
-OH replaced by -O---C-R' II II
R-C-O-C-R' (i) Basicity of the leaving group: Weaker bases are
Acid anhydride good leaving groups. Hence, the acyl~erivatives with weaker
'-~--
-OH replaced by -OR'
.. )
~
R-C-O-R'
bases as leaving groups can easily rupture the bond and are
more reactive. Chloride ion is the weakest base while -NH z
Esler
is the strongest base. Thus, acyl chlorides are most reactive and
(where Rand R' may be either same or different)
amides are least reactive,
The acid derivatives undergo hydrolysis and fOfDl the
The correct order of basicity of the leaving group and their
o tendency of leave is:
II
parent acid. (R-C-) group is common to these derivatives
HzN: > :OR > RCOO: > :CI-
and is known as acyl group and hence these derivatives are also
termed as acyl derivatives. (Basicity decreases and Reactivity increases)
Acyl derivatives are characterized by nucleophilic (ii) Resonance effect: The leaving group in each case
suhstitution reaetiens. has an atom with lone pair of electrons adjacent to the carbonyl
Nu Nu group. The compound exists, therefore, as a resonance hybrid.
~""bI);:- ----?R-6=0+:c
R""C (\0:+ :Nu-
L/" L,6"
Intermediate
cw
o R-C\.*J.
II . "-L
(L=X,NH 2 ,0-C-R or OR)
714 G.R.B. Organic Chemistry.for Competitions
This makes the molecule more stable. The greater the unknown but the mixed acetic formic anhydride,
stabilization, the smaller is the reactivity of the acyl compound. HCO . .
However, acyl chlorides are least affected by resonance. Due > 0 (Ethanoic methanoic anhydride), ·is known.
CH 3CO
to lower stabilization, the acid chlorides are more reactive as
the loss of -CI is easier. Greater stabilization is achieved by 3. Acid amides : Acid amides have general formula,
resonance in esters and amides and thus, they are less reactive. RCONH2. The -CONH 2 group is called the amide group ..
(iii» Inductive effect : Higher the -1 effect, more Primary acid amide may be regarded as acyl derivatives of
reactive is the acyl compound. Inductive effect of oxygen in ammonia obtained by replacement of hydrogen atom by acyl
ester is greater .than nitrogen in amide, hence ester is more group.
reactive than an amide. o
13.2 NOMENCLATURE NH3 -H) RCONH 2 orR-C-N~H
I /H
+RCO
1. Acid chlorides: Acid chlorides (acyl chlorides) have the
general formula, RCOCt The common names are derived by They are further classified as primary (l0), secondary (2°)
changing the suffix, '-ic acid', of the trivial names of the corre- and tertiary (3°) according as the -OH part of the -COOH
sponding acids by 'yl chloride'. group is replaced by -NH2, -NIIR' and -NRi groups
In !UPAC system, these are named after the name of respectively. Thus,
alkane by replacing the ending 'e' by 'oyl chloride'. o o o
II II I
Formula Common name IUPACname R-C-NH2 R-C-NHR' R-C-NRi
I" acid amide 2" acid amide 3° acid amide
HCOCI (Unstable) Fonnyl chloride Methanoyl chloride
In common name system, name of the primary amides are
CH 3 COCI Acetyl chloride EthanoyJ chloride
derived from the names of corresponding acids by replacing
CzHsCOCI Propionyl chloride Propanoyl chloride the suffix '-ic acid' by 'amide'. !UPAC names are derived by
C3 H 7COCI Butyryl chloride Butanoyl chloride replacing 'e' ofthe parent hydrocarbon by 'amide'.
2. Add anhydrides: The acid anhydrides may be Formula Common name IUPACname
regarded as being derived from acid(s) with the elimination of HCONH z Fonnamide Methanamide
one molecule of water from two molecules of the same or CH 3 CONH2 Acetamide Etbanamide
different acids. C2H sCONHz Propionamide Propanamide
o 0 C3 H7CONH 2 Butyramide Butanamide
RCOOH -H 20 RCO~ I I
+ -~) /0 or R-C-O-C-R' Secondary and tertiary amides are named by adding the
R'COOH R'CO/ name of the substituent present on the nitrogen atom before the
Carboxylic acids Acid anhydride name of the parent (or primary) amide. The letter 'N' is
(Same or different)
normally written before the name ofthe substituent to indicate
Anhydrides are named by replacing the word 'acid' in the that the substituent is attached to the nitrogen atom. In tertiary
name of the acid by 'anhydride' in both common and !UPAC amides, the letter N is repeated twice. For example,
names.
o 0
Formula Commoilname IUPAC name· IIII / C2H s
CH3-C-NHCH3 CH3-C-N~
Acetic anhydride Ethanoic anhydride N -Methyl ethanamide C 2HS
N,N -Diethyl ethanamide
HCOOC 2H s ; C2HsCOOH 2CH 3COONa + POCt 3 Heat) 2CH 3COCI + NaP0 3 + NaCI
, Ethyl formate Propionic acid, Sodium acetate Acetyl chloride
T
Molecular formula C3 H6 0 2
(CH 3COOhCa+S02CI2 Heat >2CH 3COCI+ CaS0 4
(ii) Chain isomerism: Calcium Sulphuryl Acetyl
CH3CH2CH2COOC2Hs acetate . chloride chloride
Ethyl butyrate 3. From ketenes: By addition of HCI.
, .
o
.
MolecUlar formula C6H120 2 H 2C=C=0 + HCI ~CH3 -C-CI
II
Acid'Derivatives of Acetic Acid Ketene Acetyl chloride
CH 3COOH o
I I
I I I CH 3CH=C=0 + HCI ~CH3CHi -C-CI
CH 3COCl CH 3CONH 2 (CH3COhO CH 3COOC2H s Methyl ketene Propanoyl chloride
Acetyl chloride Acetamide Acetic anhydride Ethyl acetate
Physical properties: Acetyl chloride is a colourless
Acetyl chloride, acetamide, acetic anhydride and ethyl
lachrymatory (tear producing) 1iquid with a pungent odour. It
acetate are the acid derivatives of acetic acid. These are the
boils at 52°C. It fumes in moist air due to the fonnation of
typical compounds of their homologous series and thus, the
hydrogen chloride. It is soluble in ether, acetone and acetic
chemistry of these fuur compounds has only been discussed
acid. They are incapable of forming the H-bond and thus have
here.
lower boiling points than parent carboxylic acids.
1'3.3 ACETYL CHLORIDE OR ETHANOYL Chemical properties: Among the different acid deriva-
CHLORIDE, CH 3 COCI tives, acyl chlorides are the most reactive. In acyl chlorides, the
Acetyl chloride is the most important acyl chloride or acid o
chloride. The first member of the series, fonnyl chloride " . Iy eIectronegative
. '
carbonyl group (-C-) is attached to high
(HCOCI) is an unstable compound and readily break up into
carbon monoxide and hydrogen chloride. chlorine atom. Due to strong electron withdrawing effect of
chlorine atom (-I effect), the electron ,density, on the carbonyl
Methods of Preparation
carbon is reduced further and at the same time, it has a weak
. 1. Acetyl chloride is prepared by heating glacial acetic electron releasing resonance effect (+R effect).
acid with phosphorus trichloride, phosphorus pentachloride or
thionyl chloride. Thionyl chloride is the better reagent because
..0: ..
<:.0:
..
:0:-
the byproducts of the reaction are the gases S02 and HCI,
which are easily separated.
II lin· I +
R-C+-CI [R-C-~!: ~ R-C-Cl:1
(Strong -J effect)
3CH 3COOH + PCl 3 Heat) 3CH 3COCI + H3 P0 3 (Weak +R effect)
Ethanoic acid Ethanoyl chloride
716 G.R.B. OrganicChemistry for Competitions
As a result of combined influence of both these effects, the CH3COCI + H 2NOH ~ CH3CONHOH + HCI
acyl camon atom becomes sufficiently electron deficient. Hydroxyl- Acetyl hydroxylamine.
Hence, acyl chlorides readily undergo a number of amine (Hydroxamic acid)
nucleophilic substitution reactions. in which the attacking CH 3COCI + HzNNH z ~CH3CONHNH2 + HCI
nucleophile can easily attack the electron deficient carbon Hydrazine Acetyl hydrazine
atom. (Hydrazides.)
(vi) Reduction: (a) Acetyl chloride on reduction with
<:11 . _ (.((n "_ hydrogen in presence of palladium over barium sulphate and
R-C-Cl+ .Nu ~R-C-CI~R-C+CI partially PQisoned with a small amount of sulphur or quinoline,
t I I I as catalyst (to avoid further reduction of aldehydes to alcohols)
Nu Nu to form acetaldehyde (Rosenmund's reduction).
CI- + H+ ~HCl CH 3 COCl+ Hz
Pd/BaSO
. 4 ) CH 3CHO + HCI
Compounds which contain strong electron donor group S or qllinoline
with a replaceable hydrogen atom, (e.g., -OH, -NHz, (b) When reduced with LiAlH4 or NaBH 4 , it gives ethyl
-NHR, etc.) readily react with acetyl chloride with the result alcohol. .
that their hydrogen atom is replaced by acetyl group, LiAIH
CH)-CO. This is known as acetylation. CH 3COCI +2H2 4 )CH3CHzOH
Ether Ethyl alcohol
Some of the important reactions of acetyl chloride are
given below: (c) Acid chlorides are reduced to aldehydes by LiH or
(i) Hydrolysis: Acetyl chloride readily reacts with lithium tri-tert.-butoxy aluminium hydride.
water when chlorine atom is replaced by -OH group to form (d) Acid chlorides are reduced to esters of an enediol by
acetic acid. • Na-Hg ~n an inert solvent.
------1
CH)cq~Lt.H!OH~CH3COOH+HCI • o
Acetyl chloride Acetic acid ~ H R", /R
An aqueous solution of aliphatic acid chlorides gives 4R-C-CI + 4Na -14 /C=c., + 4NaCI
RCOO· "OOCR
white precipitate with AgN03 solution.
(vii) Action with salts of carboxylic acids: It reacts
RCOCI + HOH + AgNO) ~ R-COOH + HNO) + AgCl
with sodium salts of carboxylic acids to form anhydrides.
(White ppt.)
(ii) Action with alcohols (Alcoholysis): Acetyl chloride
CH 3COCI + NaOOCCH3 ~ (CH3CO)z0 + NaCI
Sodium acetate Acetic anhydride .
reacts with an alcohol in presence of pyridine base when the
-Cl is replaced by alkoxy group (-OR) to form an ester. o 0 00
CH 3
I I
CCI + HOCCH CH
P 'd' IIII
CH)CQGC-f!IjOCzH s Base) CH 3COOC z Hs + HCI z 3 yn me ) CH 3COCCHzCH 3 + HCI
Alcohol Ethyl acetate Ethanoyl Propanoic acid ~ Ethanoic propanoic
Thioalcohols are acetylated to thioesters. chloride anhydride
~
H. +CIOCCH
P 'd'
ynme)
©t0CCH3
+HCI Acetyl urea
CooH 3 COOH (xvi) Action with alkene: Acetyl chloride adds to an
Salicylic acid Acetyl salicylic acid alkene in presence of catalyst (ZnCh or AlCI3) to form a
(Aspirin) chloroketone which, on heating eliminates HCI to give an
(xiii) Peroxide formation: Acetyl chloride reacts with unsaturated ketone.
+ - .- + ZnCl2
sodium peroxide (N aD-ON a), to form acetyl peroxide. (CH 3hC=CH 2 +CH 3COCl )
2-Methyl propene
0 . 0 0
I + - - + 1:1 . I I o 0
2CH 3-C-CI + N aD-ONa ~CH3C-0-0-C-CH3 \I 1:1 \I
Acetyl chloride Acetyl peroxide (CH3hC-CH2C-CH3 ~(CH3hC=CHC-CH3
+2NaCI
I -HCI 4-Methyl pent-
CI 3-en-2-one
(xiv) Action with diazomethane: Acetyl chloride readily 4-Chloro-4 -methyl
reacts with diazomethane (CH 2N 2) to form diazoketone. pentan-2-one
Diazomethane (CH 2N 2) is used in the Arndt-Eistert Synthesis
(xvii) a-Halogenation : Acid halides undergo
to convert a carboxylic acid into the next higher homologue. tautomerization and so they proceeds fora-halogenation.
0 0 o OH OH
. II - + .. II + I I - CI I
CH3-C-CI+2CH2-N N ~CH3-C-CH-N=N CH 3 -C-Cl 2
CH 2=C-CI ~CH2 -C-Cl
Diazomethane Diazoacetone Acetyl chloride Enol form I I
+ CH3CI +N 2 Cl CI
Diazoketone gives different compounds as follows:
o
HCl
CH3COCH2CI +N2 1:1
---'-'~) CH 2 -C-CI
I
Chloromethyl ketone
-HCI I
CH 3 COCHN 2 _-+-__NH---=3_~CH3CH2CONH2 + N2 CI
. . Diazoacetone Ag2 0 catalyst Propanarnide ... ChIoroacetyl
chloride
H 20
~-=---~CH3COCH20H (xviii) Reaction with HBr, m and HF :
• HCOOH Hydroxy acetone RCOCI + HBr ~ RCOBr + HCI
This diazoacetone loses nitrogen to form a ketene by RCOCI + HI ~ RCOI + HCI
rearrangement when warmed in the presence of silver oxide as
catalyst. RCOCI + HF ~ RCOF + HCI
718 G.R.B. Organic· Chemistryfor Competitions
CH 3COONa + CICOCH 3 Pyridine) (CH 3COhO +NaCI (v) From acetaldehyde: The air oxidation 'of acetalde-
Sodium acetate Acetyl chloride Heat Acetic anhydride hyde is done in presence of cobalt acetate--copper acetate
catalyst at 50-700C under pressure.
Acetic anhydride is prepared in the laboratory by this
reaction. o
o 0 0 0 CH 3CHO +0 2 Catalyst )CH3-~-O-0-' H CH3CHO,
I I C 6 H 6 , ;l
R-C-CI + H-O-C-R' ---':........:...~)R-.
I I
C-O-C-R'
Acetaldehyde 50-70°C Intermediate
Pyridine (CH 3 COhO+H20
+ Acetic anhydride
+ [C5 H5N H]CI-
(vi) From acetic acid :
3. Manufacture: Acetic anhydride is prepared indus-
trially by the following methods: 2CH 3COOH Quartz tube) (CH CO) 0 + H 0
(i) By heating anhydrous sodium acetate with thionyl Acetic acid Porcelain chips, 800°C Aceti:anhYl~ide 2
chloride, sulphuryl chloride or phosphorus oxychloride : Physical properties: It is a colourless, pungent smelling
One half of the sodium acetate is first converted into acetyl liquid. It boils at 139SC. It is sparingly soluble in water but
chloride which then reacts with remaining half of sodium soluble in ether, alcohol and acetic acid.
acetate to give anhydride. Chemical properties: It resembles acetyl chloride in its
CH 3COONa +SOCI2 ~CH3COCI +S02 + NaCI action towards compounds having active hydrogen but it is less
Sodium acetate Thionyl reactive than acetyl chloride. One half of the acetic anhydride
chloride is used for acetylation while the other half is converted into
CH 3COCI +CH3COONa~ (CH 3COhO + NaCI acetic acid. Acetylation is best carried out in presence of
Acetyl chloride Acetic anhydride sodium acetate or cone. H 2S0 4 ,
Oi) By passing chlorine in a mixture of sodium acetate and The following are the important reactions of acetic
sulphur dichloride and distilling the mixture so obtained. anhydride:
8CH 3COONa + SCh +2C1 2 Distill) 4(CH 3COhO (i) Hydrolysis: The hydrolysis of acetic anhydride
Sulphur Acetic anhydride occurs with water or alkalies.
dichloride (CH 3COh 0 + H 20 --'--42CH 3COOH
Acetic anhydride Acetic acid
Acid Derivatives 719
(NH4')2SX "I Jl a .
C6HsCOCH2CH2CH3 -......;...=--~) C6HsCH2CH2CH2CONH2
CH 3COONH 4 Heat) CH 3CONH 2 + H 20
Phenyl propyl ketone Heat "I-Phenyl butyramide
Ammonium acetate Acetamide
(Butyrophenone)
Simple heating of ammonium acetate presents the
following two difficulties: 6. Amide is also obtained by heating diazoacetone with
(a) Some of the ammonium acetate dissociates into acetic NH 3 ·
acid. o 0
CH 3COONH 4 ~ CH 3COOH + NH3 II NH3 II
CH3-C-CHN2 >CH 3CH 2 -C-NH 2 +N2
(b) Some of the acetamide gets hydro lysed into acetic acid
Diazoacetone Propanamide
by the water formed in the reaction. '
CH 3CONH 2 + H20 ~ CH 3COOH + NH3 Physical properties: Acetamide is a colourless crys-
talline solid. It melts at 82°C and boils at 222°C. It is readily
To avoid the above two reactions, ammonium acetate is
soluble in water and alcohol. It exists as a dimer due to
always heated in presence of glacial acetic acid.
hydrogen bonding. Impure acetamide has mousy odour.
2. Acetamide is obtained by the action of concentrated
Chemical properties : (i) Hydrolysis: Acetamide is
ammonia solution on acetyl chloride, acetic anhydride or ethyl
hydrolysed slowly by boiling with water, rapidly by acids and
acetate. These reactions are termed as ammonolysis.
far more rapidly by alkalies (Laboratory test of amide
CH 3COCI +2NH3~CH3CONH2 + NH 4CI group).
Acetyl chloride Acetamide
CH 3CONH 2 + H 20 Boil) CH 3COOH + NH3
(CH3CO)z0 +2NH3 ~CH3CONH2 +CH 3COONH 4
Acetic anhydride Acetamide
CH 3COOC 2H s + NH3 ~CH3CONH2 + C 2H sOH Amides are decomposed by alkali solution liberating NH 3
Ethyl acetate Acetamide gas which gives white fumes with HCI.
3. On heating glacial acetic acid with urea, acetamide is RCONH 2 + NaOH A) RCOONa + NH3 t
formed.
(NH3 + HCI ) NH 4CI)
CH 3COOH+H 2NCONH 2 Heat >CH 3CONH 2 + C02 + NH 3 White fumes
Acetic acid Urea Acetamide CH 3CONH 2 + NaOH A )CH 3COONa + NH3 t
4. Acetamide is also obtained when partial hydrolysis of (ii) Amphoteric nature (Salt formation) : Acetamide
methyl cyanide is done either by alkaline H 20 2 or by dilute behaves as an amphoteric compound, i.e., shows feebly acidic
sulphuric acid or conc. HCl as well as feebly basic nature. It forms salts with acids and
H20 2 (alk.) bases both.
CH 3CN +H 20 ) CH 3CONH 2
Methyl cyanide or cooc. HCI Acetamide
CH 3CONH 2 + HC1(conc.)~ CH 3CONH 2 ·HCl
Acetamide Acetamide hydrochloride
o (only stable in aqueous solution)
R-C=N + H 20
II
Cooc. HCI ) R-C-NH2 2CH 3 CONH 2 + HgO ~ (CH 3CONHh Hg + H 20
Alkane nitrile (Cold) Acid amide Acetamide Mercuric Mercuric acetamide
oxide
5. By Wilgerodt reaction: This reaction was originally This behaviour is due to the presence of tautomerism.
carried out by heating a carbonyl compound (aryl alkyl ketone) o OH
with an aqueous solution of yellow ammonium poly sulphide II ' I
(NH4 h SX to give an amide with the same number of carbon CH3-C-NH2 ~ CH 3 -C=NH
atoms. (Forms salts with acid) (Forms salts with base)
o CH 3CONH 2 + Na Ether) CH 3CONHNa +lH2
II (NH4)2 SX .
Sodium acetamide 2
C6HS -C-CH3 ---~) C6HsCH2CONH2
Methyl phenyl ketone Phenyl acetamide (iii) Reduction : Acetamide undergoes reduction with
(Acetophenone) sodium and alcohol or' ethereal solution of LiAlH4 and is,
+C 6 H sCH 2COONH 4 converted into ethyl amine.
The amide group is always formed at the end of the chain
whatever the size of R-group in C 6 H sCOR. CH 3CONH 2 +4[H] Na + C2HsOH) CH3CH 2NH 2 + H 20
Ethylamine
(" y,·'\c~:<"-:·' -,
.,,:;":;>-';:~:" , ,,~-; •
"c;.' ,'",' ~",¥
(iv) Dehydration: When heated with phosphorus pentoxide or SOCl 2 or POCl 3, it loses a molecule of water and forms
methyl cyanide (nitrile).
P20S
CH3CONH2 ) CH3CN + H 20
Acetamide, Heat Methyl cyanide
(v) Action of nitrous acid: The amino group is replaced by -OH group with evolution of nitrogen when treated with
nitrous acid (NaN02 + HCI), i. e., acetic acid is formed.
CH3CONH2 + HN0 2 ----+CH 3COOH + N2 + H 20
Reaction with HN0 2 is slow, a better method is to use butyl nitrite.
CH 3CONH 2 +C4H90NO----+CH3COOH + N2+ C4H90H
(vi) Action of PCI s : When heated with PCl s , acetamide forms methyl cyanide.
CH 3CONH 2 + PCIs ----+CH 3CCI 2NH 2 + POCl 3
(viii) Hofmann bromamide reaction or Hofmann degradation: Amides when heated with bromine and caustic soda or
caustic potash solution, yield primary amines c~)Dtaining one carbon atom less than the amide. This is an important reaction for
reducing a carbon atom from a compound, i.e., -CON02 is changed to -NH2 group.
When acetamide is treated with bromine and caustic soda, methylamine is formed.
(ii)
(iii) .
R_ .O=C~N-R
Unstable (acyl nitrene)
(iv) ~_~(lN:]
~ (Intramolecular) Isocyanate .
Instead of KOH, other alkali like NaOH can be used. Similarly,Cl 2 andI2 may be used in place ofBr2'
Uses: Acetamide is used :
(i) .in organic synthesis. The compounds like methyl cyanide, methylaniine and ethylamine can be prepared.
(ii) in leather tanning and paper industry.
(iii) as a wetting agent and as soldering flux.
(iv) as a solvent for organic and inorganIc compounds.
13.6- ETHYL ACETATE, CH 3 COOC 2 H s OR ETHYL ETHANOATE
It is the ethyl ester of ~etic acid~
Methods of Preparation
1. By the action of acetyl chloride or acetic anhydride on ethyl alcohol:
CH3CO" . .
/O+C2HsOH~CH3COOC2Hs +CH 3COOH
CH 3CO/ . Ethylacetate . Acetic acid .
Acetic anhydride .
2. By the action of ethyl halide on silver acetate :
'.
Acid Derivatives
H 2S04 (conc.) ,
CH3COOH +C 2H s OH , ~ CH3COOC 2H s +JhO
. . Acetic acid Ethyl alcohol E$yl acetate Water
This reaction is termed Fischer esterification. It is a reversible reaction and the yield of theetltyl acetate can be increased by
using excess of acid or alcohol and removing water as it is formed. Water may be removed by using Conc. sulphuric acid or
hydrogen chloride. Thus, sulphuric acid acts both as a catalyst and a dehydrating agent in the process of esterification.
The ease of esterification of alcohols is as follows: . ",
1°>2°> 3°·
The ease of esterification with fatty l\cids is as follows: . ,
HCOOH> CH3COOH> CH3CH2COOH> (CH3hCHCOOH> (CH 3 hCCOOH
0 0
1\ 18 H+ \\ 18,' .. , '
CH3-C-OH +CH 3 -QH ~ CH 3 -C-QCH3+ H20
[For mechanism of esterification, see Seetionl2.ll problem 8.]
Direct esterification can also be done by passing the vapours ofalcohols and acids over a heated catalyst like titanium dioxide, .
thoria and alumina at 3000C.
5. By the aetionof carb~n monoxide on ethel' :
(iii) Reaction with phosphorus pentachloride or thionyl chloride: Both react with ethyl acetate to fonn acetyl chloride.
CH 3COOC 2H s + PCIs ~CH3COCI +C 2H s CI + POCl3
CH3COOC2Hs +SOCI 2 ---+ CH 3COCI + C2HsCI +S02
Ethyl etbanoate .,. Ethanoyl chloride Chloroethane
(iv) Reduction: (a) With sodium and alcohol, ethyl acetate is reduced to ethyl alcohol.
Na+ C2H sOH
CH3COOC2HS +2H2 ~ 2CH 3CH 20H
Ethyl acetate Ethyl alcohol
This reduction is known as Bouveault Blanc reduction.
(b) LiAlH4 in ether, LiBH4 in THF or B2H6 in THF, etc., also reduce ethyl acetate into ethyl alcohol.
LiAIH4
CH3COOC2HS +2H2 ~ 2CH3CH20H
Ether
o
(c)
II
R-C-OR'+H~
CuO CuCr204 .
, ,R-CH 20H+R'OH
Ester 200-300 atm, 250°C
(v) Reaction with Grignard reagent: Grignard reagent reacts with ethyl acetate and fonns a ketone which at once reacts
with more of Grignard' reagent to give tert.-butyl alcohol (3t».
0, 0
r-------------, I I /1 .
CH 3 -j.M8:-::-!.:t_<';;2.tI.s9J-C-CH3 ----.CH 3-C-CH3 + Mg'-...,. .
Methyl magnesium Ethyl acetate Acetone OC2 H S
iodide
CH 3 CH 3 CH 3
I. I: H O/H+ I /1
CH3MgI +CH 3 -C=O ----. CH 3- C - 0: MgI 2 ) CH3-C-OH+Mg,
Acetone I H: OH (decomposes) 'OH I .
CH 3 I CH 3
Adduct Tert. butyl alcohol
Formic acid esters give 2t> alcohols.
(vi) Reaction with hydroxylamine: Ethyl acetate reacts with hydroxylamine in presence of ethanolic KOH to form
hydroxamic acid (a test of ester group).
o 0
. II ~---------, Base I
CH3 -C~~.2J:h .:tJ~!HNOH -=:.::.~) CH 3 -C-NHOH + C2 HsOH
Ethyl acetate Hydroxyl- Hydroxamic acid
amine
(vii) Reaction with hydrazine: Ethyl acetate reaets with hydrazine to fonn acid hydrazide.
CH3COOC2HS + H2NNH2 ----.CH3LONHNH2 +C 2H sOH
. Hydrazine Acid hydrazide
(viii) Halogenation: Ethyl acetate reacts with chlorine or bromine in presence of red phosphorus to fonn a. -hal~genated
ethyl acetate.
RedP
CH3COOC2HS + Br2 ) CH2 BrCOOC 2Hs + HBr
a. -Bromoethyl acetate
(ix) Claisen condensation: Ethyl acetate (two molecules) undergoes Claisen condensation in presence of sodium ethoxide
involving a.-hydrogen atom. Two molecules of ethyl acetate combine together to fonn ethyl acetoacetate or acetoacetic ester
(a,p-keto ester). . .
C2HSONa
CH3COOC2HS +CH3COOC2HS ---=::.....!C._~) CH 3COCH 2COOC 2 H s +C 2H sOH
Ethyl acetate or (Na) Ethyl acetoacetate
(Acetoacetic ester)
Acid Derivatives 725
In place ofC2HsONa, other bases like sodamide. triphenyl methyl sodium. etc.• can also be used.
If two molecules of different esters (e.g., ethyl acetate and ethyl propionate) are used then four different keto esters are fonned.
(x) Alcoholysis (Splitting by alcohol): When an ester is refluxed with excess of alcohol (other than present ill ester) in
presence of a little acid (HCI gas) or sodium alkoxide as catalyst. a partial exchange of alcohol takes place. This is tenned
trans-esterification.
C2 HSONa or H+
CH3COOC2Hs + CH 30H < > CH 3COOCH) + C2 HSOH
Ethyl acetate Methyl alcohol Methyl acetate Ethyl alcohol
(xi) Acidolysis (Trans-esterification by acid) : When an ester is heated with other acid. it is the acid residue present in ester
is partially replaced by other acid residue.
o <H~>
. Note: (i) Cyclic esters on hydrolysis give hydroxy acid.
CH 0H CH2 -CH2
---=~)
3 I . I
OH COOCH3
,7-
NucleDphilic attack Dn tetrahedral alkyl carbon invDlves crowded transition state containing pentavalent carbon.
,
/
L
Leaving
A
Attac~g
"I
A .... ·........ C······ .. •..··L - A .. ·.... ·....·C- + L
group group,
I
Due to. fDrmatiDn DfcrOwded transitiDn state, alkyl cDmpDundS are less reactive towards nucleophilic substitution.
Nucleophilic attack Dn planar acyl cDmpDund involves less crowded transitiDn state leading to. a tetrahedral intermediate.
R L R A
U yI · A-C~r-L
0
YI + r
o 0
Note: Greater is the Lewis basic character more is the nucleophilic character of the group.
NH3 < R'OH < H 20 < RCOOH < Hel (Acidic character)
cr < RCOO- < mr < RO- "".NlI2 (Basic character)
. Leaving tendency of nucleophiles lie in following sequence:
, NlI2 < RO- < OIr <RCOO- < CI-
i.e,NHi can substitute all other groups, eg., RCOO-, OIr, RO- ,cr '
RO- tan substitute all other groups, eg.,OIr,RCOO'-, Cl-
OIr can substitute all other groups, eg., RCOO-, cr
CI- cannot substitute any of these groups.
Acid Derivatives
ILLUSTRATIONS OF OB~ECTIVE QUESTIONS S. When propanamide is reacted with Br2 and NaOH, the prod-
1. In the following reaction, (X) and (Y) are respectively: uctformedis: (eMC (Vellore) PMT 2003)
(a) propanamine' 0 (b) etbanamine 0
CH3COOH + NH3 ~ (X) -~""Hy) H20 + (c) propanaldehyde 0 (d) propionic acid 0
(EAMCET (Engg.) 2002) [Ans.(b)]
(a) CH3CONH2, CH4 o 6.. At higher temperature, iodoform reaction is given by:
(b) CH3COO~, CH 3CONH2 0< . (AIIMS 2003)
(c) CH3CONH2, CH3COOH o ~ (a) CH3C02CH3' 0 (b) C6HSCOOCH3 0
(d) CH3NH2, CH3CONH2 o (c) CH3C02C2Hs . 0 (d) CH3COOC6Hs. 0
[Ans. (b)] [Ans. (c)l
2. In the following reaction, (X) and, (Y) are respectively: 7. Theesu:ramong the following is: .. (PMT(Keraia)2003)
KMn°41H+ (a) ca1ciumlactate 0 (b) ammoniumacetate 0
C2HSOH (Y)
) (X) H SO ) CH COOC H (c) sodium acetate 0 (d) methyl butyrate 0
IA 3 2 S
2 4
[~ns. (d)]
(a) CH3 0H, C2HSOH o
(b) CH3CHQ CH 30H
(c) H2C=CH2, CH3COOH
o
o ~
8. Ca3-C-CH2-COOYHs NaOH ) (A)
(d) CH3COOH,yHsOH o (H 20)
[Ans. (d)] The product (A) in above reaction is: [PET (Raj.) 2003)
3. In the following reaction, (X) and (Y) are respectively: (a:) CH3COOH 0 (b) C2HSOH 0
(c) CH 3COCH3 0 (d) C2HSCHO· 0
(X) Aq. NaOH) CH COOH (Y) (CH CO) 0
Solution 3 3 2 . [Ans. (c)]
(EAMCET (Med.) 2002) 9. The order of~ydrolysis for the following is:
(PET (Raj.) 2003; DPMT 200S]
(a) CH3CHO,PCIs 0
(b) CH3 CN,P2 0 S 0 (a) RCOX > RCONH2 > RCOOCOR > RCOOR . 0
(c) CH3CH20 H , N a O A c D (b) RCOX > RCOOCOR > RCOOR > RCONH2 0
(d) CH3COCHJ, H2S04 0 (c) RCOOR > RCONH2 > RCOX >RCoOCoR 0
[Ans. (b)] .
. (d) RCOOCOR > RCOOR > RCOX >RCONH2 .0
4. Pineapple flavours is obtained from which of the following [Ans. (b)]
esters? . (MGIMS (Wardba) 2003) 10. Which one of the following can produce hydrogen when
(a) Iso-butyl ester 0 (b) Iso-amyl ester 0 treated with metallic sodium?
(c) Iso-octanoyl ester ·0 (d) Ethyl methanoate 0 (CPMT 2003; PMT (Raj.) 2005]
[Ans. (a)] (a) (CH3hNH o (b) CH3NH2 0
(e) C6.lIsNH2 o (d) CH3CONH2 0
[Ans. (d)]
/OC2 H S . a /NH2
O=C", +2NH3 ~O=C", +2C 2H s OH
OC2H S NH2
Ethyl carbonate Urea
Similarly ethyl carbamate (urethane) can be converted to urea.
. ' 1---------1
/<<.?~J!!s_2"_l!iNH2 /NH2
O=C~ ~O=C, +C2HSOH
NH2 . NH2
Urea
3. Manufacture: (i) By partial hydrolysis of calcium cyanamide: Calcium cyanamide is obtained by passing nitrogen
over calcium carbide at 8000C.
CaC 2 .+ N 2 Heat) CaCN 2 + C
Calcium Calcium
carbide . cyanamide
The cyanamide is treated with dilute sulphuric acid at 400C where partial hydrolysis occurs with the fonnation of urea.
H2S04 H 20
CaCN 2 ) H2NCN ) H2NCONH2
. - CaS04 Cyanamide (H 20 2 ) Urea
o
H+ It
NH2 -eN + HOH ) NH2 -C-NH2
A, 70°C Urea
(ii) From carbondioxide and ammonia : Urea is made commercially by the reaction of liquid carbondioxide and liquid
ammonia at 150-200°C under high pressure. Ammonium carbamate is first fonned which decomposes at 1400c to fonn urea.
Chemical properties : (i) Basic nature (Salt formation): The aqueous solution of urea is neutral in nature but urea
behaves as a weak monoacidic base (Kb =1.5 x [0- 14 at 25°C). It fonns salts with strong acids.
NH 2 CONH 2 + HN03 (conc.) ---+ NH2CONH2·HN03 .
Urea nitrate
2NH 2CONH 2 + H 2C 20 4 ---+ (NH 2CONH 2h H2C20 4
Oxalic acid Urea oxalate
Urea is a stronger base than ordinary amides. It is due to resonance stabilization of cation. The negatively charged oxygen atom
iscapabte of coordination with one proton (therefore, urea will be a monoacidic base) and thus the salt may be fonnulated as a
resonance hybrid.
(0) Hydrolysis: Like other amides, urea is hydrolysed when boiled with either acids or alkaHes giving ammonia and carbon
dioxide.
OH
(Aq.) alkali or )O=C/ + 2NH 3
acid "'-OH Ammonia
Carbonic acid
,}
CO 2 +H 2 0
[Acid will combine with NH3 to fonn ammonium compound while alkali will combine with CO 2 to fonn carbonate.]
NH 2CONH 2 +2NaOH---+2NH3 + Na2C03
An enzyme, urease, present in soyabean and soil, also brings hydrolysis. It converts urea into ammonium carbonate. This
reaction is rapid and quantitative and can be used for the estimation of urea.
NH 2CONH 2 +2H 20---+ (NH4hC03 ---+2NH3 +C0 2 + H 20
Annnonium
carbonate
(iii) Action of beat: (a) On heating at 132°C, urea melts. The liquid on gentle heating at a slightly higher temperature at
150°C, evolves ammonia and leaves a solid white residue known as biuret.
r:------~ Heat
NH 2COiNH
L _ _ _2
+ H:HNCONH 2
___ _
) NH 2CONHCONH 2 + NH3
(Two molecules of urea) Biuret
G.R.B. Organic Chemistry (or Competitions
NH2-C-NH2 ~ H-N=C=O+NH3
o 0 H 0 0 0
I I I I I I
NH2-C-NH2 +H-N=C=O~NH2-C-. $N-C-.N-H....--'" NH2-C-NH-C-NH2
. . I. e , Biuret
'H
Urea is, identified by the test known as biuret test The biuret residue is dissolved in water and made alkaline with a few drops
ofNaOH. When a drop of copper sulphate solution is added to the alkaline solution ofbiw:et~a violet colouration is produced.
This reaction is called Biuret test and is a characteristic of proteins, peptides and all other compounds containing -CONH-
group.
(b) When heated rapidly above 170°C, urea decomposes into ammonia and cyanic acid. Cyanic acid undergoes
polymerization forming cyanuric acid (a cyclic compound).
NH 2CONH 2 H~at) NH3 + HOCN (H-. N' C=O)
Urea Cyanic acid
H
I
/~
O=C c=o
I I
H
H-N"'C/-
II
o
Cyanuric acid
(iv) Reaction witb nitrous acid: Urea is decomposed by nitrous acid into nitrogen, carbondioxide and water.
H 20+C0 2
(v) Reaction witb alkaline bypobaUdes: Urea is oxidised to nitrogen when heated with excess ofalkaline hypochlorite or
hypobromite (NaOH + Br2= NaOBr + HBr).
NH2CONH2 +3NaBrO~N2 +2H20+C02 +3NaBr
NH2CONH2 +3NaOCI~N2 +2H20+C02 +3NaCI
This reaction forms the basis ofHufner's metbod for the quantitative estimation of urea.
(vi) Reaction witb acetyl cbloride or acetic anbydride: Urea reacts withacetylating agents to form N-acetyl ureas which
are known as Ureides.
NH2CONH2 + CH 3COCI ~ NH 2CONHCOCH 3 + HCI
Acetyl chloride Acetyl urea (Ureide)
NH 2CONH 2 + (CH3CO)zO ~ NH2CONHCOCH3 +CH3COOH
Acetic anhydride Acetyl urea Acetic acid
(vii) Reaction witb bydrazine: Urea reacts with hydrazine at 10WC to form semicarbazide with evolution of an ammonia
molecule.
100°C
NH 2CONH 2 + H2NNH2 ) NH 2CONHNH 2 + NH3
Urea Hydrazine Semicarbazide
(viii) Reaction witb etbanol: When urea is heated with ethanol, urethane (ethylcarbamate) is produced.
Acid Derivatives
H 2NCO 1INH2
r-------
+ H ...bC 2H s
_______
H t .
ea) H 2NCOOC 2H s + NH3
Ethanol Urethane
(ix) Reaction with chlorin~ water: Urea reacts with aqueous solution of chlorine to fonn N, N'-dichlorourea.
/NH2·. /NHCl
O=C"" +2C1 2 ---to=C"" +2HCl
NH2 NHCl
.. Urea. N,N'-Dicblorourea
(x) Dehydration: On dehydration with SOC1 2, urea gives cyanamide.
NH2CONH2 +SOC1 2 ---tH 2N-C==N+S02 +2HCl+H20
(xi) Reaction with fuming sulphuric acid: Urea reacts with fuming sulphuric acid (oleum) to yield sulphamic acid.
. NH2CONH2 + H2S04 + S03 ---t 2NH2S03H +,C0 2
~ Sulpbamic acid
(xii) Formation of cyclic ureides: Urea reacts with malonic and oxalic esters in presence of sodium ethoxide (C2H sONa)
or phosphorus trichloride to fonn cyclic ureides.
o 0
r----------- U
/NH:~ ___ ~}_f!~~!C"'_ L1 /NH-C",
~
O=C~ r;--:!--------- /CH2 ~O=C""", /CH2 +2C2H sOH
NH,H C2HSO:C NH-C
Urea ·-----------11 I
· 0 0
Diethyl malonate Barbituric acid
(Malonyl urea)
r:-----------
/NH IH C2H sO:CO /NH-C=O
O=C/ 1---+------.,. .. 1· ~O=C/ I
""'NHaI----CiHsO:CO . ""NH;-C=O
1- - - - - Die-thyl oXalate Parabanic acid
(Oxalyl urea)
NH
1:----- ---I
0=C/ :!.l--+-_1!<21 0CI L1 )O=C/NH-CI =0
""'NH:H----fIo:OC POCl 3 ""'NH-C=O
- - - - -oxaifc acid Oxalyl urea
;,---------1
NH.H C2HSO,C=0 NH-C=O
I ~---------, I I I
CO CH )CO CH
I ~ ________. I I I
NHl!:l.. ___ !:l..<!yC-CH3 NH-C-CH 3
Urea Enolic form of AAE 4-Methyl uracil
(xiii) Reaction with form·aldehyde : Urea and fonnaldehyde react to fonn urea-fonnaldehyde resin which is used in the
fonn of plastic.
HCI . CH -:-0 Urea
H2C=0 + NH2CONH2 ) CH2 (OH)NHCONH 2 - - - .2 - + ) CH2 (OH)NHCONH(OH)CH2 ) Resin
Formaldehyde Monomethylol urea Dimethylol urea (Urea-Formaldehyde)
Fonnation of resin can be represented as:
o H· o H 0
\I I I I I
nNH 2 -C-N-H + nHO-CH 2-NH-C-NH-.CH 2-OH + nH-N-C-' NH2
1
Heat Condensation
-nH20
0 0 0 ]
[ NH-':"~-NH-CH2Linear,
-NH-~-NH-CH2
condensation polymer
-NH-~-NH n
732 G.R.B. Organic Chemistry for Competitions
(xiv) Reaction with ethylene oxide : In this reaction, Three acyl groups present in the molecule may be same or
epoxy bond is broken to form an intermediate in the production different. When all the three are same, the triester is known as
of non-ionic detergents. simple glyceride, (i.e., three -OH groups of glycerol are
o esterified with the same acid) and if two or all the three are
I CH2~ different, the triester is known as mixed glyceride, (i.e., three
NH2 -C-NH2 + 2 I / 0 -----)
-OH groups of glycerol are esterified with two or three
Urea CH 2/
Ethylene oxide different acids).
/NH-CH2 -CH 2 -OH CH 2 00CR CH 2 OOCR I CH 200CR 1
O=C~ I I I
NH-CH2 -CH 2 -OH CHOOCR CHOOCR 2 CHOOCR 1
Bis (Hydroxy methyl urea) I I I
Uses: Urea is used: CH 200CR CH
, 200CR 3 CH zOOCR 2,
(i) mainly as a nitrogen fertilizer. It has 46.6% nitrogen. Simple glyceride
Mixed glycerides
(ii) in the manufacture of formaldehyde-urea. plastic and The monocarboxylic acids that form ester chains in natural
semicarbazide. oils and fats may be saturated or unsaturated. The most
(iii) as animal feed. common monocarboxylic acids present in oils and fats are
(iv) for making barbiturates and other drugs. listed below:
(v) as a stabilizer for nitrocellulose explosives. Saturated Unsaturated
Tests: C ll H 23 COOH C I7 H 33 COOH
(i) When heated with sodium hydroxide, ammonia is (Lauric acid) (Oleic acid)
evolved. C13 H 27 COOH C 17 H 31 COOH
(ii) When heated gently, it forms biuret which gives violet (Myristic acid) (Linoleic acid)
colouration with sodium hydroxide and a drop of C 15 H 3l COOH C 17 H 29 COOH
copper sulphate solution. (Palmitic acid) (Linolenic acid)
(iii) Its aque0 1'" solution with concentrated nitric acid C17H3SCOOH
gives a whIte precipitate. (Stearic acid)
(iv) On adding sodium nitrite solution and dil. HCl It has been observed that an ordinary oil or fat is a mixture
(i.e., HN02) to urea solution, nitrogen gas is evolved of various glycerides; simple and mixed both, the latter
and gives effervescence due to carbondioxide. predominating to a considerable extent.
The glycerides are named according to the acid residue
13.8 FATS, OILS AND WAXES present in them by replacing the terminal 'ic acid' by 'in'.
Oils, fats and waxes belong to nal ,rally occurring groups of
CH20COCISH31 CH zOCOC 17 H35
compounds called Lipids. When plant or animal tissues are
extracted with a non-polar solvent, (e.g~, ether, chloroform or I I
CHOCOC 1S H 31 CHOCOC 17 H3S
benzene) a portion of the material usually dissolves. The
component of this soluble fraction are called lipids. Lipids
I I
CH20COC15H31 CH zOCOC 17 H 35
are thus constituents of plants and animals that are Tripalmitin Tristearin
insoluble in water but soluble in organic solvents. Lipids (Simple) (Simple)
include compounds of many different kinds such as oils and
fats, waxes, phospholipids, glycolipids, terpenes, steroids, CHzOCOC17H33 CH 20COC 17 H35
etc. In the following discussion, we shall be studying only I I
oils, fats and waxes. CHOCOC 15H 31 CHOCOC 17 H 35
Oils and fats are the triesters of glycerol (a trihydric I I .
CHzOCOC17H35 CH 20COC I5 H31
alcohol) with a long chain monocarb9xylic acids (usually 12 to
Oleopalmito-stearin Palmito-distearin
20 carbons). These esters are known as Triglycerides or (Mixed) (Mixed)
Triacyl glycerols or Glyceryl esters. The following general
structure represents an oil or a fat. At ordinary temperature, the glycerides of saturated
carboxylic acids such as palmitin, stearin are solids while that
CH 2 -O~-OCRI
of unsaturated acids such as olein are liquids.
I :
I
CH-O-----i-OCR 2 Difference between oils and fats: Oils and fats belong
I :
I
to the· same chemical group, yet they are different in their
CH 2 -O-l-OCR 3 physical state.
I
Glycerol Acyl group
part (Acid part)
Acid Derivatives 733
1. Oils are liquids at ordinary temperature (below 20°C) (i) Hydrolysis: They are hydrolysed by heating with
while fats are semi solids or solids (their melting points are superheated steat)1, acids or alkalies.
more than 200C). A substance may be classed as fat in one sea- '(a) By superheated steam: Under'a pressure of about
son and oil in another season or the same glyceride may be 8 atmospheres at 170°C in the presence of lime, zinc oxide or
solid at a hill station and liquid in plains. Thus, this distinction magnesia, oils and fats are hydrolysed. On cooling, free fatty
is not well founded as the physical state depends on climate and acids separate with some calcium soap (or zinc or magnesium
weather. soap).
2. The difference in oils and fats is actually dependent on I
CH 20:COC 17 H 35 CH 20H
the nature of monocarboxylic acids present in the glyceride.
Oils contain large proportion of the glycerides of lower I: +3H2 0 I
CHO :COC 17 H 35 ) CHOH +3C 17 H 35 COOH
carboxylic acids, (e.g., butyric acid, caprylic acid and caproic
acid) and unsaturated fatty acids, (e.g., oleic, linoleic and
I : I Stearic acid
CH20:COC17H35 CH20H
linolenic acids) while fats contahi a large proportion of glycer- Tristearin Glycerol
ides of higher saturated carboxylic acids, (e.g., palmitic, stearic
acids). (b) Base hydrolysis: When fats and oils are heated
Lard (fat of hogs) is a solid fat and its composition in terms with NaOH (or KOH) solution, the products are glycerol and
of fatty acids produced on hydrolysis is approximately 32% sodium or potassium salts of higher fatty acids. The sodium or
palmitic acid, 18% stearic acid, 45% oleic acid and 5% potassium salts of fatty acids are called soaps and the basehy-
linolenic acid. Olive oil on the other hand, contains 84% oleic drolysis of fats or oils is termed as saponification.
acid, 4% linoleic acid, 9% palmitic acid and 3% stearic acid. CH 20COR CH 20H
Occurrence: Oils and fats occur widely in animals and I I
plants. In plants, oils and fats are found mainly in seeds, roots CHOCOR + 3NaOH -------+ CHOH + 3RCOONa
and fruits, while in animals, they are present under the skin in I I Salt offatty acid
(Soap)
tissues and muscles. Few examples are given below: CH 2 0COR CH20H
Fat or oil Glycerol
Vegetable oils Vegetable fats
(c) Enzyme hydrolysis: Enzyme like lipase, when
Til oil Coconut oil added to an emulsion offat in water, hydrolysis it into acid and
Linseed oil Vegetable ghee glycerol in about two or three days.
Mustard oil Margarine (ii) Hydrogenation: The vegetable oils containing gly-
,Ground-nut oil cerides of unsaturated fatty acids undergo catalytic
Animal oils Animal fats hydrogenation with hydrogen at low pressure in presence of
Whale oil Lard (fat of hogs) finely divided nickel. This results in the formation of saturated
Cod-liver oil Tallow (fats of sheep or horses) glycerides which are solid fats at room temperature. The hy-
Sardine oil Butter drogenation process is called Hardening of oils.
Properties of Oils and Fats o 0
Physical properties:' (i) At room temperature, fats are I I
solids, whereas oils are liquids. CH 20qCH 2 hCH=CH(CH 2hCH 3 CH 20CC 17 H 35
(ii) They are insoluble in water but soluble in ether, chlo-
roform and benzene. I ~ , +3H
2
I~ ~
(iii) They have less specific gravity than water and conse-
quently float on the surface when mixed with it I
CHOC(CH2hCH=CH(CH2hCH3
~ , .
Nl, Heat I ~.
) CHOCC17 H ,:,
(iv) Pure fats and oils are colourless, odourless and taste-
CH 20C(CH 2hCH=CH(CH 2hCH 3 CH 20CC17 11 35
less but natural fats and oils possess a characteristic odour due
Glyceryl trioleate or triolein Tristearin
to presence of other ~ubstances. (Liquid oil) (A solid fat)
(v) They have spc;.:ilic melting points, specific gravity
and refractive index hence they can be identified by these oil
Partial hydrogenation of oils is used for the manufacture of
constants.
vegetable ghee. Complete hydrogenation would produce a
(vi) Animal fats contain cholesterol, an unsaturatedalco-
hard brittle fat.
hoI, whereas vegetable fats contain phytosteroL (iii) Hydrogenolysis (Reduction tc) alcohols) : If ex-
Chemical properties: Fats and oils are triesters of glyc-
cess of hydrogen, under pressure, is passed through oil or fat in
erol (triglycerides) with saturated and unsaturated fatty acids.
the presence of copper-chromium catalyst, it is converted into
Thus, they give reactions of carbon-carbon double bonds and
glycerol and higher aliphatic alcohols. This process of splitting
ester groups.
up of the fat molecule by hydrogen is termed hydrogenolysis.
G.R.B. Organic'Chemistry (Or Competitions
Difference between Vegetable oils and Mineral oils Potassium laurate, C n H 23 COO-K+
Sodium oleate, C17H33COO-Na +, etc.
These. are triesters Types of Soaps
glycerol ~fu' higherlrJiTlhnns
fatty acids. Kelrose:ne--AJLKarleS 1. Hard soaps: These are obtained from cheap oils and
fats using sodium hydroxide. These contain free alkali and are
2. Source Seeds, root and. fruits . occur inside used for washing purposes.
pf plants. el'Iith. s crilst in the 2. Soft soaps: These are obtained from good oils using.
fonn of petrolewn. potassium hydroxide. These do not contain free alkali and are
3. Hydrolysis Undergo hydrolysis . hydrolysis occurs. used as toilet soaps, shaving creams, in shaving sticks (Pot.
with alkali. Fonn sod. stearate) and shampoo.
and .glycerol. 3. Transparent soaps: T'nese are formed by dissolving
4. On adding Decolourization toilet soaps in alcohol and evaporating the filtrate. They
and pink colour occurs. contain glycerol.
phenolphthalein 4. Medicated soaps: Toilet soaps contaihitig some
5. Burning Burn slowly. Burn very readily. . medicinal important' substances are called medicated soaps~
6.. Hydrogenation Hydrogenation occurs No hydro~nation S. MetaWc soaps: These are soaps of metals other than
in' presence of nickel occurs. . sodium and potassium..
catalyst. Solid glyce-
Manufacture of soap.
are formed.
The following raw materials are used for the manufacture
13.9 SOAP of soap: .
1. 0iI~ or fats: Coconut oil, mustard oil, mahua oil,
Soaps are the metallic salts of higher fatty acids such as
cotton seed oil, tallow, lard, etc., are generally used.
palmitic, stearic, oleic, etc. The sodium and pptassium salts are
2. Caustic soda for hard soaps and potash for soft soaps is
the common soaps which are soluble in water and used for
employed for saponification.
cleansing purposes. Soaps. of other metals such as calcium,
3. Filler: Certain substances, called fillers, are usually
magnesium, Zinc, chromium, lead, etc., are insoluble in water.
added to increase the weight and volume of the soap. These
These are not used· for cleansing purposes but for other
substances also help in solidification. Sodium silicate, soap
purposes (lubricants, driers, adhesives, etc.).
stone, rosin, starch, sQ<lium carbonate, etc., are generally added
. Ordinary soaps (sodium and potassium) are the products of
to washing soaps.
hydrolysis. of oils and fats with sodium hydroxide or potassium
Perfumes are added to toilet soaps to make them pleasant
hydroxide. This process is called saponification of oils and
smelling.
fats. The oils and fats are mixed glycerides and thus soaps are
The following methods are employed for the manufacture
mixtures of salts of saturated and unsaturated long chain of soap:
carboxyHc acids containing 12 to 18 carbon atoms. This 1. The cold process; The oil or fat is taken in a big
process always yields glycerol as a byproduct.
vessel and heated to about 50°C. A calculated quantity of
o caustic soda is added with constant stirring. Some amount of
o ~ filler like starch or sodium silicate is then mixed. The whole
II R1-C-ONa
mass is left as such for 12 to 24 hours. It sets to a solid mass. It
CH20-C-R1 +
.,
CHO-C-R2
~
+3NaOH~CHOH
I H20H
+R2-C-ONa
~
is cut into pieces of desired shape. The soap obtained by this
process always consists glycerol, alkali and free oil or fat. It is
used for washing purposes.
spent lye and used for the recovery of glycerol. The soap left in A synthetic detergent is the sodium salt of a long chain
the kettle still contains some unreacted fat. It is boiled with alkyl hydrogen sulphate or the sodium salt of a long chain
fresh supply of NaOH solution. More soap is formed. The benzene sulphonic acid. Like soap, they contain both hydrop-
lower layer is drawn off. The soap layer is boiled with water to hilic (water soluble) and hydrophobic (oil soluble) parts in the
wash away excess of NaOH. The soap, while still molten, is molecule.
pumped into the crutcher. Here, the soap is mixed with colour,
/C12 H 2SI /OS03Nal ICI5 H 311 ICOONal
perfumes, germicides, etc., and stirred. In case oflaundry soap,
some fillers like rosin, sodium silicate, sodium carbonate, etc., Hydrophobic Hydrophilic Hydrophobic Hydrophilic
part part part part
are added. These have some detergent values and are cheaper Sodium Iauryl su1pbate Sodium palmitate
than soap. '. (Detergent) (Soap)
The crutched soap is poured into frames and on
Classification of detergents: Detergents are mainly
solidification cut into cakes.
classified into three categories, namely anionic, cationic and
3. Modern process: In this process, the oil or fat is non-ionic.
hydrolysed with superheated steam under pressure in the
(i) Anionic detergents: These are of two types:
presence of a catalyst like zinc oxide. The fatty acids produced
(a) Alkyl hydrogensulphates: They are obtained
as a result of hydrolysis float on water as these are lighter than
from long chain aliphatic alcohols (C IO - C I5 ) by treatment
water. These are separated and neutralized by calculated
with conc. H 2SO 4 followed by neutralization with NaOH. The
quantity of alkali solution when soap is obtained. This method
alcohols are obtained from oils or fats by hydrogenolysis.
is simple and cheap.
The aqueous solution is treated for the recovery of CH3(CH2)IOCH20IH+ Hols03H ---+
n-Lauryl alcohol Sulphuric acid
glycerol.
But hard water contains certain metal ions, such as calcium CH 3 (CH 2 ) lO CH 20S0 3H
and magnesium. These ions (or their salts) react with soap to n-Lauryl hydrogen su1pbate
produce a curdy white precipitate of calcium and magnesium
salts. 1 NaOH
0 > 'CH3(CHZl9bH~
13.10 NON-SOAPY DETERGENTS (SYNTHETIC CH3
DETERGENTS) CH3(CHzl9CH CH2+( AIel)
These are also called synthetic detergents or syndets or
Dodec-I-ene Benzene
soapless soaps or just detergents. They have cleansing power
as good or better than ordinary soaps and can be used for
washing even with. hard water and do not precipitate in
presence ofCa 2+IMg2+ or in acidic solution.
(iv) Mild bleaching agent (Sodium perborate)-to give The negative ions aggregate to fonn a micelle of colloidal
whiteness in clothes. size. The negative ion has a long hydrocarbon chain and a polar
Surfactants (Surface Active Agents) group (-COO-) at one end. In micelle fonnation, the long
Substances like soaps and synthetic detergents concentrate hydrocarbon chain (tail) which is insoluble in water is directed
at the surface of the solution or interfaces, fonn surface films, towards the centre while the soluble polar head is on the
the non-polar hydrocarbon chains of the soap or detergent surface in contact with water (Fig.). The charge on the micelle
dissolves in oil or grell,se and the other part (Carboxylate group is responsible for the stability of this system.
of the soap or sulphonate group of synthetic detergent) is held The initial concentration at which micellization begins is
by surrounding water. , called critical micellization concentration (eMC). Every
This lowers the surf~ce tenSion between water and grease associated colloid has a: definite CMC at a given temperature.
solution and helps in removing dirt and dust by emulsifying Increase of temperature lowers CMC. The fonnation' of
grease. Such substances are called surface active agents or micelles starts only above a certain temperature called Kraft
surfactants. The molecule of a surfactant contains two temperature denoted by (Tk)' For miceiles of soap, cMC is
characteristic groups~ 10-4 _IO~3 mol L-1 . The micellization is a reyersible process,
(a) Hydrophilic-water soluble, hence, by diluting an associated colloid, it is possible to revert
, (b) Hydrophobic,(Lyophilic)-oil soluble. to the original simple solution. The cleansing action of soap is
Advantages of Synthetic Dt:tergents Over Soaps due to micelles. The grease stain is absorbed into the interior
of the micelle and gets detached from the fabric.
Synthetic, detergents are superior and most widely used
cleansing agents due to the following properties:
(i) These can be used both in soft and hard waters
whereas ordinary soaps cannot be used in hard water.
(ii) Synthetic detergents are prepared from the
hydrocarbons obtained from petroleum while soaps
are prepared from vegetable oils and fats.
(iii) The aqueous solution of detergents are neutral and
hep,ce, can be used for washing all types of fabrics
without any damage. The solution of ordinary soap is
alkaline and thus, cannot be used to wash delicate
fabrics.
The dust particles sticking to the stain are also removed.
(iv) These can be used even in acidic medium as they are
This action is similar to emulsification of grease.
the salts of strong acids and 'J.re not decompdsed in
acidic medium whereas soaps are decomposed into 13.11 WAXES
carboxylic acids in acidic medium. Waxes are the esters of higher saturated and unsaturated fatty
Disadvantages of Synthetic Detergents acids with higher monohydric alcohols. The acids and alcohols
Some of the synthetic detergents are not biodegradable. In commonly found in waxes are palmitic,cerotic acid
the past, many detergents caused pollution in river and (C 2s H s1 COOH), melissic acid (C 30 H 61 COOH) and cetyl
waterways. It has,been found that if straight chain hydrocarbon alcohol (C 16 H 33 0H), ceryl alcohol (C26HS30H), myricyl
is used in the detergent instead of branched chain hydrocarbons alcohol (C 30 H 61 0H), etc:
then the detergent is biodegradable because detergent Waxes are insoluble in water but are readily soluble in
mQlecules associated with branched chain hydrocarbon tail is a benzene, petroleum, carbon disulphide, etc. Waxes on
source of pollution. ' hydrolysis with water yield higher fatty acids and higher
Cleansing action' of soaps and detergents monohydric alcohols.
The molecules of soaps and detergents are usually smaller ClsH31COOC16H33 + H2 0 ~ C1s H 31COOH+ C 16H 33 0H
than the colloidal particles. However, in concentrated Cetyl palmitate Palmitic acid Cetyl alcohol
,.soll1tions, these molecules associate and fonn aggregates of When hydrolysis is carried with caustic alkalies, soap and
collQ!4al size. These aggregates, of soaps or detergents . higher monohydric alcohols are fonned.
, " ,mol~cules are called micelles~