Untitled

Contents
Chapter 1: Nomenclature ............................................. 01 – 16

Previous Year Questions ................................. 11 - 16
Answers .......................................................... 16 - 16
Chapter 2: General Organic Chemistry ....................... 17 – 108

Chapter Assignment ....................................... 88 - 93
Previous Year Questions ................................ 94 - 102
Chapter Test ............................................... 103 - 105
Answers ...................................................... 106 - 106
Hints and Solutions .................................... 107 - 108
Chapter 3: Hydrocarbons ........................................ 109 – 226

Chapter Assignment ................................... 195 - 202
Previous Year Questions .............................. 203 - 216
Chapter Test ............................................... 217 - 221
Answers ...................................................... 222 - 223
Hints and Solutions .................................... 224 - 226
[2022]
Chapter - 1
NOMENCLATURE
There are two systems of Nomenclature.
I. Common Name System
II IUPAC System of Nomenclature.
I Common Name System : According to this system of nomenclature the names are given to the
compounds according to their origin.
Ex. (a) Acetic acid is derived from the greek word acetum (meaning vinegar)
(b) Formic acid is derived from the word Fermicus (Red ant)
II IUPAC System of Nomenclature : Following are the steps which must be used to write the
IUPAC names of different organic compounds having Polyfunctional groups.
PRIORITY LIST (Table - A)
S.No. Functional group Formula Family name Substituted prefix/suffix
1. Sulphonic acid –SO3H Alkane Sulphonic acid Sulpho

2. Carboxylic acid * Akanoic acid or Carboxy, carboxylic acid
–COOH
3. Carboxylic acid –C–O–C– Alkanoic acid anhydride

O O
anhydride
*
4. Ester –COOR Alkyl alkanoate Alkyl carbonyl
5. Acid halide * Alkanoyl halide Haloformyl,
–COX
halocarbonyl
*
6. Acid Amide –CONH2 Alkanamide Carbomyl, carbamoyl,
carboxamido
7. Cyanide * Alkanenitrile Cyano
–C N
8. Aldehyde * Alkanal Formyl. Aldo, Oxo

–CHO
O
9. Ketone Alkanone Oxo, Keto
–C–
10. Alcohol –OH Alkanol Hydroxy
11. Amines –NH2 Alkanamine Amino
12. Thiols –SH Alkane thiols Sulphamyl
13. Ethers –OR Alkoxyalkane Alkoxy
14. Alkene, alkyne C = C, C  C Alkene, alkyne
15. Nitro –NO2 Nitroalkane Nitro
16. –X –X Haloalkane Halo
17. –R, Alkyl, Phenyl.
Amity Institute for Competitive Examinations : Phones: 24336143, 24336144, 25573111/12/13/14,95120-2431839/42 [1]
Nomenclature AICE (IIT-JEE)
Note: 1. Those functional gps which have been marked (*) if they behave like main functional
groups then there carbon atom must be included in the main chain.
2. Those functional gps which have been marked (*) if they behave like substituents then
their carbon atom should not be included in the main chain.
3. If CHO gp is the only substituent then its carbon atom may or maynot be included in the
main chain.
Step-I : Indentification of functional groups and classifying them into main, subsidiary and substituent
groups.
1. Main Functional group : The functional group getting highest priority is called main functional
group.
2. Subsidiary group : If the molecule contains C = C or C  C apart from Main functional

group then the C = C or C  C are called subsidiary group.
3. Substituent group : Any other functional group apart from main or subsidiary are called
substituents.
1. CH3CH2COOH
Main functional group = – COOH
Subsidiary = Nil
Substituent = Nil
2. CH3 – CH – CH = CH – CONH2
OH
Main Functional group = –CONH2

Subsidiary = –C = C– [see Table-A]
Substituent = –OH.
3. CH3 – CH = CH – CH – COBr
CH = CH2
Main = –COBr
Subsidiary = C = C
Substituent = NIL
Step-II: Identification of main chain:
Following points should be considered for choosing the main chain:
1. The main chain must contain maximum number of main functional groups.
2. It must contain maximum number of subsidiary groups.
3. The main chain must contain maximum number of substituent carrying carbon atoms or side
chain carrying carbon atoms.
4. The main chain must contain maximum number of carbon atoms.

Use the above points for identifying the chain.
correct chain wrong chain

1. CH CH COOH
3 2 CH3CH2 – COOH
Here the main functional group is –COOH its carbon atom must be included in the Main
Chain.
correct chain wrong chain

2. CH – CH = CH – CHO CH3 – CH = CH – CHO
3 2
Reason same as above.

correct chain
3. CH3 – CH – CH = CH – CH – CH3
Br OH
Chain–3
O O
CH3 – C – CH2 – CH – C – CH3
4.
CH2 – Br
Chain–1
Chain–2
Here Chain–1 is correct chain. This is because it contains maximum number of main functional
groups which is – C – group.

O
Chain–1
O
CH3 – CH2 – CH2 – CH2 – CH – C – CH3
5. CH = CH2
Chain–3
Chain–2
Here chains–3 is correct chain. This is because it contains the main functional group, the
subsidiary group
Wrong chain
6. CH3 – CH – CH = CH – CH – CN
OH CH = CH – CH = CH2
Wrong chain Correct chain
This is because the main chain must contain maximum number of main functional group
(i.e., CN) and maximum number of subsidiary groups.
Step-III: Numbering the Main Chain
Numbering of the main chain is done according to :
Lowest Number Rule : After selecting the continuous main chain, the numbering is done in
such a manner that :
(a) The main functional group gets the lowest number.
(b) The second lowest number is given to the subsidiary groups.
(c) The third lowest number is given to the substituent carrying carbon atom or side chain
carrying carbon atom.
(d) If the main functional group gets the same number in two different ways of numbering then
give lower number first to subsidiary and then to substituent carrying carbon atoms.
1 2 3 Incorrect
1. CH3 CH2 COOH
3 2 1 Correct
(Main functional group given lowest number)

1 2 3 4 Incorrect
2. CH3 – CH = CH – CHO
4 3 2 1 Correct
1 2 3 4 5 6 Incorrect
3. CH3 – CH – CH = CH – CH – CH3
6 5 4 3 2 1
OH Correct
O
3 2 1 Correct
4. CH3 – CH2 – CH2 – CH2 – CH
3
– C – CH3
4 5
2 Incorrect
1
CH = CH2
4 5
O O
1 2 3 4 5 6 Incorrect
5. CH3 – C – CH2 – CH – C – CH3
6 5 4 3 2 1
CH2 – Br Correct
1 2 3 4 5 Incorrect
6. CH3 – CH – CH – CH = CH2
5 4 3 2 1
Correct
Br OH
Lowest Sum Rule at the First Sight of Difference : If more than one main functional group
or substituents are present in the chain, then their positions are noted and the sets are made of all
possible numberings. Then these sets are compared term by term. The preferred numbering is
the one which has the lowest term in the set at the first point of difference, e.g.
1 2 3 4 5 Set - 1 (incorrect numbering)

1. CH3 – CH2 – CH – CH – CH3
5 4 3 2 1 (correct numbering)
Set - 2
Cl Br
Term - I Term - II
Set -1 3 4
Set -2 2 3
First point of difference the term I - ‘2’ of set - 2 is lower than term I - ‘3’ of set-1.
Therefore, set - 2 is preferred.
1 2 3 4 5 6 7 8 9 10 Set - 1
C–C–C–C–C–C–C–C–C–C
2. 10 9 8 7 6 5 4 3 2 1 Set - 2
C C C
Term - I Term - II Term - III Sum Rule
Set -1 3 4 9 Set - 1 : 3 + 4 + 9 = 16
Set -2 2 7 8 Set - 2 : 2 + 7 + 8 = 17.
According to sum rule set - 2 is incorrect numbering.
According to sum rule set - 1 is correct numbering.
Sum rule is followed.
Step - IV: Writing the name

This part consists of:
(a) Noun String (Family Name).
(b) Adjective String (Substituents or Side chains).
The adjective string is written first and then the noun string, e.g.
3 2 1
1. CH3 – CH – CHO
Br
Adjective String = 2-Bromo

Nounstring = Alkanal = Propanal
2-Bromo proponal.
4 3 2 1
2. CH3 – CH = CH – CHO
Family Name = Alkenal

But -2-en-1-al.
6 5 4 3 2 1
3. CH3 – CH – CH = CH – CH – CH3
Br OH
Adjective String = 5-Bromo
Noun String = Hex-3-en-2-ol.
5-Bromo hex-3-en-2-ol.
O O
6 5 4 3 2 1
CH3 – C – CH2 – CH – C – CH3
4.
CH2 – Br
Adjective string = 2-Bromo methyl.
Noun = Hexan -2, 5-dione.
3-Bromo methyl hexan -2, 5-dione.
3 2O 1
5. CH3 – CH2 – CH2 – CH2 – CH – C – CH3
CH = CH2 wrong chain
4 5
Adjective String = 3-Butyl correct chain
Noun String = Pent-4-en-2-one.
3-Butylpent-4-en-2-one
5 4 3 2 1
CH3 – CH – CH – CH = CH2
Br OH
6.
Adjective string 4-Bromo
Noun string pent-1-en-3-ol
4-Bromopent-1-en-3-ol.
3' 2' 1' 2 1

7. CH3 – CH – CH2 – CH – CN
Br CH = CH2
3 4
Adjective String = 2-[2- Bromo Propyl]

Noun String : But -3-ene-1-nitrile.
2-[2-Bromo propyl] but-3-ene-1-nitrile.
Nomenclature of Specific Families (Few selected)

1. Alkanes: Here since there are no functional groups so the first two points of Step-II (Identification
of Main Chain) do not find application hence that chain must be chosen which has maximum number
of side chains and maximum number of carbon atoms, e.g.
CH3
CH – CH3
Wrong Chain - 1  Wrong Chain - 3
1. CH3 – CH2 – CH – CH2 – CH3
Wrong Chain - 2
CH3 – CH – CH3  Correct Chain - 4
5
1 CH
3
2 CH – CH
3
4
3
CH3 – CH2 – C – CH2 – CH3
3
4 CH – CH3
2
Set - 2 – 5 CH
– Set - 1
1 3
Term-1 Term-2 Term-3 Term-4
Set - 1 2 3 3 4
Set - 2 2 3 3 4
Here both numberings are correct.
2,4-Dimethyl - 3, 3-diethyl pentane.
CH3 CH3
1 2 3 4 5 – Set - 1
CH3 – C – CH2 – CH – CH3
2. 5 4 3 2 1 — Set - 2
CH3 CH3
Term-1 Term-2 Term-3 Term-4
Set - 1 2 2 3 4 Correct
Set - 2 2 3 4 4 Wrong
2, 2, 3, 4 - Tetramethyl pentane.
1 2 3 4 5 6 – Set - 1
C–C–C–C–C–C
3. 6 5 4 3 2 1 — Set - 2
C C–C
Set - 1 3, 4 (wrong numbering)

Set - 2 3, 4 (correct numbering)
When the set rule comes out to be same give preference to alphabetical order, hence Set(2)
numbering is prefered.
3-Ethyl-4-methyl hexane
2. Esters: The name written is Alkyl alkanoate.
R – C – O – R Alkyl
O
Alkanoate
If substituent/Side chain present on alkyl part write these substituents / side chains before writing
the alkyl part.
If substituent/side chain present on alkanoante part write before writing the alkanoate part.
CH3 – C – O – CH3 Alkyl

O Methyl ethanoate
Alkanoate
4 3 2 1
CH3 – CH = CH – C – O – CH2CH3
Ethyl but-2-en-1-oate
O
3 2 1
CH3 – CH – C – O – CH3
Methyl 2-hydroxypropanoate
OH O
3. Secondary Amines: Those amines in which the Nitrogen is attached to two carbon atoms are
called s-amines.
R–NH – R
Name : N-alkyl alkanamine
1. Here ‘N’ represents Nitrogen so the alkyl group attached to N is called N-alkyl.
2. The alkanamine part must satisfy all the conditions for main chain,
CH3–NH–CH2 CH3 N-Alkyl = N-methyl
Alkanamine = Ethanamine
N-methyl ethanamine
2 3
CH3 – CH2 – NH – CH – CH3
CH3
1
N-Ethylpropan-2-amine.
1 2
CH3 – CH2 – NH – CH2 – CH2
Br
N-Ethyl-2-bromo, ethanamine
4. Tertiary Amines : Where the nitrogen atom is attached to 3-carbon atoms is called t-amines.
Name: N-Alkyl-N-alkyl alkanamines [when alkyl groups attached to nitrogen are different]
: N, N-Dialkyl alkanamine. [when alkyl groups attached to nitrogen are same], e.g.
1. CH3 – N – CH2 – CH3

CH2 – CH2 – CH3
1 2 3
N-Ethyl-N-methyl propan-1-amine
2 3
CH3 – N – CH – CH3
1
CH3 CH3
N, N-Dimethyl propan-2-amine
5. N-Substituted Amides : Where in an amide molecule an alkyl group is attached on the nitrogen
atom, such molecules are called N-substituted amides, e.g.
R – C – NH – R N-Alkyl
O
Alkanamide
N-Alkyl alkanamide.
1. CH3 – C – NH – CH3
O
N-Methyl ethanamide
2. CH3 – CH2 – C – NH – CH – CH3

O CH3
N-(1-Methyl) ethyl propan amide
3. CH3 – CH – C – NH – CH3
Br O
N-Methyl-2-bromo propanamide
4. CH3 – C – NH —
O
N-Phenyl ethanamide
CH3 – CH – C – C – NH–
5. Br O O
N-Phenyl-3-bromo, 2-oxo butanamide
N-phenyl-3-bromo-2-oxobutanamid
CH3 – CH – C – NH– Cl
Br O
N-[Chlorocyclohexyl-2-bromopropanamide
Nomenclature of Bicycloalkanes
These are compounds containing two fused rings. Following points are taken into consideration while naming
such compounds:
1. Compound is named as bicycloalkane corresponding to total number of C-atoms.
2. The number of carbon atoms in each of the bridges are written in brackets in descending order.
For example,
Bicyclo [3.1.0] hexane Bicyclo [3.3.0] octane Bicyclo [4.2.0] octane
3. In case of substituents present in bicyclic compounds, the numbering of chain is done from the
longest bridged ring beginning at one bridge head. The numbering is the next longest bridge and thus
shortest bridge is numbered at least.
For example,
This structure has two rings. One is a six membered and other one is five membered. While numbering
it starts from longest bridge (showing six membered) then shortest bridge (five membered) followed
by third bridge. Thus its numbering is done as,
7 I
1 2
C2H 5
7 1 2
8 3 4 3
6
6 5 4
5
IUPAC name is 8-methyl bicyclo [3.2.1] octane. 2-Ethyl-7-iodo bicyclo [2.2.1] heptane
10 2
9
1 C2H5
3
8 4
6
7 5
3-Ethyl bicyclo [4.4.0] decane
Nomenclature of spiro compounds

If two rings are joined by quaternary carbon at the apex, then they are prefixed by the word spiro followed by
brackets containing the number of carbon atoms in each ring of both side of common point in ascending order
and then by the name of parent hydrocarbon containing total number of carbon atoms in the two rings. The
numbering starts from the atom next to the spiro atom (atom joining the ring) and process through the smaller
ring first. For example

7 6 1 2 6 5 1
4 2
8 5
9 10 4 3 7 8 3
Spiro [4.5] decane 2,6-di(cyclopropyl)-spiro [3.4] octane
Nomenclature of unbranched identical hydrocarbon ring systems having NO common

points
1. Unbranched assemblies consisting of three or more identical hydrocarbon ring systems are named
by placing an appropriate numerical prefix before the name of the hydrocarbon corresponding to the
repetitive unit. The following numerical prefixes are used:
3: ter 4 : quater 5: quinque 6: sexi 7: septi

8: secti 9: noni 10 : deci
2. Unprimed numbers are assigned to one of the terminal systems, the other systems being primed
serially. Points of attachment are assigned the lowest number possible. For example,
2 2´´ 3 4 4´´ 3´´
1 1´ 3´ 1´ 2´
3
1´´ 3´´ 2 1 1´´ 2´´
2´ 4´ 3´
1–1´, 3´ - 1´´-tercyclopropane 1, 1´, 2´, 1´´ - tercyclobutane
3. As exceptions, unbranched assemblies consisting of benzene rings are named by using the appropriate
prefix with the radical name “phenyl”.
4´´ 3´´
3´´ 2´´ 3´ 2´ 2 3 5´´ 2´´

1´´ 1´ 3´ 2´ 2 3
4 6´´ 1´´
4´´ 4´ 1 1´
4
5´´ 6´´ 5´ 6´ 6 5 4´ 1
5´ 6´ 6 5
p-terphenyl or 1, 1´, 4´, 1´´-terphenyl m-terphenyl or 1, 1´, 3´, 1´´-terphenyl

Amity Institute for Competitive Examinations : Phones: 24336143, 24336144, 25573111/12/13/14,95120-2431839/42 [ 10 ]

PREVIOUS YEAR QUESTIONS
1. The correct IUPAC name of the compound, is [IIT 1990]
(a) 5,6-Diethyl-8-methyldec-6-ene (b) 6-Butyl-5-ethyl-3-methyloct-4-ene

(c) 5,6-Diethyl-3-methyldec-4-ene (d) 2,4,5-Triethylnon-3-ene
2. Choose the correct IUPAC name for

CH3 CH CHO
[IIT 1993]
CH2 CH3
(a) Butan-2-aldehyde (b) 2-Methylbutanal
(c) 3-Methylisobutyraldehyde (d) 2-Ethylpropanal
3. In compound, CH2=CH–CH2–CH2–CH, the C2–C3 bond is of the type [IIT 1999]

2 3 3 3 2 3
(a) sp–sp (b) sp –sp (c) sp–sp (d) sp –sp
4. Which of the following represents the given mode of hybridization sp2 –sp2–sp–sp from left
to right? [IIT 2003]
CH2
(a) H2 C=CH–CN (b) HCC–CH (c) H2C=C=C=CH2 (d)
H 2C
COCl
5. IUPAC Name of the [IIT 2006]
(a) Chlorophenyl ketone (b) Chloroaceto benzene

(c) Benzencarbonyl chloride (d) Benzoyl chloride
6. The number of structural isomers for C6H14 is [IIT 2007(P-1)]

(a) 3 (b) 4 (c) 5 (d) 6
7. The hybridization of carbon atoms in C–C single bond of HCC–CH=CH2 is [IIT 1991]
(a) sp3 – sp3 (b) sp2 – sp3 (c) sp – sp2 (d) sp3 – sp
8. The correct statement(s) about the compound given below is (are) [IIT 2008]
Cl H
CH3
H 3C
Cl H
(a) The compound is optically active (b) The compound possesses centre of symmetry
(c) The compound possesses plane of symmetry (d) The compound possesses axis of symmetry
9. The correct statement(s) concerning the structures E, F and G is (are) [IIT 2008]
HC O HC OH H C CH3
3 3 3
H 3C CH3 H 3C CH3 H 3C OH
(E) (F) (G)
(a) E, F and G are resonance structures (b) E, F and E, G are tautomers
(c) F and G are geometrical isomers (d) F and G are diastereomers

OH
10. The IUPAC name of the following compound is [IIT 2009]

CN
Br
(a) 4-Bromo-3-cyanophenol (b) 2-Bromo-5-hydroxybenzonitrile
(c) 2-Cyano-4-hydroxybromobenzene (d) 6-Bromo-3-hydroxybenzonitrile
11. The correct statement(s) about the compound H3C/(HO)HC – CH = CH – CH(OH)CH3 (X) is(are)
(a) The total number of stereoisomers possible for X is 6 [IIT 2009]
(b) The total number of diastereomers possible for X is 3
(c) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible
for X is 4
(d) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for
X is 2.
12. The total number of cyclic structural as well as stereo isomers possible for a compound with the
molecular formula C5H10 are [IIT 2009]
X
H3C CH3
13. In the Newman projection for 2,2-dimethylbutane H H X and Y can respectively are
Y
[IIT 2010]
(a) H and H (b) H and C2H5 (c) C2H5 and H (d) CH3 and CH3
14. The total number of cyclic isomers possible for a hydrocarbon with the molecular
formula C4H6 is [IIT 2010]
15. Amongst the given options, the compound(s) in which all the atoms are in one plane in all the possible
conformations (if any), is (are) [IIT 2011]
H H H
(a) C C (b) H C C–C (c) H2C C O (d) H 2C C CH2
H 2C CH2 CH2
16. The number of optically active products obtained from the complete ozonolysis of the given
compound is [IIT 2012]
CH3 H
H3C CH CH C CH CH C CH CH CH3
H CH3
(a) 0 (b) 1 (c) 2 (d) 4
17. Which of the following molecules, in pure form, is (are) unstable at room temperature? [IIT 2012]
O O
(a) (b) (c) (d)

18. Which of the given statement(s) about N, O, P and Q with respect to M is (are)
correct? [IIT 2012]
Cl
HO H HO H
H OH CH3 CH3
Cl CH3 H OH HO H
HO H H OH HO H
HO OH HO H
CH3 Cl CH3 Cl Cl
M N O P Q
(a) M and N are non-mirror image stereoisomers

(b) M and O are identical
(c) M and P are enantiomers
(d) M and Q are identical
Paragraph for Question 19 to 20

P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O. On heating. P forms
the cyclic anhydride.
Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one
from S, T and U. [IIT 2013]
COOH COOH COOH
H OH H OH HO H
H OH HO H H OH
COOH COOH COOH
S T U
19. Compound formed from P and Q are, respectively,

(a) Optically active S and optically active pair (T, U)
(b) Optically inactive S and optically inactive pair (T, U)
(c) Optically active pair (T, U) and optically active S
(d) Optically inactive pair (T, U) and optically inactive S
H / Ni
20. In the following reaction sequences V and W are, respectively Q 
2

V
AlCl3 (anhydrous) 1. Zn  Hg / HCl

V   
2. H PO
W
3 4
CH2OH
O and and
(a) (b)
CH2OH
O V W
O
V W

O HOH2 C
and
(c) O and (d) CH2 OH CH2 OH
V W
O
V W
21. The compound which contains all the four 1°, 2°, 3° and 4° carbon atoms is [DCE-2000]
(a) 2,3-Dimethylpentene (b) 3-Chloro-2,3-dimethylpentene
(c) 2,3,4-Trimethylpentane (d) 3,3-Dimethylpentane
22. Indicate the wrongly named compound [DCE-1994]

CH3 CH C C COOH
CH3 CH CH2 CH2 CHO
(a) (b) CH3
CH3
(4-methyl-2-pentyn-1-oic acid)
(4-methyl-1-pentanal)
O
(c) CH3CH2CH2 CH COOH (d) CH3CH2 CH CH C CH3
CH3 (3-hexen-5-one)
(2-methyl-1-pentanoic acid)
23. The IUPAC name of C=O is [DCE-2000]
(a) Cyclohexanone (b) Cyclohexylmethanone

(c) Oxycyclohexene (d) Cyclohexylidenemethanone
H Br
24. The IUPAC name of CH3– C CH2 –CH2 –CH2 – C CH3 is [DCE-2001]
OH Br
(a) 6,6-Dibromoheptan-2-ol (b) 2,2-Dibromoheptan-6-ol

(c) 6,6-Dibromoheptan-2-al (d) none of these
25. Which of the following compound has wrong IUPAC name? [AIEEE-2002]
(a) CH3 CH2 CH2 COO CH2CH3 (b) CH3 CH CH2 CHO
Ethyl butanoate 3-methylbutanal
CH3
CH3 CH CH CH3 2-methyl-3-butanol CH3 CH C CH2 CH3

(c) (d) CH3 O
OH CH3
2-methyl-3-pentanone
26. The IUPAC name of CH3COCH(CH3)2 is [AIEEE-2003]

(a) 2-methyl-3-butanone (b) 4-methylisopropyl ketone
(c) 3-methyl-2-butanone (d) Isopropyl methyl ketone
27. The IUPAC name of the compound is [AIEEE-2004]
(a) 3, 3-dimethyl-1-cyclohexanol (b) 1, 1-dimethyl-3-hydroxy cyclohexane
(c) 3, 3-dimethyl-1-hydroxy cyclohexane (d) 1, 1-dimethyl-3-cyclohexanol
28. Which one of the following does not have sp2 hybridized carbon? [AIEEE-2004]
(a) Acetonitrile (b) Acetic acid (c) Acetone (d) Acetamide
29. The IUPAC name of the compound shown below is [AIEEE-2006]

Cl
Br
(a) 1-bromo-3-chlorocyclohexene (b) 2-bromo-6-chlorocyclohex-1-ene
(c) 6-bromo-2-chlorocyclohexene (d) 3-bromo-1-chlorocyclohexene
30. The IUPAC name of is [AIEEE-2007]
(a) 5, 5-diethyl-4, 4-dimethylpentane (b) 3-ethyl-4, 4-dimethylheptane

(c) 1, 1-diethyl-2, 2-dimethylpentane (d) 4, 4-dimethyl-5, 5-dimethylpentane
HO2C CO2H
31. The absolute configuration of is: [AIEEE-2008]
HO H H OH
(a) R, R (b) R, S (c) S, R (d) S, S
32. The correct decreasing order of priority for the functional groups of organic compounds in the
IUPAC system of nomenclature is [AIEEE-2008]
(a) –SO3H, –COOH, –CONH2, –CHO (b) –CHO, –COOH, –SO3H, –CONH2
(c) –CONH2, –CHO, –SO3H, –COOH (d) –COOH, –SO3H, –CONH2, –CHO
33. The IUPAC name of neopentane is: [AIEEE-2009]
(a) 2,2-dimethylpropane (b) 2-methylpropane
(c) 2,2-dimethylbutane (d) 2-methylbutane
34. The alkene that exhibits geometrical isomerism is: [AIEEE-2009]
(a) 2-methyl propene (b) 2-butene (c) 2-methyl-2-butene (d) propene

35. The number of stereoisomers possible for a compound of the molecular formula
CH3 – CH = CH – CH(OH) – Me is: [AIEEE-2009]
(a) 2 (b) 4 (c) 6 (d) 3
36. Identify the compound that exhibits tautomerism. [AIEEE-2011]

(a) 2-Butene (b) Lactic acid (c) 2-Pentanone (d) Phenol
ANSWERS
1. (c) 2. (b) 3. (d) 4. (a) 5. (c)

6. (c) 7. (c) 8. (a) 9. (b,c,d) 10. (b)
11. (c,d) 12. 7 13. (b,d) 14. 5 15. (a,b,c)
16. (a) 17. (b,c) 18. (b,c) 19. (b) 20. (a)
21. (b) 22. (d) 23. (d) 24. (a) 25. (c)
26. (c) 27. (a) 28. (a) 29. (d) 30. (b)
31. (a) 32. (a) 33. (a) 34. (b) 35. (b)
36. (c)


Chapter - 2
GENERAL ORGANIC CHEMISTRY
Introduction
Organic chemistry deals with so many compounds made up of only few types of atoms such as Carbon,
Hydrogen, Oxygen, Nitrogen, etc. So for the study of Organic Chemistry, it is important to have a good
knowledge of structure of atom and its property.
STRUCTURE AND PROPERTY OF ATOM

2.1 Atoms
Atom is the smallest particle of element made up of atomic sub-particles – electrons, protons and
neutrons. Protons, neutron are present in nucleus and electrons are present outside the nucleus
arranged in the shells called energy level represented by K, L, M, N as per distance from nucleus.
These energy levels are also called Quantum Shells and are also represented by the No 1, 2, 3, 4
respectively. Protons are positively change and electrons are negatively charged in an atom and
both are present in equal number, and makes atom electrically neutral.
Maximum number of electrons that are present in the shell = 2n2. What n is the Quantum number.
Thus, first, second, third and fourth shell can accommodate around 2, 8, 18 and 32 electrons
respectively.
Shells are further composed of subshells which are known as Atomic Orbitals.
According to Quantum Mechanics, an atomic orbital is a three dimensional space within an atom
where electron is most likely to be found. Each orbital has a characteristic shape and energy are
indicated by the symbol s, p, d and f. Each quantum shell contains its own s-orbital, 3p-orbital, 5d-
orbitals and 7f-orbital. Each 3p-orbitals have equal energy which are called degenerate orbitals.
Similarly 5d-orbitals have 5 degenerate orbital and f has 7 degenerate orbitals.
In the orbital (may be degenerate or not) can accommodate only two electrons of opposite spin.
Energy of electron increases with increase in quantum number of, i.e., energy of 2s orbital is greater
than energy of 1s orbital and so on.
Atomic Orbitals
Electron is a very small atomic sub-particle and its properties can be explained ideally by wave -
particle duality, i.e., electron has dual behaviour, it behaves as wave as well as particle. But it cannot
behave as both at the same time. At one time electron can behave either only as wave or as particle.
In wave mechanics, a moving particle like electron is represented by the wave function  (psi) and
 2 is the probability of finding the electron in an unit volume.
When the wave equation of an electron for a particular point is calculated in space relative to the
nucleus, the result may be positive or negative or zero. These signs are often called phase sign.

General Organic Chemistry AICE (IIT-JEE)
Wave property of the electron can be explained and understand with simple analogy of wave moving
across a lake. It moves with crests and troughs above and below the average level, where wave
function i.e., zero ( = 0). Electron wave is represented in a similar manner where crests and trough
are indicated by (+) and (–) phase sign. The point at which the crests and trough meet together
represent the average level, where  = 0, are called nodes.
Theoretically, would have a finite value at any distance from the nucleus, but inpractice there is a
very little probability of finding the electron beyond 2-3Å. The spacial behaviour of the electron is
known as orbital. The orbital associated with single nucleus is called atomic orbital.
Integration of  over all the space (x, y and z axis) must be equal to 1, i.e., probability of finding an
electron all over the space is 100%. The plots of  in three dimensions generate the shape of the
atomic orbitals, known as s, p, d and f-orbitals. Organic chemistry mainly deals with carbon and
therefore, s and p orbitals the more important than d and f orbitals.
The s-orbital is spherical around nucleus. The 1s orbital has no node while 2s orbital has one nodel
surface or radical node. As 2s orbital is bigger and has higher energy then 1s. The p-orbitals have the
shapes like dumbbell consisting of two almost touching spheres indicated by (+) and (–) signs separated
by the nodal plane. Three such p-orbitals are arranged in space in such a way that their axes are
mutually perpendicular to each other. These p-orbitals have the same energy degenerate orbitals. It
may be noted that (+) and (–) signs simply represent arithmetic signs of the wave functions. By no
means, they imply greater or less probability of finding an electron. The shapes of s and p-orbitals are
shown in figure.
2.2 Chemical Bonds

Structure and reactivity of organic compound needs a good knowledge of bonding by organic
molecules, i.e.., how they are formed from the constituent atoms.
How the atoms are held together in molecules was remain unknown by early 20th century. In 1920,
G.N. Lewis proposed the concept of electron pair for bonding. After the development of quantum
mechanics, explanation of chemical bonding and basic structural theory was developed. Quantum
mechanics deals with the concept by atomic and molecular orbital, which is the basis of understanding
chemical bonding.
Theories of Bonding
In 1926, G.N. Lewis and W. Kossel proposed two types of chemical bonds - Ionic and Covalent, on
the basis of the idea that, after getting bonded, atoms acquire noble gas configurations and achieve
their stability. The ionic bond is formed by transfer of one or more electrons from one atom to
another creating two oppositely charged ions. Attraction, of these ions for each other would account
for ionic bonding.
Na   Cl 
 Na   Cl
A covalent bond is formed when two atoms combine by sharing of their electron/s so that, both the
atoms can fulfill their octet by enjoying the common electron pair.
Cl  Cl 
 Cl Cl 
 Cl  Cl
O  O 
 O O 
 OO
The bonding character between cation and anion in organic compounds involve the formation of
ionic bond.
Modern Theory of Bonding : Molecular Orbitals Theory

When two atoms approach from infinite distance, each nucleus increasingly attract others electrons
by lowering the energy of the whole system. When they get too close, the repulsion between two like
charged electrons will dominate and the energy will increase rapidly. As a result, at an optimum
equilibrium distance, called bond distance the energy will be the lowest and there will be a bonding
between two concerned atoms.
In bonding process, two atomic orbitals (AOs) of combining partners overlap and fuse into Molecular
Orbitals (MOs). Mathematically, MOs may be obtained by an approximation called “Linear
Combination of Atomic Orbital” (LCAOs). The combination yields as many as molecular orbitals
() as the number of atomic orbitals () combined. When two atoms A and B combine, their atomic
orbitals  A and  B interact in two possible ways leading to the formation of two MOs,  1 and  2.

In  1, electron is available between two nuclei A

and B and hence the repulsion between them is
minimum and it is called Bonding MO.  2 on the
other hand represents Anti-bonding MO in which
there is no electron between the two nuclei as
indicated by the node and therefore, it is the high
energy molecular orbital due to internuclear
repulsion. Formation of bonding and anti-bonding
MOs during the formation of hydrogen molecule
is shown in figure.
In this molecule two electrons are occupied in lower energy bonding MO and the antibonding. MO
remains vacant. This represents the ground state electronic configuration of the molecule. Irradiation
of the molecule with correct frequency of light, one of the electrons may be promoted from bonding
MO (more precisely, from highest occupied MO) to the antibonding MO (more precisely, the lowest
unoccupied MO) and this situation represents the excited state of the molecule. Withdrawing the
energy source, the molecule returns to its ground state and the energy is released.
A -bonding is formed in a similar manner, when two p orbitals combine sideways. During the
formation of C = C bond, two carbons combine with their 2p orbitals (figure). Two electrons are
occupied in bonding -MO while the antibonding *-MO remains vacant in the ground state of the
molecule. During photochemical excitation, one of the p electron is promoted from -MO to *-MO.
Heteronuclear bonds are also formed by similar process. Figure represents the formation of carbon-
oxygen -bond by combination of p-orbitals of carbon and oxygen atoms. More electronegative
atom (here oxygen) contributes more to the bonding. MO while the less electronegative atom
(here carbon) contributes more to the antibonding MO.
Covalent Bond and Hybridization

Combination of two AOs explains well the formation of simple molecules like H2, HCl, etc., but it
cannot account many of the bonding characteristics of more complex molecules. Let us consider the
formation of methane, a hydrocarbon with a tetracoordinated carbon atom. Carbon has electronic
configuration 1s22s22p2 in its ground state. Such a carbon does not form any compound. So excited
2 1 1 1 1
carbon may be considered having electronic configuration 1s 2s 2p x 2p y 2p z ; achieved by the
promotion of one of the 2s electron of the ground state carbon to 2p level. Having four unpaired
electrons, excited carbon might combine with four H atoms and would form methane, CH4 (figure).
However, this theoretical model still cannot explain the bonding properties of methane, such as the
uniformity of C–H bond lengths and HCH bond angles. This excited state theory speaks about two
kinds of C–H bonds in methane: one is of C 2s – H 1s and three are C 2p – H 1s type,
which is not true.
Another serious drawback of excited state theory lies with C–H bond strength. When combines with
s-orbital, the p-orbital leaves half of the original orbital uninvolved in bonding and hence C2p – H1s
bond would not be strong enough. But this is not true, i.e., C – H bond of methane is quite strong.
Similarly C2s – H1s bond would also be weak since two nuclei were very close to each other (figure).
Further, the excited state theory cannot explain the regular tetrahedral shape of methane. To overcome
those limitations of excited state theory, Pauling in 1931 introduced the concept of Hybridisation for
proper understanding of chemical bonding. This states that, the atomic orbitals of similar energy may
mix together to generate Hybrid Atomic Orbitals which actually take part in bonding.
1. sp3-Hybridisation: Formation of saturated molecules: Let us see the formation of methane.

It involves all the 2s and 2p orbitals of carbon in bonding. They first can be mixed to form hybrid
atomic orbitals. This requires first the excitation, i.e., the promotion of one of the 2s electron of
carbon to the vacant 2p-orbitals. This is possible because 2s and 2p-orbitals do not differ much
in their energy content. One s and three p orbitals then blend and generate four hybrid atomic
orbitals, designated by sp3. These hybrid orbitals are identical in shape, size and in energy
content but they differ from those of pure atomic orbitals. In contrast to pure p orbitals, nearly all
the orbitals is concentrated on one side of the nucleus (head) although a small tail is there
extending to the opposite side. Four sp3 hybrid AOs of carbon contain one electron in each and
are distributed in space with an angle 109.5° with respect to each other, i.e., they are directed to
the corners of a regular tetrahedron. This particular arrangement of orbitals corresponds to the
most stable structure, as they are farthest away from each other with minimum electronic repulsion.
To form methane the larger lobe of each sp3 hybridized AO, overlaps with 1s orbital of H atom.

In this way, four C – H bonds Csp3 – H character are formed and arranged with HCH angle
109.5°. This explains the equivalent character of four C – H bonds as well as the regular tetrahedral
structure of methane.
An simple drawing, two C – H bonds of methane are shown in the plane of the paper and two
other bonds in a plane perpendicular to it extending below (dotted line) and above (thick line).
Fig.: sp3 Hybridisation of carbon and formation of methane
It may be noted that the energy liberated in bonding process may compensate the initial investment
of energy during the excitation of ground state carbon.
Ethane and other saturated hydrocarbons are similarly constituted with sp3 hybridized carbons, where
C – C bonds are formed by Csp3 – Csp3 overlap. Not only saturated carbon, saturated nitrogen,
oxygen etc. are also sp3 hybridized. Thus, LCAO structure of ammonia, ethanol, and dimethyl ether
may be drawn (figure) where non bonding pair of electrons resides in sp3 hybrid orbitals.
Not only neutral atoms, positively or negatively charged elements may also be sp3 hybridized. Some
ions having sp3 central element are shown in figure.

H H
+ - +
N B O
H H H H H H
H H H
Ammonium ion Borohydride anion Hydronium ion
2. sp2-Hybridization: When bonding is required for three atoms, only three of the atomic orbitals,
one s and two p are hybridized and form three sp2 hybrid orbitals. These hybrid orbitals contain
one electron in each and are distributed in space with orientation of angle 120° about their axes.
One p-orbital does not participate in hybridization and remains perpendicular to the plane of the
three sp2 hybrid orbitals. The simplest example of sp2 hybridization is the formation of BF3.
Three sp2-hybrid orbitals of boron overlap with p-orbitals of three F atoms and the unhybridized
p-orbital remains vacant (figure).
In terms of orbital picture:
A presentable model for C = C bond is based on sp2 hybridization of carbon atoms. Let us
consider the formation of ethylene. Each of the two sp2 carbons is used to form two -bonds
with two H atoms C – C -bond is formed by Csp2 – Csp2 overlap. Unhybridized p-orbitals of
carbons carrying one electron in each overlap sideways and form the -bond. Formation of
ethylene molecule may be depicted below (figure).

Here four H-atoms and two carbon atoms lie in the same plane and the p-orbitals overlap above and
below the -framework to form the -bond. Double bonded compounds of first row elements such
as carbon, nitrogen, and oxygen are much more common than those of the second row elements.
- and -model explains why there is a large barrier for free rotation associated with the units
(carbon atom) joined by a double bond. When one carbon of C = C bond is rotated by 90°, the -bond
is broken and the axes of p-orbitals then become perpendicular to each other without having any
overlap between them. Restricted rotation around C = C bond is the origin of -diastereoisomerism
i.e., the non interconvertibility of the cis and trans isomers.
Non-interconvertible
H 3C CH3 H 3C H
H H H CH 3
cis-2-Butene trans-2-Butene
P P P H
P
H3 C CH3 H3 C
90 rotation
C C 
 C C
π bond breaks
H H H
H
-diastereoisom erism Non-planar
H3C H3C H H H H
sp2 sp2 sp2 sp2 sp2 sp2 sp2
C O C C 2 2H C C 2 N N
sp sp sp
H3C H C C H C N sp2 Ph
H CH3 H CH3
Fig.: Some compounds with sp2 hybridized atoms
3. sp-Hybridization: Formation of triple bonds in alkynes is explained by sp-hybridization. One 2s

and one 2p-orbital of carbon may participate in hybridization and form two sp-hybrid orbitals
oriented with an angle 180° between them. Two p-orbitals of carbon remain unhybridized and lie
perpendicular to the line of hybrid axis. As per LCAO model C – C -bond of ethyne is formed
by Csp – Csp hybrid orbital overlap and two -bonds are formed by sideways overlap of the
unhybridized p-orbitals of each carbon form Csp – H1s bonds (figure).
Two carbon atoms and two hydrogen atoms lie on the same plane on a straight line and two
-bonds are on two -bonds are on two perpendicular planes. In this way, -bonds in alkyne
create a cylinder of -electrons around -bond and as a result there is no restricted rotation of
the groups joined by triple bonds.
BeF2 is another example of sp-hybridization. Here, two sp-orbitals of berylium overlap with p-
orbitals of two F atoms (figure).

Some other compounds having sp hybridized atoms:
sp3 sp sp sp2 sp sp2 sp2 2

sp sp sp sp sp sp
H3C C CH H2C C CH2 H2C C O HC C C N
Success of Hybridization
1. Hybridization explains the actual shape of molecules and their properties related with molecules
shape. For example, CH2Cl2 has a finite dipole moment and it has no isomer because of sp3
hybridization of carbon and the tetrahedral shape of the molecule. If the molecule was square
planar, it would have two geometrical forms: trans and cis (figure) and the former would have
no dipole moment.
H Cl Cl Cl Cl
C C
H H
Cl
Cl H H H
trans cis Actual shape
Fig.: Possible structures of CH2Cl2
2. It predicts bond length and bond strength. Larger and weaker bonds are formed by overlap of
orbitals of large sized (orbitals with enriched p-character) while smaller and hence stronger
bonds are formed by overlap of smaller sized orbitals (orbitals with enriched s-character). Thus,
the length and the strength of bonds are altered with the state of hybridization of the
concerned atoms.
Hybridization also accounts why a -bond is weaker than a -bond. This is due to the fact that
a -bond is formed by lateral overlap of the p-orbitals having a less penetration of orbitals while
a -bond is formed by head on overlap of the orbitals creating deeper penetration.
3. Hybridization influences electronegativity of an atom. Greater the s character of the hybrid

orbital, the greater is the electronegativity of the atom. Thus, an sp carbon is more electronegative
(3.0 ev) than an sp2 carbon (2.6 ev) which in turns is more electronegative than an sp3 carbon
(2.4 ev). This difference of electronegativity explains many of the physical and chemical properties
of organic compounds.
(a) The relative order of basicity decreases as indicated below with the increase of
electronegativity of the donor atom (here nitrogen) due to change of its hybridized character.
CH3  CH 2  CH2  NH2  CH3  CH2  CH  NH  CH3  CH2  C  N

sp 3 sp 2 sp
Alternatively, due to the smallest size of an sp orbital, the electron pair in it is least polarizable
and hence least basic. Electron pair in largest sized sp3 orbital on the other hand is most
polarizable and makes n-propylamine the strongest base in the above series.

(b) The acidity of hydrocarbons increases in the following order as shown below. This is due to
the increasing stability of the conjugate bases by the enhancement of electronegativity of
carbons along with gradual increment of s-character with the change in hybridization from
sp3 to sp2 and then sp.
CH3  CH3  CH 2  CH 2  CH  CH
sp3 sp 2 sp

Acidityincreases
(c) The acidity of carboxylic acids increases in the order.

sp 3 sp 2 sp
CH3CH 2COOH  CH 2  CH  COOH  CH  C  COOH

Acidity increases
The sp carbon being most electronegative makes –COOH of propynoic acid most active to
release H+ as well as to stabilizes the corresponding conjugate base to a maximum extent.
Propenoic acid having a less electronegative sp2 unit is less acidic than propynoic acid. With
sp3 hybridization, the ethyl group exerts +I effect and deactivates the –COOH group of
propanoic acid as well as destabilizes the corresponding conjugate base.
(d) C-H bond moments () increase in the following order as the electronegativity of carbon
atom increases with gradual enhancement of s-character.
Csp 3  H Csp 2  H Csp  H
μ (D): 0.31 0.63 1.05
Modified Hybrid Orbitals

Though integer combinations of atomic orbitals (sp, sp2, sp3, etc.) commonly represent hybrid orbitals,
non integer combinations like sp2.5, sp3.1, etc., may also be derived because hybrid orbitals are basically
formed by mathematically combination of atomic orbitals. In such cases the total of orbital combinations
assigned to a particular atom must equal the number of atomic orbitals used by the atom. This
change in orbital designations is arised when bond angle deviates from the normal value. For example,
in cyclopropane, carbon atoms are sp3 hybridized but internal CCC ˆ angles are only 60° instead of
109.5° (figure). Thus, for the formation of C – C bonds of cyclopropane, carbon atoms use more p-
character rather than the ideal sp3 character and proportionately they use greater amount of s-
character for the formation of C – H bonds to balance their sp3 status. Due to enriched s-character
towards C – H bonds, cyclopropane is more acidic than propane or its higher homologs where
carbon atoms use their normal sp3 character for the formation of C – C bonds.

Modified hybrid orbital concept is also consistent with the change in electron density along a bond. In
chloromethane, highly electronegative chlorine attracts electron pairs of C – Cl bond towards itself
and hence more p-character is being accumulated to that bond (with the analogy that, p-electrons
are farther away from the nucleus) and accordingly, proportionate amount of s-character will be
distributed towards C – H bonds instead of typical sp3 character. It has been calculated that, the
orbital character of carbon in chloromethane towards C – Cl bond is about sp3.1 and that for C – H
bond is about sp2.9.
PROPERTIES OF MOLECULES
2.3 Bond Polarity and Dipole Moment
In some covalent bonds the electrons are not shared equally between two bonded atoms because of
their different electronegativities. Such covalent bonds are called polar covalent bond.
Polarity due to unequal distribution of bond pair of electrons in a compound like HCl is expressed by
Dipole moment. A quantitative statement of dipole moment is  = e × d where, e = magnitude of
charge of any of the polar end and d = distance of separation between (+) and (–) charges. Dipole
moment () is expressed in the unit, Debye (D), in honour Peter Debye, who introduced it. Since the
charge of electron is 4.8 × 10–10 electrostatic unit (e.s.u) and the distance within a molecular is
considered usually is Angstron range (1Å = 10–8 cm), molecular dipole moment are in the order
10–10 × 10–8 = 10–18 e.s.u. cm. For simplicity, 10–18 e.s.u. cm = 1D. Experimentally, dipole moment of
HCl is 1.04 × 10–18 e.s.u. cm. The value of dipole moment can be used to determine the percentage
of ionic character of a compound. Thus, for HCl, the percentage of ionic character can be calculated
by the following ratio:
μ observed  1.04 1018 e.s.u. cm 

 100   10 8  100
μ ionic  4.8 10 e.s.u. 1.275  10 cm 
Where, 1.275 × 10–8 cm is H – Cl bond length. The term ionic is used on considering complete ionic
character of HCl.
Dipole moment is a vector quantity having magnitude as well as direction. Dipole moment of a
polyatomic molecule is the resultant of the vector sum of individual bond moments. Many molecules
do not possess molecular dipoles in spite of polar bonds because individual moments of those bonds
are so oriented that they cancel the one another. Any molecule that has a centre of symmetry will
have no dipole moment. Direction of polarity is shown by where, crossed end of the arrow
is that (+) end and arrowhead is the (–) end of the dipole. Some molecules without bonding any
dipole moment in spite of polar covalent bonds are shown in figure.
Cl Cl
D Cl
H Cl
O C O Cl H C
C C Cl H Cl Cl
Carbon dioxide D Cl
Chlorine Cl H
trans-1,2-Dichloroethene Cl Cl Carbon tetrachloride
trans-1,3-Dibromo 1,2-Dichloroethane
1,3-dichlorocyclobutane (staggered form)
Fig. Molecules without having dipole moment

Symmetrical molecules without having centre of symmetry may have finite value of dipole
moment is the individual bond moments do not cancel each other in figure.
Cl Cl
sp2
Oxygen is more
O S S
H H Me Me Me Me O O electronegative
than sulphur
cis-1,2-Dichloroethene Dimethyl ether Dimethyl sulphide Sulphur dioxide
(nonlinear) (nonlinear) (bent structure)
Fig. Symmetrical molecules having finite dipole moment
The amount and direction of the net molecular moment depend on the amount as well as
the direction of contributory bond moments. In NH3, net N – H bond moment and the contributory
moment, of the unshared pair of electron act along the same direction resulting in high value of its
dipole moment acting towards nitrogen. In NF3 on the other hand, the resultant N – F bond moment
opposes the effect of unshared electron pair and the net molecular moment is small and acts away
from N (figure).
H F
F is more
N N electronegative
H F
H F than N
Net moment 1.4713 Net moment 0.21D
Fig. Direction of dipole moment
Electronegativity of atoms and the distance between opposite poles (bond distance) are
often competitive in deciding the net moment of a molecule. Dipole moments of CH3F and
CH3Cl are 1.82 and 1.94 D respectively while those of HF and HCl are 1.7 and 1.0 D respectively.
In first case the distance factor predominates while in the second case electronegativity factor plays
a major role.
Conformational feature often also plays an important role in determining the dipole moment value.
Linearly acting C – NO2 group moments (contributory moment of a particular group) make
p-dinitrobenzene non polar while p-dihydroxy benzene has a finite value of dipole moment because
of conformational flexibility of O–H bonds. Anti orientations of O – H bonds contributes no net
moment while the syn conformation gives a finite value and therefore, the net moment of the molecule
is positive (figure).
 
O O H H H
N O O O
Resultant
Net  = 0 O-H O-H bond
NO2 bond moments or moment in
group moments cancel each other finite
cancel each other Conformational Net  0
N O isomers O O
O O H H H
  =0
Fig. Dipole moment and conformation

In disubstituted aromatics,  can be calculated by using the formula.

μ xy  (μ 2x  μ 2y  2μ x μ y cosθ)1/2
where xy is the net molecular moment x and y are the contributory moments of the substituents x
and y respectively and  is the angle of orientation of those groups, e.g., 60° for ortho, 120° for meta
and 180° for para x and y may be positive or negative if the substituents are electron releasing or
electron withdrawing respectively. Considering molecular moments of PhCl, PhNO2 and PhCH3 as
1.55, 3.93, 0.40 D respectively, dipole moment values of different disubstituted benzenes are calculated
using the above formula.
Intermolecular Forces of Attraction

Intermolecular force of attraction may be defined as the force that holds neutral molecules together.
Such a force is electrostatic in nature and is developed from the interaction between (+) and (–)
poles among the molecules. Thus, intermolecular forces are due to “dipole interaction”. As it involves
the attraction of neutral molecules but not the ions, it is often called van der Waals’ force of attraction.
Thus, force of attraction is considerably important in liquid and in solid state rather than the gas phase
where, the molecules are dispersed and are too far to attract.
van der Waals’ forces may be classified as follows:
1. Dipole – dipole attraction
2. Dipole – induced dipole attraction
3. Induced dipole – induced dipole attraction, of which last two are often called on London force
are Dispersion force.
1. Dipole - Dipole Force of Attraction: This is developed from attraction between positively
polarized region of a polar molecule and the negatively polarised region of another. For example,
in CH3Cl, partially negative Cl atom in one molecule is attracted by partially positive carbon in
another (figure).
H H H H
+  +  +  + 
H C Cl C Cl C Cl C Cl
H H H
H H H H
Dipole-dipole attraction
Fig. Dipole-dipole attraction in methyl chloride
Only the molecules which have permanent dipole moment are associated by dipole-dipole attraction.
This kind of attraction is the strongest of all kind of van der Waals’ force of attractions. The
extreme case of this kind of attraction is the hydrogen bond which explains many of the
physical and chemical properties of organic molecules. Hydrogen bond may be considered as
weak chemical bond formed between at electropositive H-atom (attached with an electronegative
atom) and a heteroatom such as O, N, F, Cl or S of the same or different molecule. A hydrogen
bond is thus formed when a heteroatom group ,e.g., OH, NH, SH or a COOH functional unit is

close enough to a heteroatom. Hydrogen bond is about 10-15 times weak than the
corresponding covalent bond but its effect is quite significant. When it formed within the
same molecule it is known as intramolecular hydrogen bond while with different molecules it is
intermolecular (figure).
Hydrogen bond
O H O
+  +  + 
H F H F H F Me O H O Me Me O Me
Hydrogen fluoride
H O H O
(Associates)
Methanol Acetic acid
O (Associates) (Behaves as dim er)
+ H
H O O
+ O C CH
N
Et Me
O
o-Nitrophenol Ethyloacetate in enol form
(Describe molecule) (Describe indicator)
Intram olecular hydrogen
bonding
Fig.: Intramolecular and intramolecular hydrogen bonding
Strength of a hydrogen bond depends on the electronegativity of the heteroatom. The strongest
hydrogen bond is F  H  F  H having energy  25  30 KJ mol1, while O  H  O  H and
N  H  N  H have their energy values  12  25 KJ mol1 respectively.. Hydrogen bonds are
not always equidistant and depend on the distance between interacting units. For example,
O  H bond distance in ice is 0.7Å while that in water is 1.79Å at 25°C. Hydrogen bond may
also be formed in gas phase. Dimeric structure acetic acid in gas phase is due to intermolecular
hydrogen bonding (figure). Intramolecular hydrogen bonding occurs most commonly and
effectively when a six membered ring is formed including the hydrogen atom, while five membered
rings are less common. Existence of hydrogen bonding can be established in many ways like,
measurement of dipole moment, solubility behaviour, etc., but more precisely by IR spectroscopy.
Besides oxygen, nitrogen, fluorine, etc., weaker hydrogen bonding is also observed in thiols,
HCN, CHCl3, etc., because of their weakly acidic hydrogens. A carbanion (R  C  C ) or
isocyanide (R  N   C ) can form strong hydrogen bonds in protic solvents. Hydrogen bonding
can influence many of the physical properties of organic molecules as discussed below:
(i) Boiling points and melting points: Compounds with intermolecular hydrogen bonding are
associated and have higher boiling points, since extra heat energy is necessary for breaking
of those bonds during boiling, than those compounds of similar molecular weights without
having intermolecular hydrogen bonding CH4, HF and H2O have comparable molecular
weights but have different boiling points, e.g., –162°, 19.5° and 100° respectively. Higher
boiling points of HF and H2O are due to intermolecular hydrogen bonding, which is not
possible in CH4. Though, hydrogen bonding in H2O in weaker than in HF, the former has
higher boiling point, because it is more associated with intermolecular hydrogen bonding
using both of its hydrogen atoms.
O
H F H F H F O H O H H O H O H
O H H O
Greater number of H bonds
(stronger association)
Fig.: Hydrogen bonding in HF and H2O
Similar reflection of intermolecular hydrogen bonding is on melting points. CH4 ,

HF, and H2O have their melting points –190°, –110° and 0°C respectively.
When there is a possibility for the formation of the both, the intramolecular hydrogen bonding
is preferred over the intramolecular hydrogen bonding and without being associated they
have lower boiling points and lower melting points than their isomers having been associated
through intermolecular hydrogen bonding. Thus, para nitrophenol due to association through
intermolecular hydrogen bonds melts at 114°C while ortho nitrophenol having intramolecular
hydrogen bonding (figure) melts only at 45°C.
H O + O
O N
O H
+ O
N
+
N O O
O H O
p-Nitrophenol o-Nitrophenol
Fig.: Inter and intramolecular hydrogen bonding in para and ortho-Nitrophenol
(ii) Solubility: Hydrogen bonding makes a compound soluble in water or other solvent capable
of forming hydrogen bond. During dissolution, the hydrogen bonds of the solute molecules
and those of the solvent molecules break and new hydrogen bonds are formed between
solvent and solute molecules. Extent of solubility depends on the principle “like dissolves
like”. Methanol and ethanol are miscible in all proportions with water but octanol is almost
insoluble because of the hydrophobic effect of large alkane chain. This is believed that
dissolution of large alkyl part requires its high degree of ordering involving a high drop of
entropy in water which is not desirable (loss of entropy is not a favourable process). Thus,
the large monopolar hydrocarbon chain is not being accommodated by water and octanol
remains insoluble.
(iii) Stability of Molecules: Intramolecular hydrogen bonding often stabilizes a molecule. Liquid
acetylacetone remains mainly in enol form as it is stabilized through intramolecular hydrogen
bonding as shown in figure. For this reason ethylene glycol, halohydrins, etc., exist mainly in
the gauche form rather than the antiform (figure).
O O
H
O O
Me 

Me 
H H
Keto form Me Me
H
Enol form
More stable
Acetylacetone
O H OH O H OH
H O H H H Cl H H
H


 

H H H H H H H H
H OH H Cl
(Gauche) (Anti)(Gauche) (Anti)
More stable More stable
Ethylene glycol Chlorohydrin
Steric interaction invovling CHI/CHI and OHI/Cl are less important
Fig.: Stabilization of molecules by intramolecular hydrogen bonding
(iv) Acidity and Basicity: Acid base properties are greatly influenced by hydrogen bonding.
We know that greater the electron density on donor atom, the greater is the basicity. But
when measured in aqueous solution, Me2NH is found more basic than Me3N, though, in
latter nitrogen has a greater electron density because of an additional electron pumping.
Me-group. This is due to the fact that the conjugate acid, Me2 NH 2 is more stable than
Me3NH+ for greater number of hydrogen bonding with water.
Better solvation Me Weaker solvation

Me H OH2
+
Me 2 NH  H  
H2O
 N Me 2 N  H  
H2O
 Me N H OH2
Me H OH2 Me
o-Hydroxybenzoic acid is more acidic than p-hydroxybenzoic acid as the conjugate base,
o-hydroxybenzoate is more stable than its para analogue due to intramolecular hydrogen
bonding is former.
OH
O
H
O
O -
O O
o-hydroxybenzoate p-hydroxybenzoate
(v) Structure and Properties of Biomolecules: Highly organized structures as well biochemical
activities of proteins, enzymes, nucleic acids, etc., are maintained by inter molecular and
intramolecular hydrogen bonding.
2. Dipole-Induced Dipole Force of Attraction: A polar molecular may alter distribution of

electrons of a nonpolar molecule and may develop an attractive force. This is known as dipole-
induced dipole force of attraction. This explains dissolution of a nonpolar compound in a polar
solvent, i.e., benzene in methanol.
3. Induced Dipole-Induced Dipole Force of Attraction: This type of dispersion force accounts
the intermolecular attraction of typical nonpolar molecules like alkanes. One may understand
the origin of these forces by the application of quantum mechanics. The average distribution of
charge in a typical nonpolar molecule over a period of time is uniform. But at a particular instant,
the electrons (and hence the charge) may not be uniformly distributed. Electrons by virtue of
its property in one instant may slightly be accumulated in one part of the molecule developing a
small temporary dipole or better to say an instantaneous dipole. This temporary dipole of one
molecule may distort the electron field of neighbouring molecules, inducing opposite (attractive)
dipole in them. In this way, dipole in one molecule induces dipole in another molecule. As a
result, all such molecules get associated through the attraction of the opposite poles, i.e., electron
deficient part of one molecule is attracted by the electron rich part of another molecule. Individual
induced dipole-induced dipole attraction is very weak, but in all together it is quite high and
enough to explain the liquid as well as the solid state of so called nonpolar molecules. Induced
dipole induced dipole force of attraction may be understood from the figure.
Attractive force between two

opposite poles
A B
Molecules approaching each other A B
Distortion of electron cloud and
development of attraction between
opposite poles
Fig. Induced dipole-induced dipole attraction
Magnitude of this type of van der Waals’ force of attraction mainly depends on two factors: (a)
surface area of the molecule and (b) the polarizability of the atoms present. In isomeric alkanes,
the straight chain molecule due to its zig-zag structure has the greatest surface area and hence
allows largest number of molecules for contract, than the branched isomers which having sphere
like shape allow relatively fewer number of molecules to contact (figure). Thus, straight chain
molecules (e.g., n alkanes) have higher boiling points than their branched isomers.
Me
Me CH2 CH2 CH2 Me Me CH CH2 Me Me C Me
Elongated Me Me
(Largest surace area)
Almost spherical
(Smallest surface area)
n-Pentane Isopentane
Neopentane
30° 25°
9.5°
Fig.: Surface area of isomeric alkanes and their boiling points.

Induced dipole induced dipole force of attraction may be increased with the polarisability of the
atoms present in molecules. Polarisability of an atom is measured by the ease of distortion
of its electron cloud, i.e., how loosely the electrons are bound. This is directly
proportional to atomic size and inversely with the electronegativity of the concerned
atom. Of the halogens, polarizability of iodine is the highest due to its biggest size having the
weakest control of its nucleus over the valence electrons. Fluorine on the other hand is least
polarisable since its valence electrons are very strongly bound due to its smallest atomic size.
This explains why alkyl iodides have higher boiling points than alkyl fluorides. Boiling points of
chlorinated alkanes increase with the number of quite polarisable chlorine atoms but with fluoro
compounds there is opposite trend.
CH3F CH3Cl CH3Br CH3I CH3Cl2 CHCl3 CCl4 CH3CH2F CH3CF3 CF3CF3 CH4
b.pt. (°C) –78 –24 3 42 40 61 77 –32 –47 –78 –163
It may be noted that atoms having non-bonding electron pairs are more polarisable than
those only with bonding pairs and this accounts why an alkyl halide has higher boiling point
than an alkane of comparable size. A striking observation is that, CF3 – CF3 boils at very low
temperature (–78°C), as it has minimum induced dipole induced dipole force of attraction due to
non poarizable character of fluorine atoms. Because of the weakest intermolecular force of attraction
in fluorocarbons, they are used as a polymer like Tuflon, –(CF2 – CF2)n –, is ‘non-stock’ frying
pans.
Displacement of Electrons in a Molecule
Reactivity of an organic compound depends on the relative availability of electrons in a particular

bond or atom. It is a general rule that, an electron rich bond or atom reacts with electron deficient
species and there will be no reaction between two species of the same electronic character as they
repel each other. Thus ammonia, an electron rich species reacts with electron deficient
borontrifluorides but not with benzene, which itself is an electron rich compound. It is essential to
know the distribution of electrons in a molecule in order to predict as well as to explain its chemical
behaviour in organic reactions. These are some factors discussed below which are responsible in
affecting relative electron density in organic molecules.
Inductive Effect: This is a permanent effect caused by displacement of -electrons along the
covalent bonds because of different electron sharing properties of bonded atoms or groups. This
effect originates in a small part of a molecule and transmits along the carbon chain. Consider n-
butylchloride. Chlorine having greater electronegativity than carbon pulls the electron pair of
C – Cl bond towards itself and gets slightly negative charge and makes C1 slightly electropositive.
Electron deficient C1 then withdraws -electron of C1 – C2 bond and induces slight electropositively
over C2. In a similar way, C3 also acquires very small positively by induction of C2. This type of
displacement of -electrons along a chain is called Inductive or Transmission effect itself by
which the polarity of C – Cl bond transmits from C1 to C2 to C3. This effect gradually decreases
with distance from its source and is found practically negligible beyond C3.

δδδ δδ δ δ
4 3 3 1
CH3  CH 2  CH 2  CH 2  Cl (δ  δδ  δδδ)

 Direction of dipole moment
Depending upon the direction of electron movement inductive effect may be classified as negative
and positive. Atoms or groups that withdraw electrons towards themselves are said to have the
negative inductive effect and are commonly known and –I groups, while those which push electrons
to carbon are said to have positive inductive effect and are called +I groups.
Common - I groups: –+NR3, –+SR 2 , –+NH3, –NO2 , –SO3 H, –CN, –CHO, C = O, –COOH,
–COOR, –F, –Cl, –Br, –I, –OAr, –OR, –OH, –SR, –C  CR, C = CR2, –Ar.
Common +I groups: Metal atoms, –SiR3, –O–, –COO–, –CMe3, –CHMe2, –CH2Me, –CH3.
Inductive effect influences a number of fundamental properties of organic molecules.
1. Effect on Dipole moment: Inductive effect creates a permanent polarization of covalent bonds
which is the main cause of dipole moment of organic molecules. The direction as well as the
value of dipole moment depends on the magnitude of inductive effect. For example, in
H2C = CH – CH  CH dipole moment acts towards C4 due to greater –I effect of –C  CH
than that of –CH = CH2 (sp carbon is more electronegative than sp2 carbon) while in H2C = CH
–CH2CH3, the dipole moment acts along C2 due to combined inductive effect of ethyenyl (–I)
and ethyl (+I) unit.
1 2 3 4 1 2 3 4
C H 2  C H  C  C H C H 2  C H  C H 2 C H 3
 Direction of dipole moment 
cis-2-Butene has a finite value of dipole moment while that of trans-3-butene is zero, as in latter
the bond moments i.e, +I effects of CH3 groups act in opposite direction (figure) and hence
cancel each other.
Me Me Me H
Group moments
C C Net measured C C caused each other
H H find H Me
Net =0 Net =0

cis-2-Butene trans-2-Butene
Fig. Dipole moment of cis and trans-2-butenes
2. Effect on Basicity and Acidity: Availability of unshared pair of electrons on nitrogen for a
proton usually measures the strength of a nitrogenous base and the basicity is proportional to the
electron density on the donor atom. Therefore, CH3NH2 is more basic than NH3 as in former +I
effect on CH3 group enhances electron density over N. Alternatively, the conjugate acid
CH3 NH3 , formed by protonation of CH3NH2 is more stable than NH 4 , the conjugate acid of
NH3. This is again due to +I effect of CH3 group which reduces the amount of positive charge
over nitrogen. For similar reasons, CH3NH2 is more basic than CF3NH2 because, in latter
strongly electronegative F atoms exert that –I effects and pull electron pair of nitrogen reducing
its availability to a proton.
High F Low
H
electron electron
NH2 density NH2 density
H F
More basic F Less basic
H
Methylamine Trifluoromethanamine
Acidity on the other hand is the tendency of a species to release H+. Let us explain, why
CH3COOH is weaker acid than HCOOH. Methyl group in CH3COOH reduces electropositive
character of carboxylic proton by it’s +I effect and hence lowers the acidity, which does not
happen in HCOOH. Alternatively, the conjugate base CH3COO– is less stable than HCOO–,
because of higher charge density in former due to electron pumping nature of CH3 group,
ClCH2CH2COOH in weaker acid than CH3CH(Cl)COOH, since the carboxylic proton of latter
feels stronger –I effect of Cl and becomes more electropositive than that in ClCH2CH2COOH,
where intervening –CH2 – reduces the effect of Cl.
Resonance and Resonance Effect: Resonance is the phenomenon of delocalization of - and

nonbonded electrons of a molecule within the molecular framework, without changing the position
of any atom. This yields several Lewis structures for the molecule which are commonly known as
Canonical or Resonating structures or Mesomers.
None of these structures individually can explain all the physical and chemical properties
of the compound and hence they cannot represent the real structure of the molecule.
Real structure is the composite or hybrid of all the possible mesomers.
Therefore, the mesomers are also called the contributing structures, as they contribute to the real
species, the Resonance Hybrid, Contributing structures are written by relating them with double
headed arrow and the hybrid is written just after an equivalent sign The term resonance is an
adjective, not a verb, as the individual structures do not resonance. An example is benzene, in which
uniformity of carbon-carbon bond length and bond strength cannot be explained by the structures
(A) and (A) as they have typical C – C -bond of 1.54Å and C = C bond of 1.34Å (figure). Real
structure is therefore, (B), the hybrid of (A) and (A) which explain the actual C – C bond length in
benzene having value of 1.39Å.
The hybrid (B) actually refers to the

1.34Å 1.54Å 1.30Å
orbital structure of benzene. Benzene
is composed of six sp 2 hybridised
carbons arranged in a shape of 1.54Å
regular hexagon, i.e., p-orbtials of 1.34Å B
A A Resonance hybrid
carbons overlap sideways and form
Canonical structures
-bonds extending equally around the Fig.: Resonance in benzene
ring (figure). Structure (B) thus
differentiates benzene from hypotheticaly 1,3,5-cyclohexatriene and also explains why benzene
yields a single 1,5-dibromobenzene during its dibromination. If the structure (A) or (A) was correct
for benzene, two isomeric 1,2-dibromobenzene would be produced (figure).

P P
H
C C
P P
H C C H
P P
C C
H H
Fig.: Orbital structure of benzene
Single bond Double bond

Br Br Br
Br Br
Bromination Bromination
  +
A Isomeric 1,2-dibromobenzenes
INCORRECT?
Br Br Br
Br Br
Bromination Bromination
  or
A IDENTICAL
Fig.: Formation of single 1,2-dibromobenzne.
Carbon-oxygen bond length in sodium acetate is 1.26Å, which is neither is single bond (1.43Å) not
a double bond (1.20Å) but it is intermediate between the two (1.26Å) due to the resonance as
shown below figure.
O 
-
O 120Å O 1.26Å
H3C C H3C C H3C C
- 
O O O
143Å
Fig. Resonance in acetate ion
Steric Inhibition of Resoance: In terms of MO theory, delocalization of electrons involves the

lateral overlap of p-orbitals of the participating atoms. This is possible only if the involved p-orbitals
lie in a same plane or nearly so. By any steric or electronic reason, if the participating orbtils are
forced out of planarity, the resonance is inhibited without having appreciable overlap of the orbitals.
Let us see an example C2 – N bond C4 – N bond lengths in picryl iodide (Figure) differ significantly.

An explanation may be as follows. Steric interaction between bulky iodine and ortho nitro groups
causes to displace the plane of latter out of the plane of the ring and hence no resonance occurs
between the ring -bonds and those nitro groups, while nitro group at the para position without
having such interaction remains in the same plane with the ring and participates in resonance. This
results in the development of partial double bonds character in C4 – N bond accounting its shorter
size than C2 – N or C6 – N bonds.
-
O I O O I O O I O
+ + + 1 + + +
N N - N 6 2 N - N N -
O O O O O O
5 3
4
+ + Bond is +
N - N - - N -
O O O O shortened O O
Fig. Steric inhibition of resonance
Normally, amides are not basic due to resonance involving nitrogen and the C = O group, but an
amide having nitrogen at the bridge head position is an exception. Resonance is not possible here
because, the bridgehead position for steric reason will not allow to accommodate a double bond and
the lone pair of electron is quite available on nitrogen. This is an example of steric inhibition of
resonance in favour of basicity.
No  bond
here
+ - N electron pair is +
N O N O N O N OH
Bridge bond readily available
Me N elecron pair Me nitrogen
is less available
Effect of Resonance: Resonacne imparts stability of organic compounds by delocalizing its reactive
electrons.The hybrid has much lower energy than any of the cannonical forms and the difference in
energy of the most stable contributor (calculated value) and the resonance hybrid is called Resonance
Stabilization Energy or in short the Resonance Energy of the species. Let us calculate the resonance
energy of benzene from the following thermochemical results.
Cyclohexene on hydrogenation yields cyclohexane. H0 for this reaction is 28.6 kcal/mole. This is
known as heat of hydrogenation of cyclohexene. Hydrogenation of 1,3-cyclohexadiene gives H0 =
–55.44 kcal/mol which is almost equal to the theoretical value 2 × (–28.6) = –57.2 kcal/mole. If one
proceeds further and consider benzene simply as 1,3,5-cyclohexatriene, the heat of hydrogenation
of benzene would almost be equal to 3 × (–28.6) = –85.8 kcal/mole. But the experimental value is
smaller, i.e., –49.5 kcal/mole. Thus benzene is more stable than so called 1,3,5-cyclohexatriene by an
amount 85.8 – 49.8 = 36.0 kcal/mole, which is known as resonance stabilization energy of benzene.

1H2

cat
 23.6 kcal mol1 (Theo, and Expt.)
cyclohexene
2H 2 1
cat

  57.2 kcal mol (Theo) = 55.4 (Expt.)
[Nearly same as theo value]
cyclohexa-1,3-diene
3H2 1

cat
  85.8 kcal mol (Theo); 49.8 (Expt.)
[Much less by a amount
cyclohexa-1,5-triene 85.8  49.8  36 kcal mol 1]
Real chemical behaviour of organic compounds are often guided by the effect of resonance (Resonance
effect or Mesomeric effect). For example, nonpolar structure by acetone (Figure) cannot explain its
high value of dipole moment and its reactivity with HCN, etc., while its resonance structure (A)
explains these.
H3C H3C H3C CN

+ - HCN O
C O C O  
H3C H3C H3C H
A A Cyanohydrin
Fig. Chemical behaviour of acetone due to resonance
Resonance effect or mesomeric effect is thus a permanent effect which causes dipolmoment of 
and n (non-bonded) electrons in the molecular framework. This effect may be transmitted via the
electrons of the conjugated system. It is much more effective and pronounced than the inductive
effect because it involves n and p electrons, which are much more polarizable than the -electrons
participating in inductive effect. Thus, in contrast to inductive effect which is transmitted only over
a small distance, mesomeric effect acts over a quite long range, even from one end to another end
of the molecule:
 Me  CH  CH  CH  CH  CH  O 
Me  CH  CH  CH  CH  CH  O 
Similar to inductive effect, mesomeric effect has also a directional property. Unsaturated groups
containing heteroatoms withdraw electrons towards themselves and are said to have negative
mesomeric or negative resonance effect and are designated by –M or –R groups. Heteroatoms or
negatively charged oxygen, sulphur or nitrogen when attached to a -unit through a single bond,
they may release their n electrons and are said to have positive mesomeric or positive resonance
effect and are designated +M or +R groups. Common –R and +R groups and their electronic
behaviour are shows in figure. Phenyl ring (or C = C) may behave either as +R group depending
upon the electronic nature of the group attached with it. In nitrobenzene phenyl ring acts as +R
group (source) as it supplies electrons to NO2 group while in aniline it acts as –R group by withdrawing
n-electrons from NH2 group.

Common –M (or –R) groups:

O O O
+
N , C N , CH O , OR , S OH
-
O O
Common + M (or +R) groups:
O , S , OR , NR , NR2
Behaviour of –M and +M groups
+ -
H2N CH CH CH O 
 H3N CH CH CH2 O
+R-group R
group
Ring supplies electron
-
O O
+
N 
 N NH2 
 NH2
- -
O O
R Ring R +R
+R group receives
group group group
eletrons
Fig. +R and - R groups
Rules of Writing of Resonance Structure

1. Resonance structures exists only in paper. None of these structures (resonating structure) will
be a correct representation for the molecules or ion.
2. In representing a resonating structures we are allowed to move only  electron and non bonding
electron not nuclei, e.g.,
(a) From a  bond to adjacent bond position.
A  B  C  
 A   B  C  (-vacant orbital conjugation).
(b) From a  bond to adjacent atom
A  B  C
A  B  C  
(c) From a atom (having non bonded pair of electron) to adjacent on bond.
A  B  C  (lone pair orbital conjugation)

A  B  C  
3. All the structure must be proper Lewis structure, i.e., their should not be any violation of octate
rule.
4. The energy of the actual molecule (real structure) is lower than the energy that might be estimated
for any contributing structure. This is called resonance stabilization.
5. Equivalent resonance structure make equal contribution to the hybrid and a system described by
them has a large resonance stabilization.

6. The contributing structure (resonating structure) may or may not contribute equally to the hybrids.
Their contribution to the resonace hybrid actually depends upon them relative stability. The
more stable a structure is, the greater is its contribution to the hybrid.
Relative stability of a resonating structure assessed by the following guidelines:
(i) Greater the no. of covalent bonds higher will be the stability of resonating structure.
 CH 2  CH  CH  CH 2 
CH 2  CH  CH  CH 2   CH 2  CH  CH  CH 2
e.g., This structure is more stable

as it contain move covalent
bonds.
(ii) Structure in which all of the atom have a complete valence shell of electrons (i.e., the noble
gas structure) are especially stable and make large contribution to the hybrid, e.g.,
+ +
H2 C O CH 3 
 H2 C O CH 3
Here this carbon atom has Carbon has eight atom, i.e.,
only six electron, i.e., electron complete octate
deficient
(iii) Charge separation decreases stability of the resonating structure. Separating opposite charges
need energy. Therefore, structure in which opposite charges are separated have greater
energy (lower stability) than those that have no charge separation, e.g.,
H2C CH Cl 
 H2C CH Cl
I II
Strucutre I has a large contribution as it has no separate charge but Structure II has a
smaller contribution than I.
(iv) Resonance contributors with –ve charge on highly electronegative atoms are more stable
than this with –ve charge on less or non electronegative atom.
(v) To predict the energies of resonance structure we can consider the energy of resonance
hybrid structure. Resonance hybrid is considered average if the resonance contributors.
Overall the following structure are consider relatively stable.
(a) Structure having complete octate for second period elements (C, N, O, F).
(b) Structure having minimum no. of formal charge and maximum no. of bonds.
(c) Structure in which –ve charge in the most electronegative atom (C < N < O).
(d) Structure in which this minimal charge separation, while keeping the formal charge
closer together.
Aromaticity
Aromaticity is a property which describes “unusual stability” of a class of organic compounds.
Benzene as an example is very inert towards addition reactions due to its aromaticity. The phenomena
of aromaticity can be described in terms of Molecular Orbital (MO) theory. Cyclic planar structures
having a particular stable arrangement of occupied (filled)  – MOs are aromatic. A simpler expression
relating the MO description of structure and aromaticity is known as Huckel’s rule (1937). It
states that, planar monocyclic conjugated polyene will be aromatic if the ring contains (4n + 2)
-electrons, where n is an integer (0, 1, 2, 3, etc.). Benzene belongs to this category as it is a planar
hexagon consisting of three conjugated C = C bonds, i.e., 6 electrons (n = 1).
Let us understand the

π*6 Antibonding MOs
aromaticity of benzene in terms π4*
π*5 (Unfilled)
Energy
of MO theory. The carbocyclic New bonding -orbital
ring of benzene is composed of π2 π3 Bonding MOs
2
six sp hybridised carbons. The π1 (Filled)
unhybridized p-orbital with one Fig.: Molecular orbitals of benzenes
electron of each carbon lies at right anlge to the molecular plane. All six adjacent p-orbitals overlap
resulting in the formation of six p-MOs of which three are Bonding (1 , 2, 3) and three are
Antibonding (π4 , π 5 , π6 ) . Energy levels of those MOs can easily be represented by using polygon
circle rule (Frost’s circle). The hexagon similarly the polygon of any other (aromatic species) is
inscribed in a circle with one vertex at the bottom. The vertices then represent the energy levles of
the MOs that increase upward. A horizontal line passing through the centre divides the circle in two
halves and the vertices below that line represent bonding MOs while those above that line are
antibonding MOs, 2 and 3 having identical energy are called degenerate bonding MOs and
similalry π4 and π5 are called degenerate antibonding MOs. Six p-electrons are then accommodated
in the bonding MOs. All three bonding MO’s are thus filled with spin paired electrons and compose
a “closed shell of sextet responsible for aromaticity (figure).
Not only benzene, any other species which bears a closed shell of p-electrons (filled bonding MOs)
possesses aromaticity. In this way, cyclopentadienyl anion, cycloheptatrienyl cation, etc., are aromatic
due to their closed shell of sextet (6e) and cyclopropenyl cation is aromatic for its closed shell of
duet (2e, n = 0). Molecular orbitals of some aromatic species and their electron filling are shown
in figure.
π *4 π*5 Vacant antibonding MOs

NH 2

 Nonbonding -orbital
 NH 2
π2 π3
π1 Filled Bonding MOs
H H 6e
Cyclopentadienylanion
π *6 π*7 Vacant Antibonding MOs

* *

π 4
π 5
Ag Nonbonding -orbital

 AgCl
 π2 π3
π1 Filled Bonding MOs
Cl 6e
Cyclopentadienylanion
π *2 π *3 Vacant Antibonting MOs

SbCl2
 Nonbonting -orbital
π1 Filled bonding MOs

Cl e
Cyclopentadienyl anion
Fig.: Molecular orbitals of some aromatic ions

Monocyclic polyenes having (4n + 2) -electrons are not always aromatic due to lack of planarity,
[10] Annulene (annulene is a polyene higher than benzene) in spite of its 10 electrons (n = 2) is
nonaromatic as it is nonplanar in its all possible conformations (figure). Its all-cis and
mono-trans froms are not stable due to high degree of internal angle strain (144° instead of 120°)
while the cis-trans-cis-cis-trans form is nonplanar due to H/H interactions at C1 and C6 though it is
free from any angle strain. Bridging of C 1 -C 6 however avoids that interaction and
restores the planarity and therefore, bridged [10] annulenes become aromatic (figure).
trans
High angle
H H H H
strain
H H H H
141°
H H H
H H
H H H H
H H H
All-cis Meso-trans
Unstable the to Unstable due to
high strain angle strain
trans
H H cis H H
H 10 H H H
9 3 1
Strong H/H
cis
H1 H intera ction X
H 8 6 4 H H 6 H
7 5
cis
H H H H
trans
C 1 -C 6 bridge [10] annulene
cis-trans-cis-cis-trans x = O, S, NH, Cl2 etc.
non-planar
non-arom atic
Fig.: [10]-Annulene system
[14]-Annulene, having 14-electrons (n = 3) also possesses internal strain, but it is much less due to
large inside area. It is aromatic but not to a great extent as the ring slightly deviates from planarity.
Bridge [14]-annulenes are however aromatic due to perfect planarity without having any H/H
interaction. The trans15,16-dimethyldihydropyrene is an example of aromatic bridged [14]-annulene
(figure). [18]-Annulene is more stable than [14]-annulene as the inner H/H interaction is much less
due to much bigger size of the ring (figure).
H/H
Me Interaction is not
H so strong due to
HH H H
X I5 larger space inside
I6
HH H H
H/H H
Interaction Me
makes ring
nonplanar
(14)-Annulene trans-15-16-dimethyldihydropyrene [18]-Annulene
Wenkly arom atic arom atic [14e] n = 3 Planar, aromatic [18e],
[14e] n = 3
n=4
Fig.: Arom atic annulene

Other than annulenes, aromaticity is also observed in a variety of organic species including polynuclear
hydrocarbons, heterocyclic compounds, etc, if they are planar and contain Huckel’s number of -
electrons delocalized into the rings (figure).
Napthalene (10e) Anthracene (14e) Phenanthrene (14e)

Polynuclear aromatic hydrocarbons
NH O S N
Pyrole (6e) Furan (6e) Thiophene (6e) Pyridine (6e)
Fig.: Some aromatic compounds other than annulenes
In five membered heterocycles, i.e., pyrrole, furan, thiophene, etc., the p-orbital holding ‘n’ electrons
of heteroatom is parallel to the p-orbitals of ring carbons and therefore, delocalized into the ring to
form aromatic sextet. In pyridine however, n-electrons of nitrogen reside in sp2 orbital and therefore,
do not participate in resonance because, its plane is perpendicular to the plane of the p-orbitals .
Aromaticity may also be observed in cyclic dianions or dications, if Huckel’s rule is obeyed (figure).
2 Na 

  
 
 2
( 2e)
10e
Cl 2SbCl5
  2+
Cl 2SbCl6
2e
Fig.: Aromatic dications an dianions
There are a number of compounds which are aromatic due to their polar resonating strucures.
cyclopropenone, tropenone, azulene, calicene, etc. (figure) are examples. Since, these compounds
are more stable in their polar structures, they have considerable dipole moment. Thus, dipole moment
of naphthalene is zero while it is 1.0D isomer azulene.
- - - -
O 
 O O , O  O O
Cyclopropenone, 2 e Tropenone, 6 e



6e
Azulene,  = 1.0


Calicene 2e
6e
Fig.: Aromaticity due to polar structure

Nonaromatic and Antiaromatic Compounds

Cyclic polyenes with 2, 4, 8, 16 -electrons (non Huckel number) are not aromatic as they do not
have closed shell electrons in bonding -MOs. Polygon-circle model shows that square planar
cyclobutadiene has two unpaired electrons to non-bonding level and hence it is expected to behave
as very reactive diradical.
Antibonding MO
Nonbonding -orbital
Filled Bonding MOs
Fig.: Electron distribution in cyclobutadiene
Its isolation has not been possible due to its rapid dimerisation. Thus, planar cyclic species with
4n-electrons are highly unstable with respect to their acyclic analog and are called anti-aromatic.

 
Fig.: Dimerization of cyclobutadiene
Cyclooctatetraene (COT), in spite of 8-electrons (4n, n = 2), is not anti-aromatic because the
molecule is not planar and therefore, it is nonaromatic. The molecule is tub shaped through which is
avoids internal angle strain of its planar conformation. X-ray studies show that, C – C and C = C
bonds are alterantively long and short having lengths 1.48 and 1.34Å respectively (figure).
Angle strain, as
1.34Å CCC angle > 120°
1.48Å


Real
nonplanar structure
Planar, not a real structure
No resonance is possible
Fig.: Structure of cyclooctatetraene (COT)
Hyperconjugation
Common delocalisation of electrons invovles the conjugation of - and n-electron system. However,
under special circumstances electron pair of a -bond may also participate in delocalisation which is
known as Hyperconjugation, -Electrons of C – H bond of -position with respect to a sp2 carbon
may participate in resonance yielding canonical structure/s as shown below:
Non bond
here
H R R H R
sp2 H+

R C C C  R C C C 
 R C C C
H+
H R R H R R R R

Participated hydrogen does not leave the -carbon though the contributor does not have formed
C – H bond and for this reason, it is often called NO Bond Resonance. The number of
hyperconjugative structures is equal to the number of H atoms present at -carbon. Thus, 1-butene
has only two such contribution, while 2-butene has six (Figure).
H H
  sp H+ - -
H3C C CH CH2 
 H3C C CH CH2 
 H3C C CH CH2
H+
H H
1-Butene
H H H H H
 sp2 sp2  H+
- -
H C CH CH C H 
H C CH CH C  H+ C
H  CH CH C H
H 2-Butene H H H H H
H H H H
- H+
H C CH CH C H 
H C CH CH C H 
H C CH CH C H
H+
H H H H H
Two more structures

Fig.: Hyperconjugation in 1- and 2-butenes
As the number of resonating structure determines the stability of a molecule 3-butene is more stable
than 1-butene due to greater number of no bond resonating (hyperconjugative) structures in former.
In terms of MO theory, hyperconjugation is regarded as an overlap of C-H -orbital with C = C

-orbitals as shown in figure, analogus to a - or n- overlap in common case of conjugations.
H



H R
R R R
C C C C
R C R R R
C
R
Fig.: MO nodel of hyperconjugation
The concept of hyperconjugation was developed when the common order of electron releasing
effect of alkyl groups Me3C – > Me2CH– > MeCH2 – > Me was found opposite in their attachment
to an unsaturated system. This was observed by Baker and Nathan who were comparing the rate of
reaction of pyridine with para alkyl benzyl bromide.
Br 
R CH2 Br  N R CH2 N
p-Alkyl bromide
Thre reaction rate was fastest when R = CH 3 – and slowest when R = (CH 3 ) 3 – C –.
Hyperconjugation has introduced many fundamental properties of molecule. For example:

(a) Methyl protons of toluene are poorly acidic due to hyperconjugation but those of methyl
cyclohexane are not.
H H H
 H+ +
+
H C H H CH H C H HC H
sp2

 
 

(b) Propene is slightly more stable and less reactive than ethylene (heat of hydrogenation of ethylene
is about 2.5 kcal mol–1 higher than that of propene) for its decreased double bond character due
to hyperconjugation.
H H H
- - -
C CH H
CH2  C CH CH2  H+ C
 CH CH2 
H C CH CH2
H H+
H H H
Propene Double
bond Single bond
(c) C-C -bond of propene is smaller and stronger than that of propane due to hyperconjugation in
former by which it acquires slight double bond character.
(d) Greater thermodynamic stability of a nonterminal alkene like (CH3)2C = CHCH3 than its isomeric
terminal alkene, CH3CH2C(CH3) = CH2 is a consequence of hyperconjugation. Former has
nine hyperconjugation hydrogens while the latter has only five.
Steric Effect
Steric effect controls electron density in bonds or on an atom and therefore, explains molecular
reactivity. Consider the reaction of N,N-dimethylanaline and its 2,6-dimethyl derivative, with the
diazocation, PhN=N+. In former, –NMe2 exerts its +R effect to enrich electron denstiy at the para
position of the ring which is then attacked by electrophilic PhN = N+ and forms para azocoupled
product.
Electron pair is less

available here
Me Me Me Me Me Me
+
N N N
P P
Me

PhN  N H
    N
Me
N,N-dimethylaniline H N N Ph
N N Ph
para-Coupled product Planar and hence overlapped
MO of N,N-dimethyl aniline
This does not happen in 2,6-dimethyl derivative of N,N-dimethylaniline. Here, two ortho alkyl groups
sterically interact with –NMe2 group and displace its plane out of the plane of benzene ring. For this
reason, p-orbital of nitrogen and those of the ring carbons cannot overlap. This prohibits the resonance
and –NMe2 unit no longer behaves as +R group to make the para position electron rich for electrophilic
attack by diazocation.

Me
Me Me Me
P Me
Me Me Me
P +
N N N 
 N
Me Me Me
Me Me
Me Me
Unstable conformation Stable conformation Me Nonplanar p-orbitals,
due to steric strain without steric strain no overlap possible
Steric effect explains why triethyl amine is a weaker base than quinuclidine. Ethyl groups in former
are flexible to adopt several conformations creating steric obstacle (front strain) for a proton towards
nitrogen and its electrons. Alkyl groups in quinulidine on the other hand are held back with a fixed
conformation (back strain) keeping the front end of nitrogen quite exposed to a proton. Thus, it
behaves as stronger base and stronger nucleophile and triethyl amine.
H H
H H H Electron pair is
H
H H H quite exposed to H +
H
H H H H
H H H
N H H H
H H N H N N
H
H H H H H
H H H H H
H CH3
H H H H H H H Quinolidine
H
Electron pair is Trethylamine H
less available
p-Nitroaniline is a weaker base as –NO 2 group exerts its –R effect and reduces the electron
availability at amino nitrogen for a proton. However, 3,5-dimethyl-4-nitroaniline is fairly basic because,
–NO2 group is displaced out of the plane of the ring due to steric influence of methyl groups and is
made deactivated to exert any –R effect.
+
NH2 NH2 NH2


Me Me NO2 nonplanar cannot,

+ + withdraw electrons from NH2
N - - N - N -
O O O O O O more bsic
6-Nitroaniline 3,5-Dimethyl-4-nitroaniline
NO2 withdraws
electrons from NH2 less basic
Amides are non basic due to –R effect of adjacent >C = O group which makes electron pair on
nitrogen less available. A bridged amide however does not participate in resonance as the bridge
head position cannot adopt a -bond (Bredt’s rule) for severe angle strain and hence behaves as a
strong base.
This structure
+ + does not exist
NH 
 NH N 
 N
- -
O O O O
Non basic Basic
Electron pair but available on X Electron pair to
readily available on X

SAMPLE PROBLEMS 2.1 and 2.2 (MCQ)

Problem 1: Although N – S bonds are much polar than N – H bonds, but NF3 (0.268) has a much
smaller dipole moment than NH3 (0.463) because
(a) F is higly electronegative (b) H is less electronegative than F
(c) Dipole moment depends upon vector (d) N is larger in size
Solution: (c)
N N
H H F F
H F
Problem 2: Unlike 1`,3-dichloroprop-1,2-diene (ClCH = C = CHCl) one sterioisomer of cis

1,4-dichlorobut-1,2,1-triene (Cl – CH = C = C = CHCl) is polar and the other is non-polar.
(a) The outside -orbital in 1,4-dichlorobut-1,2,3-triene are oriented at right angle to the
central -orbitals.
(b) The terminal CHCl units are coplanar
(c) Both (a) and (b) are correct
(d) Both (a) and (b) are wrong
Solution: (c) Cl Cl
Cl 60° Cl
C C C C
H H 0
Problem 3: The dipole moment of ethyl chloride, CH3 – CH2 – Cl (2.05D) is larger than that of vinyl
chloride CH2 = CH – Cl (1.44D). Because
(a) Vinyl chloride has less number of hydrogen
(b) Industine effect in vinyl chloride is high
(c) Lone pair of electron present in Cl in vinyl chloride is in conjugation with double bond.
(d) Chlorine is larger in size than fluorine
Solution: (c)
H3 C CH2 Cl H2 C CH Cl 
 H2 C CH Cl
 = 2.05D  
Vector sum
Problem 4: For gaseous phase which alcohol is most acidic

(a) Me3 – COH (b) Me2CHOH
(c) MeCH2OH (d) MeOH
R Electrostatic force of
attraction
Solution: (a) R O
R
In gaseous phase -alkyl substituents stabilize the charged alkoxide anion by a polarization
mechanism which distert the electron clouds of each alkyl group, so that the electron
cloud more away from the –ve charge on the alkoxide deoxygen.

Problem 5: p-Xylene boils at a lower tempeature than d-xylene

(a) p-xylene moelcule is symmetrical in nature
(b) 0-xylene molecule is non-polar
(c) p-xylene molecule is non-polar
(d) o-xylene molecule is polar
60°
180°
Solution: (d)
Br
Br
Problem 6: Br Br
I II
(a) I is soluble in n-octane
(b) II is soluble in CH3OH
(c) Both are soluble in n-octane
(d) I is soluble in CH3OH but II is soluble in n-octane
Solution: (d) Diequational form is polar and therefore were soluble in polar solvent CH3OH. Diaxial
form being non-polar is soluble in n-octane a non polar solvent.
Problem 7: Arrange the following cations in decreasing order of stability:
+ + +
H2C CH CH2 Ph CH2 H3C CH2
(P) (Q) (R) (S)

(a) P > R > Q > S (b) R > P > S > Q
(c) Q > R > P > S (d) P > Q > S > R
Solution: (a) P is most stabilized as it is aromatic.
Problem 8: + + +
CH2
+
CH2 CH2 CH2
OH O NH NO2
CH3
(P) (Q) (R) (S)
(a) P > R > Q > S (b) Q > R > S > P
(c) R > S > Q > P (d) P > R > S > Q
Solution: (a) ERG stabilized C+ but EWG destabilized C+.

Problem 9: Most contributing structure in nitroethene is:

O O
+ - + +
(a) H2C CH N (b) H2 C CH N
- -
O O
-
O O
+ - + + +
(c) H2 C CH N (d) H2C CH N
- -
O O
Solution: (a) All have complete octate.
Problem 10: There are three canonical structures of naphthalene. Examine them and find correct statement
among the following:
1 1 1
2 2 2

 

3 3 3
4 4 4
(a) All C – C bonds are of same length
(b) C1 – C2 bond is shorter than C2 – C3 bond
(c) C1 – C2 bond is larger than C2 – C3 bond
(d) None of the above
Solution: (b) C1 – C2 is more double bond in nature than C2 – C3.
ACID-BASE CONCEPT
Acidic and basic nature of organic compounds are explained by three theories:
1. Arrhenius Theory: According to Arrhenius (1884), the acids are compounds which produces
H+ ion in aqueous solution.
e.g., H2 O
HCl   H   Cl
Base is a compound which produces OH– ion in aqueous solution.
H2 O
NaOH   Na   OH
H2 O
NH3  H 2 O 
 NH 4 OH   NH 4  OH
2. Bronsted Lowery Theory or Conjugate acid-base theory or proton donar

acceptor theory: According to Bronsted and Lowery (1923), Acid is a compound or ion which
donates proton i.e., protogenic and base is a compound or ion which accepts proton i.e.,. protophilic.
e.g., Acid (A1) + Base (B2) Acid (A2) + Base (B1)
 H3 O   Cl 
HCl  H 2 O 
(a) Conjugate
Conjugate

 NH 4  OH
H 2 O  NH 3 
(b) Conjugate
Conjugate
Note:
(i) H2O acts both as acid and base depending on reaction.

(ii) Acid –H+ = Conjugate base, Base +H+ = Conjugate acid
(iii) More the acidic strength of acid, less will be basic strength of conjugate base of that acid and
vice versa.
(iv) Water, alcohol etc., show the nature of autoprotolysis.
 H3 O  OH 
H 2 O  H 2 O 
A1 B2 A2 B1
 C 2 H 5 OH 2  C 2 H 5 O 
C 2 H 5OH  C 2 H5 OH 
A1 B2 A2 B1
(v) Solvent such as water which can undergo autoprotolysis, are called amphiprotic.
(vi) Solvent which are neither proton donors or acceptors are called aprotic solvents.
(vii)The Bronsted - Lowery theory is more general than Arrhenius theory since the Bronsted-Lowery
theory is applied for any solvent where as the Arrhenius theory is applied only for water.
3. Lewis Theory: According to Lewis (1938), Lewis acids are the molecules or ion which has
tendency to accept at least one lone pair of electrons, i.e., electron deficient molecules or ions are
called Lewis acids.
Lewis bases are molecules or ion which has tendency to donate the lone p air of electrons, i.e.,
electron rich molecules or ions are called lewis bases.
Lewis acids: H+, R+, Br+, AlCl3, BF3, AlCl3, ZnCl2 etc.
Lewis bases: X , R , OH, NH3 , H 2 O , R  O  H, R  O  R etc.
Strength of Acid and Bases
There are many factrors which control of acids and bases, are steric effect, resonance, I-effect, solvantion
effect, H-bonding, entropy, conformation, configuration, etc. The strength of an acid is measure of tendency
to lose a proton and the strength of a base is a measure of tendency to take up a proton.
Ionisation constant (Ka and Kb)
Ka = Ionisation or dissociation constant of acid

Kb = Ionisation or dissociation constant of base
Ka  Acidic strength
i.e., more the Ka value more will be the acidic strength of a acid.
Similarly,
Kb  Basic strength.

In aqueous solution
 H 3O   A 
HA  H 2 O 
(Acid) From law of mass action
[H 3O  ][A  ]
K 
[HA][H 2 O]
[H3 O ][A  ]
 Ka 
[HA]
[H2O] is effectively constant
1
PKa  log10   log10 K a ,
Ka
1
PKa 
Acidic strength
Similarly, in aqueous solution
 BH   OH
B  H 2 O 
(Base) From law of mass action
 
[BH ][OH ] [BH  ][OH  ]
K  , Kb 
[B][H 2 O] [B]
[H2O] is effectively constant
1 1
PKb  log10  log10 K b , PK b 
Ka Basic strength
Effect of Structure on Acidity
The strength of an acid is a function of the stability of its conjugate base.
More stable the conjugate base, more acidic will be the acid.
Structural features which stabilise the acidity of hte acid is the stability of conjugate base (an ion oftenly).
The main factors which stabilises the anion (conjugate base) of the acide are:
(i) Inductive effect which can stabilis the –ve charge, –I effect increase the stability of conjugate base and
hence increases the acid strength.
(ii) Resonance effects more the resonance structures more will be the stability of anion and therefore, more
will be the acidic strength.
Note: (a) Resonance effect is more dominant than inductive effect generally.
(b) If the resonance structure are of identical energy and contribute equally to the resonance
hybrid becomes more stable than the ions containing more resonanting structure but not
contributes equally.
Organic Compounds as Acids
1. Hydrocarbons and their acidic strength
Compounds Hybridisation s-character p-character
Alkane 25% 75%

3
H C , sp
Alkene 2 33.33% 66.66%

H C , sp
Alkyne H C , sp 50% 50%
As the s-orbital is nearer to nucleus than p-orbital, more the s-character in hybrid orbital more will be the
electronegativity of carbon and hence more will be the acidic nature.
 The trend of acidic nature of hydrocarbon is given as:
H C  H C  H C
sp3 sp 2 sp
2. Acidic Strength of Alcohols and Phenols: More the stability of anion of alcohol more will be
the acidic strength of the alcohol.
(a) Inductive effect: –I effect tendency increases the acidic strength whereas + I effect decreases
the same
H3C CH3
H3C OH  H3C  OH  H3C OH
Example: (i)
O H H3C CH3
Cl Cl
Cl  OH  Cl OH
(ii)
OH Cl Cl
(b) Resonance: As the resonance increases the stability of anion increases and hence, the acidic nature
increases with increasing in resonating structures of anion.
Hence, phenol is more acidic than any alcohol.
Acidic strength of substituted phenol
Case 1: When group contain +I and R.

-
O
CH3
at ortho, destabilise by +I as well as s bond
delocalisation and these tendencies are maximum.

-
O
at meta destabilise by +I effect.
CH3
-
O
at para destabilise by +I and hyperconjugation but

these tendencies are minimum.
CH3
Hence, the order will be
PKa o  derivative < p-derivative < m-derivative < phenol

10.28 10.19 10.08 9.95
Note: This trend also hold good in case of +I and +R effects.
Class 2: When group contain –I and –M tendencies
Acidity of nitrophenols is given as:
PKa C6 H 5 OH  m  O 2 NC6 H 4 .OH  o  O 2 NC6 H 4 .OH  p  O2 NC6 H 4 OH

9.95 8.35 7.2 7.14
 2,4(O2 N) 2 C6 H 3OH  2,4,6  (O 2 N)3 C6 H 2 .OH

4.01 1.02
Acidic strength of Phenols and Substituted Phenol:
X = H CH 3 Cl OCH3 NO 2
o 9.95 10.28 8.6 10.0 7.2
m 9.95 10.08 9.1 9.6 8.35
p 9.95 1.19 9.4 10.2 7.14
PK a of 2,4-dinitrophenol is 4.01; PK a of 2,4,6-trinitrophenol is 1.02

PK a of 1-Naphthol is 9.2; PK a of 2-Naphthane is 4.01
The electron density of o and p-position are more in case of –OH group hence,
m-nitrophenol is less basic than o and p-nitrophenols but the p-nitrophenol is more acidic
than o-nitrophenol. The o-nitrophenol is slightly less acidic due to intra molecular
H-bonding.
H
O O
N
O
CH3

Case 3: When group contains R and –I tendencies

-
O
OR
I is maximum and stabilised by it, +R effect
destabilises.
-
O
stabilised due to I effect tendency.
OR
-
O
destabilised by +R effect tendency, stabilised by I

but it is minimum.
OR
The acidic order in this case is o-derivative < p-derivative < m-derivative
Case 4: Presence of fluoro group
Acidic order increases as: phenol o > m > p
Case 5: Presence of halo group (except fluoro group)
phenol < p-derivative < m-derivative < o-derivative
Acidic Strength of Carboxylic Acid
Acidic nature of carboxylic acid is due to equally contributing resonating structure of carboxylic acid.
-
O O O
-
C O H 
H
 C O 
 C C
Note 1: Any alcohol is less acidic than carboxylic acid because there is no any resonating
structure.
Note 2: The carboyxlic acid is more acidic than phenol while phenoxide ion has more resonating
structures than carboxylate ion equally contributing resonating structure of carboxylate
ion is more stable than phenoxide ion.
A] Acidic strength of aliphatic acids
Effect of I effect: I effect increases the acidic strength where as the +I effect decreases the
same acidic strength of following acid varies as:
(a) CH3 – COOH < ClCH2 – COOH < Cl2CH – COOH < Cl3C.COOH
(b) CH3 – CH2.COOH < CH3COOH < HCOOH
Effect of hybridisation: As the s-character of C-atom increases, the acidic nature also increases

Propionic acid Acrylic acid Propynoic acid

H3C H2C HC COOH
COOH COOH
4.88 4.25 1.85
B] Acidic strength of aliphatic acids: All three acids oxalic acid, malonic acid, succinic
acid are in general stronger than monocarboxylic aliphatic acids (except H.COOH) but are
weaker in their dissociation. This is due to the fact that the second proton which has to be
removed from a negatively charged species containing an electron donating COO– indency
which might be expected to destabilise the anion with respect to the undissociated acid.
With respect to first dissociation as the number of sp3 hybridised carbon atom increases between
two —COOH groups the acidic nature decreases.
COOH COOH
COOH
H COOH H2C (H2C)2
COOH
COOH COOH
PK1 3.77 1.27 2.86 4.21
a
Pa 2 X 4.27 5.70 5.60
Configuration factor in dibasic acid: Due to change in configuration the acidic nature also
changes.
H C COOH HOOC C H
H C COOH H C COOH
Maleic acid Fumaric aicd
PK1 1.92 3.02
a
Pa 2 6.23 4.38
Similarly, maleic acid, having cis-placing of two carboxylic groups and involving in chelation,
records a higher value of first ionisation constant ( pK a1 1.92 ) than its trans-isomer fumaric
( pK a1 3.02 ). The second dissociation of fumaric ( pK a 2 4.38 ) occurs more readily than that of
its cis-isomer ( pK a 2 6.23; because of still strong chelation). There is no question of chelation in
fumaric or in its anion after first ionisation; hence, observed pK a2 for fumaric registers a low
value, i.e., higher value for second ionisation constant (+1 of COO group lowers second ionisation).
O
O O H
O
H H O
OH O H


 OH

 H ; H H
O
H H O O
O O
H
maleic acid cis- maleate ion in more fumaric acid trans
stabilized cyclic system
Acidic strength of aromatic carboxylic acid
(i) Electron group (–I effect group) increases the stability of anion hence increases the acidic
strength.
(ii) Electron releasing group (+I effect group) decrease the stability of anion hence decreases
the acidic strength.
(iii) Ortho substituted acid is always a stronger acid than m-, p-derivative due to ortho effect.
Case 1: When the group is a halo group, then acidity depends only on –I effect.
Benzoic acid < p -derivative < m-derivative < o-derivative

Acidity in increasing order
H F Cl Br I OMe OH NO 2 CH 3
o- 4.20 3.3 2.94 2.85 2.9 4.09 2.98 2.21 3.89
m- 4.20 3.9 3.83 3.81 3.9 4.09 4.08 3.46 4.28
p- 4.20 4.1 3.99 4.00 4.0 4.47 4.58 3.40 4.35
Case 2: When group is –R and –I group.
- - Carbon becomes electron

O O O O - deficient due to
O O resonance. This electron
N N -
deficient carbon
O O withdraws electrons from


the carboxylate group by
(a) inductive effect.
Thus, anion is stabilised by –R and –I effect and –I power is maximum.

-
O O
Anion is stabilized only by I effect

NO2
(b)
- -
O O O O
Anion is stabilized only R and I effect
NO2
(c) (d)
Thus (a), (b) and (c) are more stable than (d) and hence o-derivative is more acidic than
p-derivative and p-derivative is more acidic than meta-derivative.
Benzoic acid < m-derivative < p-derivative < o-derivative


Case 3: When group has +R and +I effect

HO O
CH3
Ortho derivative will be most acidic due to ortho effect
(a)
Note: Carboxylic group and carboxylate ion is not in the plane of the ring. These two
groups will not take part in delocalisation with benzene ring. Group present at o- or p-
position creates charge (+ve or – ve) on the carbon of the ring on which carboxylic
group or carboxylate group is present.
HO O
CH3
Ortho derivative will be most acidic due to ortho effect
(a)
HO O
Anion is destabilised due to +I effect

CH3
(b)
HO O
Anion is destabilised due to +R and +I effect end +I

power is minimum
CH3
(d)
Case 4: When group has +R and –I effect.
-
O O
Stabilised by I effect
OCH 3
(a)
-
O O
Destabilised by R
effect stabilised by I
effect
OCH 3
(b)
p-derivative < benzoic acid < m-derivative < o-derivative

Thus,
ORGANIC REACTION MECHANISM

2.4 Reaction Mechanism
How and why a reaction occurs? In an organic reactions basically there is breaking of weaker
convalent bonds and the formation of stronger ones, so that a relatively more stable molecule is
formed from a less stable molecule. Energy is needed to break a bond while during the bond formation
an equivalent amount of energy is released. In the formation of new bond there may be two possible
mechanism for fission of a covalent bond. One is Homolytic and the other is Heterolytic.
Homolytic Fission
In this mode of fission a relatively non polar covalent bond A-B broken in such a way that each of
the fragments carries one unpaired electron. This fission is effected by sunlight or heat. Electron
movement in this fission is shown by Fish-hook arrow ( ) and the fragments are called Free
Radicals or Radicals.
A B A  B (Radicals)
Heterolytic Fission
In this mode of fission a polar covalent bond say, X-Y breaks in such a way that the electron pair of
the bond stays with the more electronegative fragment. This fission therefore, produces ions. Fragment
with the electron pair is anion and that without electron is cation and if, the fragments are carbon
species, they are called Carbanion and Carbocation respectively. This fission is effected by the
influence of reagent or solvent and rarely by heat or sunlight. Electron movement in heterolytic bond
fission is shown by Curly arrow ( ).
Free radicals, carbocations and carbanions are called Reactive Intermediates as these are highly
reactive species and are produced as intermediate during the course of a chemical reaction.
Reagent Types
An organic reaction may be written in this form :
SUBSTRATE + REAGENT = PRODUCT(S)
Now, what is meant by substrate and what is the reagent? Substrate may be defined as organic
compound which undergoes a structural or functional group change during a chemical reaction. A
reagent on the other hand is the component of prominent electronic character (very often inorganic
species) that reacts with the substrate and constitues the chemical reaction. Electronically, reagents
may be of two types: electron deficient, i.e., Electrophilic (electron loving) reagents, and Nucleophiles
(Nucleous loving). Electrophilic reagents usually consist of an atom which is electronically unsaturated
due to its sextet and may be reactive to electron rich substrates with an aim to fulfil its octet (except
H+, which fulfils its duet) but not with electron deficient substrates. Similarly, nucleophilic reagents

having one or more atoms with unshared pair of electrons may react with electron deficient substrates
but not with electron rich substrates. In this way, phenoxide ion, PhO– , is an electron rich substrate
and reacts with an electron deficient reagent like aryl diazocation, Ph – N  N+ to form a red dye,
but not with a nucleophile like CN. Thus, a common organic reaction may be written as:
Electron rich substrate + Electrophilic reagent (electrophilies)  Product
OR
Electron deficient substrate + Nucleophilic reagent (nucleophiles)  Product
Common Electrophiles :
Common Nucleophiles :
    *    
H  , BH*4 , R O, R S, C  N, HSO3 , RCO, S C  N, RC  C
* * * * * * * *
O
CH NH 2, NH3 , H 2O, RMgX, RLi 
R O
R
Star (*) indicates the reactive site. Since the electrophiles are electron deficient, they are very
similar to oxidizing agents or Lewis acids while nucleophiles are electron donors and therefore,
behave as reducing agents or Lewis bases. Some nucleophiles however may have more than one
(generally two) electron rich atoms and are called Ambident nucleophiles. For example,

   
: C  N :, : S C  N, RCO C H 2 etc. The particular atom of such a nucleophile which will actually

participate in reaction, will depend upon the reaction condition as well as the nature of the substrate.
It may be mentioned here, that the reactions involving electrophiles and nucleophiles are known as
Ionic Organic Reactions while reactions involving free radicals are called Radical Reactions.
Reactivity as well as the reaction rate of an ionic organic reaction depends on the pH, the nature of
solvent and on the influence of catalyst if used, but radical reactions are not appreciably affected by
those external influences.
Types of Organic Reactions
Let us classify the organic reactions known so for. From mechanistic point of view, organic reactions
may be of the following types : Substitution, Elimination, Addition, Rearrangement, and Molecular
Reactions (Pericyclic Reactions).
REACTIVE INTERMEDIATES
The organic reaction completes in so many steps. From initial to final it passes through the formation of
reaction intermediates. These reaction intermediates are:

2.5 Carbocations
A carbocation is the cation of carbon in which the positively charged carbon has only six electrons
around it. Its general formula is R 3C having a formal charge on carbon. Depending upon the
number of the carbon fragment attached to the positive carbon, a carbocation may be classified as
primary (1º), secondary (2º) and Tertiary (3º).
 
CH3 CH 2 CH 2 C H 2 CH3 C HCH 2 CH 3  CH 3 3 C 
n  Butyl cation Iso  butyl cation Tetiary butyl cation
Pr imary 1º  carbocation Secondary  2º  carbocation Teritary 3º  carbocation
Structure
The electron deficient carbon of a carbocation is sp2 hybridized and it uses three sp2 orbitals for its
three valences with the distribution of angle 120º. The unhybridized p-orbital of a carbocation is
vacant and lies perpendicular to the plane of three -bonds attached to the electropositive carbon
(figure).
It may be noted that distribution of valence angle by 120º minimizes the bondpair-bond pair repulsions
in a carbocation which is essential for its stability hence for its existence. In this way, the cationic
structures (a) and (b) as shown figure do not exist because they can not achieve the necessary
planarity ? expansion of CCC bond angle to 120¦ due to rigidity of cage like structures. Carbocation
however exists, as it can expand the CCC bond angle to the required extent because of its better
flexibility due to larger size of the bridge (figure.).
Stability
Carbocations are highly reactive species due to electronic sextet of the cation carbon. Relative
stabilities of carbocations in the gas phase can be expressed in their hydride ion affinities which
actually mean the heterolytic dissociation of R-H bond:
E
RH   R   H

Let us now discuss the factors which affect the stabilities of carbocations. A carbocation acquires
stabilisation by reducing the electropositivity of the cationic carbon. This may be effected through (a)
+I effect (b) hyperconjugative effect (c) resonance effect and (d) solvation. The first three factors
are guided by the own structure of a carbocation (internal stabilisation) while the last one is the
stabilisation by the environment (external stabilisation).
Alkyl groups are electron pumping and hence they reduce electropositivity of the cationic carbon
when directly attached with it. This effect of alkyl group is known as +I effect and thus, more the
number of alkyl groups attached to a cationic carbon more stable is the carbocation. In this way,
stability of the carbocation decreases in the order.
CH3 CH3
+ + + +
H3C C H3C C CH2 CH3
CH3 H
Tertiary (3°) Secondary (2°) Primary (1°) Primary (1°)
–I group (i.e., EWG) on the other hand destabilises a carbocation by further accumulation of positive

charge over the cationic carbon. Thus, O 2 N  CH 2  CH 2 and ClCH 2  CH 2 are less stable than
CH 3  CH 2 due to -I effect of CH 2 NO2 and  CH 2 Cl groups respectively..
An alkyl group also reduces the positive charge of a carbocation by hyperconjugative effect. Here,
the filled C-H -orbitals adjacent to electropositive carbon overlap with the empty p-orbital of cationic
carbon. This leads to the formation of several no bond resonating structures for a carbocation by
which the stabilisation is achieved through dispersion of positive charge (figure).
H
p (vacant)
CH3 + H H H
H
+ +
H3C C CH2 
H C CH2 
H C CH2 
H C CH2 C C
CH3 H
+ sp3C H sp2C
H H
Dispersion of positive charge H
H
Overlap of C - H s orbital
and p-orbital of cationic
carbon
Fig.: Stabilization of a carbocation by hyperconjugation
Degree of dispersion of the positive charge increases with the number of the no bond resonating
structures and hence the stability of a carbocation increases with the number of alkyl groups directly
attached to the electropositive carbon. Thus, the order of stability of the carbocations decreases in
  
the series  CH 3 3 C   CH 3 2 CH  CH 3CH 2  CH 3 as they yield nine, six three and zero
hyperconjugative structures respectively.
Resonance is the most powerful factor to stabilise a carbocation as there involves a direct transfer of
loosely bound -electrons. A C=C -bond adjacent to the cationic carbon takes part in resonance to
disperse the positive charge. This explains why alkyl and benzyl cations are more stable than
corresponding alkyl cations (figure).
+
H2C CH CH3   H2C CH CH2
Stabilization of allyl cation
+
CH2 
 CH2 
 CH2 
 CH2
Stabilization of benzyl cation

(Positive charge spreads)
Fig,: Stabilization of allyl and benzyl carbocation
Stability of an aryl cation may be further increased by the presence of +R groups (electron releasing
groups) like NH 2 , CH 3 O, Br, etc., particularly at the para or ortho position of the ring with respect
to the cationic carbon. They participate to extend the conjugation.
+ +
H2N CH2 
 H2N CH2 
 H2N CH2 
 H2N CH 2
+R group stabilizes a carbocation by

+R group dispersion of charge
CH2 
 CH2
+
NH2 NH2
R groups like NO 2 , CHO, COOH, SO 3H, CN etc., however destabilised an aryl cation especially
at the ortho and the para position of the ring by further enhancement of the positive charge on the
cationic carbon.
Two (+) charges on

a djacent centre II
O O
+ + +
N CH2 
 N CH 2
O O
Highly unstable due to (+)
R group
charges on adajcent centers
A carbocation acquires maximum stability if it possesses aromaticity with delocalisable (4n + 2)
electrons. Thus, cyclopropenyl cation and cycloheptatrienyl cation are fairly stable due to their
aromaticity having 2- and 6-electrons respectively. Cyclopentadienyl cation with 4-electrons on
the other hand highly unstable due to antiaromaticity.
Cyclopropenyl Cycloheptatrienyl Cyclopentadienyl

cation ca tion cation
2e, aromatic 6e, arom atic e, antiaromatic
Participation of heteroatom in resonance when directly attached to cationic carbon also accounts
the stabilisation of a carbocation. This resonance satisfies the octet of the cationic carbon, though
there developed a positive charge over the heteroatom. Thus due to resonance, CH 3OCH 2 is more

stable than  CH 3 2 CH , in spite of its primary nature.

+ +
H 3C O CH 2 
 H3 C O CH2
Less stable More stable
(Cationic carbon has sextet) All the atoms have octet
C-C -bond may also stabilise a carbocation under special circumstances. Cyclopropylmethyl cation
in the bisected conformation is believed to the stabilised by a considerable overlap of -like C-C
banana bond of cyclopropane ring and the vacant p-orbital of cationic carbon. Such an overlap is not
possible in the perpendicular conformation. It may be noted that C-C -bonds in cyclopropane are
not formed by normal head on overlap of sp3 orbitals, rather they overlap almost laterally (similar to
p-p overlap) in order to maintain CCC bond angle 60º. The orbital structure of cyclopropylmethyl
cation may be shown in figure.
p-like sp 3 p-orbital
H orbital -p-overlap
H H
C
H
C
H H
+ +
60° CH2 H CH2 H C C CH C
H H
C
C H
H
+ H
H3C CH2 H
H3C Bisected conformation
+
C CH2
H
C C
H H
H
Perpendicular conformation
Fig. Stabilization of cyclopropylmethyl cation

Compared with alkyl, allyl and benzyl cations alkenyl, alkynyl cations are highly unstable due to
strong electronegativity of sp 2 and sp hybridised carbons respectively holding the positive charge.

Therefore, CH 2  CH  , Ph  , CH  C etc., are extremely uncommon.
Sometimes steric effect may increase the stability of carbocations. Tri t-butylcation is far more
stable than t-butylcation as the former reacts much more slowly with a nucleophile like water. This
stability here is not due to dispersion of the charge but due to its inertness towards a nucleophile. The
bulky groups oppose the approach the nucleophile because the corresponding reaction is a “strain
imposing process”, where CCC bond angles have to be reduced from 120º to 109º. This may not be
comfortable for three bulky alkyl groups.
H3C CH3 H3C CH3 CH3
H3C C 120° CH
3 H3C C 109° only
CH3
+ H 2O
C C CH3 
Very slow
 C CH3
H3C C CH3 H3C C OH
H3C CH3 H3C CH3
Free steric strain High steric strain
External stabilisation of a carbocation refers to its solvation by a polar protic solvent like H 2 O, ROH
etc. Solvation reduces the positive charge of cationic carbon through coordination with heteroatoms
of the solvent molecules.
OH2
H2 O OH2
H2 O R OH2
H2 OOH2
OH2
Solvation (hydration) of a carbocation
In absence of a polar protic solvent a carbocation remains as an ion-pair, R  X  .
Generation
Carbocations are generated by the following general processes.
1. Heterolysis of a Neutral Substrate : Substrates having good leaving groups, most commonly
alkyl or allyl halides (expecting fluorides) undergo heterolysis of C-X bond by influence of polar
protic solvents like H 2 O, ROH, RCOOH, etc. Those solvents stabilise the polar transition state
for heterolysis as well as the ions formed thereafter.
OH 2
Me Me Me HO H H OH
HO +
Me Br 
CBr bond
 H 2O
2
C OH 2  H O H Br H OH
cleavage
Me H 2O Me OH 2 HO H H OH
Hydrated carbocation Hydrated anion
Rate of heterolysis of an alkyl halide is often enhanced by addition of metal ions like Ag  ,Hg 
2
etc., which on coordination with halogen helps the dissociation of C-X bond. Those metal ions
form insoluble precipitate of metal halides and make the heterolysis irreversible.
R  X  Ag  
Faster heterolysis
R   AgX 
2. Addition of Electrophilic reagent to a neutral species : A variety of electrophilic reagents
are used for generation of a carbocation from a neutral substrate. Following are the examples :
O O
+ +
C Cl 
AlCl3
C 
 R C O AlCl4 (R = alkyl or aryl group)
(a) PbNO 2
R R
(b) (CH 3 ) 2 CHF  SbF5 

liq. SO 2
(CH 3 ) 2 CH SbF6
3. Other process :
(a) Deamination of primary amines by HNO 2 :
H
 +
H +
NaNO 2  HCl 
 NaCl  HO  N  O  HO N
 H2 O
  N O
O
H H

 H
Ph CH 2 
N O
 Ph CH2 N
+
N 
  Ph

 CH2 N N 

+
NH 2 H O OH
+  N N +
N  Ph CH2
 H 2O
Ph CH2 N N    Ph CH 2 N
+
OH2

(b) Removal of H from a hydrocarbon :

CH3
H3 C  (CH3 )3 C SbF5 FSO3  H2
H  FSO 3 H  SbF5 
CH3
H H
Ph
+
C Ph   Ph 3 C H 

Ph
Aromatic
Reaction: C+ ion is highly reactive due to electronic sextet.

1. Reaction with a Nucleophile: When a carbocation comes in contact with a nucleophile (solvent
or reagent) the cationic carbon receives an electron pair and forms a neutral product. This is the
most common reaction of a carbocation where it behaves as Lewis acid and the nucleophile or
solvent acts as Lewis base.

Mg3 CCl 
2
 AlCl H 2O
 Me 3CAlCl 4   Me3 COH( HCl  AlCl3 )
ROH
  Me3COR(  HCl  AlCl3 )
2. Elimination of a proton
H 3C CH2 H3C CH2
C2H 2SO 4  H 2O
CH CH 3  (H   HSO4 )
CH CH3  
HO H2OHSO4
H3C
(a) CH2  H 3C
CH2   H3C  H2SO4
H H CH3 CH2
HSO4 Major (A), disubstituted Major (B), monosubstituted
+ R
R OH R OH2 HsSO 4
H 2SO 4
  
 O  H 2 O  H 2SO 4
H   HSO  4
(b) R OH R O H R
(Gem diol)
H HSO 4
+
Ph
Ph C2H 2SO4
  CH 
  H 2SO4
(c) (H HSO  ) 4 CH3
CH2 H3C CH3
3. Addition to C=C bond

CH3
CH3
H
 H3C Cl 
AlCl3
 CH3 AlCl 4 
 
  HAlCl4
(a)
AlCl4
H SO  H 2O H O
 2
 4   + 
 
H
2
 
+ CH2
OH OH2
OH
(b)
First Second
carbocation carbocation
4. Rearrangement reactions : If a carbocation formed in a reaction is not stable enough, it may

rearrange to form a more stable carbocation if its structure permits. Generally, two types of
rearrangements are observed : either by shifting of hydrogen or alkyl or aryl group, or by migration
of C-C -bond. Hydrogen shift is often called a hydride shift and it does not change the basic
carbon skeleton the basic carbon skeleton of the carbocation. 1, 2-alkyl or aryl shift or C-C -
bond migration changes the skeletal pattern of the carbocation.
It is believed that the departure of the leaving group and the migration of C-C bond take place
simultaneously and this need anti periplanar geometry of the leaving group and the migrating
group. This is probably for achieving the best interaction of the orbitals of the migration origin
and the migration terminus.
A C=C bond adjacent to cationic carbon may also change its position to yield ? canonical
structure without changing its basic skeleton which is often called allylic Rearrangement. Different
kinds of rearrangement process of carbocations are discussed below.
(a) Rearrangement of carbocations involving 1, 2 shift of H

H3C H
H3C NaNO 2 / HCl + 1,2 H shift
 
  N2
CH2 
NH2
+ H3C
N
N 1° carbocation
(less stable)
H3C
+ H 2O
H3C CH 
H
  H3C
H HO H OH
2° carbocation Major Minor
(More stable)
(b) Migration of C=C bond
+
+ CH
CH2 
H 2O
  H3C 
 H3C CH3 Cl
H3C Cl Boil
H3C
H 2O

 HCl
 H3C OH  [Allylic rearrangement]
Normal alcohol HO CH2
Rearranged alcohol
(c) Rearrangements of carbocations involving 1, 2- alkyl or aryl shift
(i) 1, 2-alkyl shift
H3C H3C H3 C CH3

H + 1, 2CH3 shift
H3C  H 3C CH 

H3C CH2 H3C CH 3 H3 C CH3
2° carbocation 2° carbocation
(More stable)
H 2C CH3 H +
H+
H3 C CH3
H 3C CH3
Major
(Less substituted H3 C CH3
Less stable) Major
(More substituted
More stable)

CH3 CH3 CH3 CH3 CH3 CH3

H 
 H2 O +
H3C CH3  H3C CH3   H3C C
+ CH3
OH OH OH OH2 OH
Pinacol
1,2-CH3 shift
H3C CH3 H3C CH3

H  +
CH3   C CH3
O CH3 HO CH3
Pinacolone
(ii) 1, 2-aryl shift
CH3 Ph H3C
H + 1,2 Ph shift +
H3C 
 H3C
 H 2O CH2   C
CH3 OH CH3 H3C Ph H 
H  H3C
H3C
H2C Ph
Minor
H3C Ph
Major
More stable due to
extended conjugation
(iii) Migration of C-C -bond.
Me 
H (CH 2SO 4 )
Me
   H 2O
  +
CH
+
Me OH Me OH2 Me Me
Five membered ring

H
(a) (strainless)
CC bond migration C C bond migration
  Me   Me
Me Me
Four membered ring

H
 C C bond migration
H
   

H
(b)  
Five membered ring

strainless
Four
membered ring +
OH OH2
  H 2O
H
   
H
(c)
C C bond migration H  Five membered ring
    strainless
Ring contraction
Me
Me
5 1 5 1
6
OH 6 +

H (C.H 2SO 4 )
OH2
 
3 OH
4 3 OH
2 4 2
H Me H Me
Me Me
5 1
 H 2 O followed by 6 O O
migration of anti
C 2  C 3 to bond 2 H 
H
   
Me Me
OH OH
4
3
H Me H Me
(Stable carbocation)
Here, C 2  C3 bond being stereochemically anti to the departing -OH actually migrates and leads to
contraction of carbocyclic ring. The C5  C6 bond which is also anti to -OH group does not migrate
because this can not produce a stable carbocation.
Carbanions
Carbanions are the anions of carbon having formal charge -1. A carbanion is produced in situ during
the course of a reaction and is extremely useful reaction intermediate in organic synthesis as well as
a potential base and a powerful nucleophile.
Structure
A simple isolated carbanion, R 3 C is pyramidal having sp3 hybridized anionic carbon rather than sp2
because of strong lone pair-bond pair interactions in later. The structure is similar to that of ammonia.
Thus, unlike a carbocation, a carbanion can be formed at the bridgehead carbon. The anionic carbon
in conjugation with a -bond is however planner (sp2) in order to achieve the electron delocalisation
by p-orbital overlap and therefore, stabilised through resonance (figure).
90°
>109.5° R sp2 R
3
sp C 130° sp2 C CH O C CH O
R R R R
R
< 109.5°
Pyramidal Planar
(a)
R R
CH O 
C  C CH O
R (b) R
Resonance stabilized
Fig.: Nonplanar and planar carbanions

Stability
A carbanion is stabilised by reduction of the density of negative charge on anionic carbon. The
following factors are responsible to stabilise a carbanion.
1. Stability of a carbanion depends on the hybridised state of the anionic carbon. More the s character
of the anionic carbon the greater is its electronegativity and hence the more stable is the carbanion.
Thus the stability order CH 3  CH 2
CH3  CH 2  CH 2  CH   CH  C
2. A -I group attached to the anionic carbon stabilises it by reduction of negative charge while a +I
group destabilises the same by further accumulation of negative charge on the anionic carbon.
This explains the decreasing order of stability of the carbanions with gradual increase in the
   
number of alkyl groups on anionic carbon, e.g., CH 3  CH 3CH 2   CH 3  2 CH   CH 3  C .
Greater stability of  CCl3 over CH3 is due to -I effect of Cl atoms. -I effect of CF3 group is

stronger than that of F atom itself and hence  CF3 3 C is more stable than F3C  as evident from
pK a values of their conjugate acids:  CF3 3 CH  pK a  28  . Lower stability of F3C is due to the
electronic repulsion involving lone pair on carbon and those of F atoms acting over a very short
distance. A carbanion may also be stabilised by the field effect which is very similar to the
inductive effect. Thus, carbanion (I) is more stable than (II) due to field effect arised from the
resonance involving the amide linkage which is not possible for the carbanion (II).
Ph CH Me Ph CH Me
+
N 
 N
O Me O Me
(I) Electropositive N stabilizes
negative charge on carbon
- -
Ph CH2 Ph CH2
+
C CH2 N 
 C CH2 N
O Me O Me
(II)
The electropositive nitrogen in the charged canonical structure of (I) is responsible or stabilise
the negative charge on adjacent carbon.
3. If a double or triple bond is located at the  position to the anionic carbon, the carbanion is
stabilised by resonance involving electron pair of carbon and the -electrons of the multiple
bond. This explains why allylic and benzylic carbanions are more stable cum their saturated
analogues.

H2 C CH CH2 
 H2 C CH CH3
-
CH2 
 CH2 
 CH2 
 CH2

- - -
H2C O H3C CH H3C
+ - +
N O 
 H2C N CH3 
 CH3
-
O O O O
More stable More stable
Oxygen and nitrogen are more electronegative
than carbon and hence better recipitent of -ve charge.
- -
H2C C N 
 H2C C N
Triphenylmethyl anion is so stable that it can be stored for a long time in absence of water.
Stability of a carbanion is increased in many fold than benzyl carbanion, if a –R group is attached
to the aromatic ring. This is because of the fact that the electronegative atoms of the –R group
are better recipient of negative charge than a carbon. Such a –R group stabilizes an aryl anion
particularly when they are at the para or ortho position with respect to the anionic carbon unit.
- -
CH2 CH2 CH2 CH2
N N
C C

 

+ +
N - N -
O O O O
4. Atoms like sulphur, phosphorous, chlorine, etc. use their vacant ‘d’ orbital to stabilise a carbanion,
when they are directly attached to an anionic carbon. Here, p-orbital of anionic carbon overlaps
with the d-orbital of the heteroatom leading to the formation of p-d bond.

 

S S S S S S
p-d bond
p-d bond
Ph Ph
+
H2 C P Ph 
 H2 C P Ph
Ph Ph
Stabilization of carbanion
by p-d bonding
This explains why CCl3 is more stable than CF3 , in spite of higher electronegativity of fluorine
than chlorine. Fluorine without having ‘d’ orbital exerts only the -I effect but can not participate
in resonance.
Delocalisation of electrons can give maximum stability for a carbanion if it achieves aromaticity
by possessing (4n + 2)- electrons. Cyclopentadienyl anion as an example is highly stable
carbanion due to its fully delocalised 6-electrons. Cyclopropenyl anion on the other hand is
highly unstable due to its antiaromaticity for 4-electrons.

 

6e Aromatic fairly stable



Antiaromatic, highly stable

5. Sometimes a carbanion may be stabilised by resonance with a non-adjacent bond. Homoenolate
ion may be an example.


O O
Homoenolate ion
Apart from these, a carbanion is stabilised by solvation. Larger anions are weakly solvated and
hence less stabilised than smaller ions.
Generation
A carbanion may be generated by the following general methods.
1. By abstraction of acidic hydrogen from a carbon : Compounds having acidic C-H bond may
undergo deprotonatio by influence of strong base and produce carbanions.
Ph
Na 
Ph Ph
EtONa  /EtOH -

  EtOH CH2 
 CH2
(i) O H O Na 
O
Carbanian Enolate ion
-
H O O
+
(ii) CH2
NaOH
NO2 
 H 2O
 NaCH2 N  H2C
 N
-
O ONa
(iii) RC  C  H  NaNH 
 RC  CNa  NH 3
2
Though yields are electrically neutral due to dipole stabilisation they behave like carbanions.
2. By metal-halogen exchange : A very popular method for generation of carbanion is the treatment
of organic halogen compounds with strongly electropositive metals like ‘Li’, ‘Na’ etc. in an inert
solvent. Exchange of metal with halogen generates a carbanion, as a form or organometallics.
Organometallics are the compounds having highly polar carbon-metal bond. These are very
important reagents in synthetic organic chemistry. Polar character of an organometallic is as
follows : R   M  , where, M stands for metal.
Ether
CH3  Br  2Li   CH3 Li  LiBr

H3C CH3 H3C

- Li 
Ether
 2Li 
 C  LiBr
H3C CH3 H3C CH3
Ether
Ph 3CCl  2Na   Ph 3C Na   NaCl
Ether
Ph 3CCl  2Na   Ph 3C Na   NaCl
3. By insertion of metal like Mg to a carbon-halogen bond : This is the basis for preparation of
Grignard reagent when metallic magnesium is inserted to carbon-halogen (chlorine, bromine,
and iodine) bond in presence of ether as a solvent.
+   +
Mg
CH3  Br  CH 3MgBr (Methyl magnesium bromide, a Grignard reagent)
4. By decomposition of carboxylates : Decarboxylation of some metal carboxylates may yield

carbanion.
Cl O Cl
 CO 2
Cl 
 Cl ONa
Δ
+
Cl ONa Cl
O ONa
Na 
O2 N NO2 O2 N NO2
 CO 2

 Δ
NO2 NO2
5. Addition of an anionic nucleophile to a suitably substituted multiple bond.
F H F H F H
 K K
K F

 Cl F
F Cl F F F Cl
Less stable carbanion
not formed
Cl Cl Cl Cl Cl
O O O O
CH3 CH3 CH3 CH3
CH 3O
  
 
 

+ + + + +
N N - N -
N - - N -
-
O O O O O O O O O O
6. Additional of electrons to a compound : Sometimes a compound may accept electrons from a

suitable source to generate a carbanion. Cyclooctatetraene for example, on treatment with metallic
sodium is converted to cyclooctatetraenyl dianion. The dianion is aromatic with 10-electrons
and hence isolable as crystalline salt.

2K

( 2e)

8e Diamon
10e, Aromatic
Reactions
1. Additions : Carbanions are effective nucleophiles and add to polar multiple bonds like C=O,
C=S, C=N, CN etc. and electrons deficient C=C. Carbanions do not add to simple olefinic
unsaturation unless it is being activated by electron withdrawing groups.
-
O HO
HO H 3CCH  O
H3C CHO 
 H3C  H2O 
 H2C 

Condensation 
 H 2O
 HO 
(a) O O
-
H3C O H3C O
Nucleophile Aldol
This is a case of aldol condensation.

R
COOEt COOEt O OH COOEt

EtO /EtOH - R
H2C  HC
 EtOH 
 EtOH
 R COOEt
COOEt COOEt R H
R COOEt
(b) EtO 

 EtOH

 HO
R COOEt
(Knoevenagel reaction)
Me Me
 +
MeMgX H 2O
O C O  Et 2 O
OMgX   Mg (OH )X OH
(c) O O
(Synthesis of carboxylic acid)
2. Substitution  SN 2 displacement  : Carbanions are powerful nucleophiles perform a variety of

nucleophilic displacement reactions to form C-C -bond either by intermolecular or intramolecular
process.
2 Na MeCH 2  Br
Me 
Ether
 Me CH2 
 NaBr
 Me
 NaBr
(a) Br Na Me
(Nucleophile) (Wurtz reaction)
+
(b) Ph C C
NaNH 2
Ph   Ph C C Me Br
Na   Ph C C Me
 NH3  NaBr
3. Elimination: Carbanions may expel a leaving group either from the anionic carbon or from its
adjacent carbon, which are referred to  and -eliminations respectively. -Elimination forms
another reaction intermediate, called Carbene while -elimination generates a -bond.
-Elimination is the most common process of elimination.
O O O
 EtO  Cl 
(a) 
 EtOH
   (-Elimination)
 Cl Cl
HO HO H3C
-  HO

 HO/ H 2o
 H 2O
CH 

(b) H C CHO H3C CHO O
3
(-Elimination)
4. Rearrangements : Unlike carbocations, rearrangement, reactions of carbanions are less common
but not rare. Sommelet-Hauser rearrangement is a typical example of carbanion rearrangement
leading to alkylation of an aromatic ring by ArSN 2 mechanism.
Me Me
+ + CH2
N NH 2 N
Me 
  NH 3 -
Me 
 CH3
H2C N
H H
CH3
Me
Me
Isomerization
 H

N
Me
5. Abstraction of acidic proton : Acarbanion is a very strong base and can be used for deprotonation
to create a new carbanion. CH3Li, BuLi, PhLi, etc., are often used as base in many organic
syntheses. Ph 3CNa being very strong and bulky base may be used for deprotonation under
kinetic condition from the less hindered -carbon of a ketone, in order to have regioselective
alkylation.

PhNa 

Reproduction
 O CO


H 3O
 
-phH Na O
(a) S H S S S COOH
- +
O Na
+
O O O Na O
H Et Na  Et Et Me Et
Ph 3C Na  Me  I

 
 
(b) More exposed Deprotonation
(  Ph 3CH)  NaI
proton
Enolate ion
Free Radicals
Electrically neutral species carrying unpaired electron is called Radical or Free Radical. Though
they do not have any formal charge, they are electron deficient species having an unpaired electron
and therefore, highly reactive. Few free radicals are however due to extensive resonance are not
reactive and hence long lived. Due to unpaired electron, a radical has a net magnetic moment and
hence paramagnetic. Radicals are detected by Electron Paramagnetic Resonance (EPR) spectroscopy
which is popularly called Electron Spin Resonance (ESR) spectroscopy.
Structure and Stability

Carbon radicals may be planar or pyramidal. Simple alkyl radicals or radicals having -unsaturation
are planar with sp3 hybridised central carbon carrying the odd electron in the unhybridised p-orbital.
Formation of recemic alkyl chloride during photochemical chlorination of 3-methylhexane as shown
below proves the planar geometry of the alkyl radical formed as intermediate during the course of
the reaction.

C3 H7 C3 H7 C3 H7
H7 C3 sp2
Cl2 /hν
H3C H   HCl  Cl  Cl
C C 2 H5   H3C Cl  Cl CH3
  Cl
(Cl )
H3C sp2
C2 H5 C2 H5 C2 H5
3-Methylhexane Racemic mixture
Planar alkyl radical
A radical may be non-planar when it is formed either at the bridgehead carbon or at the carbon that
bears heteroatoms. Strong repulsive interaction between odd electron on carbon and the non-bonding
electrons on heteroatoms forces CF3 to be pyramidal rather than planar..
Strong electronic
repulsion
F 90°
100° sp3
Bridgehead C C F
radical F F F
F
Tetrahedral Pyramidal Unstable planar structure
A radical may be stabilised in three ways; i.e., by resonance, by hyperconjugation and by steric
hindrance.
H2C H2C


CH2 CH2 CH2 
 CH2
Allyl radical
Allyl and benzyl radicals are stabilised by delocalisation of odd electron involving the vinyl and aryl
group.
Triphenylmethyl radical, Ph 3C  is so stable that it remains as yellow solution for a long time in
absence of air. Its stability is not only die to high degree of delocalisation of odd electron but also due
to steric reason, which causes impairing of radical dimerisation and boosts the equilibrium towards
radical side. Presence of methyl group at the ortho position of aromatic ring magnifies the steric
effect causing further enhancement of the stability of an arylmethyl radical. This is also true for any
other bulky group. Examples of some stable radicals are given below.
O
Me Me
Me Me
C
Me Me
Fig.: Stabilized Free Radicals

Radicals are stabilised by adjacent functional group capable for resonance irrespective of electron
withdrawing or electron releasing nature of the group. Thus, radicals next to carbonyl, nitrile, nitro, or
other functional group or centered on a carbonyl carbon are more stable even than a tertiary alkyl
radical while vinyl  CH 2  CH   alkynyl  HC  C   and aryl  Ar   radicals are less stable than
an alkyl radical, without having any stabilising factor.
Hyperconjugation effect accounts the stability of alkyl radical, where a -electrons of C-H bond that
is adjacent to the radical carbon involves in resonance. Stability order of alkyl radicals
 CH 3 3 C    CH 3 2 CH   CH 3CH 2   H 3C  is explained on the basis of the number of
hyperconjugative structures, which are nine, six, three and zero respectively.
H H H H
H C CH2 
H C CH2 
 H C CH2 
H C CH2
H H H H
Fig.: Stabilization of Ethyl Radical by Hyperconjugation
Formation
Radicals are usually produced in gaseous phase or in inert solvent by homolytic cleavage of a relatively
weaker covalent bond under influence of heat or sunlight or radical producing substances like H 2 O 2
or organic peroxides, commonly known as radical Initiators.
Homolytic bond cleavages are shown by Fish Hook arrows ( )
Thermolysis
Thermolysis is the process of homolytic cleave of a covalent bond by influence of heat. Compounds
having weaker -bonds like O-O, C-N, C-S, C-H, N-N, O-N, etc. form free radicals in solution by
thermolysis. Organic peroxides which suffer homolysis of O-O bond often act as initiators
(radical initiator).
O
Ph O C
Ph  2 Ph O
50 100
C O 
 2Ph  2CO 2
C
O O
Dibenzoyl peroxide
Me Me
110
Me O   Me O  N O
Me N O Me
Alkyl nitrite
Me Me Me
180 200
Me N N  Me
Me  C
Me Me Me
Azo compound
Very reactive alkyl radicals are also generated by thermal decomposition of organometallic compound
like tetraalkyl lead in an inert atmosphere.
Alkyl radicals are also produced during radical-induced cracking of long chain alkanes.
Photolysis
Photolysis is the process of homolysis of covalent bonds under influence of sunlight. This is better
than a thermolysis because it may cleave comparatively stronger bonds which are not possible by
thermolysis at a reasonale temperature. Further, it is more selective and the unwanted pyrolysis may
be avoided. Conditions for photolysis is that the molecule should be capable of absorbing UV or
visible radiation.
O
hν hν
CH3   CH3  H3C C R N   2R  N 2
H3C O N R
O O
hν hν
O O  2 R Cl Cl  2 Cl
R O O
R
Flash photolysis is an interesting method which uses a very intense pulse of UV radiation for generation
of free radicals in high concentration. This is often used for study of free radicals rather than the
preparative purpose.
Carbenes
Carbenes are electrically neutral, divalent species of carbon having general formula : CR 2 , the
simplest cabene is :CH2 often called methylene or simply carbene is the parent. In spite of two
unpaired electrons, carbenes are electron deficient due to sextet of divalent carbon and hence it is
strongly reactive. Carbenes are named by indicating the substituents attached to the divalent carbon
e.g., : CCl 2 , dichlorocarbene; : CHPh, phenylcarbene etc. But when the divalent carbon of a carbene
is a part of a ring or an unsaturation, suffix-ylidine is used, e.g.,
Sextet
Carbon
H2C C
Vinylidine
Cycloohexylidine
O C  O C R N C 
R N C
Carbene Octet Carbene Octet
structure structure structure structure
Carbon monoxide Isonitrile
Structure and Stability
Spectroscopic investigation of a number of carbenes shows that two types of structures are possible
for carbenes:
1. The triplet carbenes, which on ESR spectroscopic studies show the presence of two unpaired
electrons of parallel spins having bond angles  130  136º and
2. The singlet carbenes, which are not observed by ESR spectroscopy due to paired spin with
bond angle  100  110º.
Since most of the carbenes are bent, the divalent carbon is considered to be sp2. One of the two
unpaired electrons in triplet carbene remains in sp2 orbital and another in p-orbital. In singlet carbene
on the other hand the spin paired electrons remain in one of the sp2 orbital keeping p-orbital vacant.
P P
vacant
sp2 sp2
R R
 130  125 C  100  110 C
R R
Triplet carbene Singlet carbene
Smaller bond angle in singlet carbene from the normal value (120º) is believed due to strong repulsion
involving lone pair and bond pair of electrons. A triplet methylene without having spin-spin repulsion
of electrons is slightly more stable than the singlet methylene though, it may not be true for
dichlorocarbene. The nature of substituent often determines the state of a carbene, i.e., whether it is
triplet or singlet. If a carbene is attached with n electrons donors, it prefers to be singlet as it is more
stable due to the following resonance, where, n electrons are delocalised in the vacant p-orbital of
carbene.
vacant +
Cl Cl
Cl
C 
 C 
 C
Cl +
Cl Cl
Dichlorocarbene
In this way, : CCl2 , : CHCl, : CF2 : C  OMe 2 , etc., are singlet while : CH 2 , : CHR, : CR 2 , etc. exist
mainly in triplet state. : CF2 is more stable than : CCl 2 because of its more effective 2p-2p overlap
than in : CCl 2 where the overlap is of 3p-2p type. It is believed that during its generation, methylene
is formed as singlet which may lose its energy and becomes triplet during its collision with reaction
vessel or inert gas like nitrogen, if present in reaction media.
Chemical Behaviour
Due to electronic sextet of divalent carbon, a carbene is electron deficient and hence behaves as
electrophile. Electrophilicity of a carbene is enhanced by -R group attached to divalent carbon. Thus,
:CHCOOEt is more electrophilic than : CH2 itself. On the contrary, a +R group attached to divalent
carbon makes a carbene more stable by reducing its electrophilicity. Thus, :C(OEt)2 is less reactive
than : CH2. Sterically hindered carbenes are also less reactive.
Generation
Carbenes are generally formed from their precursors by loss of small stable molecules either by
thermal or photochemical decomposition or by -elimination.
1. Carbenes by thermal or photochemical decomposition.

Δ or hν
CH 2  N  N   CH 2  N 2
(a) Diazomethane
Δ or hν
H2C C O  CH2  CO
(b) Ketene

Cl R
hν or Δ
(c) Cl R  C  CH2
Cl R Cl R
N N Δ or hν
(d)   N 2  CH 2
2. Carbenes by -elimination : In -elimination both the atoms/groups are lost from the same
carbon.
Cl Cl Cl
HO  Cl
Cl H 
 Cl
 H 2O C  C
Cl Cl Cl
Cl Li  ClCl

PhLi  LiCl
Cl H 
 PhG
 Cl C   C
Ph Ph Ph
Reaction of Carbenes
1. Cycloaddition: The most important reaction of a carbene is the cycloaddition to C=C bond to
form a three membered ring. Singlet carbene having paired electrons with opposite spin attaches
the -bond by a concerted mechanism (one step process) and constitues a stereospecific reaction
i.e., the product of a particular geometry is formed in the reaction.
Me Me Me Me
CH 2 N 2 , Δ

H H
H H
CH2 (Singlet) cis-1,2-Dimethylcyclopropane
One step addition

Stereospecific addition
Me Me Me Me Me Me
spin inversion

 CH 2 N 2 , Δ , N2 gas C 
 C
H H H H
H H
CH 2(Triplet) CH 2 CH 2
io n
ta t
ro
nd
Stepwise addition bo
C
Stereoelective addition C- C-C bond
formaton
Me Me
Me Me Me Me
C  C bond formation
 C
H H H H H
H
trans-1,2-dimethyl CH 2 cis-1,2-dimethylcyclopropane
cyclopropane

H OPh H PhO OPh OPh

 C 
 C 

OPh H Endo
Exo
More favoured Less favoured
Cl
Cl
  Cl
HCCl4 , tBuO
  Cycloaddition
 CC2   
Ring exp ansion

 tBuOH,  Cl
Cl
N N N N
H Six membered ring
Five membered
ring
H3C H
1 2 3 4 CH2 Δ
CH 2 N 2 , Δ
H2C CH CH CH2 
N
Vinylchloropropane 

2
1,2addition
H
2. Electrophile substitution: Carbenes with –R group/s behave as effect electrophile and may
attack activated (electron rich) aromatic ring. Thus  CCl2 attacks phenoxide ion and forms
phenolic aldehyde by Reimer Tiemann reaction.
- -
OH O O O Cl
H Cl
-
CHCl2 , OH  C H  Cl
( CCl 2 )

  CCl2 
 
Aromatization

Cl
Phenol Phenoxide ion
- -
O Cl O O

HO , H 2 O
O O O

Hydrolysis
 
  HCl 
  Cl
H
3. Inversion Reaction: A carbene may be inserted to a -bond, especially to C – H bond either

it singlet or its triplet state as per following mechanism.
R R
H
C  H 
 
 H
C
H
R R
Singlet H
R R R
C  H 
 C  C
H  
 H
R R R
Triplet
4. Rearrangemens: Carbenes often undergo rearrngement involving migration of alkyl group or

aryl group as well as C – C -bonds.
Me Me Me Me Me
PhLi Ph migration

  HCl


Ph Cl Ph CH Me Ph

O O
 N2 Me migration
Me CH
Me C N2   Me CH  
C O
Nitrenes
Nitrenes are the nitrogen analogs of carbenes and are closely related to them so far as their structures
and properties are concerned. Here nitrogen is monovalent and hence nitrenes are too reactive.
Nitrenes can be generated in both triplet and singlet state.
R N R N
Singlet Triplet
Generation and Reactions: Two general methods are often used for the generation of nitrenes.
1. Removal of leaving groups L and H from a substrate like R-NH-L under influence of base: This
invovle a typical -elimination process. A nitrene so formed readily undergoes rearrnagment to
isocyanate and the process is very similar to the rearrangement of a carbene.
O O O O
Br2 , HO HO  Br 
R C NH2  R C NH Br 
R H 2O
C NH Br 
R C N
Primary amide
Nitrene
(a)
Rearrangement
R N C O
Isocyanate
This is called Hofmann reaction.
(b) Lossen, Curtius and Schmidt reaction. Also follow the same principle and involve nitrene as
intermediate which also rearrnages to isocyanate.
O O O
N
HO  R1COO 
R C NH O 
 R  H2O
C N O 
 N 
 R C
O
O O R (Lossen)
R1 R1
Hydroxanic acid ester
O O O
O
C NaNO2 /H  C  H C  N2
R NH  R NH 
R NH N2 
 N
NH2 N2 Acylazide R
Acid hydroxide
N
R C
O
(Curtius)
O
O O
N 3H C  N2
N
C 
R N2 
NH  N 
R C
 H2 O
R OH O
Acylazide R (Schmidt)

2. Thermal of photochemical decomposition of azides

This is a very common route to reaction.
Δ or hν
R  N  N  N   N2  R  N
Azide
R R R R
R1N


R R
(a) Addition to C = C: R R
R1N

 +
 RN  
 N
H
R   NH R 
 NH  
H

R
H NH 2
(b) Dimerisation
2R  N 
 R  N  N  R (Dimide)
SAMPLE PROBLEMS 2.3 (MCQ)

Problem 1: Which C – N bond length in the below given molecule is larger?
NO2
1
Me Me
2
NO2
(a) 1 (b) 2
(c) Both are equal in length (d) Can’t say
Solution: (a) At 1 C – N bond there is steric inhibition of resonance so C – N bond is single in nature
but at 2 partially double in nature due to resonance.
Problem 2: Which molecule of below the has highest electron density at C4?
Me
Me Me CH3
(I) (II)
(a) I (b) II
(c) Both have same (d) Can’t say
Solution: (a) No. of hyperconjugated H is more.
Problem 3:
This molecule is
(a) Aromatic (b) Antiaromatic
(c) Non-aromatic (d) None of these
Solution: (a) Benzene ring is forced out of plane.

Problem 4: Steric inhibition is not applicable in:

H3C CH3
NH2 N
OH CH3
(a) (b)
H3C CH3
N NO2
H3C CH3 H3C CH3

(c) (d)
Solution: (a) No bulky group is present at nitrogen as well as on benzene ring. Only one bulky group
is present.
Problem 5: The abstraction of proton will be fastest which carbon in the following compound?
O
Y
X P
H3C CH3
Z
(a) X (b) Y
(c) Z (d) P
Solution: (a) As anion is resonance stabilized with maximum conjugation.
O
Y
X P
-
H2C CH3
Z
Problem 6: What is the increasing order of bond lengths of bonds indicated as p, q, r and s in following
compound?
s
q r
(a) P < q < r < s (b) q < r < s < p

(c)) s < q < r < p (d) s < p < q < r
Solution: (d) Bond length of r is maximum as have no hyperconjugation and no resonance so it is
single in nature.
Problem 7: Which of the following molecules is expected to have the greatest resonance stabilization?
(a) (b)
(c) (d)

Solution: (b)
Both rings are aromatic

Problem 8: Which one of the following compounds is not aromatic?
CH3
(a) (b) H
(c) (d)
Solution: (c) No conjugate system is present as one of the carbon atoms is in sp3 hybridisaiton.
Problem 9: Which one of the following is the strongest acid?
(a) (b)
(c) (d)

 H

Solution: (c)
H
Anion is aroamtic hence highly stable.
Problem 10: Acylium cation has two resonating structure I and II

+ +
R C O 
R C O
I II
Which statement is correct for I and II
(a) I is most stable than II (b) Stability of II is more than I
(c) Both have same stability (d) None of these
Solution: (b) All atoms have complete octate.


CHAPTER ASSIGNMENT
MULTIPLE CHOICE QUESTIONS (Single Correct)
1. Which of the following has a bond formed by overlap of sp3 – sp2 hybrid orbitals ?
(a) CH3 – C  C – CH3 (b) CH3 – CH = CH – CH3
(c) CH2 = CH – CH = CH2 (d) HC  CC2H5
1
CN
2
2. The bond between carbon atom (1) and carbon atom (2) in compound,
(a) sp3 and sp2 (b) sp2 – sp3 (c) sp and sp2 (d) sp and sp
3. In the compound CH2 = CH – CH2 – CH2 – CH2 – C  CH, the C2 – C3 bond is of the type is
(a) sp – sp2 (b) sp3 – sp3 (c) sp – sp3 (d) sp2 – sp3
4. Which of the following species has a trigonal planar shape ?

(a) CH3– (b) CH3+ (c) BF4– (d) СH2
5. The stability order of alkenes is given as CH3 – CH = CH2 > CH2 = CH2, the reactivity order
towards electrophillic addition reaction is given by
(a) CH2 = CH2 > CH3 – CH = CH2 (b) CH3 – CH = CH2 > CH2 = CH2
(c) CH3 – CH = CH2 equal to CH2 = CH2 (d) None of these
6. Formic acid is considered as a resonance hybrid of the four structures.

O– O– O
O
.. 
H–C=O H–C=O–H H–C–O–H
H – C – OH .. – H
 –
I II III IV
which of the following order is correct for the stability of the four contributing structures ?
(a) I > II > III > IV (b) I > II > IV > III (c) I > III > II > IV (d) None of these
7. Examine the following two structures for the anilinium ion and choose the correct statement from the
ones given below.
NH
3
NH3
I II
(a) II is not an acceptable canonical structure because carbonium ions are less stable than
ammonium ion.
(b) II is not an acceptable canonical structure because it is non-aromatic.
(c) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons.
(d) II is an acceptable canonical structure.
8. Find out the stability order the following compounds:
I II III
(a) I > II > III (b) III > II > I (c) II > III > I (d) III > I > II
9. The most unlikely representation of resonance structure of p-nitrophenoxide ion is

O O
O O
– O O– O O–
+ N
N N N
(a) (b) (c) (d) –
O O O
O–
10. Which of the following is an electrophile ?
(a) AICI4– (b) BCl3 (c) NH3 (d) CH3OH
11. The compound which gives the most stable carbonium ion on dehydration is
CH3
(a) CH3– CH – CH2OH (b) CH3– C – OH

CH3 C6H5
(c) CH3–CH2–CH2–CH2OH (d) CH3– CH – CH2– CH3

OH
12. Geometrical isomerism is shown by
H F H F
(a) C=C (b) C=C
H Br H3C Br
H3C Cl H Br
(c) C=C (d) C=C
H3 C I H3C Br
13. Polarisation of electrons in acrolein may be written as
– + – +
(a) CH 2 = CH – CH =O (b) CH 2 = CH – CH = O
– + + –
(c) CH2 = CH – CH = O (d) CH2 = CH – CH = O
14. What is the basic strength order?
H 
H2N

A. N: B. N: C. CH3  C  N D. 
C = NH
H2N
(a) A > B > C > D (b) D > A > B > C (c) D > C > A > B (d) C > D > A > B

15. The stability order for the compounds
A. 0
B. 0
(a) A < B (b) A > B
(c) A = B (d) Stabilities cannot be compared
INTEGER TYPE QUESTIONS

16. In below mentioned molecules, How many have sp3 hybridization in their central atom?
CH4, NH3, CH2 , CH3 – OH, C2H4, NH+4 , BH-4 , H3O+
17. How many molecule, mentioned below have zero dipole moment?
CO2, trans-1,2-dichloroethane, cis-1,2-dichloroethane, 1,2-dichloroethane (staggered), dimethyl
sulhide, p-dinitrobenzene,
18. How many molecules, mentioned below can exhibit intramolecular hydrogen bond?
HF, CH3OH, CH3COOH, o-nitrophenol, ethylacetoacetate
19. No. of groups that exhibit + I effect.
 
 N R 3 ,  SR 3 ,  O  ,  SiR 3 ,  COO 
20. No. of molecules exhibits resonance.
CH2
Ph
+ -
O2 N NO2
H2C P Ph , C O , H2C , ,
Ph NH2
N O
NO2
21. How many carbocation are stable?
+
CH2
, , , , , ,
22. How many carbanion are stable?
-
S S , , , , H2C C N
23. How many molecules have acidic hydrolysis?

O
O O O
CH3
H3C CH3 , H3C NH2 , , H3C OH ,
H3C O CH2 CH3,

24. How many carbocation of following will rearrange by 1,2-shift?

Ph + Me
CH2 Ph
H3C +
Ph Me C
(a) + (b) (c) (d)
CH2 +
Ph CH CH3 Me Me
Me Me
+ + H2C
Me C C
(e) (f) (g) (h) +
CH2
Me O Et OH
25. Degree of unsaturation in combine C8H8.
MULTIPLE CHOICE QUESTIONS (More than one Correct)

26. Resonance sturcture of a molecule should have
(a) identical arrangement of atoms (b) nearly the same energy content
(c) the same number of paired electrons (d) identical bonding
27. Which anion among the following is resonance destabilised?
(a) (b) (c) (d)
28. Arrange in decreasing order of stability:

+ + + +
CH2 CH2 CH2 CH2
OH NH2 CH3 NO2

I II III IV
(a) I > II > III > IV (b) II > IV > III > I (c) II > I > IV > III (d) II > I > III > IV
29. Which of the following statements are correct?
+ +
(a) R C O and R C O are resonance structures.
(b) Methyl carbanion is both isostructural and isoelectronic with ammonia.
4 3 2 1
(c) In CH2 CH CH O , nucleophilic centre is position 4 while electrophilic centre is position 1.
(d) SnCl4 acts as an electrophile.
30. Which of the following species are planar?
(a) tert-Butyl free radical (b) tert-Butyl carbocation
(c) tert-Butyl carbanion (d) Allyl carbanion
31. Which of the following compounds contains only sp3-hybridized carbons?
(a) Cycloalkanes (b) Straight chain alkanes
(c) Branched chain alkanes (d) Benzene
32. Which of the following are nucleophile?
(a) NH3 (b) OH– (c) R – O – R (d) AlCl3

33. Which of the following are electrophile?

(a) CN– (b) BF3 (c) NO2+ (d) AlCl3
34. Which of the statements are correct?

(a) – NH2 is ortho-para directing group (b) – CHO is meta directing group
(c) : CCl2 is an electrophile (d) OH is (–M) group
35. – CX3 group is associated with

(a) m-directing (b) increasing acidic
(c) ring deactivation (d) increasse of stability of carbocation
MATRIX MATCH TYPE QUESTIONS

36. Column - I Column - II
A. Singlet carbene (p) Diamagnetic
B. Triplet carbene (q) Paramagnetic
C. Free radical (r) Formed by homolytic fission
D. Carbocation (s) Formed by heterolytic fission.
+ - 
A. (CH3)2C N N (p) Free radical is formed
C
O
B.  (q) N2 will be liberated
C. 
R  N  N  R   (r) Carbene will formed
+
N NCl
D. H3PO2 (s) Nucleophilic aromatic substitution reaction.
COMPREHENSION TYPE QUESTIONS

Comprehension I1
Conformation are structures obtained by rotation around  bonds without breaking and remarking the bonds.
Ethane has staggered and eclipsed conformations. Staggered conformation is more stable than eclipsed
conformation.
38. The total number of possible conformation of ethane are

(a) 2 (b) 3 (c) infinite (d) zero
39. Which conformation of cyclohexane is most stable?

(a) Chair (b) Boat (c) Half-chair (d) Half boat
40. Which of the following is correct?

(a) Conformations cannot be isolated due to less difference in their energy
(b) Conformations can be isolated
(c) Conformations are obtained by breaking and remarking the bonds
(d) Conformations are same as configurational isomers
Comprehension II
Those compounds which rotate plane polarised light are optically active compounds. They must be chiral, i.e.,
should not have any plane of symmetry. They should have chiral carbon atom. Meso compounds have
internal plane of symmetry.
41. Which of the following alkane shows optical isomerism?

(a) 2-methyl pentane (b) 3-methyl pentane
(c) 2,3-dimethyl pentane (d) Both (b) and (c)
42. Which of the following are enantiomer?

(a) d-glucose and l-glucose (b) D-glucose and L-glucose
(c) Racemic-tartaric acid (d) Meso-tartaric acid
43. Which of the following is meso compound?
COOH COOH CHO

CHO
H OH H OH H OH
(a) HO H (b) H OH (c) HO H (d) H OH
CH 2OH
COOH COOH CHO



1. The most unlikely representation of resonance structure of p-nitrophenoxide ion is [IIT 1999]
O O O O O O O O
N N N N
(a) (b) (c) (d)
O O O O
2. Number of -electrons in cyclobutadienyl anion (C4H4)2– is [IIT 1991]

(a) 2 (b) 4 (c) 6 (d) 8
3. The correct stability order for the following species is [IIT 2008]
O O
(I) (II) (III) (IV)
(a) (II) > (IV) > (I) > (III) (b) (I) > (II) > (III) > (IV)
(c) (II) > (I) > (IV) > (III) (d) (I) > (III) > (II) > (IV)
4. Among the following compounds, the most acidic is [IIT 2011]

(a) p-nitrophenol (b) p-hydroxybenzoic acid
(c) o-hydroxybenzoic acid (d) p-toluic acid
5. Which of the following compounds does not show Lassaigne’s test for nitrogen? [DCE-2000]
(a) Urea (b) Hydrazine (c) Phenylhydrazine (d) Azobenzene
6. How many structural isomers are there of C4H10O that are ethers? [DCE-1994]
(a) 1 (b) 3 (c) 2 (d) 4
7. The most stable carbanion among the following is [DCE-2000]
CH2 CH2¯ CH2¯ CH2¯ CH2¯
(a) (b) (c) (d)
OCH3 NO2
8. In a compound of C, H and N atoms are present in 9 : 1 : 3.5 by weight. If molecular weight of
the compound is 108, then molecular formula of the compound is [AIEEE-2002]
(a) C2 H6 N 2 (b) C 3 H 4 N (c) C6 H8 N 2 (d) C 9 H 12 N 3
9. Rate of the reaction 
is fastest when Z is [AIEEE-2004]

(a) OC 2 H 5 (b) NH 2 (c) Cl (d) OCOCH3
10. Due to the presence of an unpaired electron, free radicals are : [AIEEE-2005]
(a) Chemically reactive (b) Chemically inactive (c) Anions (d) Cations
11. The decreasing order of nucleophilicity among the nucleophiles [AIEEE-2005]
(i) CH 3C – O – (ii) CH 3 O –
|| O
||
O S – O–
(iii) CN – (iv) H3 C
|
O
(a) (i), (ii), (iii), (iv) (b) (iv), (iii), (ii), (i) (c) (ii), (iii), (i), (iv) (d) (iii), (ii), (i), (iv)
12. The correct order of increasing acid strength of the compounds [AIEEE-2006]
Me
(i) CH 3 CO 2 H (ii) MeOCH2 CO 2 H (iii) CF 3 CO2 H (iv) CO2 H
Me
(a) (i) < (iv) < (iii) < (ii) (b) (ii) < (iv) < (i) < (iii)
(c) (iv) < (i) < (iii) < (ii) (d) (iv) <(i) < (ii) < (iii)
13. Among the following mixtures, dipole-dipole as the major interaction, is present in [AIEEE-2006]
(a) benzene and carbon tetrachloride (b) benzene and ethanol
(c) acetonitrile and acetone (d) KCl and water
14. The increasing order of stability of the following free radicals is [AIEEE-2006]
   
(a) (CH3)2 CH < (CH3)3 C < (C6H5)3 C < (C6H5)2 CH
   
(b) (CH3)2 CH < (CH3)3 C < (C6H5)2 CH < (C6H5)3 C
   
(c) (C6H5)3 C < (C6H5)2 CH < (CH3)3 C < (CH3)2 CH
   
(d) (C6H5)2 CH < (C6H5)3 CH < (CH3)3 C < (CH3)2 CH
15. CH3Br + Nu–  CH3 – Nu + Br–

The decreasing order of the rate of the above reaction with nucleophiles (Nu–) A to D is
[Nu– = (A) PhO–, (B) AcO–, (C) HO–, (D) CH3O–] [AIEEE-2006]
(a) B > D > C > A (b) D > C > A > B
(c) D > C > B > A (d) A > B > C > D
16. Arrange the carbanions, (CH 3 )3 C,CCl3 , (CH 3 ) 2 CH, C6 H 5 CH 2 , in order of their
decreasing stability [AIEEE-2009]
(a) (CH 3 ) 2 CH  CCl3  C6 H 5CH 2  (CH3 )3 C (b) CCl3  C6 H5 CH 2  (CH 3 ) 2 CH  (CH 3 )3 C
(c) (CH 3 )3 C  (CH 3 ) 2 CH  C6 H5 CH 2  CCl3 (d) C 6 H 5 CH 2  CCl3  (CH 3 ) 3 C  (CH 3 ) 2 CH

17. 29.5 mg of an organic compound containing nitrogen was digested according to Kjeldahl’s method
and the evolved ammonia was absorbed in 20 mL of 0.1 M HCl solution. The excess of the acid
required 15 mL of 0.1 M NaOH solution for complete neutralization. The percentage of nitrogen
in the compound is [AIEEE-2010]
(a) 23.7 (b) 29.5 (c) 59.0 (d) 47.4
18. The strongest acid amongst the following compound is: [AIEEE-2011]
(a) CH3 COOH (b) HCOOH
(c) CH3 CH2CH(Cl)CO2 H (d) ClCH2 CH2CH2 COOH
19. Arrange the follwoing compounds in order of decreasing acidity: [JEE-Mains 2013]
OH OH OH OH
Cl CH3 NO2 OCH3

(I) (II) (III) (IV)
(a) III > I > II > IV (b) IV > III > I > II (c) II > IV > I > III (d) I > II > III > IV
20. The order of stability of the following carbocations:

+
CH2
+ +
H2C CH CH2 H3C CH2 CH2 is [JEE-Mains 2013]
(I) (II) (III)
(a) I > II > III (b) III > I > II (c) III > II > I (d) II > III > I
21. The reaction of propene with HOCl (Cl2 + H2O) proceeds through the intermediate:
[JEE Mains 2016]
(a) CH3  CHCl  CH 2 (b) CH3  CH   CH 2  OH
(c) CH3  CH   CH 2  Cl (d) CH3  CH(OH)  CH 2
22. The absolute configuration of [JEE Mains 2016]

CO2 H
H OH
H Cl
CH3
(a) (2R, 3R) (b) (2R, 3S) (c) (2S, 3R) (d) (2S, 3S)
23. Which of the following compounds will form significant amount of meta product during mono-nitration
reaction ? [JEE Mains 2017]
(a) (b) (c) (d)

24. Which of the following, upon treatment with tert-BuONa followed by addition of bromine water, fails
to decolourize the colour of bromine ? [JEE Mains 2017]
(a) (b) (c) (d)
25. 3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an addition product. The
number of possible stereoisomers for the product is [JEE Mains 2017]
(a) Six (b) Zero (c) Two (d) Four
26. Which of the following molecules is least resonance stabilized ? [JEE Mains 2017]
(a) (b) (c) (d)
27. Among the following, the number of aromatic compound(s) is [JEE Advanced 2017]
28. The increasing order of basicity of the following compounds is: [JEE Mains 2018]
(a) NH2 (b) NH
NH2
(c) (d) NHCH3
NH
(1) (d) < (b) < (a) < (c) (2) (a) < (b) < (c) < (d)
(3) (b) < (a) < (c) < (d) (4) (b) < (a) < (d) < (c)
29. For the given compound X, the total number of optically active stereoisomers
is ____. [JEE Advanced 2018]
HO
HO This type of bond indicates that the configuration at the specific carbon
and the geometry of the double bond is fixed
This type of bond indicates that the configuration at the specific carbon
HO and the geometry of the double bond is NOT fixed
HO

30. The correct decreasing order for acid strength is: [JEE Mains 2019]
(a) NO2CH2COOH > NCCH2COOH > FCH2COOH > ClCH2COOH
(b) FCH2COOH > NCCH2COOH > NO2CH2COOH > ClCH2COOH
(c) NO2CH2COOH > FCH2COOH > CNCH2COOH > ClCH2COOH
(d) CNCH2COOH > O2NCH2COOH > FCH2COOH > ClCH2COOH
31. Arrange the following amines in the decreasing order of basicity [JEE Mains 2019]
N N N
H H
(I) (II) (III)
(a) I > II > III (b) III > II > I (c) I > III > II (d) III > I > II
32. The correct match between Item I and Item II is: [JEE Mains 2019]
Item I Item II
(A) Benzaldehyde (P) Mobile phase
(B)Alumina (Q) Adsorbent
(C)Acetonitrile (R) Adsorbate
(a) (A)  (Q); (B)  (R); (C)  (P) (b) (A)  (P); (B)  (R); (C)  (Q)
(c) (A)  (Q); (B)  (P); (C)  (R) (d) (A)  (R); (B)  (Q); (C)  (P)
33. Which of the following compounds is not aromatic? [JEE Mains 2019]
(a) (b) (c) (d) N

N H
34. If dichloromethane (DCM) and water (H2O) are used for differential extraction, which one of the
following statements is correct? [JEE Mains 2019]
(a) DCM and H2O would stay as lower and upper layer respectively in the S.F.
(b) DCM and H2O will be miscible clearly
(c) DCM and H2O would stay as upper and lower layer respectively in the separating funnel (S.F.)
(d) DCM and H2O will make trubid/colloidal mixture.
35. What is the IUPAC name of the following compound? [JEE Mains 2019]
H3 C CH3
H
H Br
H 3C
(a) 3-Bromo-1, 2-dimethylbut-1-enol

(b) 4-Bromo-3-methylpent-2-ene
(c) 2-Bromo-3-methylpent-3-ene
(d) 3-Bromo-3-methyl-1, 2-dimethylprop-1-ene

36. Which compound(s) out of the following is/are not aromatic? [JEE Mains 2019]
(A) (B) (C) (D)
(a) (C) and (D) (b) (B), (C) and (D) (c) (A) and (C) (d) (B)
37. Choose the correct option(s) that give(s) an aromatic compound as the major
product [JEE Advanced 2019]
Br
NaOMe
(a) NaO Et
  (b) 
UV , 5 00 K
i) alc. KOH
H3 C
 Cl2 (excess)   Br  ii) NaNH 2

(c) (d) iii) red hot iron tube, 873K
Br
38. The increasing order of pKb for the following compounds will be: [JEE Mains 2020]
H2N N NH
NH
(A)
(B)
H3C NH
CH3
(C)
(a) (A) < (B) < (C) (b) (C) < (A) < (B) (c) (B) < (A) < (C) (d) (B) < (C) < (A)
39. Which of the following has the shortest C-Cl bond? [JEE Mains 2020]
(a) Cl – CH = CH – OCH3 (b) Cl – CH = CH – CH3
(c) Cl – CH = CH2 (d) Cl – CH = CH – NO2
40. The decreasing order of basicity of the following amines is : [JEE Mains 2020]
NH2
N NH2
N
H
(II) (III) (IV)
(I)
(a) (I) > (III) > (IV) > (II) (b) (III) > (I) > (II) > (IV)
(c) (III) > (II) > (I) > (IV) (d) (II) > (III) > (IV) > (I)

41. For the following reactions : [JEE Mains 2020]

CH3 CH 2CH 2Z + Br
CH3CH=CH 2 + HZ + Br
where
CH3
kc
ka and ke, are , respectively, the rate constants for the substitution and elimination, and  
ke
correct options is -
(a) B > A and ke(B) > ke(A) (b) B > A and ke(A) > ke(B)
(c) A > B and ke(B) > ke(A) (d) A > A and ke(A) > ke(B)
42. The correct order of stability for the following alkoxides is : [JEE Mains 2020]
– –
O O O –
O2N
NO2 NO2
(A) (B) (C)
(a) (C) > (B) > (A) (b) (C) > (A) > (B) (c) (B) > (C) > (A) (d) (B) > (A) > (C)
43. An inorganic Compound ‘X’ on treatment with concentrated H2SO4 produces brown fumes and
gives dark brown ring with FeSO4 in presence of concentrated H2SO4. Also Compound ‘X’ gives
precipitate ‘Y’, when its solution in dilute HCl is treated with H2S gas. The precipitate ‘Y’ on
treatment with concentrated HNO3 followed by excess of NH4OH further gives deep blue coloured
solution, Compound ‘X’ is: [JEE Mains 2020]
(a) Co(NO3) 2 (b) Pb(NO2) 2 (c) Cu(NO3 )2 (d) Pb(NO3) 2
44. [JEE Mains 2021]
Among the given species the Resonance stabilised carbocations are:

(a) (C) and (D) only (b) (A), (B) and (D) only
(c) (A) and (B) only (d) (A), (B) and (C) only
45. In Carius method, halogen containing organic compound is heated with fuming nitric acid in the
presence of : [JEE Mains 2021]
(a) HNO3 (b) AgNO3 (c) CuSO4 (d) BaSO4
46. When 0.15 g of an organic compound was analyzed using Carius method for estimation of bromine,
0.2397 g of AgBr was obtained. The percentage of bromine in the organic compound is _______.
(Nearest integer)
[Atomic mass : Silver = 108, Bromine = 80] [JEE Mains 2022]
47. Which purification technique is used for high boiling organic liquid compound (decomposes near its
boiling point)? [JEE Mains 2022]
(1) Simple distillation (2) Steam distillation
(3) Fractional distillation (4) Reduced pressure distillation
48. Which of the following compounds does not exhibit resonance? [JEE Mains 2022]
(1) CH3CH2OCH = CH2 (2)
(3) CH3CH2CH2CONH2 (4) CH3CH2CH = CHCH2NH2

49. Which of the following molecules does not show stereo isomerism ? [JEE Mains 2022]
(1) 3,4-Dimethylhex-3-ene (2) 3-Methylhex-1-ene
(3) 3-Ethylhex-3-ene (4) 4-Methylhex-1-ene
50. The number of acyclic structural isomers (including geometrical isomers) for pentene
are ____ [JEE Mains 2022]
51.
Consider the above chemical reaction. The total number of stereoisomers possible for Product ‘P’ is
__________. [JEE Mains 2022]
52. 0.8 g of an organic compound was analysed by Kjeldahl’s method for the estimation of nitrogen. If
the percentage of nitrogen in the compound was found to be 42%, then __________ mL of 1 M
H2SO4 would have been neutralized by the ammonia evolved during the analysis.[JEE Mains 2022]
53. Choose the correct name for compound given below : [JEE Mains 2022]
(1) (4E)-5-Bromo-hex-4-en-2-yne (2) (2E)-2-Bromo-hex-4-yn-2-ene

(3) (2E)-2-Bromo-hex-2-en-4-yne (4) (4E)-5-Bromo-hex-2-en-4-yne
54. Given below are two statements : one is labelled as Assertion (A) and the other is labelled as
Reason (R) : [JEE Mains 2022]
Assertion (A) : A simple distillation can be used to separate a mixture of propanol andpropanone.
Reason (R) : Two liquids with a difference of more than 20°C in their boiling points can be separated
by simple distillations.
In the light of the above statements, choose the most appropriate answer from the options given
below :
(1) (A) is false but (R) is true.
(2) Both (A) and (R) are correct but (R) is not the correct explanation of (A)
(3) (A) is true but (R) is false
(4) Both (A) and (R) are correct and (R) is the correct explanation of (A)
55. The major component/ingredient of Portland Cement is : [JEE Mains 2022]
(1) tricalcium aluminate (2) tricalcium silicate
(3) dicalcium aluminate (4) dicalcium silicate
56. Monomer of Novolac is : [JEE Mains 2022]
(1) 3-Hydroxybutanoic acid (2) phenol and melamine
(3) o-Hydroxymethylphenol (4) 1,3-Butadiene and styrene

CHAPTER TEST
SECTION - I: MULTIPLE CHOICE QUESTIONS (Single Correct)
1. Which of the following is aromatic

H
(a) (b) (c) (d) H
2. In the identification of phosphorus, the phosphorus in the organic compound is converted to PO43–
using
(a) NaOH (b) Na 2O (c) Na 2O2 (d) NaO2
3. The acidic strength of chloro substituted benzoic acid is

(a) Benzoic acid > o-chloro > m-chloro > p-chloro
(b) o-chloro > m-chloro > p-chloro > benzoic acid
(c) m-chloro > o-chloro > p-chloro > benzoic acid
(d) none of these
4. The Lassaigne’s extract is boiled with dil.HNO3 before testing for halogens such that
(a) AgX is soluble in HNO3 (b) Na2S and NaCN are decomposed by HNO3
(c) Ag2S is soluble in HNO3 (d) AgCN is soluble in HNO3
5. Which one among the following geminal dihydroxy compound is most stable?
OH
(a) CH3 – CH (b) CH3 – C(OH)2 – CH3
OH
CH (OH) 2
(c) CCl3 – CH(OH)2 (d)
SECTION - II: MULTIPLE CHOICE QUESTIONS (More than one correct)
6. Which of the following are electrophiles?
+
(a) BF3 (b) 2CCl2 (c) NH4 (d) I–
7. Br has low reactivity in CH2 = CH – Br because:

(a) The C – Br bond has a partial double bond character
(b) Of the + M effect bromine
(c) Br is electronegative
(d) None of the above
8. Find out structures which can form stabilized enol structure:
O O O
O
CH3
(a) (b) (c) H3C O (d)
H3C
O Ph
9. Tautomerism is exhibited by:

OH
NH
O NH
(a) (b) (c) (d)

O
NH
10. Which of the following compounds would exhibit aromatic properties?

N O
(a) B (b) N (c) N (d) N
H H H H
SECTION - III: INTEGER TYPE QUESTIONS
11. Degree of unsaturation in C5H5N.
12. The total number of cyclic isomers possible for the hydrocarbon with molecular formula C4H6 is
13. Total number of alkyl groups having the molecular formula C4H9 are
14. Amongst the following the total number of electrophiles is

CN–, H+, NO2+, Cl+, OH–, H3O+, :CH2, :NH3, Na+
15. Amongst the following the total number of nucleophiles is

SO3, NH2–, R–, H2O, OR–, ROH, AlCl3, H–, BF3
16. How many of following cannot show tautomerism? acetophenone, acetaldehyde, cyclohexanone,
acetylacetone, benzoquinone, acetone, benzaldehyde, butanone, ethyl acetoacetate.
17. How many of the following are heterocyclic aromatic compounds?
18. The total number of contributing structures showing hyperconjugation (involving C – H bonds) for
the following carbocation is.
H3C CH2CH3
SECTION - IV: MATRIX MATCH

+
(A) H3C CH2 (p) Resonance
(B) H3C CH2 (q) Hyperconjugation
Cl + Cl
C
(C) (r) + I effect
Cl
H
-
(D) O (s) – I effect
O
(a) (A) – (q), (r); (B) – (q), (r);(C) – (p), (s), (D) – (p), (s)
(b) (A) – (p), (B) – (q) (C) – (s), (D) – (q), (r)
(c) (A) – (q); (B) – (p), (C) – (r), (D) – (p), (r)
(d) (A) – (r); (B) – (s); (C) – (p), (D) – (q)
SECTION - V: COMPREHENSION TYPE QUESTIONS
Comprehension-II
Hyperconjugation describes the orbital interaction between -system and the adjacent  bond of the substituent
group in organic compounds. Thus, the sufficient condition for the hyperconjugation are:
i) The presence of at least one sp2-hybrid carbon as in alkenes, carbocation and alkyl free radical.
ii) The presence of a-carbon, with at least one hydrogen, with respect to sp2-carbon atom.
More the number of hydrogen atoms attached on the -carbon(s) of the sp2-hybrid carbon, more will the
hyperconjugative, also called resonating structures of the compound.
Number of resonating structures due to hyperconjugation = n + 1 where n is the number of -hydrogen.
20. Which of the following has highest number of hyperconjugative structures?
(a) 2-methylbut-2-ene (b) But-2-ene
(c) tert-Butyl cation (d) Hex-2-ene
21. Which of the following does not show hyperconjugation?

+
CH2
+
CH2
H3C CH
(a) (b) H3C CH2 (c) (d)
CH2
22. Hyperconjugation is possible in

H3C
+ H3C C CH
(a) CH3 (b) H5C6 CH3 (c) HC CH (d)
H3C CH2
ANSWERS
CHAPTER ASSIGNMENT
MULTIPLE CHOICE QUESTIONS (Single Correct )
1. (b) 2. (c) 3. (d) 4. (b) 5. (b)

6. (b) 7. (c) 8. (c) 9. (c) 10. (b)
11. (b) 12. (b) 13. (d) 14. (b) 15. (a)
16. (6) 17. (4) 18. (2) 19. (3) 20. (3)
21. (4) 22. (4) 23. (4) 24. (4) 25. (5)
MULTIPLE CHOICE QUESTIONS (More than one Correct )
26. (a,b,c) 27. (c) 28. (d) 29. (a,b,c,d) 30. (a,b,d)
31. (a,b,c) 32. (a,b,c) 33. (b,c,d) 34. (a,b) 35. (a,b,c)
36. A-(q); B-(p); C-(p),(r); D-(p), (s)
37. A-(q),(r); B-(r); C-(p), (q); D-(q), (s)
38. (c) 39. (a) 40. (a) 41. (c) 42. (a)
43. (b)
1. (c) 2. (c) 3. (d) 4. (c) 5. (b)

6. (b) 7. (d) 8. (c) 9. (c) 10. (a)
11. (c) 12. (d) 13. (c) 14. (b) 15. (b)
16. (b) 17. (a) 18. (c) 19. (a) 20. (b)
21. (c) 22. (c) 23. (c) 24. (a) 25. (d)
26. (d) 27. (5) 28. (4) 29. (7) 30. (a)
31. (d) 32. (d) 33. (c) 34. (c) 35. (b)
36. (b) 37. (b), (d) 38. (c) 39. (d) 40. (c)
41. (c) 42. (a) 43. (c) 44. (c) 45. (b)
46. (68) 47. (4) 48. (4) 49. (3) 50. (6)
51. (2) 52. (12) 53. (3) 54. (4) 55. (2)
56. (3)
CHAPTER TEST
1. (c) 2. (c) 3. (b) 4. (b) 5. (c)

6. (a, b) 7. (a, b) 8. (a, c) 9. (a, c, d) 10. (a, b, c)
11. (4) 12. (5) 13. (4) 14. (3) 15. (6)
16. (2) 17. (0) 18. (6) 19. (a) 20. (c)
21. (a) 22. (b)
HINTS AND SOLUTIONS

sp2 sp sp2
N
H3C sp2
1. (b) CH3 2. (c) 3. (d) H2C CH
sp3 sp3
4. (b) –C is in sp2 hybridisation
5. (b) CH3 – is an ERG and hence increase the electron density at sp2 carbon.
6. (b) Follow the rule of resonance.
7. (c) Here the violation of octate rule hence no resonance.
8. (d) Both ends of glucose molecule is unlike.
9. (c) N has 10 valence electrons that the violation octate rule.
10. (b) B has incomplete octate.
11. (b) Carbocation is resonance stabilized.
12. (b) Unlike group are present on both carbon atom.
13. (d) Postive charge lies on electropositive element and negative on electronegative element.
14. (b) D - negative charge on nitrogen due to resonance.

C - nitrogen is in sp hybridisation
B - nitrogen is in sp2 hybridisation
M - nitrogen is in sp3 hybridisaion
15. (a) B is aromatic A is anti-aromatic.

16. (6) Central atom by calculation has sp3 hybridization.
O O
N
Cl
H Cl H
O C O, , H ,
H
17. (4) Cl H H
Cl
N
O O
H
O O
N H
O O O
18. (2)
H3C CH3
NH2
19. (3) –O– –SiR3, –COO–
20. (3) Nitrogen is at carbon head hence the lone pair cannot conjugate with double bond.
N O
+
CH2
21. (4) , , ,
-
S S , , , H2C C N
22. (4)
O
O
O O O
23. (4) H C CH3

3 CH3 , H3 C NH2 , , H3 C OH
24. (4) Crbocation a strong tendency to rearrange itself.

25. (5) 18 – 8 / 2 = 5
26. (a,b,c) In resonance only there is dislocation of electron not nucleus.
27. (a,b,c) Both nitrogen are in sp2 hybridisation.
28. (a,b,c) Followed the rules of resonance.
29. (a,b,c,d) Factual
30. (a,b,d) tert-butyl carbon carbanion is in sp3 hybridisation in others it is in sp2 hybridisation.
31. (a,b,c) Factual
32. (a,b,c) In AlCl3 Al has incomplete octate.
33. (b,c,d) (b), (c), (d) has incomplete octate and hence electron deficiency.
34. (a,b) In –OH lone pair on oxygen is in conjugation with benzene ring and hence ortho-para
directive.
35. (a,b,c) – CX3 is EWG hence it will destabilized the carbocation.

36. A-(q); B-(p); C-(p),(r); D-(p), (s)
(A) Singlet has the pair of electron positive one orbital.
(B) Triplet has two electron which are unpaired.
(C) Free radicals have one unpaired electron and formed by the homolytic fission.
(D) Carbocation have paired electrons formed by heterolytic fission.
37. A-(q),(r); B-(r); C-(p), (q); D-(q), (s)
(A) Carbenes are electron deficient species formed by the decomposition of diazonium ion and N2
will be liberate.
(B) On heating homolytic cleavage is possible.
(C) On heating of N – N bond homolytic cleavage is possible and formed free radicals.
(D) Aromatic diazonium ions gives nucleophilic aromatic substitution reaction.

Chapter - 3
HYDROCARBONS
ALKANES
Introduction
Alkanes (Paraffin): The compounds of carbon and hydrogen with the general formula CnH2n+2 are called
alkanes. These are also known as saturated hydrocarbons or Paraffins.
Structure and Reactivity: The simplest member of this family is methane (CH4) where the C-atom is sp3
hybridized, which overlaps with the s-orbitals of H-atoms at the corner of regular tetrahedron. This structure
is verified by electron diffraction method. The next higher member in the family is ethane (C2H5) here again
each C-atom is sp3-hybridized with a dihedral angle of approximately 109.5º.
H H H
C
H
1.53 Aº
109.5°
Aº C
1.10 Aº C
H H 1.10
H H H
H
109.5º
If one considers a molecule of methane or ethane or any other alkane, we find that all these molecules are
nonpolar and hence the interactive forces operative are van der waal’s forces. Within the family one with
large surface area of molecule would have stronger intermolecular forces.
Table: Melting and Boiling of Alkanes
Name Formula M.pt ºC B.pt ºC
Methane CH4 –183 –162
Ethane CH3CH3 –172 –88.5
Propane CH3CH2CH3 –187 –42
n-Butane CH3CH2CH2CH3 –138 0
n-Pentane CH3–CH2–CH2–CH2–CH3 –130 36
n-Hexane CH3–CH2–CH2–CH2–CH2–CH3 –95 69
n-Heptane CH3–CH2–CH2–CH2–CH2–CH2–CH3 –90 98
Hydrocarbons AICE (IIT-JEE)
However if branching of alkyl chain takes place, its surface area decreases and the molecular forces of
attraction decrease.
e.g., n-Butane B.Pt = 0ºC  CH3–CH2–CH2–CH3 Large Surface area
Isobutane B.Pt = –12ºC  CH3 – CH – CH3 Smaller surface area

CH3
This shows as branching takes place the molecular force of attraction decreases and the boiling point decreases.
Except for very small alkanes, the boiling point rises by 20 to 30ºC for each carbon atom that is added to the
chain. Being saturated hydrocarbons they are least reactive and most of the reactions correspond to the
C-H bond cleavage which are very strong bonds.
Physical Properties
1. The first four members are colourless gases. The next thirteen members (C5 to C17) are colourless
liquids and the higher ones are colourless solids.
2. The boiling points of the straight chain alkanes increases regularly with increase in molecular mass.
On the average boiling point increases by 20-30 K, for the addition of each carbon atom
(i.e., –CH2 group) exept for very small alkanes. Among the isomeric alkanes the boiling point of
straight chain isomer is greater than branched chain isomers
H H H H H
e.g. n-pentane H–C–C–C–C–C–H B.pt. 309 K
H H H H H
CH3
isopentane CH – CH2 – CH3 B.pt. 301 K
CH3
CH3
Neopentane CH3 – C – CH3 B.pt. 282.5 K
CH3
Thus, boiling point order is n-pentane > isopentane > neo-pentane.
However, melting point order is Neopentane > Isopentane > n-pentane.
This is because as branching takes place the molecule assumes a spherical form that leads to a much
more closed packing.
3. The melting points of the alkanes do not show a regular trend. In general alkanes with even number
of carbon atoms have a higher melting point as compared to the next alkane with odd number of C-
atoms. This is called alteration effect or oscillation effect. Which is due to compact backing of
molecules of even carbon atom numbered alkanes.
4. Alkanes are non-polar and hence are soluble in non-polar solvents but insoluble in solvents
such as water.
3.1 Preparations
A. REDUCTION METHODS
1. Hydrogenation of Alkenes and Alkynes :
When unsaturated hydrocarbons are catalytically hydrogenated alkanes are obtained.

Ni
CH2 = CH2 + H2 
300°C
 CH3 – CH3
Ni
CH  CH + 2H2 
200 300°C
 CH3 – CH3.
In the above reactions, Raney nickel is often used as an effective catalyst. It is obtained by
adding Ni-Al along to NaOH solution, when Aluminium dissolves leaving nickel in finely
divided state with nacent hydrogen adsorbed at its surface. It is then filtered and stored in
absolute alcohol. When palladium or platinum is used the reactions can be carried even at
room temperature.
2. Reduction of Alkyl Halides

Zn  Cu
(a) R – X 
C 2 H5OH, 
 R – H.
Mechanism
Zn – Zn2+ + 2e–
. .
R – X – R + X ,
. – . –
R + e– – R , X + e– – X
– –
R + H – OC2H5 – R – H + C2H5O
Zn/HCl
(b) R – X  R – H.
Zn/CH3COOH
(c) R – X 
R–H
Zn/NaOH
(d) R – X  R–H
[Mechanisms for the reaction (b), (c) and (d) are the same as that of (a)]
LiAlH4
(e) R – X R–H

Note: [p and s- alkyl halides give alkanes but t- gives alkenes]
Mechanism
–
LiAlH4 – Li+ + Al3+ + 4H
– –
4R – X + 4H – 4R – H + 4X
–
Li+ + X – Li X
–
Al3+ + 3X – AlX3
NaBH 4
(f) R – X 
C2 H5 OH
 R–H
Note: [Here s- and t- are converted to alkanes but not p-]
Ph 3SnH
(g) R – X  Δ
R–H
[All types of alkyl halides undergo this reaction.]

HI/Red P
R – X 
150 C
 R–H
3. Reduction of Alcohols
Red P
(a) R – OH + HI 
150 C
R – H
Red P
CH3CH2 – OH + 2HI 
150 C
 CH3 – CH3 + I2 + H2O
(b) R – OH + LiAlH4 
Δ
 R – H + side products
LiAlH 4
CH3 CH2 CH – CH3 
Δ
 CH3CH2CH2CH3
OH
B. DECARBOXYLATION METHODS
1. Soda Lime Decarboxylation

CaO
RCOONa + NaOH 630 K R – H + Na2CO3
CaO
CH3COONa + NaOH 630 K CH4 + Na2CO3
2. Kolbe’s Electrolytic Decarboxylation
The electrolysis of aqueous salt solutions of carboxylic acids give alkane at anode.
Electrolysis
2RCOONa + 2H2O R – R + 2NaOH + 2CO2 + H2
Electrolysis
2CH3COONa (aq) CH3 – CH3 + 2NaOH + 2CO2 + H2
Mechanism
R – C – ONa — RCOO– + Na+

O
H2O — H + OH–
Reaction at cathode
Na+ + e– — Na (Not possible)

1
H+ + e– — H (Possible)
2 2
(Because the discharge potential of H+ is less than the discharge potential of Na+)
Reaction at anode
4OH– — 2H2O + O2 + 4e– (Not possible)
Side Reaction
.. –
–
. . .
. .: — R – C – O R–C–O–R
2R – C – O . .: + 2e R + RCOO
O O O
(Because discharge potential of RCOO– < OH–)
. . .
2 R – C – O — R + 2CO2 CH3CH2 CH2 = CH2 + H
O
. .
CH3CH2 + H CH3 – CH3
. .
R +R — R – R Here ROH is side product: Also proper conjugation
.
effects of R leads to the formation of alkene as
side products.
Limitations:
1. Methane cannot be perpared by this method.
2. Only symmetrical alkanes can be prepared by this method.
C. THROUGH FORMATION OF ORGANOMETALLIC COMPOUNDS
1. Wurtz reaction: When alkyl halides are reacted with Na in the presence ether we get
alkane.
Dry
2R – X + 2Na ether R – R + 2NaX
Dry
2CH3Cl + Na ether
CH3CH3 + NaCl
Other metals in a finely divided state may also be used in place of Na, e.g., Cu or Ag.
Limitations
1. Methane cannot be prepared.
2. This reactions is not suitable for preparing unsymmetrical alkanes, e.g., propane or
pentane, etc.
1. Mechanism
Ionic
. .
R–X R +X
Na Na+ + e–
. –
R + e– R
. –
X + e– X
–
R + Na RNa (organometallic compound)
–
X + Na NaX
RNa + R – X R – R + NaX
Note: Side Products are also formed due to elimination reaction on R–X by RNa
giving a mixture of alkene and alkane.
Free radical Mechanism

. .
R–X R +X
Na Na + e–
. –
X + e– X
. .
R +R R–R + other side products
The side products e.g., alkene is also formed due to disportionation of free radical
C2 H5  C2 H5 
 C2 H 6  C2 H 4
2. From Grignard’s Reagent: When Grignard’s reagent is made to react with any
compound containing active hydrogen, i.e., H-atom attached to highly electronegative
atom like O, N or F will give alkane corresponding the alkyl part of Grignard’s Reagent.
RMg X + H – OH R – H + MgX (OH)
R Mg X + H – OR R – H + MgX (OR)
R Mg X + H – NH2 R – H + MgX (NH2)
R Mg X + H – NHR R – H + MgX (NHR)
RMgX  H  O  C  R  
 R  H  MgX  O  C  R  
||  || 
O  O 
3. Frankland Reaction
2RX  Zn 
 R  R  ZnX 2
RX  Zn 
 RZnX
The alkyl zinc halide or dialkyl zinc may be isolated and made to react with different
alkyl halide or same alkyl halide.
RZnX  R X 
 R  R   ZnX 2
(Unsymmetrical alkane)
e.g., CH3 ZnCl  CH3 CH 2 Cl 

 CH3CH2 CH3  ZnCl2
RZnX  R  X 
 R  R  ZnX 2
(symmetrical alkane)
e.g., CH3 ZnCl  CH3 Cl 

 CH 3CH 3  ZnCl2
Hence Frankland reaction is useful for preparing both hydrocarbons containing odd number
of C atoms as well as even number carbon atom. i.e. for preparing symmetrical as well as
unsymmetrical alkanes.
4. Corey House Synthesis
This reaction is very much useful in the preparations of unsymmetrical alkane.

ether
R 2 CuLi  R   X   R  R   RCu  LiX .
(unsymmetrical)
ether
R 2 CuLi  R  X   R  R  RCu  LiX .
(symmetrical)
2Li
CH3CH2 – Br Dry ether
CH3CH2Li + LiBr.
2CH3CH2Li + CuI (CH3CH2)2CuLi + LiI

CH3 – Cl
(CH3CH2)2CuLi CH3CH2– CH3 + CH3CH2Cu + LiCl.
CH3CH2 – Cl
(CH3CH2)2CuLi CH3CH2– CH2CH3 + CH3CH2Cu + LiCl.
D. SOME SPECIAL METHODS
1. From Carbides:
Al 4 C3  12H 2 O 
 4Al(OH)3  3CH 4
(steam)
Be2 C  4H 2 O 
 2Be(OH)2  CH 4
2. From carbon monoxide:
Ni
CO  3H2 
300
 CH 4  H2 O
3. From CS2 and H2S :
hν
CS2  2H 2S  Cu   CH 4  4Cu 2S
4. Berthlot’s reaction :
1200 C
C  2H 2 
electric spark
 CH 4
3.2 Chemical Properties

The alkanes are referred to as paraffins and the reactivity depends upon the choice of reagents.
Alkanes are inert towards hydrochloric acid and sulfuric acid but they react with acids like HFSbF5
and FSO3 H–SbF5 (Magic acid) to form the corresponding fluoro compounds.
Much of the chemistry of alkanes involves free-radical chain reactions which takes place under
vigorous conditions and usually yield mixtures of products.
The reactions of alkanes can be classified under the following headings.

(A) Substitution reactions
(B) Combustion reactions
(C) Special reactions
Substitution Reactions
1. Halogenation
| |
250  400 C
 C  H  X 2 
or light
  C  X  HX
| |
U.V.
CH 4  X 2   CH 3  X  HX
(excess)
UV X2 X2 X2
CH 4  X 2  CH 3  X 
UV
CH 2 X 2 
UV
CHX 3 
UV
CX 4
(excess)
diffused
CH3  CH 3  Cl 2 
sunlight
CH 3CH 2  Cl  HCl
(excess) (1 mol)
Mono halogenation of propane and Butane
H3C 45%
hν Cl
H3C  Cl2  
(1 mol) H3C
CH3
CH3 55%
Cl
H3C 28%
h
Cl
H3C  Cl2
(1 mol)
h
CH3
H3C 72%
CH3
Cl
H3C
CH3 (96.5%)
h
H3C Br
 Br2 h
(1 mol)
CH3 H3C
Br (3.5%)
Hence, these reactions show that the reaction depends upon the abstracting power of the halogen
atoms as well as the number of H-atoms present in the ethane molecule.
The abstracting power of the halogen atoms refers to the selectivity factor which includes the
HX bond energy as well as bond dissociation energy of the C–H bond.
Mechanism of Halogenation of CH4 (monohalogenation)
diffused
CH 4  X 2 
sunlight
CH 3 X  HX

Initiation Step - I X 2 
hν
2X ....(i)
 
Propogation Step - II X  CH 3  H 
 C H 3  HX ....(ii)
 
CH 3  X  X 
 CH 3 X  X ...(iii)
 
In this whole reaction the reactive species is C H 3 . The formation of C H 3 depends upon the
abstracting power of halogen which in turn depends upon the bond strength of HX formed which
is HF > HCl > HBr > HI and also bond dissociation energy of X2 which is Cl2 > Br2 > F2 > I2.
Reactivity of halogen is
Reaction reversible and highly endothermic, so moves more
F2 > Cl2 > Br2 > I2 in backward direction
(reacts explosively)
.
Termination Step-III The free Radicals present in the reactions are CH3 and
.
X . The different ways in which they can combine for
terminating the reaction is

. .
CH3 + X CH3 – X
. .
CH3 + CH3 CH3 – CH3
. .
X +X X2
Reactivity of different H-atom
The general order of reactivity of different H-atoms is tertiary -H > secondary-H > primary-H
because the stabilities of the corresponding free radicals are tertiary > secondary > primary free
radical.
Though the basic reactivity of H-atom is tertiary > secondary > primary but their reactivity ratio
with chlorine or bromine differs.
p : s : t
The reactivity order with chlorine 1 : 3.25 : 4.43
The reactivity order with Bromine 1 : 82 : 1600
The reaction of alkane with I 2 can be performed by addition of oxidising agents like
HNO3 or HIO3.
HIO3

CH 4  I2   CH 3  I  HI

This reaction is highly reversible with reactions proceeding more in backward direction. But on
adding HNO 3 or HIO 3 the HI gets oxidised to I 2 thereby preventing the reduction of
CH3-I to CH4.
5HI  HIO3 
 3I 2  3H2 O
Ex. Calculate the % of yield of A and B in the following reactions.
CH3CH2CH3 + Cl2 hv CH3CH2CH2 – Cl + CH3 CH CH3

Cl
(A) (B)
A = p-Alkyl chlorideB = s-Alkyl chloride
Here the different types of H-atoms are p- and s- types :
a) Reactivity p : s H-atoms to chlorine (selectivity) 1 : 3.25

b) Number of such atom available 6:2
Yield ratio 6 : 6.5 (obtained by multi playing reactivity factor with availability factor).
6
 Percentage of 1- chloropropane = × 100 % = 48% approximately
12.5
7.6
 Percentage of 2- chloropropane = × 100 % = 52% approximately
12.5
Ex. Calculate the percentage yield of 1-bromopropane (primary) and 2-Bromopropane

(secondary) in the following reaction.
hv
CH3CH2CH3 + Br2 CH3CH2CH2 – Br + CH3 – CH – CH3
Br
p:s
a) Reactivity of H-atom with Bromine 1 : 82
b) Number of such H-atom 6:2
c) Yield ratio 6 : 164
6
Percentage of 1-bromo propane = × 100 = 3.5%
170
164
Percentage of 2- bromo propane = × 100 = 96.5%
170
Laboratory Chlorination
The laboratory chlorinations are usually done using SO2Cl2 (sulphuryl chloride) in the presence
of alkyl peroxides as initiator.
R – H + SO2Cl2 R–O–O–R R – Cl + SO2 + HCl.

.
Initiation Step - I R–O–O–R 2R – O
. .
Step - II R – O + R – H R – OH + [R
. .
Propogation Step - III [R + SO2Cl2 RCl + S O2Cl
. .
Step - IV SO 2Cl SO2 + Cl
. .
Step - V Cl + R – H [R + HCl.
Then there is repeatition of step III, IV and V.
. . . .
Termination : The different free radicals are R , S O2Cl and Cl , R – O which can combine in
many ways.
Evidence in support of free radical mechanism
(i) Effect of U.V. light : The reaction does not take place at room temperature. This is because
energy is needed to cleave chlorine molecule homolytically into chlorine free
radical.
(ii) Effect of number of photon : For each photon or quantumn of light used, several thousand
molecules of alkylhalide are formed.
(iii) Effect of Tetraethyl Lead : It has been observed that if 0.02% of tetra ethyl lead is added
to reaction mixture, chlorination of methane takes place at 140ºC. This is because at 140ºC
tetra ethyl lead decomposes to give free radicals which cleave Cl2 molecule into Cl free
radical.
Pb(C2H5)4 140ºC .
4C2H5 + Pb
. .
C2H5 + Cl2 – C2H5Cl + Cl
(iv) Effect of Adding Inhibitors : Inhibitors are substances which slow down the rate of reaction
even when present in small amounts. It has been observed that when a small amount of
oxygen is added in the reaction mixture, halogenation of alkanes slows down due to the
formation of less reactive peroxy alkyl free radical.
. .
R + O = O — R–O–O
Peroxyalkyl free radical
1. Nitration: Under certain conditions, alkanes react with HNO3, H atom of an alkane is
substituted by nitro group (–NO2) is called nitration.
High
R — H + HO NO2 R – NO2 + H2O
Temp.
Alkane Nitroalkane
Normally hexane and higher alkanes can be Nitrated very easily but will give many side
products.
H3C – (CH2)4 – CH3 + HNO3  H2O + H3C – (CH2)4 – CH2 – NO2

Hexane Nitrohexane
Recently, developed technique of vapour phase nitration, has made nitration of lower alkanes
possible. But the vapour phase nitration also causes cleavage of C–C bond and results in the
formation of more than one nitro compounds,
Vapour phase
H3C – CH3 + HNO3 
500 C
 H3C – CH2 – NO2 + H3C – NO2
Ethane Nitroethane Nitromethane
V.P.
H3C – CH2 – CH3 + HNO3 H3C – CH2 – CH2 – NO2 + H3C – CH – CH3
Propane 500ºC 1-Nitropropane
NO2
2-Nitropropane
+ H3C – CH2 – NO2 + H3C – NO2
Nitroethane Nitromethane
2. Sulphonation : The reaction in which H atoms of alkanes are replaced by sulphonic group
(–SO3H) is called sulphonation. A normal alkane from hexane onwards may be sulphonated
using oleum.
H3C – (CH2)4 – CH2 — H + HO SO2OH 400ºC H3C – (CH2 )4 – CH2 – SO3H + H2O
Hexane
SO3 Hexanesulphonic acid
(conc.)
The mixture of H2SO4 + SO3 =H2S2O7 is called as oleum or Fuming sulphuric acid.
3. Oxidation of alkanes :
(a) Combustion (complete oxidation).
Like other organic compounds alkanes on complete combustion form CO2 and H2O.
CH4 + 2O2 —CO2 + 2H2O

Methane
7
C2H6 + 2 O2 — 2CO2 + 3H2O
Ethane
(b) Controlled Oxidation
(i) When alkane is oxidised at 250ºC under 100 atm. in the presence of Cu, an alcohol
is formed.
1 Cu/250ºC CH3OH
CH4 + 2 O2
Methane 100 atm. Methane
(ii) Methane on oxidation in the presence of molybdenum oxide forms formaldehyde

(HCHO)
CH4 + O2 Mo2O3 HCHO + H2O

Methane 270ºC, 100 atm Formaldehyde
(iii) Alkanes on oxidation in the presence of manganese acetate forms an acid.
3 (CH3COO)2Mn
R – CH3 + O2 High pressure RCOOH + H2O
2 Acid
3 (CH3COO)2Mn CH3 – COOH + H2 O

CH3 – CH3 + O High pressure
2 2 Acetic acid
(c) Chemical oxidation : Alkanes are usually not affected by oxidising agents like KMnO4
or K2Cr2O7, but, alkanes having 3º H atoms are easily oxidised by these oxidising
agents to alcohols.
H3 C H3 C
KMnO4
H3 C C – H + [O] H3 C C – OH
H3 C H3 C
Isobutane tert. butyl alcohol
Special Reactions
(i) Isomerisation : The process of conversion of one isomer into an other is called isomerisation.
CH3
AlCl3 + HCl
H3C – CH2 – CH2 – CH3 H3C – CH – CH3
Butane 200ºC, 35 atm. Isobutane
(ii) Aromatisation : The conversion of aliphatic compounds into aromatic compounds is known as
aromatisation.
CH3
H2 C CH3 Cr2O3/Al2O3
+ 4H2
H2 C CH3 600ºC/15 atm.
CH2 Benzene (C6H6)
Hexane (C6H14 )
(iii) Reaction with nitrogen :

electric 2HCN + 3H
2CH4 + N2 spark Hydrogen cyanide 2
(iv) Action with steam :

CH4 + H2O Ni/Al2O3
(steam) 800ºC
CO + 3H2
(v) Insertion of methylene: Methylene can be inserted into any C–H bonds of alkanes yielding
higher alkanes.
Sunlight
CH3CH2CH2CH3 + CH2N2 CH3CH2CH2 CH2CH3 + CH3 – CH – CH2 – CH3
Diazomethane –N2 n-pentane
CH3
Isopentane
(vi) Pyrolysis (cracking) of Alkane: Pyrolysis of alkanes occurs by heating in the absence of air.

CH3CH2CH2CH2CH2CH3 CH3 – CH = CH2 + CH3 – CH2 – CH3
770 K

CH3CH2CH2CH3 CH3 – CH = CH2 + CH4
Illustration 1: Draw the staggered and eclipsed sawhorse drawings and Newman projections of
1,1,1-trimethylethane.
H
H H
H
H3C H H3C H
Solution: H3C CH3 H3C CH3

Staggered Eclipsed
Sawhorse drawings
CH3 CH3
H H H
H H
CH3 CH3 CH3 CH3
H
Newmam projections
llustration 2: Label each carbon atom in the follwing molecules as primary (1°), secondary (2°) and
tertiary (3°).
and
1 1°
1
1° 3
2 2 3 1
2 2 3 3 2
4 2
2 3 2 , 2 3
Solution: 3 3 3 3 1
2 2
2 2
1 1
Illustration 3: Write a complete reaction mecanism for the formation of 2-bromo-2-methylpropane by the
free radical bromination of 2-methylpropane.
CH3 CH3
Br2
H3C C H  H3C hν
C Br  HBr
CH3 CH3
Solution: A free radical mecahnism takes place in three steps.

Initiation step: hν
Br2   2Br 
CH3 CH3

H3C C H  Br 
 H3C C  HBr
Propagation step:
CH3 CH3
The Br  pulls a H  to generate the most stable tertiary radical.
CH3 CH3
H3C C  Br2 
 H3C C Br  Br 
CH3 CH3
Termination step: Br   Br  
 Br2
CH3 CH3 CH3 CH3

H3C C  H3C C 
 H3C C C CH3
CH3 CH3 CH3 CH3
Illustration 4: Describe a mechanism for the formation of benzyl chloride from toluene by photochlorination.
CH3 CH2 Cl
UV
(excess)  Cl 2 
 light
 HCl
Solution: hν
Initiation step: Cl2   2Cl
CH3 CH2
 Cl 
  HCl
Propagation step:
CH2 CH2Cl
 Cl2 
  Cl
CH2 CH2Cl
Termination step:  Cl 

Cl  Cl 
 Cl2
Illustration 5: A sample of gaseous hydrocarbon occupying 1.12 litres at N.T.P., when completely burnt in
air produced 2.2 g of CO2 and 1.8 g of H2O. Calculate the weight of the compound taken
and the volume of oxygen at S.T.P., required for its burning. Find the moelcular formula of
the hydrocarbon.
Solution: Weight of CO2 = 2.2 g

2.2
Weight of carbon =  12  0.8g
44
Weight of water = 1.8 g
1.8
Weight of H =  2  0.2g
18
0.6 0.2
Atomic ratio : C : H  :  1: 4
12 1
Threfore, empirical formula is CH4
Weight of the hydrocarbon : 0.6 + 0.2 = 0.8g
0.8
In 22.4 l (1 molar volume) the hydrocarbon is  22.4 or 16g
0.12
Weight of 1 mole of the hydrocarbon = 16g
Molecular formula is CH4
0.6 0.2
Moles of oxygen required for C  and for H 
12 2
Total oxygen requried = 0.05 + 0.05 = 0.1 mole
Illustration 6: State the dihedral angle between the bromine atoms in each of the following compounds.
H CH3 Br
H Br
(a) Br (b) H
H
H3C Br H H
Br Br
H CH3 H Br
(c) (d)
CH3 H H H
Br H
Solution: Any conformation of a compound can be specififed by a dihedral angel — the anlge between
the C – H bonds on the front carbon and C – H bonds on the back carbon atom in the
Newman projection.
Illustration 7: Name one isomer of octane which on chlorination will give only one octyl chloride.
CH3 CH3
H3C C C CH3
1 2 3 4
Solution: CH3 CH3
2,2,3,3-tetramethylbutane
Illustration 8: Isopropyl bromide on photochlorination gives 1-bromo-2-chloropropane but isobutyl bromide

gives 1-bromo-2-chloro-2-methyl propane. Account for this observation.
Solution: hν
Cl2   2Cl
H3C H H3C H3C

Cl Rearrangement
CH Br  H3C C Br 
 CH  Cl2
CH Cl  Cl
(i)
H3C CH2 Br CH2 Br CH2
H3C H3C Cl
CH CH2  Cl Cl2
C CH2  H3C C CH2  Cl
(ii)
H3C Br H3C Br Br
CH3
Illustration 9: What are the products formed during the monohalogenations of ethane in the presence of
diffused sunlight.
Solution : The monohalogenation of ethane proceeds via free radical mechanism as follows :
hv
CH3 CH3 + Cl2 CH3 CH2 – Cl + HCl
. .
During such a mechanisms the different free Radicals formed are CH3 CH2 and Cl
During the termination process these free radicals combine as follows:
. .
CH3 CH2 + CH3 CH2 CH3 CH 2 CH2 CH3
. .
CH3 CH2 + Cl CH3 CH2Cl
. .
Cl + Cl Cl – Cl
. .
CH3 CH2 CH2 = CH2 + H
. . CH3 CH3
CH3 CH2 H
. .
H + Cl HCl
Hence apart from CH3CH2 – Cl the other products would be CH2 = CH2, CH3CH2CH2CH3,
CH3CH3 and HCl.
Illustration 10: What happens when an alkane is reacted with tertiary butyl hypochlorite. (t-BuOCl). Explain
Solution : When an alkane is reacted with t-Bu OCl an alkyl chloride is obtained
R – H + (CH3)3 COCl R – Cl + (CH3)3 COH

Mechanism
CH3 CH3
. .
CH3 – C – O – Cl CH3 – C – O + Cl
CH3 CH3
CH3 CH3
. .
CH3 – C – O + R – H CH3 – C – O – H + R
CH3 CH3
CH3 CH3
. .
R + CH3 – C – O – Cl R – Cl + CH3 – C – O
CH3 CH3
Illustration 11: Which of the following species have not been identified. Explain the bonding.
 
CH3 and CH5
 
Solution : Both the species CH3 and CH5 have been detected.
The electronic configuration of carbon is

1s2 2s2 2p x 2p y
1s 2s 2p
E.S.

But in CH3 one electron is less hence the electronic configuration is,
ES. (Carbon)
H sp2
S - obitar
C—H
sp2 – HO
H
We have therefore 3 – sp2–s overlap with the sp2 HOs of carbon and s – AO of H.

In CH5 it contains 3-identical bonds of sp2–s overlap of carbon and hydrogen.
Each lobe of carbon’s remaining p-AO bonds with one H each above and below the plane
of the carbon and the three H’s.
H
P
S
C —2 H
sp — S
S P
Illustration 12: Among CH4 and CD4 which is more reactive towards chlorine and why ?
Solution : CH4 reacts approximately ten times faster than tetradeutro methane CD4.
This is because C – D bonds are stronger than C – H bonds.
Illustration 13: Complete the following equations.

Mg
(a) Cl – CH2 CH2 CH2 – Cl 
Mg
(b) Cl – CH2CH2CH2CH2–Cl 
CH(Br)CH
3 Zn
(c) CH2 CH(Br)CH
3
CH2
Solution : (a) CH2 CH2 This reactions is called (Freunrd reactions)
CH2 – CH2
(b) This reactions again is called (Freunrd reactions)
CH2 – CH2
CH3
CH
(c) CH2 (Wurtz reaction)
CH
CH3
Illustration 14: A certain compound “A” has a molecular formula C6H13Br. When reacts with Mg metal in
anhydrous ether, a Gringnard’s reagent is formed which upon hydrolysis with acid produces
the compound n-hexane as a product. When the compound A reacts with sodium metal in a
Wurtz reaction, the product obtained is 4, 5-diethyl octane. What is A ? Draw its structure
and give its IUPAC name.
Mg H2O
Solution : 1. C6H13Br Dry ether
C6H13MgBr C6H14
H+
n-hexane
2. Wurtz reaction involves coupling of 2 moles of an alkyl halide to give an alkane. Since
the alkane is 4, 5-diethyloctane, i.e.
CH3 – CH2 – CH2 – CH – CH – CH2 – CH2– CH 3
C2H5 C2H 5
 The alkyl halide must be CH3CH2CH2CHBr C2H5 i.e., 3-Bromohexane. Thus :

Dry ether
CH3 – CH2 – CH2 – CH Br + 2Na + Br – CH – CH2 – CH2– CH3
C2H5 C2H5
Illustration 15:a) Arrange the following compounds in order of their increasing boiling points ? n-pentane,
2-methyl pentane, n-hexane, 2,2-dimethyl pentane, ethane.
b) An unknown alkyl halide, C4H9Br, reacts with sodium to give a hydrocarbon C8H18. The
hydrocarbon is shown to be identical to that produced by the Kolbe’s electrolysis of the
CH3 – CH – CH2 – COOH
sodium salt of the acid CH3
What are the structures of the hydrocarbon and the alkyl halide ?
c) Give the structural formulae and names for all dibromo derivatives of propane.
Solution: a) Ethane < Pentane < 2-Methyl pentane < n-Hexane < 2, 2-Dimethyl pentane.
This is because the boiling point is directly propotinal to molecular forces of attraction
which in turn being van der waal’s is directly proportional to surface area.
Dry ether
b) RI + 2Na + IR R – R + 2NaI (Wurtz reaction)
2RCOONa + 2H2O Electrolysis R – R + CO2 + 2NaOH + H2
The sodium salt of the acid, CH3 – CH – CH2 – COOH should give alkane
CH3
2H3C – CH – CH2 – COONa + 2H2O Electrolysis H3C – CH – CH2 – CH2 – CH – CH3 + 2CO2 + 2NaOH + H2
CH3 CH3 CH3
This alkane with molecular formula C8H18 (2, 5-dimethylhexane) can be obtained by
Wurtz synthesis by coupling 2 moles of CH3 – CH – CH2 Br , i.e., Isobutylbromide

CH3
2CH3 – CH – CH2 Br + 2Na Dry ether CH3 – CH – CH2 – CH2 – CH – CH3 + 2NaBr
CH3 CH3 CH3
Thus, the alkyl bromide C4H9Br is Isobutyl bromide (1-Bromo-2-methylpropane).

c) The two Br’s are placed first on the same carbon and then on different carbons of
propane.
Br Br
(i) Br – CH – CH2 – CH3 (ii) CH3 – C – CH3
1,1-Dibromopropane
Propylidene dibromide
Br
2,2-Dibromopropane
Br Isopropylidene dibromide
(iii) Br – CH2 – CH – CH3 (iv) BrCH2CH2CH2 Br

1,2-Dibromopropane 1,3-Dibromopropane
Propylene dibromide Propane ,  - dibromide component
Illustration 16: A 1.37 g sample of n-butyl bromide was converted to the Grignard’s reagent. What volume
of butane, measured over water at 20ºC and at 750 mm pressure will be produced on
addition of water to the Gringnard’s reagent ? Aqueous tension at 20ºC is 17.4 mm.
Dry ether
Solution : C4 H9Br + Mg C4 H9 MgBr
n-Butyl bromide Butyl magnesium bromide
1 mole
C4 H9 Mg Br + HOH C4 H10 + Mg (OH)Br

H OH Butane
1 mole (22.4 L at NTP)
Given weight of n-butyl bromide = 1.37 g

Molecular weight of n-butyl bromide = 12  4 + 1  9 + 80 = 48 + 9 + 80 = 137
m 1.37
No. of moles of n-butyl bromide = = = 0.01 mole
M 137
1 mole of n-butyl bromide gives butane = 0.01 mole

Hence volume of 0.01 mole of butane at 750 mm pressure and temperature.
293 K = PV = nRT
nRT
 V=
P
732 .6
n = 0.01, R = 0.082, P = (750 – 17.4) = 732.6 mm = 760 atm., 293K
0.01  0.082  293  760

 = 0.24934 litre = 249.24 ml.
732.6

Problem 1: On halogenation, an alkane gives only one monohalogenated product. The alkane may be:
(a) 2-methyl butane (b) 2,2-dimethyl propane
(c) cyclopentane (d) both (b) and (c)
Solution: (d)
cyclopentane
All are 2° carbon. Therefore, it gives only one monohalogenated product.
H3C
Cl2
CH CH2 
Problem 2: hν
H3C CH3
Number of chiral centres generated during monochlorinationi in the above reaction:

(a) 1 (b) 2
(c) 3 (d) 4
1°
H3C Cl CH2 CH3 H3C CH3
3° 2°
Cl2 CH HC
CH CH2 
hν
CH2 HC 
Solution: (b)
H3C CH3 CH3 H3C Cl
1° 1°
Problem 3: Draw an energy profile diagram for a three step reaction in whcih first step is slowest and
last step is fastest. (Assume that reaction is exothermic).
(a) (b)
(c) (d) None of these
Solution: (c)
(E1 > E2 > E3)

H3C
Cl2
CH CH2  (X)  Number of monochloro product including stereoisomers
Problem 4: hν
H3C CH3
(a) 4 (b) 5
(c) 6 (d) 7
1°
H3C
Solution: (c) 3° 2° Cl2 Four different carbon atoms will form
CH CH2 
hν
products
H3C CH3
1° 1°
H3C CH2 CH3 CH3 H3C CH3 H3C
CH2 HC  H3C C CH2  CH HC  CH CH2
CH3 Cl CH3 H3C Cl H3C CH2 Cl
2 optical isomers) (1 isomer) (2 optical isomers) (1 isomer)
Pd
H  H 2  
Problem 5: CH2
CH3
Product of the above reaction will be
(a) Racemic mixture (b) Diastereomers
(c) Meso compound (d) Constitutional isomers
Pd H
H  H 2  
CH2 CH3
Solution: (b) CH3 CH3
forms a diastereomers
Na/Dry ether
Problem 6: Cl Br   (A)
97%
Product (A) of above reaction is:
(a) (b)
(c) (d)
Na/Dry ether
Solution: (b) Cl Br  
CH3
Problem 7: Br2 /hν

  Monobromo derivatives
The number of possible monobromo products is (excluding stereoisomers)
(a) 4 (b) 5
(c) 8 (d) 10
1°
CH3
3°
2° 2° Br2 /hν
Solution: (b)   Forms five monobromo product corresponding to five
2° 2° different carbon atom.
2°
H3C Ha
Hb
 Br  

Problem 8: d
H OH
H2C c
H
Br will abstract which of the hydrogen most readily?
(a) a (b) b
(c) c (d) d
H3C Ha H3C Br
3°
2° Hb
2°
2°  Br  

2°
Solution: (a) OH OH
3°
H2C c CH3
H
Ph CH2
Br2 /hν
Problem 9: CH CH3   Product
D
2°
Ph CH2 Ph H
Br2 /hν
CH CH3   CH C CH3
Solution: 3° 1°
D Br D
Formation of a diastereomer
CH2 Cl
Na/Dry ether
 ?
H3C
Problem 10:
H2C
Cl
Product of the above reaction will be:
CH3
(a) (b)
H3C CH3 H3C
(c) (d) Both (a) and (b)

H3C CH3
Solution: (d)
CH2 Cl
Na /Dry ether
 
H3C
H2C H3C CH3
Cl
CH3
H3C
ALKENES
Alkenes are substances which contain less hydrogen than the maximum number of hydrogen which a carbon
atom can have. Hence, these are referred to as unsaturated hydrocarbons. They have general
formula CnH2n.
Structure: Any alkene consists of two carbon atom linked via a carbon–carbon double bond.
The simplest member of series is ethene or ethylene,. i.e., C2H4CH2 = CH2
According to Lewis concept of electron dot structure the ethene molecule can be
represented as
H H H
:
H .. C : : C .. H C=C
: H H
H ethylene
Hence the carbon–carbon double bond is the distinguishable feature of the alkene structure :
Hybridization, orbital size and comparitive Bond length

S S H-atom H S – 
H
Sp 2  2 –S
H-a S 2 2
Sp
tom p Sp
2 2
Sp Sp
2 -bond Sp 2 C C
Sp sp2–sp2  Sp2 Sp2 Sp2
S S H-atom 
H- a S–
tom Sp 2
 –S
H
H Pz — Pz 
P2 P7
121º
H H
+ +
C C C C
1.103 Å – –
H 1.34 Å H ethylenic gp.
ethylene
3.3 Preparations
I) From Alcohols
TsCl base
R  Tosylate   alkene
R  OH
H 2SO4
Alkene
Dehydration of Alcohols can be represented as follows:
acid
C C   C C  H2O
Alkenes
H OH
Ease of dehydration of alcohols is t > s > p
(i) By heating alcohol with conc. H2SO4 or phosphoric acid at 200ºC.
(ii) By passing vapours of alcohols over Alumina (Al2O3) at 350º – 400º.

H H
95% H 2SO 4
H C C H 
170
H2 C CH2
H OH
E-1 Mechanism
conc. H 2SO4
R  OH 
170 C Δ
 alkene  H 2 O
O
+
(1) R OH  H O S O H 
fast R OH2  HSO4
O
 
(2) R OH2 R + H 2O
slowest
(3) R  fast stable R+ (Rearrangement if possible)
 HSO4–
(4) Stable R Alkene + H2SO4

(–H 
Fast

Since the slowest step is the rate determining step, the Rate = K[R – OH2]
Hence, it is a first order reaction with E-1 mechanism.
This reaction is always accompanied by rearangements.
75% H2SO4
(1) CH3 CH2 OH CH2 CH2 + H2O
170º C
75% H2SO4
(2) CH3 – CH2 – CH2 – OH 140º C
CH3 – CH = CH2
75% H2SO4
(3) CH3 CH2 CH2 CH2 – OH CH3 – CH = CH – CH3
140º C But-2-ene
(Major)
CH3
20% H2SO4 CH3
(4) CH3 – C – OH 85 – 90º C C = CH2
CH3 CH3
If one looks at the various reactions and conditions it clearly tells us that for dehydration of p-
alcohol one required highly concentrated acid while for t-alcohol one requires less concentrated
acid. This proves that the reactivity order of alcohols for dehydration is t- > s- > p.
Which could be reasoned out on the fact that during C–OH bond cleavage, the substrate undergoes
easy dehydration where the intermediate formed is most stable. Since the stability order of
carbocation in alcohol is t > s > p. Hence, the reactivity of alcohol is t > s > p.
Dehydration of n-prophyl alcohol.
CH3 – CH2 – CH2 – OH + H2SO4 — CH3 – CH = CH2 + H2O


CH3 – CH2 – CH2 – OH + H2SO4 — CH3 – CH2 – CH2 – OH2
 
CH3 – CH2 – CH2 – OH2 — CH3 – CH2 – CH2 + H2O
 Rearangement 
CH3 – CH– CH2 CH3 – CH– CH3
Hydride shift
H –
 HSO4
CH3 – CH – CH3 CH3 – CH = CH2 + H2SO4
CH3
Dehydration of CH3 – C – CH – CH3
CH3 OH
CH3 CH3
HSO4
CH3 – C – CH – CH3 CH3 – C – CH – CH3
CH3 OH CH3 OH2

CH3 CH3 CH3

CH3 – C – CH – CH3 Rearrangement
CH3 – C – CH – CH3 CH3 – C – CH – CH3
Methyl shift
 
CH3 OH CH3 CH3
2

CH3 CH3 CH3

–
HSO4
CH2 – C = C – CH3 + CH2 = C – CH – CH3
(Major) (Minor) CH
3
Thionyl chloride and phosphorous halides convert hydroxy group to a good leaving group when
heated with alcohol and thereby promote the dehydration.
OH Ph Ph
SOCl 2 /Chloroform
C CH 
 C C
Ph Ph
E-2 Mechanism
 R  OH 2  HSO 4
R  OH  H 2SO 4 
R  OH 2 
 Alkene  H2 O
The second method of converting alcohol into alkene is by passing alcohol vapours over almina
or thorium oxide as catalyst.
Al2 O3
H3 C CH2 
350 C
 H2 C CH2  H 2 O
OH
H3C
Al2 O3
CH OH 
250 C
 H3C CH
H3C CH2
CH3 H3C
Al2 O 3
H3C OH 
150 C
 C CH2
CH3 H3C
Dehydration of alcohols using Al2O3 follows Satyzeff’s elimination, but dehydration of alcohols
using thorium oxide favours the Hoffmann elimination.
Al2 O3
CH3– CH – CH = CH – CH3 (90%) + (CH3)2 – CH – CH2
300º C – 400º C Hoffmann
CH
(Saytzeff's Product) (10%) CH
3 Product
(CH3)2 – CH CH2 CH – CH3
CH2
OH ThO2
CH3 – CH – CH = CH – CH3 (3%) + (CH3)2 – CH – CH2
380º C (Saytzeff's Product) Hoffmann
CH3 (96%) CH
Product
CH2
II) Dehydrohalogenation Method

From alkyl halides
alc KOH + H2O.
C–C C=C
H X
The reaction of an alkylhalide with alcoholic KOH is called dehydro halogenation. It can also be
termed as elimination reaction. The ease of dehydrohalogenation of alkylhalide is 3º > 2º > 1º.
alc KOH
CH3 – CH2 – Cl CH2 = CH2
e.g. 
Ethyl chloride Ethene
In such reactions the hydrogen from the -position is lost. Hence these are also called -elimination
reactions.
alc. KOH
CH3CH2 CH2 Cl   CH3CH  CH 2
alc. KOH
CH3CH2 CH 2CH 2Cl   CH3CH2 CH  CH2
alc KOH
CH3 CH2 CH – CH3 CH3 – CH = CH – CH3

Cl 81% + (Major)
CH3 – CH2 – CH = CH2
19% (Minor)
The fact that 1-chlorobutane yields only But–1–ene and not But–2–ene proves beyond doubt
that the - H atoms to the carbon carrying halogen is removed. Also the fact that 2-Chlorobutane
which contains 2–– carbon atoms gives both But–1–ene and But–2–ene confirms that the
reaction is -eliminations.
Elimination Reactions
L
C C + :B C C + HB + : L
The reaction base
H
Substrate
L = Leaving – group
Elimination reaction occurs in two ways
1. Bimolecular mechanism.
2. Unimolecular mechanism
The two ways in which such a reaction can take place are.
E–2 Mechanism
L
C C C C H BL
H
B L

Slow
 C C
H
The transition state has a higher energy. Here, since the formation of transition state is different,
therefore, formation of transition state is rate determining.
Applying kinetics Rate [R–X][B:]
The molecularity involved in the rate determining step is 2. Hence, it is a bimolecular reaction.
This reaction involves the transition state where there is simultaneous removal of halogen from
-carbon with simultaneous removal of H-atoms from -carbon atom. Hence, it is known as
1,2 elimination or -elimination.
Such reactions are characterised by:
(a) Leaving group, an atom, or group that leaves the molecule taking its pair of electrons with it
(b) In a position - to leaving group, the substrate contains a H-atom.
(c) Reactions is brought about by action of above. (OH– C2 H5O–, (CH3)3C–O–, etc.)
Sometimes the solvent itself behaves as a base (alcohol or water).
In elimination, a good leaving group is a weakly basic anion. The examples given under dehydro
halogenation are all examples of E-2 mechanism.
E-1 Mechanism: Hughes and Ingold proposed that in the 1st step the halogen atom leaves first
giving rise to a carbocation and then from the -position to the carbocation the -H atom leaves as
H+ forming the alkene.
X
– +  
1. C C : X C C 2. – C – C – C=C + HB
Slow Fast
H H H :B
Here, the 1st step involves only the breakage of bond where as step-2 involves the removal of
H and forming of -bond. This leads to the formation of alkene.
Since, step -1 involves only cleavage of bond so it is the rate determining step. Hence ,
Rate = K[R–X]
On the proposed mechanism in step-2 it is possible that the carbocation:
(a) may combine with nulceophile to form substituted product.
(b) rearrange to form stable carbocation.
(c) eliminate proton to form alkene.
H3C CH3 H3C H3C H2C


CH HC OH
  C CH  CH CH  C CH2
(i)
H3C OTs H3C CH3 H3C CH2 H3C CH3
CH3 CH3 H3C CH3 H3C CH2


H3C C HC OH
  C C  CH C
(ii)
CH3 Br H3C CH3 H3C CH3
CH3 H 3C H3C
H C C CH2 OH


 C CH  C CH2
(iii) 3
CH3 Br H 3C CH3 H2C CH3
Mechanism
CH3 CH3 CH3 H3 C CH3 H3C

 OTS  + +
H3 C C HC  H3C C CH 
Rearrangement
 C HC  C CH

(i) H OTS H CH3 H3 C H H3 C CH3
2° carbocation 3° carbocation ( Major product)
H3 C CH3
C HC
CH3 CH CH3 H2 C CH3
3 H3 C CH3
Base + +
H3 C   H3C C CH   C HC
(  Br  )
(ii) CH Br CH CH 3 H 3 C CH3 H3 C CH3
3 3
2° carbocation 3° carbocation C C
H3 C CH3
H3C
CH3 C CH2
CH3
+ H2C CH3 H3C
H3C   
Br 
 H3C C CH2  Br   Re
arrangement
   +
H3C C CH2
(iii) CH3 Br CH3
H3C CH3
C CH
p-carbocation t-carbocation
H3C CH3
Evidence for E–1 mechanisms:
(1) Follows 1st order kinetics.
(2) Are not accompanied by primary Hydrogen isotope effect.
(3) Where structure permits, are accompanied by rearrangement.
The general reactivity order of alkyl halides for eliminations are. (Both E–1 and E–2).
(a) R–I > R–Br > R–Cl.
(b) 3º > 2º > 1º.
(c) The general ease of formation of alkenes is:
R2C = CR2 > R2 C = CHR > R2 C=CH2> RCH=CHR > RCH = CH2 This is because the general
order of stability of alkene is R2C=CR2 > R2C = CHR > R2C = CH2 > RCH = CHR > RCH =
CH2 > CH2 = CH2
On the basis of this we can support Saytzeff’s Rule according to which greater the number of
alkyl groups attached to the doubly bonded carbon atoms greater is stability of alkene. i.e.
alc KOH
CH3 CH2 CH CH3 CH3 CH2 CH = CH2 + CH3 CH = CH CH3

1– Butene 2-Butene
Cl
Here, 2-Butene is the saytzeff’s product.
Now, if we see the number of hyperconjugations in 1–Butene it is 3 and the number of

hyperconjugations in 2-Butene is 7. Hence, 2-Butene is more stable than 1-Butene.
Hence, 2-Butene is the predominant compound. We can also recast Saytzeff’s rule as : in
dehydrohalogenation, the more stable the alkene, the faster it is formed also the predominant
formation of the more stable isomer is Saytzeff’s orientation.
Stereochemistry of Elimination Reaction:
There is evidence that an E-2 elimination proceeds only when the hydrogen to be removed and
the leaving group are in an anti conformation with respect to each other.
e.g. (2R, 3R)-3-Phenyl-2-butyl tosylate gives exclusively (E)-2-2Phenyl-2-butene where as its

diastereomer (2S, 3R)-3 Phenyl-2-butyl tosylate gives (Z) 2-phenyl-2-butene.
:B
H
Me
Me H H Me Me
H –
Me C2H5O
 C–C C=C
Me C6H5
OTS C 6 H5 C6H5
H
OTS
:B
H
H Me
H H
H Me –
CH3 Me C2H5O
 C–C C=C
Me C6H5 C6H5
OTS C6H5 Me
OTS
In an E-2, reactions the stereochemistry of alkene that is formed is governed by the conformation
that the starting material adopts in the transition state. So that the leaving group and the protons
being removed by the base are anti to each other. There is no such stereochemical requirement
for E-1 reaction, because the leaving group is lost and a carbocation has been formed before the
proton is removed.
This can be illustrated with an example. The compound

H H
Potassium t  butoxide
Me  55 C Δ Me and not CH3
H OTs
(Not formed)
H H
For this molecule in the most stable diequitorial conformation of trans-2-methyl cychohexyl-
tosylate, no H-atom is anti to the leaving group but if the conformation of ring changes then one
H-atom becomes anti to the leaving tosylate group.
The H atom on the carbon H OTs

adjacent to the leaving group
are gauche not anti CH3
OTs H
H
H
H Me
H
(stable)
Only this H-atom is anti to
OTs group
Although the anti orientation is most favourable it is not essentially the only one possible form.
Reactions have suggested that as-2-Phenyl cyclohexyl tosylate and trans-2-Phenyl cyclohexyl
tosylate both give 1-Phenyl cycloheptene but the rate at which the cis form reacts is nine times
the rate at which the trans form reacts.
t  butoxide

55 Fast

Anti  e lim ination
H H
TsO C 6H5 C 6H5
cis form
t  butoxide
 55  Slow
H C 6H5 Syn  e lim ination
TsO H C 6H5
trans form
Saytzeff’s Elimination vs Hoffmann Elimination:

According to Hoffmann’s elimination when an alkyl halide is treated with bulkier base then an
alkene with least substitution is found to be the major product.
CH3 CH2 CH CH3 Base CH3 CH CH CH3 + CH3 CH2 CH CH2
Saytzeff's Product Hoffmann's Product
Cl
It is observed that when 2-Chlorobutane is heated with alcoholic KOH then the major product
formed is 2-Butene and minor product formed is 1-Butene.
alc KOH
CH3 CH2 CH CH3 CH3 CH CH CH3 + CH3 CH2 CH CH2

Major (A) Minor (B)
Cl
Here, product (A) is the major product formed. Which is the Saytzeff’s product.
However when 2-chlorobutane is reacted with potassium t-butoxide the yield of 1-Butene
increases. This is because of the bulkiness of (CH3)3 CO which makes it more difficult to
abstract the more hindered 2H at
–
CH3 – CH – CH – CH2 – H OH CH3 – CH = CH – CH3 + CH3– CH2 – CH = CH2
–
H Cl (Approach of OH
(Approach of not hindered ) – Me
OH not – CH3 – CH – CH – CH2 – H O–C Me (Approach
hindered )
OH Me not hindered )
H Cl
Me
–
Me C–O
Me
(Approach hindered )
CH3 CH3 (Sytzeff's elimination) CH3

alc KOH CH3 C CH
CH3 C CH2 CH CH3 CH CH3 + CH3 – C – CH2 – CH = CH2

CH3 CH3 CH3 (Minor)
Br
CH3 (Major) CH3
t-Butoxide CH3 C CH2 CH CH2 (Major) + CH3 – C – CH = CH – CH3
(Minor)
CH3 (Hoffmann elimination) CH3
III)Dehalogenation Methods
i) From Vicinal Dihalides
CH2 – Br Alcohol CH2 = CH2 + ZnBr2

+ Zn

CH2 – Br
Alcohol
R – CH – CH2 + Zn R – CH = CH2 + Zn Br2

X X
ii) From Geminal Dihalide

X X
R – CH + 2 Zn + CH – R
X X

R – CH= CH – R + 2 Zn X2
IV) By Controlled Hydrogenation of Alkynes

Pd/BaSO4
(a) CH3  C  C  CH 3  H 2 
(Lindlar 's Catalyst)
guinoline  S
 CH3  CH  CH  CH3
This reaction always gives cis-isomer only
Na / Liq NH3 CH3 H

(b) CH3 – C  C – CH3 C=C
C2H5OH H CH3
Here the product formed is a trans-isomer and the reaction is called Birch reduction.
V) Dehydrogenation of Alkane
R Cr2 O3 , Al2 O3 R

770 K (  H 2 )

R R
H3C HC
Cr2 O3  Al2 O3
770 K
 3
CH3 CH3
H3C H3C
Cr2 O3  Al2 O3

 770 K
H3C CH3 H3C CH3
VI) Kolbe’s Electrolytic Decarboxylation: Electrolysis of aqueous solutions of sodium salts of

vicinal dicarboxylic acids leads to the decarboxylation of the compound leading to the formation
of alkenes.
Mechanism
O
–
CH2 – COONa CH2 – C– O
– + 2Na +
CH2 – COONa CH2 – C – O
O
H2 O –
H+ + OH
At Cathode
2H+ + 2e– H2
At Anode
O O
–
.
CH2 – C– O CH2 – C– O
. + 2e–
–
CH2 – C – O CH2 – C – O
O O
O
CH2 — C — O
CH2
+ 2CO2
CH2 — C — O CH2
O
The solution hence contains Na+ and OH there by becoming more and more basic. Here no
other side product is formed because the elimination of CO2 takes place without the formation of
new free Radical.
VII) By Heating Quaternary Ammonium Hydroxide


C2H5
–
CH3 – CH2 – N – C2 H5 OH CH2 = CH2 + (C2H5) 3 N + H2O

C2H5
Here the alkene with less substituted alky gps is formed, i.e., the Hoffmann product is formed.
H3C CH2 CH CH3 H3C CH3

 150 C
H3C N CH2 CH3 OH 
 CH 2  CH 2 

N  H2O
CH3 H3C CH3
VIII) By Pyrolysis
(a) Pyrolysis of Esters: When an ester containing  - H atom on the alkyl portion of the
molecule is heated to (300-600 ºC) an alkene and a carboxylic acid is formed.
(300º – 600º C)
CH3 – C – O – CH2 – CH2 – CH3 CH3COOH + CH3 – CH = CH2

O
Mechanism
CH3
C CH3
O O
(300 – 600º C) C CH2 = CH – CH3
H O O +
CH2
C 
H H
CH3
CH2 – C – O – CH2 CH2 CH2 CH3 CH3 – COOH + CH3 CH2 – CH = CH2
O
(b) Pyrolysis of Amineoxide (Cope Reaction): This method of alkene synthesis is closely
related to ester pyrolysis. The oxygen atom of an amine oxide has a formal negative charge
which functions as the internal base. Amine oxides are generally formed by peroxide oxidation
of the corresponding tertiary amine. Here the alkene formed is the hofman’s product only.
H2O2
CH3 – CH2 – CH – CH3 CH3 – CH2 – CH – CH3  Δ
 CH3 – CH = CH – CH3
MeOH
N(CH3 )2  .. – Minor
CH3 – N– O
.. :
CH3 CH3
+ CH3 – CH2 – CH = CH2 + CH N – OH
3
Major
IX) Heating with Selenium Oxide
– CH2 – CH2 – 2
 
SeO
 – CH = CH –
+H2

3.4 Structure And Physical Properties

1. Physical Properties:
(a) First three memers of alkenes are gases, those containing five to fifteen are liquids and
higher alkenes are solids.
(b) Alkenes are insoluble in water but soluble in organic solvents.
(c) The boiling points of cis alkenes are higher where as melting points of trans-alkenes are
more as cis isomers being more polar, boils at a higher temperature, where as trans isomers
being more symmetrical fits well into the crystal lattice and have higher melting point.
Cl H
Cl Cl
C=C
C=C
e.g., H Cl
H >0 H
=0
2. Structure and reactivity:
The characteristic feature of the alkene structure, is the carbon carbon double bond. It is thus
the functional group of alkenes and as the functional group, it determines the characteristic
reactions of alkenes.
The reactions of alkenes are of two kinds:
(a) First, there are those that take place at the double bond itself destroying the double bond.
(b) There are the reactions that take place, not at the double bond, but at certain positions having
special relationships to the double bond. Outwardly the double bond is not involved; but it
plays an essential, though hidden, role in the reaction and it determines how fast reactions
take place and by which mechanism.
Reactions at the carbon–carbon double bond. Addition Reactions: The double bond
consists of a strong  bond and a weak  bond; we expect, therefore, that reaction would
involve breaking of this weaker bond. The typical reactions of the double bond are of the sort
where the bond is broken and two strong bonds are formed in its place.
C C  EZ 
 C C
E Z
3. Electrophilic Addition Reaction – Mechanism
Electrophilic addition reactions involves addition of the acidic reagent, HZ.
Iinvolves in two steps:
(Z may be –Cl, –Br, –I, –CN, –OH, –OSO3H, etc.)
Step (1)the first and slow step involves the addition of H leading to the formation of carbocation.
Step (2)is the combining of the carbocation with the base : Z–.
 +
C C  H 
 C HC (slow step)
H
+ 
C HC  Z 
 C C (fast step)
Z
The evidence for this mechanism includes:
(a) The rate of reaction depends upon the concentration of both the alkene and the reagent HZ.
(b) Where the structure permits, reaction is accompanied by rearrangements. In addition, the
mechanism is consistent with structures :
(c) The orientation of addition; and
(d) The relative reactivities of alkenes.
4. Electrophilic Addition : Orientation and Reactivity
The mechanism is consistent with the orientation of addition of acidic reagents, and the effect of
structure on the relative reactivities of alkenes.
Addition of hydrogen chloride to propylene is outlined below, with the two steps of the mechanism
shown. Propylene yields isopropyl chloride according to Markovnikov’s rule.
Cl
+ Cl
H3C CH2 CH2 (not formed)  CH3
HCl
H3C H3C
+ (Product)
CH2 H3C CH CH3 (formed)
According to the mechanism, hydrogen from the reagent adds to one or the other of the two
doubly bonded carbons to give one or the other of two possible carbocations. For example, if
hydrogen goes to C–2 of propylene, we get the n-propyl cation; if it goes to C–1, we get isopropyl
cation. Once formed, the carbocation rapidly reacts to yield product. Which halide is obtained,
then depends upon which carbocation is formed in the first step. The fact that propylene yields
isopropyl chloride rather than n-propyl chloride shows that the isopropyl cation is formed, faster
than–the n-propyl cation. Thus, orientation in electrophilic addition is determined by the relative
rates of two competing reactions: formation of one carbocation or the other. Similarity isobutylene
gives tert-butyl chloride on addition in HCl.
H3C H3C CH3

HCl + Cl
CH2 
 C CH3  H3C CH3
H3C H3C Cl
1° Carbocation (Product)
CH3
HCl +
  H3C CH2 (Not formed)
H
In each of the examples given above, the product obtained shows that in the initial step a secondary
cation is formed faster than a primary, or a tertiary faster than a primary. Examination of the
orientation in many cases shows that this is a general rule : in electrophilic addition the rate of
formation of carbocations follow the sequence because of the similar order of their relative
stability.
Rate of formation of carbocations 3º > 2º > 1º
Reactivity of alkenes towards acids is
H3C
CH2 H3C H5 C 2 H3C H2C
H3C CH3 CH2 CH2 H2C CH2 Cl
5. Rearrangements in Electrophillic Addition Reaction: Where the structure permits, the

reaction is accompanied by rearrangements. The product sometimes contains the group Z attached
to a carbon that was not doubly bonded in the substrate; sometimes the product even has a
carbon skeleton different from that of the substrate.
These “unexpected”: products, are readily accounted for by rearrangements of the carbocations
as intermediates. These rearrangements follow exactly the same pattern that we have come to
expect from out study of carbocations in SN1 substitution and in E1 elimination.
For example, addition of hydrogen iodide to 3,3-dimethyl-1butene yields not only the expected 2-
iodo-3, 3-dimethylbutane, but also 2-iodo-2, 3-dimethylbutane. Since a 1,2-shift of a methyl group
can convert the initially formed secondary cation into a more stable tertiary cation, such a
rearrangement does occur, and much of the product is derived from this new ion and hence the
product obtained is 2-Iodo –2, 3– dimethyl butane.
CH3 CH3
–
CH3 – C – CH – CH3 I
CH3 – C – CH – CH3

CH3 CH3 I
CH3
Methyl shift CH3
CH3 – C – CH = CH2 HI
CH3 – C – CH – CH3
CH3  I–
CH3
(CH3)2C(I) CH(CH3)2
Chemical Reaction
1. Hydrogenation Reaction
Pt, Pd
C C  H 2 
or Ni
 C C
H H
H 2 / Ni
H3C CH  H3C
Δ
CH2
CH2 CH3
The reaction has been discussed at length in the preparation of alkanes.
2. Addition of Halogens
H 2 /Hi
C C  X 2  Δ
 C C
X X
Here, X2 = Cl2 or Br2
H3C
CCl4
H3C CH  Br2 
 CH CH2
e.g.,
CH2 Br Br
The reaction is carried out simply by mixing together the two reactants, usually in the solvents like
carbon tetrachloride. The addition proceeds rapidly at room temperatures and does not require exposure
to ultraviolet light.
Note : If high temperature, exposure of light or presence of excess halogen is there

substitution might become an important side reactions. This reactions leads to the formations
of vicinal dihalide.
Mechanism: The additions of halogens to alkenes involves two steps.
Step - 1: Halogen transfer loosing a pair of electron.
H H H H H  H
+ X
C—C C — C C — C
– +X–X + X–
H H  – T.S. H H H
H
Halonium ion
 – Complex
(cyclic intermediate)
The second step involves the attack of X– ion on the halonium ion to form the dihalogen derivatives.

H X H X H
| |
C — C
H C C H
Step - 2: H H | |
–
X H X
Anti Addition
This mechanism is proposed based upon the fact that the reaction depends upon:
(i) effect of the structure of alkene.
(ii) effect of nucleophile on the product obtained.
(iii) the fact that halogen adds with complete stereoselectivity and in the anti manner.
(iv) the role played by halonium ion in neighbouring group effects.
(i) Effect of Structure of Alkene: Alkenes show the same order of reactivity towards halogens as
towards acid.
CH3
C = CH2 > CH – CH = CH – CH > CH CH CH = CH
CH3 3 3 3 2 2
> CH3 – CH = CH2 > CH2 = CH2 > CH2 = CH – Cl

(ii) Effect of Nucleophiles on Products Formed: If a holonium ion is the intermediate and capable
of reacting with halide ion, then we might expect it to react with almost any negative ion or basic
molecule.
CH2 = CH2 + Br2 

CCl4
 CH2 – CH2
Br Br
NaCl(aq) CH2 – CH2 CH2 – CH2
CH2 = CH2 + Br2 +
Br Br Br Cl
CH2 – CH2
CH2 = CH2 + Br2 NaI(aq) + CH2 – CH2
Br Br Br I
H2 O
CH2 = CH2 + Br2 CH2 – CH2
Br OH
(iii) Stereo Chemistry of Addition
The stereochemistry of the reaction leading to anti-addition can be understood by the mechanisms.
When cis but-2-ene is treated with bromine a racemic mixture of 2,3-dibromo butane is obtained this
could be explained by the mechanism as proposed above.
Compounds I and II are mirror images of each other. Also attack of Br anti to Brcan be by
50% attack a and 50% attack b thus leading to racemization.
However addition of bromine on trans but-2-ene leads to meso compound formation.


H Me H Br
Me
C=C C–C –
+ Br2 + Br
Me H Me H
Br
Br Br
H Me
C C III
 H
H Br (a) Me
Me Br Me H H Me
C–C
Me H Br
Br Br
Me (a) Br – (b) H (b)
C C IV
H
H Me Br Me
H Me
Compound III and IV are identical and possess a plane of symmetry and hence are meso form.
3 Addition of Hydrogen Halides
An alkene is converted to alkyl halide by HCl or HBr or HI.
C C  HX 
 C C
H X
H3C
H3C CH  HCl 
 CH3
CH2 Cl
CH2 = CH2 + HI CH3 – CH2 – I
The reaction is frequently carried out by passing dry gaseous hydrogen chloride into alkene.
Sometimes it is carrried out in moderately polar solvents like CH3 COOH, which dissolves both
the polar HX and the non polar alkene.
The order of reactivity of HX is HCl < HBr < HI
When the alkene is symmetrical like CH2 = CH2 or CH3–CH=CH–CH3, etc. then the addition of
HX may go to any C-atom carrying a double bond.
CH2 = CH2 + HBr CH3–CH2–Br
CH3–CH = CH–CH3 + HBr  CH3 – CH – CH2 – CH3

Br
But if the alkene is not a symmetrical like CH3–CH=CH2, C2H5–CH=CH2 then addition of HX
takes place according to Markownikov’s rule which states that
“In addition of an acid to carbon-carbon double bond of an alkene, the hydrogen atom of the HX
attaches itself to the carbon atoms that has greater number of hydrogen.”
H3C
H3C CH  HBr 
 CH3
e.g.,
CH2 Br
H3 C CH3
C  H3 C
CH2  HCl  C CH3
H3 C Cl
Peroxide Effect: Addition of HCl and HI to alkenes follows Markownikov’s rule. But HBr
addition in the presence of peroxides gives Anti Markownikov’s product due to free radical
addition.
H3C
HBr
H3C 
 CH3
CH2 Br
Markownikov's product
HBr
H3C 
Peroxide
 H3C
CH2 Br
Anti-markownikov's product
H3C
Peroxide
H3C H3C Br
HBr Anti Markownikov's Rule
CH2
CH3
H3C No Peroxide
H3C CH3
Br
Markownikov's Rule
Mechanism of Free radical addition: Addition of HBr in the presence of peroxide is a free
radical addition.
C6 H 5  CO  O  O  COC6 H 5  2C6 H 5COO
Peroxide

C6 H5 COO  HBr   C6 H 5 COOH  Br 
 
Br
CH3  CH  CH 2  CH 3  C H  CH 2 Br (formed)
Br
CH2 (not formed)
H3 C

 CH 3CH 2 CH 2 Br  Br 
CH3 CH C H 2 Br  HBr 
4. Addition of H2 SO4: Alkenes react with cold concentrated sulphur acid to form compounds of
general formula ROSO3 H, known as alkyl hydrogen sulphate. The reactions are again highly
regeioselective and follow the Markow nikov’s Rule.
98% H 2SO 4
CH 2  CH 2  CH 3CH 2 OSO 3 H
Ethyl hydrogen sulphate
H3C
H3C 80% H 2SO 4
 CH3
CH2 O
SO 3H
Isopropyl hydrogen sulphate
The alkyl hydrogen sulphates are deliquiecent solids and are difficult to isolate.
When such an alkyl hydrogen sulphate is diluted with water and heated, we get an alcohol
bearing the same alkyl group. T
98% H2 O
CH 2  CH 2 
H 2SO4
 CH3  CH 2  O  SO3 H 
Δ
 CH3  CH 2  OH  H 2SO 4
H3C H3C
80% H 2O
H3C 
H 2SO 4 CH3 
 Δ CH3  H 2SO 4
CH2 O HO
SO3H
H3C CH3 OH
63% H2 O
CH2  H C
H 2SO 4 CH3 
 H3C CH3  H 2SO 4
3 Δ
H3C
O CH3
SO3H
This sequence of the reaction provides a good route for preparing alcohols.
5. Addition of H2O: Water may be added to alkenes in the presence of dilute acids to yield
alcohols and the reaction also follows Markow nikov’s rule.

H
CH 2  CH 2  H 2 O   CH 3  CH 2  OH
H3C OH

H
CH2  H 2 O  H3C CH3
H3C CH3
6. Addition of Hypohalous Acids: The addition of Cl2 or Br2 in the presence of water can yield
compounds containing halogen and OH on adjacent C-atoms and such compounds are called
halohydrins.
H2 O
H2C CH2  Br2   Br
OH
H3C
H2O
H3C  Cl2  
CH2 HO Cl
H 2 O  Cl2 
 HOCl  HCl
There is evidence of a kind that these compounds are not formed due to the formation of HOX
but by reactions of alkene with halogen and water.
X X
X2  C C 
 C C 
 C C
OH2 OH
These reactions follow anti addition.
Though, these reactions proceed to form products which are in accordance with Markownikov’s
rule, the stereochemistry suggests that the reaction is via halomium ion formation and not via
formation of an open carbocation.
7. Addition of Alkenes, Dimerization: When Isobutene is reacted with H2SO4 or H3PO4 that is
a protic acid then we get a mixture of two alkenes with molecular formula C8H16
CH3 CH3 CH3 CH3 CH3

H2SO4
CH3 – C = CH2 CH2 = C – CH2 – C – CH3 + CH3 – C = CH – C – CH3 H2/ Ni
80ºC 
CH3 CH3
(CH3)2CHCH2 – C(CH3)3
Isooctene
Mechanism
CH3 CH3
–
CH3 – C = CH2 + H2SO4 CH3 – C – CH3 + HSO4

CH3 CH3 CH3 CH3

CH3 – C = CH2 + CH3 – C – CH3 CH3 – C – CH2 – C – CH3
 
CH3
CH3 CH3
CH2 = C– CH2 – C – CH3
CH3 CH3 (a)
CH3
CH2 – C – CH – C – CH3 CH3 CH3
 (b)
H H CH3 CH3 – C= CH – C – CH3
CH3
–
HSO4
8. Addition of Alkanes (Alkylation): When alkenes are reacted with alkanes in the presence of
H2 SO4 or HF at 0ºC then we get a higher homologue of alkane.
CH3 CH3 Me Me
H2SO4
e.g. CH3 – C = CH2 + H – C – CH3 Me – C– CH2 – C – Me
or HF
CH3 0º C H Me
Mechanism
Me Me
–
Me – C= CH2 + HF Me – C – CH3 + F

Me Me Me Me
Me – C – CH2 – C – Me Me – CH – CH2 – C – Me + Me3 C+
 Me
Me Me
H – C– Me
Me
9. Oxymercuration - Demercuration : Alkenes react with mercuric acetate in the presence of

water to give hydroxy mercurial compounds which on reduction yields alcohols as follows.
i) C= C + H2O + Hg (OAc)2 (mercuration)
NaBH4 – C – C–
ii) (demercuration)
OH H
Oxy mercuration-Demercuration is highly regeioselective and gives alcohols according to
Markowni kov’s Rule.
CH3 CH2 CH2 CH2 CH = CH2 Me CH2CH2CH2 – CH – CH3

OH
Me Me
Me – C= CH2 Me – C – Me
OH
Me Me
Me – C – CH = CH2 Me – C – CH – Me
Me Me OH
Mechanism:
Oxymercuration involves electrophilic addition to carbon-carbon double bond with the mercuric
ion acting as electrophile.
Me Me Me Me
Since Me – C – CH = CH2 gives only Me – C – CH – Me and not Me – C – CH – Me it is indicated
Me Me OH OH
that the mechanism does not involve any rearrangement, thus carbocations is not formed. But it
proceeds via a cyclic mercurinium ions.
2+
2+ H2 O NaBH4
– C = C– + Hg – C – C– – C – C–
Hg OH H
Mercuration can be carried out in different solvents to yield products other than alcohol.
10. Hydroboration–Oxidation: When alkenes are reacted with dibroranes (B2H6) alkenes undergo
hydroboration to yield alkyl boranes (R3B) which on oxidation give alcohols.
CH2 = CH2 + B2H6 — (CH3 CH2)3B

–
(CH3CH2)3B + 3H2O2 OH CH3CH2 – OH + B(OH)3
All Hydroboration - oxidation, reactions are also highly regeioselective, however here the product
formed is according to Anti Markownikov’s Rule.
H2 O2
CH3 – CH = CH2 + B2H6 — (CH3CH2CH2)3B – CH3CH2CH2 – OH + H3BO3
OH
H2 O2
CH3 CH2CH = CH2 + B2H6 — (CH3CH2CH2CH2)3B – CH3CH2CH2CH2 – OH + H3BO3
OH
CH3 CH3
(i) B2H6
CH3 – CH = C – CH3 CH3 – CH – CH – CH3
–
(ii) H2O2 / OH
OH
Thus rearrangement does not occur in Hydroboration.
Mechanism
Just as alkenes react with HZ (acidic compounds) so also they react with BH3, which also is
a lewis acid.
H3C  
 H BH2
CH2
i.e. H3C H
2CH 3CH  CH 2
B  (CH 3CH 2 CH 2 )3 B
H
The intermediate mono-addition product is stablized as
This reaction is a syn-addition reaction
10. Oxidation Reactions in Alkene
(i) Hydroxylation (Using Bayers Reagent): When an alkene is reacted with dilute alkaline KMnO4
solution in cold condition then the alkene is converted to vicinal dihydroxy compound.
CH2 – CH2 + MnO2

OH OH
(Colourless)
alk KMnO4
CH3 – CH = CH2 CH2 – CH – CH2
(Cold)
OH OH
Mechanism
–
O
C C–O
– Mn
+ MnO 4
C C–O
O
–
O
C–O C – OH
Mn –
C–O OH + MnO2
O C – OH
This reaction which gives rise to vicinal diols and is a syn-addition reaction.
This is supported by the mechanism that the oxygen atoms of OH group in the diol formed are
from the permanganate ions which add to the alkene molecule from the same side.
(ii) With OS O4 (Osmium tetraoxide)

R H R CH OH
C R CH O O
NaHSO3
 OsO 4 
 Os 
Δ

C
R H R CH O O R CH OH
Osmic ester
This is again a syn-addition reaction
(iii) With hot KMnO4: Alkenes on reaction with hot alkaline KMnO4 give a mixture of carboxylic
acid and ketones or only ketones or carboxylic acids.
(O) (O)
CH 2  CH 2 
Hot KMnO4
2HCOOH 
Δ
2CO2  2H 2 O
(O)
CH3  CH  CH 2 
Hot KMnO4
CH 3COOH  CO2  H 2 O
H3C H3C
(O)
CH2 
Hot KMnO4 O  CO 2  H 2 O
H3C H3C
(iv) Ozonolysis Reaction: All alkenes react with Ozone to form an Ozonide.
O
C C  O3 
 C C
O O
Such Ozonides may be cleaved in 3-ways
Hydrolytic/ Reductive
C=O+O=C
Zn / H2O
O
(Removing H2 O2 formed)
Oxidative
C C Carboxylic acid + Ketones
(with out Removing H2O2 formed)
O O
Strong Reductive p- alcohol + s-alcohol

Li AlH 4 or H2 /Ni
or H2 /Pt or H 2/Pd
(i) Ozonolysis of Propene

O
O3
CH3 – CH = CH2 CH3 – CH CH2
O O
Zn/H2O LiAlH4
(Removing H2O2 (Without Removing
H2O2 formed)
formed)
CH3 CHO + HCHO CH3 COOH CH3 CH2 – OH

+ +
HCOOH CH3OH
(ii) Ozonolysis of 2-Methyl but-2-ene

CH3 O CH3
O3
CH3 – CH = C CH3 – CH C
CH3 CH3
O O
LiAlH4
Zn/H2 O (Without Removing
(Removing H2 O2 H2 O2 formed)
formed)
CH3 CH3 COOH CH3 CH2 – OH
CH3 CHO + C=O
CH3 + CH3 CH – CH3
CH3
C=O OH
CH3
Note Only
CH3CHO gets converted to acid
i.e. aldehydic part gets converted to
carboxylic acid
Ozonolysis reactions help to locate the positions of double bond in alkene.
(v) Addition of Oxygen: Alkenes add oxygen in the presence of silver as catalyst at 570K to form
epoxides.
1 Ag CH2 – CH2
CH2 = CH2 + O
2 2 570K O
Ethylene oxide
1 Ag R – CH– CH2
R – CH = CH2 + O
2 2 570K O
11. Substitution Reactions: Most alkenes contain not only the C–C double bond but also alkyl
groups which have essentially alkane character. Alkenes may undergo the free radical substitution
which is a characteristic of alkanes.
Halogenation, Allylic Substitution
H–C–C–C– + X2 X– C–C=C–

Low concentration
Cl2
CH3 – CH = CH2 Cl – CH2 – CH = CH2
700º C
Br
+ N- Bromo succinimide (This reaction is called Wohl-Zeigler reaction)
When we consider the molecule of propene

H
H – C – CH = CH2 Site - I
H
Site - II
The Site-I is the alkene site where due to the presence of reactive -bonds the reaction can take
place at low temperature, in the absence of light and generally in liquid state. While site-II is the
alkane site which requires high temperatures or U.V light. If we try to make the reaction possible
at site-II, we must take the necessary condition of high temperature or U.V. radiations.
Cl2 lower temp
CH3 – CH – CH2
CCl4 solution
Cl Cl Ionic
CH3 – CH = CH2
Cl2 500 – 600º C Cl – CH2 – CH = CH2
Gas phase (Free Radical)
Mechanism of allylic substitution:
high temp. .
Inilation X2 2X
U .V .
Propogations:
X  CH3  CH  CH 2 
 HX  CH 2  CH  CH 2
H2C  XX
CH2
X
 X (This step repeats)
CH2
H2C  Cl
 SO 2 Cl2   HCl
Also
CH2 CH2
12. Addition of Carbenes: Alkenes react with diazomethane to form cyclic compounds.
H3 C
H3 C  CH 2 N 2 
 HC CH2
CH2 CH2
- + hν
H2C N N   CH2  N 2
Mechanism, Carbene
H3 C  CH2 
 H3 C
CH2 HC CH2
CH2
13. Addition of Free Radicals: Analogous to free radical addition of HBr to alkenes, even CCl4 or
CBr Cl3, or CBr2 Cl2 can be added on to alkenes by using certain conditions favourable for free
radical addition reaction.
Cl R
R  Cl Cl 
Peroxide
Cl
CH2 Cl Cl
Cl
Cl
Mechanism:
 2C6 H 5 COO
(C6 H 5 CO) 2 O 

C6 H 5 COO   CCl 4 
 C 6 H 5 COOCl  C Cl3
Cl R
Cl   H3C CH Cl
C CH2 
Cl Cl
Cl
H3C CH Cl R Cl
C Cl  Cl 
 CH2 C Cl
Cl Cl Cl
14. Isomerization: Alkenes isomerise when heated at high temperature or at lower temperature in
the presence of catalyst.
770 870 C
CH3 CH 2 CH 2 CH  CH 2 or
 CH3  CH 2  CH  CH  CH 3
Al3 at 470 510 C
15. Polymerization
Δ/ Pr essure
nCH 2  CH 2  O2
(CH  CH) 
n Polyethene
Traces of O 2
nCH 2  CH  Cl   (CH  CH )n Polyvinylchloride (PVC)
|
Cl
Δ
nCF2  CF2   (F2 C  CF2 ) 
n Polytetrafluoro ethylane (PTFE)
Illustration 1: Give the structure of the alkene that would yield the following product (a bromohydrin)
when allowed to react with bromine water.
HO CH2 Br
Solution: The alkene is methylenecyclohexane. The addition of Br2 + H2O takes place according to
Markownikoff’s rule to give the product.
CH2 HO CH2 Br
Br2

H 2O

Illustration 2: Write the product of the following reactions:

CH3
(a) (b)  HCl 


 HBr 

H3C CH3
KMnO4
CH C 
Δ KMnO 4
(c) (d) CH3 CH2 CH2 CH CH2 
Δ
CH3
Br CH3
Solution: (a) (b)
Cl
H
H 3C
C O
(c) CH 3COOH  (d) CH2CH2CH2COOH + CO2
H 3C
Illustration 3: Write the product of the following reactions:

CH3
(i) NBS, CHCl3

(ii) (CH3 )3 N

(a)  HOBr 
 (b)
O
HO CH3
Br
O
Solution: (a) (Addition takes place (b) (Allylilc bromination
according to followed by HBr
Markownikoff rule) elimination
Illustration 4: From which alkenes could one synthesise the following alcohols by hydroboration oxidation?
CH3
CH3
OH CH2 CH2 CH2 HC
(a) (b) OH
CH3
CH3 CH3
OH
Solution: (a) BH 3 /THF
 

H 2O 2 , OH
CH3
H CH2 HC CH3
(i) BH 3
(b) C C CH3  OH CH2 CH2 CH2 HC
(ii) H 2O 2 , OH 
H H CH3
Illustration 5: An alkane (A) C 5H12 on chlorinations at 300ºC gives a mixture of four different
monochlorinated (B), (C), (D) and (E). Two of these derivatives give the same stable alkene
(F) on dehydrahalogenation. On oxidation with hot alkaline KMnO4 followed by acidification
(F), gives two products (G) and (H). Give structure of (A) to (H) with proper reasoning.
Solution : 1. Alkane (A) C5 H12 on chlorination gives four monochloro product and hence it should be
isopentane.
CH3 – CH – CH2 – CH3
CH3
n-Pentane would give 3-mono chloro Products and neopentane gives only one mono
chloro product
Cl Cl
CH3 – CH – CH2 – CH3 Chlorination CH2 – CH – CH2 – CH3 CH2 – C – CH2 – CH3
(B) (C)
CH3 CH3 CH3
Cl
CH3 – CH – CH – CH3 CH3 – CH – CH2 – CH3
(D) (E)
CH3 CH3
CH2 – CH – CH2 – CH3 Dehydrohalogenation CH2 = C – CH2 – CH3

(B)
Cl CH3 CH3
Cl
CH3
(C) CH3 – C – CH2 – CH3 Dehydrohalogenation C = CH – CH3
CH3 CH3 Major
CH3
(D) CH3 – CH – CH – CH3 C = CH – CH3
CH3
CH3 Cl (F)
CH3 – CH – CH2 – CH2 – Cl CH3 CH – CH = CH2

CH3 CH3
(E)
CH3 KMnO4 CH3
CH3 C = CH – CH3 CH3 C = O + CH3 COOH
(G) (H)
Illustration 6: A certain hydrocarbon (A) was found to contain 85.7% carbon and 14.3% hydrogen.This
compound consumes 1 mole of hydrogen to give a saturated hydrocarbon (B) 1 g of
hydrocarbon (A) just decoloursed 38.05 g of a 5% solution by weight of Br2 in CCl4. Compound
(A) on oxidation with concentrated KMnO4 gave compound (C) (molecular formula C4H8O)
and acetic acid. Compound (C) could easily be prepared by the action of acidic aqueous
H2SO4/HgSO4 on 2-butyne. Determine the formula of (A) and deduce the structure of
A, B and C.
Solution : a) Element %age At. Mass Relative No. Simple Atomic

of Atoms ratio
85.7 7.14
C 85.7 12  7.14 1
12 7.14
14.3 14.3
H 14.3 1  14.3 2
1 7.14
 Empirical formula compound = CH2
b) Synthesis of compound (C) :

O
H2O
CH3 – C  C – CH3 CH3 – C – CH2 CH3
H2SO4 + HgSO4
Butane - 2 Butanone - 2 (C)
c) Structure of A. Since A, upon oxidation gives Butanone-2 (C) and CH3COOH, it is

alkene of the type
C2H5 – C = CH – CH3
CH3
3 - Methylpentene - 2
Reaction :
O
O O KMnO 4/H 2SO4
H3 C – CH2 – C == CH – CH3 H3 C – CH2 – C – CH3 + H3C COOH
Butanone - 2 Acetic acid
CH3
CH3 – CH2 – C = CH – CH3
CH3
Thus (A) is
3 - Methylpentene - 2 - ene (C6H12 with empirical formula CH 2)
d) The compound (A) consumes 1 mole of H2 to give a saturated hydrocarbon (B). Thus
(B) should be
H H Nil
H3 C – CH2 – C == CH – CH3 + H2 H3 C – CH2 – CH – CH – CH3
CH3 CH3
3 - Methylpentene - 2 3 - Methylpentane
(A) (B)
e) (A) decolourises Br2

Br Br
H3C – CH2 – C = CH – CH3 + Br2 H3 C – CH2 – C – CH – CH3
Orange
CH3 CH3
3 - Methylpentene - 2 2, 3 - Dibromo - 3 - methylpentane
84 g of alkene (A) consumes Br2 = 160 g

160 1
1g of alkene (A) consumes Br2 = = 1.90 g
84
Wt. of Solute
Wt. of bromine in 5% solution =  100
Wt. of Solution
1.9
or 5 =  100
Wt. of Solution
1.9  100
 Wt. of Solution = = 38g
5
This is in agreement with given data.
Illustration 7: It required 0.70 g of a hydrocarbon (A) to react completely with Br2 (2.0g). On treatment of
(A) with HBr, it yielded monobromo alkane (B). The same compound (B) was obtained
when (A) was treated with HBr in the presence and absence of peroxide. Write down the
structural formulae for (A) and (B) and explain the reactions involved.
Solution : Since hydrocarbon (A) consumes only one mole of bromine, therefore, it should be an alkene.
M.W. of Br2 = 2  80 = 160
2g of Br2 reacts with alkene = 0.70 g
0.70  160
160g of Br2 reacts with alkene = = 56g
2
Since molecular weight of alkene is 56,
therefore, possible alkene may be = CnH2n  12  n + 2n = 56

 14n = 56, n = 4  CnH2n is C4H8
C4 H8 has three possible isomers as alkene
H3C – CH2 CH = CH2 CH 3 CH = CH CH3
Butene - 1 Butene - 2
H3C
C = CH2
H3C
Isobutene (2-Methylpropene-1)
Since monobromoalkane obtained on adding HBr to (A) is same with peroxide or without
peroxide, it suggests that alkene should be symmetrical, i.e. butene-2
H3 C – CH = CH – CH3 + HBr H3 C – CH – CH2 – CH3
Butene - 2
Br
2-Bromobutane Br
Since, Butene–1 and Isobutene give different products, they are ruled out.
HBr
C2H5CHBrCH3
C2H5 – CH =CH2 – HBr. Peroxide
Butene - 1 C2H5CH2CH2Br
(A)
Since, (B) is not the one single product, so this structure of (A) is ruled out.
HBr
CH3CH2CHBrCH3
CH3 – CH = CH– CH3 – HBr. Peroxide (B)
Butene - 2 CH3CH2 CHBrCH3
(A)
(B)
Since, A here gives (B) which is one single product.
Thus, (A) is Butene-2, a symmetrical alkene which shows cis-trans isomerism.
Illustration 8: Compound A, C6H12O, is reacted with conc. H2SO4 to form compound B, C6H10. When (B)
is treated with Cl2 at 400º C, compound (C), C6H9Cl, is obtained. Then (C) is treated with
alcoholic KOH to form (D), C6H8, which reacts with 1 mole of Br2 at low temperature to
form the compound (E), C6H8Br2. (E), upon ozonolysis followed by hydrolysis forms only
O O
H– C – CHBr – CHBr – CH2CH2 – C – H as a product. From the above information, deduce
the structure of compound (A) to (E)
Solution : (A) The product of ozonolysis is
O O
H– C – CH – CH – CH2 – CH2 – C – H
Br Br
Going backward
Br
2 1 Br
HC CH
2
2 1
Br – HC CH2 1
4 5
or
(C6H8Br2)
Br – HC CH2
(E)
(B) Since (E) is obtained from (D) C 6H8 on absorbing one mole of Br 2, therefore,
(D) must be
Br
Br
(D) + Br2
Cyclohexadiene (E)
(C) Since (D) is obtained from (C) C 6H9Cl on treatment with alc. KOH, it suggests
that (C) may be either 3-chlorohexene or 4-chlorohexene.
Cl
alc. KOH alc. KOH
   
(C6H9Cl) (D) 4-chlorohexene

3-Chlorocyclohexene
(D) Since (C) is obtained from (B) C6H10 on treatment with Cl2 at 400ºC, therefore, (B)
must be,
Cl
Cl2
400ºC
(B) –HCl
Cyclohexane (C)
(E) Since (B) is obtained from (A) C6H12O on treatment with conc. H2SO4, therefore, (A)
must be.
OH
Conc.H2SO4
(C6H12O) –H 2O
(B)
(A)
OH Cl Br
Br
Hence A = B= C= D= E=

Problem 1: The reaction of propene with H3O+ will proceed with which of the following intermediates?
H3C +
H3C CH
(a) + (b)
OH2 OH
+
OH2 OH
H3C
(c) H3C (d)
CH3 CH3
Solution: (c) The reaction proceed with the Markovnikoff addition of water.
Problem 2: Which is a likely product of the reaction shown?
H3C H
CH3
Br2 /CH 3OH
 
H3C Br H3C O CH
CH3 Br 3
(a) O (b) CH3
CH3
CH3 H CH3
Br O CH3
CH3 CH3
(c) (d)
Br Br
H3C H H3 C H
H CH3
CH3 CH3 O CH3
+
Br2 /CH 3OH
 Br CH 3  O  H

Solution: (d) CH3
Br
Problem 3: Addition of one equivalent of Br2 for 1,3-pentadiene produces
(a) 4,5-Dibromo-2-pentene (b) 3,4-Dibromo-1-pentene
(c) 3,4-Dibromo-2-pentene (d) 1,4-Dibromo-2-pentene
+ Br
Br 
Solution: (d) H2C CH3  Br2 

 Br
 Br
1,4-addition takes place.
Problem 4: The nodal plane in the p-bond of ethene is located in

(a) The molecular plane
(b) A plane parallel to the moleculr plane
(c) A plane perpendicualr to the molecular plane
(d) A plane perpendicular to the palne which contains the C – C  bond.
Solution: (a)
Problem 5: During debromination of meso-2, 3-dibromobutane, the major product is

(a) n-Butane (b) cis-2-Butene
(c) 1-Butene (d) trans-2-Butene
Solution: (d) racemic 2, 3-dibromobutane gives the trans-isomer
Problem 6: The principal product formed in the reaction of

Peroxide
CH 2  CH(CH 2 )8 COOH  HBr    is
Br
(a)
H3C COOH
COOH
(b) Br
Br
(c)
H2C COOH
Br
H2C
(d)
O
Solution: (b) Anti Morkovnikoff addition
OH
Problem 7: The reaction of with HBr gives.
H3C
Br
H3C
H3C
(a) Br (b) Br
Br
Br
H3C
H3C
(c) (d) OH
OH
Br
Solution: (d) By the addition of H+, following stable carbocation is formed. Which gives the desired
product.
H3C
+
CH OH
Problem 8: Which of the following alkenes will react slowest with H2 under catalytic conditions?
R R R H
(a) (b)
H H R H
R R R R
(c) (d)
R H R R
Solution: (d) Steric hindance
Problem 9: Which of the following alkene would have the highest heat of hydrogenation?
(a) CH2 = CH2 (b) CH3CH2CH = CH2
H3C CH3
(c) CH2CH = CHCH3 (d)

H3C CH3
Solution: (a) Most unsubstituted alkene
Problem 10: Hydroboration oxidation of 1-methylcyclopentene will give

(a) trans-1-Methycyclopentan-2-ol (b) cis-1-Methylcyclopentane-2-ol
(c) 1-Methylcyclopentan-1-ol (d) Mixture of A and B
Solution: (a) syn addition of diborane takes place.

ALKYNES
After having discussed about the C–C double bond, we come to carbon-carbon triple bond, i.e., the functional
group of the family of alkynes like double bond the triple bonds is unsaturated and is highly reactive.
The simplest member of the Alkyne family is acetylene, i.e., C2H2 or H – C  C – H.
Quantumn mechanics gives a good picture about acetylene and C–C triple bond.
The electronic configuration of carbon atom is 1s2 2s2 2px1 2py1.
1s 2s 2p
carbon (Ground state) =
Exited state


H-atom H-atom H H
s – sp sp – s
 bond  bond
 bond
 bond  - cylindrical chord
 bond sp – sp overlap
The structure of acetylene shows that it undergoes the same addition reactions as of alkenes.
Also if you consider the H-atom attached to the carbon atom, i.e., H-atom attached to sp hybridized carbon
atom which is more acidic than the H-atom attached to sp2–carbon as in alkenes or the sp3-carbon atom as
in alkanes.
The electro negativity of the carbon atoms is sp (carbon) > sp2 (carbon) > sp3 (carbon). Hence, acidic
character of H-atom is H(s–spC) > H(s–sp2 C) > H(s–sp3C).
3.5 Preparations
Dehydrohalogenation
1. From Alkyl Dihalides(Vicinal or geminal)

H Br H H H Br
alc. KOH NaNH 2
H C C alc. KOH
 H
H  C CH   C C  H C C H
 HBr
H Br Br Br H H
2. From Tetrahalides (Dehalogenation): All vicinal tetrahalogen compounds on heating with

zinc give alkynes
Cl Cl
2 Zn
– C – C– – C  C – + ZnCl2

Cl Cl
CHCl2
2 Zn
e.g. CH  CH + 2 ZnCl2
CHCl2 
3. From Haloform: When haloforms are heated with silver powder we get acetylene
2CHX3 + 6Ag 6 AgX + CH  CH


2CHI3 + 6Ag 6 AgX + CH  CH


4. Kolbe’s Electrolytic Decarboxylation: When unsaturated carboxylic acids salt are electrolysed
CH – COOK electrolysis
CH  CH + 2KOH + 2CO2 + H2
CH – COOK
Mechanism:
(aq) H
H COO– K C
COO–
C
electrolysis +K
C C
H COO– K (aq)
H COO–
At cathode
H2O H + OH–
2H+ + 2e– H2
At Anode
O O
H - H
O O
- 
  2e 
O O
H H
O O
O
H
O

 H C C H  CO2
O
H
O
5. From Lower Homologues to Higher Homologues
Because of the acidic characters the terminal H-atom in acetylens, the same can be replaced by
sodium with NaNH2 and finally with alkyl group by reacting with an alkyl halide.
 H  C  C Na   NH3
H  C  C  H  NaNH 2 
 Na  C  C Na   2NH3
or H  C  C  H  2NaNH 2 
H  C  C Na   R  X 
 H  C  C  R  NaX
Na  C  C Na   R  X 
 R  C  C  R  2NaX
6. Acetylene from calcium carbide: Calcium carbide when reacted with water gives acetylene
–
C
2+
Ca
C + 2H2O H – C  C – H + Ca(OH)2
–
7. Acetylene from methane: When electric arc is passed at 1500ºC on methane we get
electric arc
2CH4 1500º C
CH  CH + 3H2
1500º C
6CH4 + O2 electric arc
HC  CH + 2CO + 10H2
8. Berthlot’s Reaction
1200º C
2C + H2 electric spark CH  CH
(electrodes)
3.6 Chemical properties

The carbon-carbon triple bond (–C C–) in alkynes consists of one -bond and two -bonds. Since
the -electrons are loosely held by the carbon nuclei so alkynes undergo electrophilic addition
reactions.
Though, alkynes undergo electrophilic addition reactions they are less reactive than alkenes. This is
because of the fact that the transition state corresponding to alkenes is more stable than the transition
state formed by alkynes.

Z
C=C +Z–Z C–C

sp2 (1) (2)
sp3

Z
– CC– +Z–Z C=C

sp (3) (4)
sp2
The alkene (1) involves the formation of (2) as transition state with sp3 C-atom where the bond
angle should have been 109º but got decreased to 60º.
Whereas the alkyne (3) involves the formation of (4) with the C-atom sp2 hybridized, where the bond
angle should have been 120° but got decreased to 60°.
Hence transition state (4) is highly strained and unstable as compared to transition state (3). Thus the
formation of transition state (4) is difficult so alkenes are more reactive than
alkynes.
Alternatively
C–C triple bond length is 120 pm that of C–C double bond is 134 pm. So in the process of overlapping
of sp hybrid orbitals and sideways p-orbitals, carbon atoms come closer in alkynes than in alkenes
which involve sp2 hybrid orbitals. As a result -electron in –C C– are held firmly than in alkenes.
Hence due to less availability of -electrons to electrophiles, alkynes are less reactive.
Alkynes also give reactions which show that the H-atom attached to triply bond C-atom, i.e.,
(R – C  C –– H ) is weakly acidic
The different reactions which are given by alkynes are:
1. Electrophilic Addition 2. Nucleophilic Addition

3. Polymerization reactions 4. Oxidation
5. Reduction 6. Acidic nature of alkynes
1. Electrophilic Addition Reactions
(a) Addition of Halogens

X X
X X
CCl4 X2
– C  C – + X2 – C – C–
– C = C– CCl4
X X
Br Br
Br2 Br Br +Br2
CH  CH H– C – C – H
CCl4 H– C  C– H CCl4
Br Br
(b) Addition of Halogen Acids
The addition of halogen acids to alkynes can take place in dark but is catalysed by light.
The order of reactivity of HX is HI >HBr > HCl.
H
HBr HBr CH3 – C – Br
H–CC–H CH2 = CH – Br
Br
Br
The compound CH2 = CH–Br gives only CH3 – CH Br
and not CH2 – CH2 , this is because
Br Br
   ..
the carbocation formed is CH3 – CH – Br and not CH2 – CH2Br as CH3 – CH – Br
.. : is
resonance stabilized.
Similarly,
Br
CH3 – C = CH2 HBr
CH3 – C  CH + HBr CH3 – C – CH3
Br Br
Addition of HCl in the presence of HgCl2 gives ralogenated alkene.
HgCl2
CH  CH + HCl 65º C
CH2 = CH – Cl
(c) Addition of Hypochlorous Acid
Cl2 + H2O HCl + HOCl
Hypochlorous acid
Cl
OH –H2O Cl2 CH – C = O
CH  CH + HOCl H – C = CH H – C – CH Intramodecular
OH dehydration H
Cl OH Cl
(d) Addition of H2O (Hydration): When acetylene is passed through dil H2SO4 in the presence
of mercuric sulphate at 60ºC it forms vinyl alcohol which tautomerizes to form acetaldehyde
CH2 CH3
H C C
dil. H 2SO 4
H  H 2 O 
HgSO 4
 H3C  H3C

60 C
O H O
Vinyl alcohol Acetaldehyde
dil H2SO4
– C  C – + H2O – C  C– Tautomerization – C — C–
HgSO4
60º C OH O H
This reaction is called Kucherov’s Reaction.
CH2 CH3
dil. H 2SO 4
H3 C C CH  H 2 O  H3C
HgSO 4
 H3 C

60  C
OH O
(e) Addition of Acetic Acid
Hg2+
CH  CH + CH3 COOH CH2 = CH – O – C– CH3
(vinyl acetate) O
Hg2+
CH2 = CH – O – C– CH3 + CH3 COOH CH2 – CH (O – C– CH3 )2
O (ethylidene diacetate) O
Vinyl acetate is used to produce synthetic rubber and plastic. Ethylidene diacetate is used in
the manufacture of acetaldehyde.
(f) Addition of AsCl3
CH  CH + AsCl3 —– CHCl = CHAsCl2

Lewisite or Lewis gas (war gas)
Its antidote is British Anti Lewiste (B.A.L.)
CH 2  SH
|
CH  SH
|
CH 2 OH
2. Nucleophillic Addition Reactions: Normally alkynes do not undergo nucleophilic addition

reactions due to high electron density at the acetylenic carbons. However in the presence of
heavy metal ions like Pb2+, Hg2+, Ba2+, etc., they undergo nucleophilic addition. The heavy
metal ion forms a-complex and the loosely bound -electrons displaced towards the heavy
metal ion. As a result the electron density at the acetylenic carbon decreases and facilitate
nucleophilic attack at triply bonded c-atoms.
– C  C– + M2+ – C  C–
M2+
 - complex
M = Pb, Ba, Hg
H 2O
– C  C– – C  C– – C  C–
Nu
M+ Nu H Nu
M2+
Alkynes undergo nucleophillic addition reactions easily as compared to alkenes.
(i) Addition of HCN: When acetylene or any alkyne reacts with HCN in the presence of
Ba(CN)2 they form vinyl type cyanides.
Ba (CN)2
– C  C – + HCN – C=C–
H CN
Vinyl cyanide
Ba (CN)2
H – C  C – H + HCN CH2 = CH CN
Acrylonitrile
(ii) Addition of MeOH: Methyl alcohol adds on to acetaldehyde at 160ºC to 200ºC in the
presence of potasium methoxide and high pressure to form vinyl methyl ether.
CH3 OK
CH  CH + CH3 OH CH2 = CH – O – CH3
160 – 200º C
Vinyl methyl ether
High Pressure
(iii) Addition of Diborane
1 R R
R – C  C – R + BH C=C
2 2 6 H BH2
0º C
CH3COOH
R R
C=C
H H
(i) 1 B 2 H 6
2 CH3CH CH3
CH3CH2C C – CH3 (ii) 0ºC acetic acid C=C
H H
(i) 1 B2H6
2
R–CC–H (ii) H2O2/H
R – CH = CH – OH —– R – CH2CHO
(i) 1 B2H6
2
CH3 – C  CH (ii) H2O2
CH3 – CH2 – CHO
3. Polymerization Reactions
Re d Hot
1. 3CH  CH 
Iron tube

Ni(CN) 2
4CH  CH  
2.
Me
3. H C C
Re d Hot
CH  
3 Fe tube
Δ
Me Me
4. When acetylene vapours are passed through solutions of cuprous chloride and ammonium
chloride at 343 K, vinyl acetylene or divinyl acetylene are formed.
CuCl CH2 = CH – C  CH
2CH  CH
NH4Cl Vinyl acetylene
CuCl + NH4Cl
3 CH  CH CH2 = CH – C  C – CH = CH2
343 K Divinyl acetylene
Vinyl acetylene is the starting material for the manufacture of Neoprene.
Cl
CH2 = CH – C  CH + HCl CH2 = CH – C  CH2
(Chloroprene)
Cl Cl
CH2 = CH – C  CH2 Traces of
O2
(CH2 – CH  C – CH2 )n
(Neoprene)
4. Oxidation Reactions
(a) With alkaline KMnO4 (cold)
OH
HC OH
HC CH  alk. KMnO 4 

HC OH
OH
H
HO OH
C O 2(O)
COOH
CH HC 
  
C O COOH
HO OH
H Oxalic acid
OH OH R R
2H 2 O
R C C R   alk. KMnO 4 
R C C R   C C
OH OH O O
(b) With Selenium Dioxide:

CH  CH + SeO2 CHO – CHO

(c) With Chromic Acid:

Chromic acid oxidises acetylene to acetic acid
K2Cr2O7 + H2SO4
CH  CH + H2O + |O| CH3 – COOH

(d) Ozonolysis reactions
O
–C–C–
O–O
O3
–C  C– Zn + Acid Li AlH4
H2 O
–C–C– Alcoholic compound
Acidic and
O O + Ketonic compound O
H– C – C – H
O–O
Zn / HCl
Li AlH4
(– H2O2)
e.g. H – C  C – H + O3 (+H2O2 )
H–C–C–H COOH – COOH CH2 – CH2
O O OH OH
(e) Complete Combustion:
All alkynes undergo complete combustion to form CO2 and H2O.
 3n 1 
Cn H2n – 2 +  2  O2 n CO2 + (n – 1) H2O
 
(f) Other Reactions:

HC CH
CH  CH  S 
Δ

HC CH
(i) S
Thiophene
Electric
(ii) CH  CH  N 2 
Spark
 2HCN
Hydrocyanic acid
HC CH
CH  CH  NH3 

HC CH
(iii) NH
Pyrrole
5. Reduction Reaction
(a) Catalytic Reduction (SABETIER SENDREN’S).
H2 /Pt or Ni or
R – C  C – R R – CH2 – CH2 – R
Pd

(b) When catalytic hydrogenation is done in the presence of Pd – Ba CO3 (Lindlar’s catalyst)
only partial reduction to alkenes takes place and the alkene product is cis.
R R
R – C  C – R Na / NH 3
  C=C
H H
(cis-isomer)
This can be done on terminal as well as non-terminal alkynes
(c) Reduction with Na/liq. NH3

This reduction can be carried out to give trans products only. (Birch Reduction)
R H
R – C  C – R 
Na / NH 3
 C=C
H R
trans-isomer
6. Acidic Nature of Alkynes
Distinction Between Terminal And Non-Terminal Alkynes

All terminal alkynes contain acidic H-atom. Hence such H-atom may be replaced by metals while
non-terminal alkynes do not have acidic H-atoms hence they will not react with metals.
(a) Tollen’s Reagent
Ammoniacal Silver nitrate solution is called Tollen’s reagent.
Alkynes containing acidic H-atoms will react with Ammoniacal silver nitrate solution.
HC  CH + 2[Ag(NH3)2]+ OH– AgC  CAg

White ppt
(Silver acetylide)
R – C  CH + [Ag(NH3)2]+ OH – R – C  CAg
(b) Ammoniacal Cuprous chloride
CuCl + NH4OH NH4Cl + CuOH

CuOH + NH4 OH (Cu(NH3)2)OH + 2H2O
HC  CH + 2[Cu(NH3)2]OH CuC  CCu
(Cuprous acetylide) Red ppt.
RC  CH + [Cu (NH3)2]OH R – C  C – Cu
Illustration 1: An organic compound (A) of molecular formula C5H8 when treated with Na in liquid ammonia
followed by reaction with n-propyl iodide yields (B), C8H14. (A) gives a ketone C5H10O
when treated with dil. H2SO4 and HgSO4. (B) on oxidation with alkaline. KMnO4 gives two
isomeric acids (D) and (E), C4H8O2. Give structure of compounds (A) to (D) with proper
reasoning.
Solution : The molecular formula C5H8 suggests that , it is an alkyne, as it satisfies CnH2n–2, general
formula of alkyne, when n = 5.
As C5H8 reacts with Na/liq. NH3, therefore, it must be a terminal alkyne. So, possibly
compound is
CH3
H3C – CH2 – CH2 – C  CH or H3C – CH – C  CH
Pentyne-1 3-Methylbutyne
(A) I (A) II
Since compound (A) on treatment with Na/liq NH3 followed by treatement with n-propyl
iodide gives a compound (B) C8H14.
Therefore, (B) must be either Octyne-4 or 2-Methylheptyne-3.
(i) Na/liq. NH3
H3C – CH2 – CH2 – C  CH H3C – CH2 – CH2 – C  C – CH2 – CH2 – CH 3
(ii) CH3CH 2CH2I Octyne-4
(A) I
(B) III
CH3 CH3
(i) Na/liq. NH
3
H3C – CH – C  CH H3C – CH – C  C– CH2 – CH2 – CH3
(ii) CH3CH2CH2I
(A) II 2-Methylbutyne - 3
(A) IV
Since (B) on oxidation with alkaline KMnO4 gives two acids with molecular formula C4H8O2,
therefore, possible acids may be.
COOH
H3C – CH2 – CH2 – COOH H3C – CH – CH3
Butanoic acid
2-Methylpropanoic acid
(D or E)
(E or D)
The above two acids can only be obtained by oxidation of (B) - (IV).
CH3 CH3
Akl. KMnO4
H3 C – CH – C C – CH2 – CH2 – CH3 H3C – CH – COOH + HOOC – CH2 – CH2 – CH3
Isomeric acids
(D and E)
Where as,
CH3CH2CH2–CC–CH2–CH2–CH3 
alk. K MnO4
 CH3CH2CH2COOH
+COOH–CH2–CH2–CH3
Therefore, possible alkyne C5H8 is:
CH3
H3C – CH – C CH
3-Methylbutyne-1
(B)
Since (B) on treatment with dil. H2SO4 and HgSO4 gives ketone (C), therefore, possible
ketone (C) is CH3 – CH – C – CH3

CH3 O
Illustration 2: a) If a rocket were fueled with kerosene and liquid oxygen, what weight of oxygen would
be required for every litre of kerosene ? (Assume kerosene to have average composition
of n-C14H30)
b) How much heat would be evolved in the combustion of one litre of kerosene ? (Assume
157 kcal /mol for each -CH2-group and 186 kcal/mol for each-CH3 group).
c) If it were to be feasible to fuel a rocket with free hydrogen atoms, what weight of fuel
would be required to provide the same heat as a litre of kerosene and necessary oxygen.
(Assume H2 as the sole product). Density of n-C14H30 = 0.764 g/ml.
43
Solution : a) n-C14H30 + O  14 CO2 + 15 H2O
2 2
Density of Kerosene = 0.764 g/cc
Vol. of kerosene = 1000 cc
 Mass of kerosene = 1000  0.764 = 764 g
Mol. wt. of kerosene = 14  12 + 30  1 = 168 + 30 = 198
Given wt. 764

No. of moles of kerosene = = = 3.85 moles
Mol. wt. 198
1 mol. of kerosene requires oxygen = 43/2 mol
43
3.85 mol. of kerosene requires oxygen =  3.85 = 82.95 mol. = 82.95  32 = 2654 g
2
b) Molecular formula of kerosene = H3C – (CH2)12 – CH3

12 (– CH2 – ) = 12  157 = 1884 kcal
Also 2(–CH3) = 2  186 = 372 kcal
 Total heat of combustion = 1884 + 372 = 2256 k cal/mol
1 mol. of kerosene evolves heat = 2256 Kcal
 3.85 mol. of kerosene evolves heat = 2211  3.85 = 8512.35 kcal
c) H + H  H2, H = –104 kcal/mol.

104 kcal heat is evolved by H2 = 1 mol
8512.35
8512.35 kcal heat is evolved by H2 = = 81.84 mol = 81.84  2 = 163.69 g
104

Li, NH 3
Problem 1: C C C C  A. A is
(a) (b)
(c) Both (d) None of these
Solution: (b) Li-NH3 reduce an alkyne to give a trans alkene. No further reaction takes place.
Problem 2: Which of the following hydrocarbon will react with CH3MgBr?

(a) CH3CH2CH2CH2CH3 (b) CH3C  C – CH – CH3
(c) CH2C  CCH2CH3 (d) CH3CH2CH2C  CH
Solution: (d) It is a terminal alkyne and thus contains an acidic hydrogen.
Problem 3: Which reagent can easily distinguish between 1-butyne and 2-butyne?
(a) Amm. Cu2Cl2 solution (b) dil. H2SO4/HgSO4
(c) Br2/CCl4 (d) H2, Lindlar Catalyst
Solution: (a) 2CH 2CH 2 C  CH  Cu 2 Cl 2  2NH 4 OH 

 2RC  C  Cu  2NH 4 Cl  H 2O
2-Butyne does not react (Re d ppt.)
Problem 4: 1-Butyne reacts with hot alk. KMnO4 to produce

(a) CH3CH2CH2COOH (b) CH3CH2COOH
(c) CH2CH2COOH +CO2 (d) CH2CH2COOH + HCOOH
alc. KMnO 4
Solution: (c) CH3CH 2 C  CH  Δ
 CH 3CH 2COOH  CO 2
Problem 5: The following two reactions

(i) B2 H 6 
(i) CH3C  CCH3 
(ii) H 2O2 /OH 
 H /H 2 O/HgSO 4
(ii) CH 3C  CCH 3 
Yield
(a) same aldehyde (b) Different aldehydes
(c) Same ketone (d) Different ketone
Solution: (c)
Problem 6: The following reduction:

H2 , Pd/BaSO4
CH 2  CH  CH 2  C  C  CH 3 
Lindlar Catalyst

H2C H2C
H CH3
(a) (b)
H CH3 H H
CH3 H3C
(c) H C (d)
3 CH3
Solution: (b) a cis alkene
Problem 7: Which of the following compound is most acidic?

(a) CH2 = CH2 (b) CH  CH
(c) H2O (d) CH3Cl
Solution: (c)
Problem 8: What is the decreasing order of base strength of the following bases:
OH  , NH 2 , HC  C , and CH 3CH 2
(a) CH3CH 2  NH 2  HC  C  OH  (b) NH 2  HC  C  OH   CH 3CH 2
(c) HC  C  CH 2CH 2  NH 2  OH  (d) OH   NH 2  HC  C  CH 3CH3
Solution: (a)
Problem 9: Identify compound B in the following scheme:
HC  CH  O
3
 A  LiAlH
 4
B
(a) CH3OH (b) CH3CH2OH
H2C OH
(c) (d) CH3COH
H2C OH
O CH2 OH
O3 H H
HC CH   LiAlH 4
 
Solution: (c) CH2 OH
O O
Problem 10: Which of the following has the lowest dipole moment?
H3C CH3
(a) (b) CH3C  CCH3

H H
(c) CH3CH2C  CH (d) CH2 = CH – C  CH
Solution: (b) Because this molecule is symmetrical and linear.
AROMATIC HYDROCARBONS
Benzene C6 H6    (Phene)
The compound with pleasant smell (aroma) are called aromatic compounds.
These compounds contain Benzene ring with six carbon atoms, later on it was found that many compounds
we know resemble benzene in their structure but did not have any pleasant smell. So now the term aromatic
is not applied to compounds with pleasant smell but instead any compound which is benzene or which resembles
benzene in their chemical behaviour are called aromatic compounds.
3.7 Preparation
1. It was first isolated by Michael Faraday from the cylinders of compressed illuminating gas
obtained by the pyrolysis of whale oil.
2. From Acetylene : Berthalot prepared benzene by passing acetylene through red hot tube.
Red Hot
3 CH  CH
Iron tube
773 k
3. By Decarboxylation with sodalime.
COONa
NaOH + CaO
+ Na2 CO3

4. From Phenol
OH
Zn dust
 + ZnO
5. From Chorobenzene
Cl
Ni-Al alloy
NaOH
+ HCl
6. From Benzene Sulphonic Acid

SO3H
+ H2O 150 – 200º C + H2SO4

Steam
7. From Benzene Diazonium Chloride

N2Cl
H 3PO 2
 Δ
  H 3 PO3  HCl  N 2 
Structure of Benzene (Resonance Theory)

According to resonance theory, benzene is a resonance hybrid of two main Kekule’s structure (I) and
(II) (80% contribution) and three Dewar’s structure (20% contribution).

 
 
 
 
I II III IV V
Resonance hybrid
80% 20%
Dewar’s structures have less contribution towards the resonance hybrid as one of the bond is very
long which causes instability in structure. Thus, benzene is neither represented by structure (I) nor
by (II) but lies somewhere between the two Kekule’s structures. A resonance hybrid is always more
stable than either of two Kekule’s structures by 35 to 36 Kcal/mole. This stabilization of benzene
molecule is due to resonance and is called the resonance energy.
This resonance hybrid structure for benzene is supported by the following facts.
(i) Carbon-carbon bond lengths : According to X-ray analysis and electron diffraction studies it
is found that all the carbon- carbon bond lengths in benzene are identical (139 pm). This bond
length lies in between carbon-carbon single (C–C) bond length (154 pm) and double (C==C)
bond length (134 pm). So the character of bonds which link the carbon atoms in case of benzene
is neither single bond nor double bond but lies in between the two i.e., partial double bond.
(ii) Resonance and stability of benzene : According to resonance theory, the energy of resonance
hybrid of benzene is less than any of the contributing structures by 36 kcal/mole. The resonance
energy of benzene can be calculated from the values of heat of combustion and heat of
hydrogenation as follows :
(a) Heat of hydrogenation : The heat of hydrogenation of a substance is the amount of heat
evolved when one mole unsaturated compound is hydrogenated. The heat of hydrogenation
for each double bond is 28.6 kcal/mole.
(Ni catalyst)
150º C ; H = – 28.6 kcal/mole
Cyclohexene Cyclohexene
(Ni catalyst)
150º C ; H = – 55.4 kcal/mole
1, 2- Cyclohexadiene Cyclohexene
(Ni catalyst)
150º C ; H = – 49.8 kcal/mole
Benzene Cyclohexene
The addition of hydrogen to double bond is an exothermic reaction.
Heat of hydrogenation of benzene is 49.8 kcal/mole while the value expected on the basis of
any of Kekule’s structure is 85.8 kcal/mole. The difference of the two values gives the
resonance energy of benzene. Thus, benzene structure is stable by 36 kcal/mole which is
known as resonance energy of benzene. 36 kcal/mole of resonance energy is responsible
for new set of properties known as aromatic properties.
(b) Heat of combustion : Heat of combustion is defined as the amount of heat evolved when
one mole of the substance is completely burnt in excess of air or oxygen.
Heat of combustion values for C–H bond, C–C bond and C=C bond are 54, 49.3 and 117.4
kcal respectively.
Contribution of 6 C–H bonds = 6 × 54 = 324 kcal / mole

Contribution of 3 C–C bonds = 3 × 49.3 = 147.9 kcal / mole
Contribution of 3 C=C bonds = 3 × 117.4 = 352.2 kcal / mole
Calculated value = 824.1 kcal / mole
Thus, heat of combustion of benzene calculated from any of the resonating structures is
824.1 kcal/mole and experimentally observed value is 789.1 kcal/mole. It means resonance
hybrid structure of benzene has 35-36 kcal less energy than any of the Kekule’s structure
which gives extra stability to benzene. For this very reason, benzene undergoes substitution
reaction readily rather than the addition reactions.
Molecular Orbital structure of benzene
The structure of benzene is best explained on the basis of molecular orbital concept. Each carbon
atom in benzene is in a state of sp2 hybridisation.
6 carbon atom each = 1s22s22px12py12pz0 (In ground state)

6 carbon atom each (In excited state) = 1s22s12px12py12pz1
The 2s and two of 2p (2px, 2py) orbitals of the excited carbon atom hybridise to form three hybrid
orbitals of equivalent energy and shape. The new orbitals are called sp2 hybrid orbitals. 2pz orbital, on
each carbon atom is left unhybridised and is perpendicular to the three hybridised orbitals which
takes part in -bond formation.
Thus, the orbital picture of benzene showing the overlap of orbitals and formation of C–C and C– H
bonds is shown.
H  H H H


C C  C C

 
H–C C–H H–C C–H
 
C C C C or

 120º 
H H H H
(a) (b)
The net result is that there are two continuous hexagonal -electron clouds, one lying above and
other below the plane of the carbon atoms constituting the benzene ring.
Chemical Properties of Benzene

Benzene is very stable and is not affected by oxidising agents under ordinary conditions. The side
chains attached to benzene system are easily oxidised to carboxylic group.
Though benzene consists of 3C–C double bonds still it does not take part in addition reactions. This
is due to the extra stability which it attains due to resonance. Hence it fails to give addition itself, i.e.
does not decolourizes alkaline KMnO4 or bromine water unlike alkenes.
Benzene however undergoes substitution reaction. This is due to the fact that:
(1) there are pool of electrons above and below the bonded carbon atom.
(2) it acts as a source of electrons for electrophilic reagents.
(3) the aromatic character of benzene is preserved due to resonance stabilization.
The different electrophilic substitution reactions which benzene undergoes are:
(1) Halogenation (2) Nitration (3) Sulphonation (4) Friedel Craft reaction.
1. Halogenation: Benzene reacts with chlorine or bromine at low temperature, in the absence of
direct sunlight but in the presence of halogen carrier to form chloro benzene or bromo benzene
Fe Br + HBr
+ Br2  50 º C
Cl
Fe or
+ Cl2 Fe Cl3 (310 - 320 K) + HCl
Iron fillings are added to the reaction mixture with Cl 2 or Br 2 to form FeCl3 or FeBr 3
respectively.
The reactivity order of halogens is Cl2 > Br2. Reactions with Iodine is reversible as HI formed
reduces iodo derivative back to reactants. Direct iodination cause carried out in the presence of
oxidising agents, like iodic acid, mercuric oxide, nitric acid, etc.,which oxidise HI to iodine and
moves the reaction in forward direction.
HIO3
 I    HI
Mechanism of Electrophilic Substitution Reactions:Any electrophilic substitution reaction

involves three steps :
Step 1: Generation of electrophile.
Step 2: Attack of electrophile to form Intermediate carbonium ion through -complex.
Step 3: Loss of proton to give the product.
1. Generation of Electrophile: Lewis acid FeCl3 polarises the chlorine molecule to give highly
reactive chloronium ion (Halonium)
Cl2 + Fe Cl3 Cl + FeCl4–
2. Intermediate Carbonium ion through - compex
H Cl H Cl H Cl H E
 Cl 
 
 
 
Hybrid
–
3. Loss of Proton: The intermediate corbonium ion loses H+ ion to FeCl4 ion and thereby
form chlorobenzene.
Cl
H Cl
FeCl4 
  HCl  FeCl3
FeCl3 acts as a lewis acid

The formation of Arenium cations is the rate determining step
E H E
E H
T
TS-2
H 2
H 1
 E
+E

+H
 Hreaction
The confirmation of such a mechanism is supported by isotopic effect.

KH
i.e., K D ratio
This could be as high as 2 to 8 if isotopic effect is present. The fact that isotopic effect is absent
proves that the C-H bond cleavage is not a part of rate determining step.
These electrophilic substitution reactions are irreversible because the energy barrier H2 for the
reaction of -complex to form products is less than H reactions for the reverse reaction of E
(electrophile).Hence,
K1 +
H E K2

Ar H + E (–H+)
ArE
K –1 Ar
K2 > > > K–1
Hence the reaction is irreversible.
2. Nitration: When benzene is reacted with a mixture of conc. nitric acid and conc. H2SO4 one
gets nitrobenzene.
NO2
H2SO4
+ HNO3 60º C
At temperatures above 80ºC but below 120ºC one gets di-nitro benzene by using fuming HNO3
and fuming H2SO4.
NO2
HNO3 + H2SO4
 NO2
At very high temperature, i.e., 120ºC and above trinitro product is obtained
Mechanism
(i) Generation of electrophile:

O
 –  –
HO – N O + H– O – S – OH H2O – N O + HSO4 H2O + NO2 + HSO4
O O O
(ii) Formation of carbocation:

H NO2 H NO2 H NO2 H NO2
 NO 2 
 
 
 
(iii) Loss of H+ ion
H NO NO2
– 2
+ HSO4  + H2SO4
3. Sulphonation: When benzene reacts with conc. H2SO4 (preferably fuming) at 80ºC we get
benzene sulphonic acid.
SO3H
+ H2SO4 + H2O
Mechanism
(i) Generation of electrophile:
H2SO4 + H2SO4 H3O + SO3 + HSO4
(ii) Carbocation formation:

H
SO3–

+ SO3
(iii) Loss of Proton followed by protonation:

SO3 SO3H
H SO3
 
H
  H 3O
   H2O
4. Friedel craft’s reaction
It is of two types : (a) Friedal Craft’s alkylation (b) Friedal Craft’s acylation.
(a) Friedal Craft’s alkylation: Benzene reacts with alkyl halide in the presence of anhydrous
aluminium chloride to form alkyl benzene involving the replacement of hydrogen atom of the
nucleus by alkyl group.
R
anhydrous AlCl3
+ R – X  Δ

CH3
anhydrous AlCl3
+ CH3 – Cl  Δ


Mechanism: Methyl carbonium ion ( CH 3 ) is attacking electrophile in this mechanism and it
is formed in the presence of anhydrous AlCl3 catalyst. This mechanism involves the following
steps :
(i) Generation of electrophille

  – +
CH 3 –– CI + AlCl3 AlCl4 + CH3
Methyl carbonium ion
(ii) Intermediate carbonium ion formation. CH 3 is attacked by -electrons of the ring to

form intermediate carbonium ion which is resonance stabilised.
H CH3 H CH3 H CH3 H CH3
+
 CH3 
 
 
 

-complex
I II III
(iii) Loss of Proton.The intermediate carbonium ion loses H+ ion to AlCl4– ion to form methyl
benzene (toluene).
H CH3 CH3

+ AlCl4– Fast + AlCl3 + HCl
Toluene
In case the alkylation is carried out with higher alkyl halide, e.g., n-propyl chloride, then the
electrophile (CH3 – CH2 – CH2+) = propyl carbonium ion which is a primary carbonium ion
rearranges to form more stable secondary carbonium ion (isopropyl carbonium ion) and the
main product formed will be isopropyl benzene. This is explained as follows :
+ –
(i) CH3– CH2 – CH2 + AlCl4
n - Proplyl carbonium ion
H3C
+
rearrangement +
CH2   H3C CH
H3C CH3
Primary carbonium ion Secondary carbonium ion
(More stable)
 
The electrophile is CH 3  C H  CH 3 ion and not CH 3  CH 2  C H 2
H3C
H CH3
+ Slow
(ii)  H3C CH  
CH3
-complex
H3C H 3C CH3
H CH3
 AlCl4 
Fast
  AlCl3  HCl
(iii)
(Isopropyl benzene)
(Cumene)
(b) Friedel Craft’s acylation. Benzene can also react with acid chloride or acid anhydride in the
presence of anhydrous aluminium chloride to form aldehydes and ketones etc. by the
replacement of hydrogen atom of the nucleus by acyl group (RCO–).
AlCl3 (anlydrous) C– R
+ R– C – Cl + HCl
O
 O
O
H O
Anhydrous
C– CH3
+ Cl – C – CH3 + HCl (Acetylation)
AlCl3
Benzene Acetyl chloride
Acetophenone
+ R– C – O – C – R Anhydrous C– R
AlCl3 + RCOOH
O O O
O
H O
Anhydrous
C– C6H5
+ Cl – C – C6H5 + HCl (Benzoylation)
AlCl3
Benzene Benzoyl chloride
Benzophenone
Mechanism :
The mechanism is similar to mechanism of alkylation and involves the following steps :
O
(i) Attacking electrophile R – C (Acetyl carbonium ion) is given by acetyl chloride in the
presence of anhydrous AlCl3 which acts as a catalyst.
O O
–
CH3 – C – Cl + AlCl3 R – C + AlCl4
Acetyl chloride Acetyl carbonium ion
O
(ii) Acetyl carbonium ion (CH3 – C) attacks the benzene ring to form intermediate carbonium
ion which is resonance stablised.
O
H R
+ Slow
 O C  
R
-complex
(iii) The intermediate carbonium ion loses H+ ion to AlCl4– ion to form acetophenone.
O O R
H R
 AlCl4 
  HCl  AlCl3
Acetophenone
5. Formylation (Gattermann Koch aldehyde synthesis)

3 AlCl
C6H6 + CO + HCl C6H5CHO + HCl
In this, the electrophile is formed as :
+
CO + HCl + AlCl3 H– C = O + AlCl4–
Electrophile
H H O
O H
+
 H C 
 AlCl 4
 
O
benzaldehyde
6. Addition Reactions
Benzene undergoes a number of addition reactions only under suitable conditions.
(i) Addition of hydrogen (Catalytic hydrogenation). Benzene adds on three molecules of hydrogen
when mixture is passed over finely divided Ni at 150º–200ºC under high pressure to form
cyclohexane.
Ni
+ 3H2 150 – 200º C
Cyclohexane
(Hexahydrobenzene)
(ii) Addition of halogens. Benzene adds up three molecules of chlorine and bromine in the presence
of bright sunlight and in absence of halogen carriers, forming benzene hexachloride and benzene
hexabromide respectively.
Br Cl
Br Br Cl Cl
(i) Sunlight + 3Br2 (i) Sunlight + 3Cl2

(ii) Absence of halogen carrier

(ii) Absence of halogen carrier
Br Br Cl Cl
Br Cl
Benzene hexabromide Benzene hexachloride
BHC or Gammexane
or Lindane or 66 or
Hexachlorocyclohexane
(iii) Addition of ozone – Benzene adds up three molecules of ozone forming ozonide which gives
glyoxal upon reaction with Zn/H2O.
O3
CHO
 3O 2  
  3O 2  Zn
/ H
2O
 3
CHO
O3 O3 glyoxal
Ozonide
7. Oxidation Reactions
(a) Controlled oxidation : As benzene is very stable, it does not react with oxidising agents like
acidified potassium permanganate and K2Cr2O7. When mixture of air and benzene vapours is
passed over vanadium pentaoxide (V2O5) catalyst at 500ºC, the nucleus breaks and gets oxidised
to maleic anhydride,
Air / V2O5 CHCOOH

2 + 9O2 2 + 2H2O + 4CO2
500º C CHCOOH
Maleic acid
O
CH – C
2 O + 2H2O
CH – C
O
Maleic anhydride
Side chain on benzene ring can be oxidised to –COOH group with alkaline KMnO4 solution or
acidified KMnO4 or acidified K2Cr2O7
CH3 O = C–OH
alk. KMnO 4
+ 3 [O] + H2 O
Toluene Benzoic acid
CH2 – CH3 COOH

alk. KMnO4
+ 6 [O] + CO2 + 2H2O
Ethyl benzene
CH2 – CH2 – CH3 COOH

alk. KMnO 4
+ 9 [O] + 2CO2 + 3H2O
Ethyl benzene
Etard’s reaction
CH3 CHO
CrO2Cl2 / CCl4
Chromyl chloride
Toluene Benzaldehyde
(b) Complete Combustion. On burning in air or oxygen, benzene is oxidised to carbon dioxide and
water producing smoky flame.
15
C6H6(l) + O (g) 6CO2(g) + 3H2O(l) + heat
2 2
8. Miscellaneous reactions
1. Coupling reaction:
700 – 800ºC
Red hot iron tube
Benzene Diphenyl
2. Chloromethylation:
H CH2 Cl
ZnCl2
+ HCHO + HCl + H2O
Benzyl chloride
Effect of Substituent Rings on Electrophilic Substitution (Orientation)
When further substitution is done on mono substituted benzene some groups. (alkyl group, halogen
group, –OH group, –NH2 group) direct the new entrant to ortho as well as para positions and other
groups like, –NO2, –CHO, –COOH direct new entrant to meta position. Let us study this orientation
and the directive influence of the groups already present on benzene ring.
Type - I: Directive influence of alkyl group : Consider toluene having methyl group present on
the ring. It is an electron releasing group. The various possibilities of further substitution
can be explained by considering the relative stability of the carbonium ion when new
entrant gets ortho, para and meta position.
CH3
Toluene
1. Ortho substitution:
CH3 CH3 CH3
H H H

G G G
 
I III
II
2. Para substitution:
CH3 CH3 CH3

 
H G H G H G
IV V VI
3. Meta substitution:
CH3 CH3 CH3

 
H H H
G G G
 VIII
VII IX
Out of these carbonium ions (I) and (V) are particularly stable because the electron
releasing alkyl group is directly attached to carbon atom carrying the positive charge.
This leads to dispersal of +ve charge hence makes the carbonium ion more stable. Such
a stable structure, does not exist when meta substitution takes place. Hence the carbonium
ion formed for ortho and para and para substitution are more stable, and are actually
formed. Hence, we say that whenever benzene contains an alkyl group, further
substitution, always occurs at ortho and para position. Alkyl group is activating as it
increases the reactivity of benzene ring.
Type - II: Let us consider those compounds, in which benzene carries a group, containing a lone
pair electrons, e.g., aniline. The carbonium ions formed in these cases can be written as:
1. Ortho substitution
.. .. .. +
NH2 NH2 NH2 NH2
 H H H H
G G G G
 
I II III IV
2. Para substitution
.. .. .. 
NH2 NH2 NH2 NH2

 
H G H G H G H G
V VI VII VIII
3. Meta substitution
.. .. ..
NH2 NH2 NH2
 
H H H
G G G

X XI
IX
Out of these structures (IV) and (VIII) are particularly stable because in these cases
the octet of each carbon atom is complete. In case of carbonium ion for meta substitution
such a structure is not formed. Hence we say that the resonance hybrid for carbonium
ion in ortho and para substitution are more stable and are formed more easily. The
further substitution in such compounds always occur at ortho and para positions and not
at meta positions. Other groups in this category are
NHR, NR 2 , NHCOR, OH, OR, OCOR, O etc. (Activating groups)
Type - III: Electron withdrawing groups i.e., –NO2,–COOH, –CN etc. Consider case of nitro
benzene. The carbocations formed in these cases may be writted as follows:
O O
N
Nitrobenzene
When this compound, is attacked by an electrophile the carbonium ions which are formed
for the ortho, meta or para position can be written as follows :
1. Ortho substitution
O O O O O O
N N N
 H H H
G G G
 
I III
II
O O O O O O
N N N

 
H G H G H G
IV V VI
O O O O O O
N N N
 
H H H
G G G

IX X
VIII
Structure I and V are particularly unstable, because the –NO2 group which is attached
to the C with positive charge helps to intensify the charge. Greater the intensification
lesser is the stability. Hence in the resonating structure for ortho and para substitution
the resonance hybrid will be less stable. The resonating structures, for meta substitution,
make the hybrid more stable thus meta substitution will be preferred. Whenever the
electron withdrawing groups like –NO2, –COOH, –CN –SO3H are present on the ring
then the further substitution, will always occur at meta position. These type of groups
are deactivating as they decrease the reactivity of ring.
Type - IV: When halogen atom is present on the ring.
Consider chlorobenzene. Let us write various carbonium ions formed,
1. Ortho substituion
+
Cl Cl Cl Cl
H H H H
G G G G

 
 

I II III IV
+
Cl Cl Cl Cl

 
 

H G H G H G H G
V VI VII VIII
.. .. ..
:Cl: : Cl: : Cl:
 
H H H
G G G

IX X XI
Structures I and VI are particularly unstable, because electron attracting Cl atom is
directly attached to positively charged C atom. Thus positive charge gets intensified
which leads to instability. On the other hand structures IV and VIII are particularly
stable, because the octet of each carbon atom is complete. The contribution of structures
IV and VIII are much more towards the resonance hybrids as compared to structures
VI and I, therefore, the destabilising effect of structures I and VI can be neglected.
Hence, the hybrid for ortho and para substitution are stable. On the other hand there is
no resonating structure in meta substitution which is particularly stable. Hence, we say
that halogen atoms always direct the new entrants towards ortho and para position. The
deactivate the ring because –I effect is more predominent than +R effect.
Substitution in disubstituted benzene

In substituted benzene containing more than one substituent group, the substituents may either reinforce
each other’s directive ability, or they may oppose one another. In the case of an m-director versus an
o,p-director, remember that the meta substituent is also a deactivating group, while the o, p-director
activates the ortho and para positions with respect to the meta position. Thus the o,p-director will
dominate the orientation of the attacking electrophile.
CH3
1
2
CH2CH3
Both are o,p-directors. Attack will occur at both 1 and 2.

CH3
1 3
4 NO2
2
–CH3 is an o,p-director, –NO2 is a m-director. Attack will occur at positions 1 and 2.
and to a lesser extent at 3. Attack will not occur at 4.
OCH3
1
NO2
–OCH3 is an o,p-director, –NO2 is a m-director. Attack will occur at position 1 only.
Illustration 1: Predict the structure of the intermediate and the final product in the following reaction
sequence.
CH3 O
O
(i) AlCl3 Zn (Hg ) H 3 PO4
 O 
(ii) H3 O
 A 
HCl
B  P
CH3 OH CH3 OH CH3 O

O O O O O
Solution: A= B= P=
Illustration 2: A triene (A) can be readily deprotonated twice to give the stable dianion (B). The neutral
analog of (B), i.e., (C) however, is unstable. Explain.
H
Bose
 
H
H
H
(A) (B) (C)
Solution: The dianion(B) is an aromatic compound containing 10 electrons but pentalene (C) has
only 4n electrons, it is antiaromatic. Delocalization of electrons dostabilizes the molecule.

N N
 Ar  N  N  Cl  

Problem 1:
N + -
N Cl
Above (C – N) coupling reaction take place at:
(a) low pH (b) Intermeidate pH
(c) High pH (d) Any pH
Solution: (b) At intermeidate pH the rate of reaction is quite considerable. As the pH value decreases
the rate of the coupling reaction would decrease due to protonation of nitrogen (N<).
Problem 2: The prdouct obtained from the reaction is
ethanol
Br  NaCN  
Cl
Br Br
(a) (b)
CN Cl
Br
NC
(c) (d) Cl
CN CN
Solution: (a) Undergo nucleophilic substitution at benzylic carbon atom by means of S N 1

pathway...
Problem 3: Cyclopentadiene is much more acidic than cyclopentane. The reason is that:
(a) Cyclopentadiene has conjugated doouble bonds
(b) Cyclopentadiene has both sp2 and sp3 hybridized carbon atoms
(c) Cyclopentadiene is a strain-free cyclic system
(d) Cyclopentadienide ion, the conjugate base of cyclopentadiene, is an aromatic species
and hence has got highest stability.
Solution: (d) The compound cyclopentadiene ion is an aromatic compound.

a
Problem 4:
c
d
b
Identify the position where Electrophilic Aromatic Substitution (E.A.S.) will take place:
(a) a (b) b
(c) c (d) all the position are identical
Solution: (b) The E.A.S. will take place at more electron rich centre.
Problem 5: Which of the following procedures would be best for the preparation of phenyl benzyl ether?
(a) C6H5Cl + C6H5CH2O(–1)Na(+) (b) C6H5O(–1)Na(+) + C6H5CH2Cl
(c) 2C6H5Cl + Na2O (d) 2C6H5MgBr + CH2O
Solution: (b) The reaction takes place through nucleophilic substitution pathway.
Problem 6: Which of the following benzene ring substituents is deactivating but ortho-para directing?
(a) –N = O (b) –OCH3
(c) –COCH3 (d) –NO2
Solution:: (a) By means of –I effect , –N = O group is withdrawing electron from the ring and by
means of +R effect, it is donating electron to the ring. Because –I effect is more
predominant than + R effect, it is more deactiving. Due to +R effect it is an ortho-para
directing group.
Problem 7: Which of the following organic chlorides will not give a Friedel Craft alkylation product
when heated with benzene and AlCl3?
(a) (CH3)3CCl (b) CH2 = CHCH2Cl
(c) CH3CH2Cl (d) CH2 = CHCl
Solution: (d) Vinyl carbocation is an unstable carbocation.
Problem 8: What is correct order of rate of nitration of the following compounds?

A = C6H5CH3 B = C6H6 C = C6D6 D = C 6T 6

E = C6H5Br F  C6 H 5 N R 3 G = C6H5NMe2
(a) G > A > B > C > D > E > F (b) G >B > C > D > A > F
(c) G > A > B = C = D > E > F (d) G > A > B > C = D > E > F
Solution: (c) Self explanatory
Problem 9: Which one of the following statements is true:
(1) (2)
(a) PhLi adds to both compounds with equal ease
(b) PhLi does not add to either of the compounds
(c) PhLi reacts with 1 but does not add to 2
(d) PhLi racts readily 2 but does not add to 1
Solution: (c) Anti aromatic compounds are more reactive than aromatic compound towards PhLi.
Problem 10: The decreasing order of reactivity of meta-nitrobromobenzene (I),

2,4,6-trinitrobromobenzene(II), para-nitrobromobenzene (III) and 2,4-dinitrobromobenzene
(IV) towards HO– ions is:
(a) I > II > III > IV (b) II > IV > III > I
(c) IV > II > III > I (d) II > IV > I < III
Solution: (b) As NO2 group gets introduced on bromo benzene at ortho and para position, the rate
would increase towards OH– ion due to the stabilization of the negative charge at ortho
and para position.

CHAPTER ASSIGNMENT
1. When cyclohexane is poured on water, it floats because
(a) cyclohexane is in boat form (b) cyclohexane is in chair form
(c) cyclohexane is in crown form (d) cyclohexane is less dense than water
2. The reaction of CH3CH = CH– –OH with HBr gives
(a) CH3CHBr CH2– –OH (b) CH 3CH 2 CHBr– –OH

|
Br
(c) CH3CHBr CH2– –Br (d) CH3CH2CH Br– –Br
3. The lowest b.p. is expected for

(a) iso-Octane (b) n-Octane
(c) 2, 2, 3, 3-tetra-Methylbutane (d) n-Butane
4. Which xylene gives only one monobromo derivative ?

(a) Ortho (b) Para (c) Meta (d) None of these
5. Which order is correct for the decreasing reactivity to ring monobromination of the following
compounds?
C6H5CH3 (I), C6H5COOH (II), C6H6 (III), C6H5NO2 (IV)
(a) I > II > III > IV (b) I > III > II > IV (c) II > III > IV > I (d) None of these
6. Reaction of Br2 on ethylene in presence of NaCl gives

(a) BrCH2 – CH2Br (b) ClCH2 – CH2Br
(c) Both of these (d) None of these
7. The reaction conditions leading to the best yield of C2H5Cl are

UV dark
(a) C2H6 (excess) + Cl2 light (b) C2H6 + Cl2 room temp.
UV UV
(c) C2H6 + Cl2 (excess) light (d) C2H6 + Cl2 light
8. When nitrobenzene is treated with Br2 in the presence of FeBr3, the major product formed is
m-bromonitrobenzene. Statements which are related to obtain the m-isomer are
(a) The electron density on meta carbon is less than that on ortho and para positions
(b) The intermediate carbonium ion formed after initial attack of Br+ at the meta position is least
destabilished
(c) Loss of aromaticity when Br+ attacks at the ortho and para positions and not at meta position
(d) Easier loss of H+ to regain aromaticity from the meta position than from ortho and para positions
9. Amongst the following groups, the group that deactivates the benzene ring for electrophilic
substitution is
.. H ..
(a) CH3 (b) N (c) – .O–
. H (d) C N
H
10. Dipole moment is shown by

(a) 1, 4-dichlorobenzene (b) cis-1, 2-dichloroethene
(c) trans-1, 2-dichloroethene (d) trans-3, 4-dichloro-2-hexene
11. The reaction of 1,3-Butadiene and acetylene gives
(a) (b) (c) (d) None of these
12. Isomers which can be interconverted through rotation around a single bond are
(a) Conformers (b) Diastereomers (c) Enantiomers (d) Positional isomers
13. The compound having both sp and sp2 hybridised carbon atoms is
(a) Propene (b) Propyne
(c) Propadiene (d) None of these
14. Amongst the following, the compound that is nitrated with difficulty is
(a) Benzene (b) Nitrobenzene (c) Toluene (d) Phenol
15. Which one of the following heptanols can be dehydrated to hept-3-ene only?
(a) Heptan-3-ol (b) Heptan-4-ol (c) Heptan-2-ol (d) Heptan-1-ol
O O
H
OH
H
HO OH
(Prostaglandin E)
The number of asymmetric (stereogenic) centres present in compound _____.
17. How many isomers ‘x’ of C8H10 when reacts with hot alkaline KMnO4 give only aromatic dicarboxylic
acid? How many isomers ‘y’ of C4H8 when reacts with hot alkaline KMnO4 give carbondioxide?
Sum of x + y = ?
2H 2
(A) 
Pt

18.
O
Degree of unsaturation in compound (A) is ______.
19. One mole of 1,2-dibromopropane on treatment with X moles of NaNH2 followed by treatment with
ethyl bromide gave a pentyne. The value of X is ________.
20. The number of monochlorinated product that may be obtained when the alknae given below is
heated in the presence of Cl2 is _________
(Including stereoisomers)
Cl2

hν
(Product)
(Alkane)
CH3
H Cl 
(X); (X) = total number of dichloro product
21. H2C CH2 CH2 CH3
(S-2-chloro hexane)
Na
22. Br Br 
dry ether
(Product)
The degree of unsaturation of produt is

23.
Cubane
Double bond equivalent of cubane is ______
24. Find out the total number of stereoisomers of the given following compound:
Cl
Cl CH CH C CH CH Cl
H
25. Find the total number of isomers of C7H14 (only 5 membered ring).

HIO4
26. CH3 – CH – C– CH3 + [O] Z. Z may be
OH O
(a) CH3 – CHO (b) CH3 – COOH (c) CH3 – C – C– CH3 (d) None of these
O O
27. Which of the following species is/are aromatic?
(a) (b) (c) (d)

O O
28. Which of the following compounds is/are aromatic?

– + +
(a) (b) (c) (d)

N
29. Which of the following is/are aromatic compounds?
(a) (b) +
(c) (d)
NH2 O S
30. Allylic substitution in CH3CH = CH2 may be carried out by

(a) Sulphuryl chloride, SO2Cl2 (b) tert-butyl chloride, Me3CCl
(c) N-bromosuccinimide (NBS) (d) Chlorine at 350°C
31. Which of the following option(s) is/are correct in the following reaction?
H COOH
C
 Product
C
H COOH
COOH
H
(a) COOH
H
COOH H
(b)
H COOH
(c) The reaction is an example of Diel’s-Alder reaction
(d) It is a cyclo addition reaction
2
32. A 
dil. H2 SO4 / Hg
 1-methylcyclohexanol. Here A is
(a) (b) (c) (d)
NBS FeBr3
33. [A] [B]
hv
Which of the following facts are true regarding above reaction sequence?
(a) The product [B] is
(b) The product [B] is
(c) The sequence involves free radical and electrophilic substitution reactions
(d) The reaction involves nucleophilic and free radical substitution reactions.
34. Which of the following reactions are expected to give in yields of more than 50%?
CH3
CH3 C CH CH2
CH3
CH3 CH3
H2SO4 (CH3)3CO–K+
(a) CH3 C CH CH3 (b) CH3 C CH CH3
 
CH3 OH CH3 Br
CH3
Zn
(c) CH3 C CH (d) None of these
Acetone
CH3 Br Br
35. Which are the possible intermediates in the following reaction?

1. Br2/CCl4
CH3 CH 2 CH  CH 2 CH3 CH 2 C  CH
2. NaNH2 (110 – 160°C)
CH 3 CH 2 CH  CH 2 Br
(a) | (b) CH3CH2CH = CHBr
Br
(c) CH3 CH 2 C  CH 2 (d) None of these

|
Br

36. Match the reactions in Column I with appropriate options in Column II
Column I Column II
A. N2 Cl  OH (p) Racemic mixture
NaOH /H 2 O

0
N N OH
O
OH OH CH3
C CH3
H SO
B. H3C C C CH3 
2 4
 H3C C (q) Addition reaction
CH3 CH3 CH3
O OH
1.LiAlH 4
C 

2.H 3O 
HC
C. (r) Substitution reaction
CH3 CH3
Base S
D. HS Cl   (s) Coupling reaction
(t) Carbocation intermediate
37. Match the reactions in column I with appropriate types of steps/reactive intermediate involved in
these reactions as given in column II
Column I Column II
O
H3 C O
O
A. aq NaOH (p) Nucleophilic substitution
O
O
B. CH3Mgl (q) Electrophilic substitution
CH2CH2CH2Cl CH3
18 O
O
18 H SO
C. CH2CH2CH2OH 2 4 (r) Dehydration
H2SO4
CH2CH2CH2C(CH3)2
D. (s) Nucleophilic addition
OH H3C CH3
(t) Carbanion

Comprehension - 1
The functional group in alkenes is C-C double bond which is made of one -bond and one -bond. The
weaker -bond would tend to attract the electrophile and convert itself to a stable carbonium ion which
reacts with nucleophile remainder to form the addition product. The addition reaction of alkenes is stereo
specific as well as stereoselective. i.e., the isomeric alkenes react differently with same addendum to give
stereochemically different products. Where addition of HBr proceeds through carbocation formation and
hence racemisation is expected. With low concentration of Br2 in vapour phase substitution predominates
over addition.
38. Reaction of 1,2-dimethylcyclohexene with bromine water gives the product
(a) Br CH3 (b) Br Br (c) Br OH (d) Br CH3
CH3 Br CH3 CH3 CH3 CH3 CH3 OH
Br2 /low conc .

39. 14
CH3 –CH=CH2    
high temperatur e
Product of the above reaction is

(a) Br–14 CH 2–CH=CH2 (b) 14
CH2 =CH–CH2 –Br
(c) both (a) & (b) (d) none of these
OH
CH CH CH3 CHCH2CH3
40. H2O/H+
The stereochemistry of product is

(a) dextro (b) laevo (c) meso (d) racemic
Comprehension - II
For selective bromination of organic compounds, N-Bromosuccinimide is used for reaction system alkenes
as well as arenes that have alkyl groups on the ring react with NBS in the presence of light or benzoylperoxide
to give compounds which are bromo substituted at the -position to the double bond or benzene ring
CH3 CH2 Br
e.g. , NBS, CCl4

(C6H5COO)2
41. As given in the passage whenever allylic halogenations are performed direct use of Br2 or Cl2 is not
done. This is because
(a) for allylic halogenation high concentration of halogen is required
(b) for allylic halogenation low concentration of halogen is required
(c) NBS is highly specific
(d) direct use of halogen requires high energy for breakage
42. Which of the following will react most readily with NBS to give the allylic substituted product?
(a) CH2=CH–CH2 –CH3 (b) CHC–CH2 –CH3
O
CH2 CH CH2
C O CH2 CH CH2
(c) (d)
43. From which of the following generation of Br radical takes place when reaction is
NBS, CCl4
CH2 =CH–CH3 (C6H5COO) 2
CH2 =CH–CH2–Br?
O O
(a) N Br + HBr N H + B r2
O O
Br
+ Br Br + Br
O O
N Br N + Br
(b)
O O
(c)
O
C O
+ CO2
O O
+ N Br N + Br
O O
(d) Br radical is not produced during the reaction


1. One recently discovered allotrope of carbon (e.g., C60) is commonly kown as [IIT 1994]
(a) Flourine (b) Fullerene (c) Flourene (d) Freon
2. The C–C bond length of the following molecules is in the order [IIT 1991]
(a) C2H6 > C2H4 > C6H6 > C2H2 (b) C2H2 < C2H4 < C6H6 < C2H6
(c) C2H6 > C2H2 > C6H6 > C2H4 (d) C2H4 > C2H6 > C2H2 > C6H5
3. Homolytic fission of C–C bond in ethane gives an intermediate in which carbon is [IIT 1992]
(a) sp3-hybridised (b) sp2-hybridised (c) sp-hybridised (d) sp3d-hybridised
4. What is the decreasing order of strength of the bases?

OH–, NH2–, HCC– and CH3CH2–? [IIT 1993]
(a) CH3CH2– > NH2– > HCC– > OH– (b) HCC– > CH3CH2– > NH2– > OH–
(c) OH– > NH2– > HCC– > CH3CH2– (d) NH2– > HCC– > OH– > CH3CH2–
5. Which of the following has the lowest dipole moment? [IIT 2002]
CH3 CH3
(a) C C (b) CH3 CCCH3 (c) CH3 CH2 CCH (d) CH2 =CH–CCH
H H
6. Identify the correct order of reactivity in electrophilic substitution reactions of the following
compounds [IIT 2002]
CH3 Cl NO2
(i) (ii) (iii) (iv)
(a) (i) > (ii) > (iii) > (iv) (b) (iv) > (iii) > (ii) > (i) (c) (ii) > (i) > (iii) > (iv) (d) (ii) > (iii) > (i) > (iv)
7. Arrange the following compounds in order of increasing dipole moment: [IIT 1996]
(i) Toluene (ii) m-dichlorobenzene
(iii) o-dichlorobenzene (iv) p-dichlorobenzene
(a) (i) < (iv) < (ii) < (iii) (b) (iv) < (i) < (ii) < (iii)
(c) (iv) < (i) < (iii) < (ii) (d) (iv) < (ii) < (i) < (iii)
8. In the following groups: [IIT 2002]

(i) –OAc (ii) –OMe (iii) –OSO2 Me (iv) –OSO2 CF 3
the order of leaving group ability is
(a) (i) > (ii) > (iii) > (iv) (b) (iv) > (iii) > (i) > (ii)
(c) (iii) > (ii) > (i) > (iv) (d) (ii) > (iii) > (iv) > (i)
9. Among the following the molecule with highest dipole moment is [IIT 2003]
(a) CH3Cl (b) CH2Cl2 (c) CHCl3 (d) CCl4
10. In the following reaction, conc

 . HNO 3
  X
conc . H 2SO 4
The structure of the major product ‘X’ is [IIT 2007(P-1)]
(a) (b)
(c) (d)
11. The number of stereoisomers obtained by bromination of trans-2-butene is [IIT 2007(P-2)]

(a) 1 (b) 2 (c) 3 (d) 4
12. STATEMENT-1: Molecules that are not superimposible on their mirror images are chiral.
STATEMENT-2: All chiral molecules have chiral centres.
(a) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1
(b) Statement-1 is True, Statement-2 is True; Statement-2 is not a correct explanation for
Statement-1
(c) Statement-1 is True, Statement-2 is False
(d) Statement-1 is False, Statement-2 is True [IIT 2007(P-2)]
Me
H Me
13. H
Me
H
Hydrogenation of the above compound in the presence of poisoned palladium catalyst gives
(a) optically active compound (b) an optically inactive compound
(c) a racemic mixture (d) a diastereomeric mixture [IIT 2001]
14. Which of the following alkenes will react fastest with H2 under catalytic hydrogenation conditions?
[IIT 2000]
R R R H R R R R
(a) (b) (c) (d)
H H R H R H R R
15. (CH3)3CMgCl on reaction with D2O produces [IIT 1997]

(a) (CH3 )3 CD (b) (CH3 )3 COD (c) (CD)3CD (d) (CD)3 COD
16. The intermediate during the addition of HCl to propene in the presence of peroxide is [IIT 1997]
   
(a) CH3 CH CH2Cl (b) CH3 CH CH 3 (c) CH3 CH2 CH 2 (d) CH3 CH2 CH 2
17. The products obtained via oxymercuration (HgSO4 + H2SO4) of 1-butyne would be [IIT 1999]
(a) CH3 –CH2 –CO–CH 3 (b) CH3 –CH 2 –CH2 –CHO
(c) CH3–CH3–CHO + HCHO (d) CH3CH2COOH + HCOOH
18. Propyne and propene can be distinguished by [IIT 2000]

(a) conc. H2 SO4 (b) Br2 in CCl4
(c) dil. KMnO4 (d) AgNO3 in ammonia
19. In presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti-Markovnikov’s
addition to alkenes because [IIT 2001]
(a) both are highly ionic
(b) one is oxidising and the other is reducing
(c) one of the steps is endothermic in both the cases
(d) all the steps are exothermic in both the cases
20. Identify the reagent from the following list which can easily distinguish between 1-butyne and 2-
butyne
(a) bromine, CCl4 (b) H2, Lindlar catalyst
(c) dilute H2SO4, HgSO4 (d) ammoniacal Cu2Cl2 solution [IIT 2002]
21. 2-phenyl propene on acidic hydration gives [IIT 2004]
(a) 2-phenyl-2-propanol (b) 2-phenyl-1-propanol
(c) 3-phenyl-1-propanol (d) 1-phenyl-2-propanol
22. NOCl
CH2 = CH – CH3   X, X is [IIT 2006]
(a) CH 2 – CH – CH 3 (b) CH 2 – CH – CH 3
| | | |
Cl NO NO Cl
(c) ON – CH2 –CH2 – CH2 – Cl (d) ON– CH – CH 2 – CH 3
|
Cl
anhyd . (i ) O , heat
23.  I  2 
+ CH3CH2CH2Cl AlCl  II + Phenol. products I and II are
3 (ii ) H O heat 3
(a) and CH3COCH3 (b) and CH3CH2CHO
(c) and CH3COCH3 (d) and CH3CH2CHO [IIT 2006]
24. (a) CH3CH(Br)CD3 on treatment with alc. KOH (i) E1 reaction [IIT 2006]
gives CH2 = CHCD3 as a major product.
(b) PhCH(Br)CH3 reacts faster than PhCH(Br)CD3 (ii) E2 reaction
(c) PhCH2CH2Br on treatment with C2H5OD/C2H5O– (iii) E1 CB reaction
gives PhCD = CH2 as the major product
(d) PhCH2CH2Br and PhCD2CH2Br react with same (iv) The reaction is unimolecular rate.
25. The reagent(s) for the following conversion,
is/are [IIT 2007 (P-1)]

(a) alcoholic KOH (b) alcoholic KOH followed by NaNH2]
(c) aqueous KOH followed by NaNH2 (d) Zn/CH3 OH
26. Cyclohexene on ozonolysis followed by reaction with zinc dust and water gives compound E.
Compound E on further treatment with aqueous KOH yields compound F.
Compound F is [IIT 2007 (P-2)]
(a) CHO (b) CHO (c) COOH (d)
27. The bond energy (k kcal mol–1) of a C – C single bond is approximately [IIT 2010]
(a) 1 (b) 10 (c) 100 (d) 1000
HBr
28. In the reaction OCH3   the product are [IIT 2010]
(a) Br OCH3 and H2 (b) Br and CH3 Br
(c) Br and CH3OH (d) OH and CH3 Br
OH
29. In the reaction NaOH (aq )/Br2

  the intermediate is(are) [IIT 2010]
- -
O O O -
O
Br
(a) (b) (c) (d)

Br Br Br
Br Br
Paragraph for Question Nos. 30 to 31

An acyclic hydrocarbon P, having molecular formula C6H10, gave acetone as the only organic product
through the following sequence of reactions, in which Q is an intermediate organic compound.
(i) conc. H2SO4

(catalytic amount) O
(i) dil. H2SO4/HgSO4 (–H2O)
P Q 2 C
(C6H10) (ii) NaBH4/ethanol (ii) O3
H3 C CH3
(iii) dil. acid (iii) Zn/H2O
30. The structure of compound P is [IIT 2011]
(a) CH3 CH 2 CH 2 CH 2  C  C  H (b) CH3 CH 2 C  C  C  CH 2 CH 3
H3C H3 C
(c) H C C C CH3 (d) 3C C C
H C H
H3C H3 C
31. The structure of the compound Q is [IIT 2011]
OH OH
H 3C H3 C
(a) H C C CH 2CH3 (b) H 3C C C CH3
H 3C H H3 C H
OH OH
H 3C
(c) H C CH2CHCH3 (d) CH3CH2CH2CHCH 2CH 3
H 3C
32.  Cu   Cu || in aqueous medium at 25°C shifts towards the left in the
The equilibrium 2Cu | 
presence of [IIT 2011]
(a) NO3 (b) Cl  (c) SCN  (d) CN –
33. In allene (C3H4), the type(s) of hybridisation of the carbon atoms is (are) [IIT 2012]
(a) sp and sp3 (b) sp and sp2 (c) only sp2 (d) sp2 and sp3
34. As per IUPAC nomenclature, the name of the complex [Co(H2O)4(NH3)2]Cl3 is [IIT 2012]
(a) Tetraaquadiaminecobalt(III)chloride (b) Tetraaquadiamminecobalt(III)chloride
(c) Diaminetetraaquacobalt(III)chloride (d) Diamminetetraaquacobalt(III)chloride
35. KI in acetone, undergoes SN2 reaction with each of P, Q, R and S. The rates of the reaction vary as
O
Cl
H3C Cl Cl Cl
[IIT 2013]
P Q R S
(a) P > Q > R > S (b) S > P > R > Q (c) P > R > Q > S (d) R > P > S > Q
36. Indicate the expected structure of the organic product when ethyl magnesium bromide is treated
with heavy water (D2O) [DCE-1994]
(a) C2 H 5 –C 2 H 5 (b) C2 H5 OD (c) Sodium benzoate (d) C2 H5 D
37. Pure methane can be produced by [DCE-2001]

(a) Wurtz reaction (b) Kolbe’s electrolytic method
(c) Soda-lime decarboxylation (d) Reduction with H2
38. Two gases, P and Q decolourise aqueous bromine but only one of them gives a white precipitate
with aqueous ammoniacal silver nitrate solution. P and Q are likely to be [DCE-1994]
(a) Ethane and ethyne (b) But-1-yne and but-2-yne
(c) Ethane and but-2-yne (d) Ethyne and propyne
39. 1-Butyne on oxidation with hot alkaline KMnO4 would yield [DCE-1994]
(a) CH3 CH2 CH 2 COOH (b) CH3 CH 2COOH
(c) CH3CH2COOH + CO2 + H2O (d) CH3CH2COOH + HCOOH
40. Which set of products is expected on reductive ozonolysis of the following diolefin? [DCE-1994]
CH3
CH3 CH= C CH=CH 2
(a) CH3CHO; CH3COCH=CH2 (b) CH3 CH= C CHO; CH2 O

CH3
(c) CH3CHO; CH3COCHO; CH2 O (d) CH3CHO; CH3COCH3; CH2 O
41. When an alkyne, RCCH, is treated with cuprous ion in an ammoniacal medium, one of the
products is [DCE-1996]
(a) RCCCu (b) CuCCH (c) CuCCCu (d) RCCR
42. The conversion of ClCH=CH–Cl to Cl2CH–CHCl2 can be carried out with [DCE-2000]
(a) Cl2 (b) Cl2/hv (c) Cl2/AlCl3 (d) Cl2/aq. NaOH
43. 1,2-Dibromopropane on treatment with X moles of NaNH2 followed by treatment with ethyl bromide
gave a pentyne. The value of X is [DCE-2000]
(a) one (b) two (c) three (d) four
44. The conversion of 2,3-dibromobutane to 2-butene with Zn and alcohol is [DCE-2000]

(a) redox reaction (b) -elimination (c) -elimination (d) both (a) & (b)
45. Position of double bond in alkenes can be identified by [DCE-2001]

(a) Bromine water (b) Ammoniacal silver nitrate solution
(c) Ozonolysis (d) none of these
46. Cl2 reacts with CS2 in presence of I2 to form [DCE-1995]

(a) CHCl3 (b) CCl4 (c) C2 H5 Cl (d) Cl3 C–NO2
3 Cl /  Br 2 /Fe Zn/HCl
47. The compound C7H8  2   A   B    C.
The compound C is [DCE-2000]
(a) o-Bromotoluene (b) m-Bromotoluene
(c) p-Bromotoluene (d) 3-Bromo-2,4,6-trichlorotoluene
AgNO 3
48. X HNO
  Yellow or white ppt. Which of the following can not be X? [DCE-2006]
3
+ –
Br CH2Br N 2 Cl
(a) (b) (CH3)CCl (c) (d)
C–R
49. Fridel-craft acylation can be given by + X 
AlCl 3
 O X is [DCE-2006]
(a) R – C –Cl (b) R – C – R (c) R – C – H (d) R– O – R

|| || ||
O O O
50. Petroleum is obtained from water gas, name of the reaction involved is [DCE-2006]
(a) Fischer-Tropsch (b) Bengoic (c) Dow’s (d) Kjeldahl’s
CHO CH 2 CHO
51. Ozonolysis products of an olefin are | and | . Olefin is [DCE-2006]
CHO CH 2 CHO
(a) (b) (c) (d)
52. Which of the following is the most reactive towards ring nitration? [DCE-1994]
(a) Benzene (b) Mesitylene (c) Toluene (d) m-Xylene
53. The order of activity of the various o- and p-director is [DCE-2000]

(a) –O– > –OH > –OCOCH3 > –COCH3 (b) –OH > –O– > –OCOCH3 > –COCH3
(c) –OH > –O– > –COCH3 > –OCOCH3 (d) –O– > –COCH3 > –OCOCH3 > –OH
54. Cyanoform is a _____ acid than chloroform [DCE-2000]
(a) weaker (b) stronger (c) both acidic & basic (d) neutral
55. Write the IUPAC name of CH3 – O  CH CH2 – CH3 [DCE-2007]
|
CH 3
(a) 3-methoxy butane (b) 2-methoxy butene

(c) 3-methyl-3-methoxy propane (d) butoxy methane
56. The arrangement of (CH3)3C–, (CH2)2CH–, CH3CH2– when attached to benzene or an unsaturated
group in increasing order of inductive effect is [AIEEE-2002]
(a) (CH3)3C– < (CH3)2CH– < CH3CH2 – (b) CH3CH2– < (CH3)2CH– < (CH3)3C–
(c) (CH3)2CH– < (CH3)3C– < CH3CH2 – (d) (CH3)3C– < CH3CH2– < (CH3)2CH–
57. Which of these will not react with acetylene? [AIEEE-2002]

(a) NaOH (b) ammoniacal AgNO3 (c) Na (d) HCl
58. What is the product formed when acetylene reacts with hypochlorous acid? [AIEEE-2002]
(a) CH3COCl (b) ClCH2CHO (c) Cl2CHCHO (d) ClCH2 COOH
59. Bentene-1 may be converted to butane by reaction with [AIEEE-2003]

(a) Pd/H2 (b) Zn–HCl (c) Sn–HCl (d) Zn–Hg
60. On mixing a certain alkane with chlorine an dirradiating it with UV light, it forms one
monochloroalkane. This alkane could be [AIEEE-2003]
(a) neopentane (b) propane (c) pentane (d) isopentane
61. The reaction of chloroform with alcoholic KOH and p-toluidine forms [AIEEE-2003]
(a) H3C NC (b) H3C CN
(c) H3 C N2 Cl (d) H3C NHCH3
62. Bottles containing C6H5I and C6H5CH2I lost their original labels. They were labelled A and B for
testing. A and B were separately taken in test tubes and boiled with NaOH solution. The end solution
in each tube was made acidic with dilute HNO3 and some AgNO3 solution added. Solution B gave
a yellow precipitate. Which one of the following statements is true for the experiment?[AIEEE-2003]
(a) Addition of HNO3 was unnecessary (b) A was C6H5I
(c) A was C6H5CH2 I (d) B was C6H5I
63. Which one of the following has the minimum boiling point? [AIEEE-2004]
(a) 1-Butene (b) 1-Butyne (c) n-Butane (d) isobutane
64. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly [AIEEE-2005]
(a) 1-bromo-2-methylbutane (b) 2-bromo-2-methylbutane
(c) 2-bromo-3-methylbutane (d) 1-bromo-3-methylbutane
65. Reaction of one molecule of HBr with one molecule of 1, 3-butadiene at 40ºC gives predominantly
(a) 3-bromobutene under kinetically controlled conditions
(b) 1-bromo-2-butene under thermodynamically controlled conditions
(c) 3-bromobutene under thermodynamically controlled conditions
(d) 1-bromo-2-butene under kinetically controlled conditions [AIEEE-2005]
66. Of the five isomeric hexanes, the isomer which can give two monochlorinated compounds is
(a) n-hexane (b) 2, 3-dimethylbutane
(c) 2, 2-dimethylbutane (d) 2-methylpentane [AIEEE-2005]
67. Acid catalyzed hydration of alkenes except ethene leads to the formation of [AIEEE-2005]
(a) primary alcohol (b) secondary or tertiary alcohol
(c) mixture of primary and secondary alcohols (d) mixture of secondary and tertiary alcohols
68. Elimination of bromine from 2-bromobutane results in the formation of [AIEEE-2005]

(a) equimolar mixture of 1 and 2-butene (b) predominantly 2-butene
(c) predominantly 1-butene (d) predominantly 2-butyne
69. HBr reacts with CH2=CH–OCH3 under anhydrous conditions at room temperature to give
(a) H3C – CHBr – OCH3 (b) CH3CHO and CH3Br
(c) BrCH2CHO and CH3OH (d) BrCH2 – CH2 – OCH3 [AIEEE-2006]
70. Phenyl magnesium bromide reacts with methanol to give [AIEEE-2006]

(a) a mixture of phenol and Mg(Me)Br (b) a mixture of anisole and Mg(OH)Br
(c) a mixture of benzene and Mg(OMe)Br (d) a mixture of toluene and Mg(OH)Br
71. Which one of the following conformations of cyclohexane is chiral? [AIEEE-2007]

(a) Chair (b) Boat (c) Twist boat (d) Rigid
72. Presence of a nitro group in a benzene ring [AIEEE-2007]

(a) deactivates the ring towards nucleophilic substitution
(b) deactivates the ring towards electrophilic substitution
(c) activates the ring towards electrophilic substitution
(d) renders the ring basic
73. The electrophile, E attacks the benzene ring to generate the intermediate -complex. Of the
following, which -complex is of lowest energy? [AIEEE-2008]
NO2
NO 2 NO2
H H
(a) E (b) E (c) H (d)
E H E
74. Consider the following bromides: [AIEEE-2010]
Me Me
Me Br Me
Br Br
A B C
The correct order of SN1 reactivity is

(a) C  B  A (b) A  B  C (c) B  C  A (d) B  A  C
75. One mole of a symmetrical alkene on ozonolysis gives two moles of an aldehyde having a molecular
mass of 44 u. The alkene is [AIEEE-2010]
(a) 2-butene (b) ethene (c) propene (d) 1-butene
76. Ozonolysis of an organic compound gives formaldehyde as one of the products. This confirms the
presence of: [AIEEE-2011]
(a) two ethylenic double bonds (b) a vinyl group
(c) an isopropyl group (d) an acetylenic triple bond
77. How many chiral compounds are possible on monochlorination of 2-methylbutane? [AIEEE-2012]
(a) 8 (b) 2 (c) 4 (d) 6
78. Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer
of mono substituted alkyl halide? [AIEEE-2012]
(a) Tertiary butyl chloride (b) Neopentane
(c) Isohexane (d) Neohexane
79. 2-Hexyne gives trans-2-Hexene on treatment with [AIEEE-2012]

(a) Pt/H2 (b) Li/NH3 (c) Pd/BaSO4 (d) Li/AlH4
80. The gas leaked from a storage tank of the Union Carbide plant in Bhopal gas tragedy was:
[JEE-Mains 2013]
(a) Ammonia (b) Phosgene (c) Methylisocyanate (d) Methylamine
81. Compound (A), C8H9Br, gives a white precipitate when warmed with alcoholic AgNO3. Oxidation
of (A) gives an acid (B), C8H6O4. (B) easily forms anhydride on heating. Identify the compound (A).
[JEE-Mains 2013]
CH2 Br
CH2 Br
CH2 Br C2 H5
(a) (b) (c) (d)

CH3 Br
CH3
CH3
82. A solution of (–) – 1 – chloro – 1– phenylethane in tolune racemises slowly in the presence of a
small amount of SbCl5, due to the formation of : [JEE-Mains 2013]
(a) carbocation (b) free radical (c) carbanion (d) carbene
83. Among the following reaction(s) which gives (give) tert-butyl benzene as the major product is(are)
Br
Cl
(a)   (b) 

AlCl

 [JEE Advanced 2016]
3
NaOC H 2 5
OH
(c) 
H SO
 (d) 
BF OEt
3
 2
2 4
84. Compounds P and R upon ozonolysis produce Q and S, respectively. The molecular formula of Q
andS is C8H8O. Q undergoes Cannizzaro reaction but not haloform reaction, whereas S undergoes
haloform reaction but not Cannizzaro reaction [JEE Advanced 2017]
i) O 3 /CH 2 Cl 2
(i) P 
ii )Zn/H 2 O
Q
(C 8H 8 O)
i) O 3 /CH 2 Cl 2
(ii) R 
ii )Zn/H 2 O
 S
(C 8H 8 O)
The option(s) with suitable combination of P and R, respectively, is(are)
H3C
CH3 CH3
and and
(a) H3C (b) CH3
CH3
H3C
H3C CH3
CH3 CH3
H3C and H3C
(c) and (d)
CH3 CH3
CH3
85. The trans-alkenes are formed by the reduction of alkynes with [JEE Mains 2018]
(a) Sn-HCl (b) H2-Pd/C, BaSO4 (c) NaBH4 (d) Na/liq. NH3
86. The reaction(s) leading to the formation of 1,3,5-trimethylbezene is (are)

[JEE Advanced 2018]
O
heated iron tube
(a) conc. H 2SO 4 (b) Me Me  873 K


 
O
CHO
1) Br2 , NaOH
2) H 3 O 
(c) 

3) sodalime,  (d) Zn/Hg, HCl
 
OHC CHO
O O
87. The major product of the following reaction is: [JEE Mains 2019]
HO
(1) HCl

(2) AlCl (Anhyd.)
3

Cl HO
(a) (b)
Cl HO
(c) (d)
88. The correct order for acid strength of compounds [JEE Mains 2019]
CH  CH, CH3 – C  CH and CH2 = CH2
is as follows:
(a) CH  CH > CH2 = CH2 > CH3 – C º CH (b) HC  CH < CH3 – C  CH > CH2 = CH2
(c) CH3 – C  CH > CH2 = CH2 > CH º CH (d) CH3 – C  CH > CH  CH > CH2 = CH2
89. Which of the following reactions produce(s) propane as a major product? [JEE Advanced 2019]
HC NaOH , CaO ,  Cl Zn, dil. HCl
(a) 3 
COONa   (b) H C
3
Br
(d) H3 C
electrol ysis
(c) Br Zn  H 2O  
H3C  COONa
90. The correct order of heat of combustion for following alkadienes is : [JEE Mains 2020]
(A) (B) (C)
(a) (A) < (B) < (C) (b) (B) < (C) < (A) (c) (C) < (B) < (A) (d) (A) < (C) < (B)
91. The major product (Y) in the following reactions is: [JEE Mains 2020]
H3 C
H 2SO 4 .H 2SO 4 ( i) C 2 H5 MgBr , H 2 O
CH  H 2O
 X 
(ii) Conc. H 2SO 4 / 
Y
H3 C
H2C CH3 H3C CH 3
(a) (b)
H3C C2 H5 H3C C2H5
H3C CH3 H3C CH2
(c) (d)
H3C CH 3 H3C CH 3
92. [JEE Mains 2021]
For above chemical reactions, identify the correct statement from the following:
(a) Both compound ‘A’ and compound ‘B’ are dicarboxylic acids
(b) Both compound ‘A’ and compound ‘B’ are diols
(c) Compound ‘A’ is diol and compound ‘B’ is dicarboxylic acid
(d) Compound ‘A’ is dicarboxylic acid and compound ‘B’ is diol
93. Benzene on nitration gives nitrobenzene in presence of HNO3 and H2SO4 mixture, where :
(a) both H2SO4 and HNO3 act as a bases
(b) HNO3 acts as an acid and H2SO4 acts as a base
(c) both H2SO4 and HNO3 act as an acids
(d) HNO3 acts as a base and H2SO4 acts as an acid [JEE Mains 2021]
94. Arrange the following conformational isomers of n-butane in order of their increasing potential energy:
[JEE Mains 2021]
(1) II < III < IV < I (2) I < IV < III < II
(3) II < IV < III < I (4) I < III < IV < II
95. The major product of the following reaction is :
[JEE Mains 2021]
(1) (2) (3) (4)
96. For the following :
[JEE Mains 2022]
(1) (2)
(3) (4)
97. The major product formed in the following reaction is :
[JEE Mains 2022]
(1) (2)
(3) (4)

CHAPTER TEST
SECTION - I: MULTIPLE CHOICE QUESTIONS (Single Correct)
C6 H5 CHCl2
1. The product P in the given reaction is C6 H5 C  CC6 H5 [P]
Me3 COK
H Cl Cl Cl
C6 H5 C C C6 H5 C6 H5 C C C6 H5
(a) (b)
C6 H5 Cl H C6H5
C6 H5 C6 H5 C 6 H5 C 6 H5
(c) (d)
C6 H5 C 6 H5 Cl
2. [A] + CH2 = CH2  compound [A] is
CH=CH2
CH=CHCHO
(a) (b)
CH=CH2 CH=CH2
(c) (d)
C6 H 5  COOOH
3. + [O] Peroxy acid
Z. Z may be
O O
(a) (b) O (c) (d) all of these
O
4. Which one is the slow step in the chlorination of benzene?
(a) Cl2 + FeCl3  FeCl4– + Cl–
 Cl H
(b)  Cl  

 Cl H Cl
(c)  FeC3  HCl
(d) None of these
OH
OH OH
NO2
5. Arrange NO2
and in decreasing acidic character..
NO2
(I) (II) (III)
(a) I > II > III (b) III > I > II (c) I > II > III (d) III > II > I
SECTION - II: MULTIPLE CHOICE QUESTIONS (More than one correct)

6. Styrene undergoes following reaction in acid medium
CH CH2
CH3
H+
The various intermediates formed are

CH3
CH3
+
CH  
H
(a) (b) (c) (d)
CH3
Ozonolysis
7. Products; . The products formed are
CH3
O O O
(a) CH3 C CHO (b) CHO – CHO (c) CH3 C C CH3 (d) HCOOH
8. Kolbe’s electrolytic method can be applied on

CH2 COOK HC COOK
(a) CH3 COONa (b) (c) (d) C6 H5 COONa
CH2 COOK HC COOK
9. Which of the following will give cis-diols?

1. KMnO4 1. OsO4
(a) C C (b) C C
2. H2O 2. NaSO3
1. OsO4, 25°C 35% , H2O2

(c) 2. NaSO3 (d) HCO2H, 25°C
10. Toluene, when treated with Br2/Fe, gives p-bromotoluene as the major product because CH3 group
(a) is para directing (b) is meta directing
(c) activates the ring by hyperconjugation (d) deactivates the ring
SECTION - III: INTEGER TYPE QUESTIONS
AlCl3
  Product
11.
Cl
Find out degree of unsaturation of the product.
12. Find out number of stereoisomers obtained by bromination of trans-2-butene.
13. How many chiral compounds are possible an monochlorination of 2-methyl butane?
CH3
Cl
Cl  ( x ). (x) = total number of dichloro product.
2
H hν
14.
CH3
2-chlorohexane
15. The degree of unsaturation of the compound C4H5N is
16. Reductive ozonolysis of a terpenoid of following structure gives how many different
products?
17. The maximum number carbon atoms in the expected products of the Wurtz reaction given below is:
H3C
H3C 
Br H3C H
Na / dry ether
(Products)
18. The number of stereocentre in the given compound is_____

Br
CH3
H3C
Cl
SECTION - IV: MATRIX MATCH
19. Match the chemical conversions in Column I with the appropriate reagents in Coumn - II and select
the correct answer using the code given below the lists:
Column - I Column - II
P. Cl 1. (i) Hg(OAc)2; (ii) NaBH4
Q. ONa OEt 2. NaOEt
OH
R. 3. Et-Br
S. 4. (i) BH3; (ii) H2O2/NaOH

OH
Codes:
P Q R S
(a) 2 3 1 4
(b) 3 2 1 4
(c) 2 3 4 1
(d) 3 2 4 1
SECTION - V: COMPREHENSION TYPE QUESTIONS
Comprehension
The addition of bromine to cyclopentene provides evidence for bromonium ion intermediate in bromine
addition. It follows ionic mechanism. When cyclopentane reacts with bromine in presence of CCl4 anti
addition occurs and gives trans isomer so addition of halogen to an alkene is a sterospecific reaction. Cis
alkene on addition with halogen gives meso product and trans alkene on addition gives racemic mixture.
HCO3 H
20. 
H O
A
3
A is
(a) 2, 3-epoxy butane (b) 2, 3-butane diol
(c) 2-butanone (d) Epoxy ethane
21. Consider the following reaction:
H3C CH3
(CH3 )3 COK
 CHBr3  A
H H
The product obtained in the reaction is
Br Br Br
Br
(a) H3C Br (b) H3C Br

CH3 CH3
CH3 CH3 CH3 H
H Br H H Br CH
3
(c) (d)
Br Br
H3C CH3
OsO 4 Na 2SO3
22.   I 
H2O
II
H H
The final product is

(a) Meso 2, 3-butane diol (b) 2-butanol
(c)  2, 3-butane diol (d) 2-butanone

ANSWERS
CHAPTER ASSIGNMENT
MULTIPLE CHOICE QUESTIONS (Single Correct )
1. (d) 2. (b) 3. (d) 4. (b) 5. (b)

6. (c) 7. (a) 8. (b) 9. (d) 10. (b)
11. (d) 12. (a) 13. (c) 14. (b) 15. (c)
16. (4) 17. (5) 18. (9) 19. (3) 20. (4)
21. (9) 22. (2) 23. (5) 24. (3) 25. (8)
MULTIPLE CHOICE QUESTIONS (More than one Correct )
26. (a,b) 27. (a,c,d) 28. (a,b,c) 29. (a,c,d) 30. (a,c,d)
31. (a,c,d) 32. (a,b) 33. (b,c) 34. (b,c) 35. (a,b,c)

36. A–(r),(s), B–(t), C–(p), (q), D–(r)
37. A-(r),(s),(t); B-(s),(p); C-(r),(s); D-(q),(r)
38. (d) 39. (c) 40. (d) 41. (b) 42. (c)
43. (a)

1. (b) 2. (b) 3. (b) 4. (a) 5. (b)
6. (c) 7. (b) 8. (b) 9. (a) 10. (b)
11. (a) 12. (c) 13. (b) 14. (a) 15. (a)
16. (b) 17. (a) 18. (d) 19. (c) 20. (d)
21. (b) 22. (b) 23. (c)
24. (a)-(ii); (b)-(ii); (c)-(iii), (iv); (d)-(i), (iv) 25. (b) 26. (a)
27. (c) 28. (d) 29. (a,c) 30. (d) 31. (b)
32. (c,d) 33. (b) 34. (b) 35. (b) 36. (d)
37. (c) 38. (b) 39. (c) 40. (c) 41. (a)
42. (a) 43. (c) 44. (c) 45. (c) 46. (b)
47. (b) 48. (a) 49. (a) 50. (a) 51. (c)
52. (d) 53. (a) 54. (b) 55. (b) 56. (a)
57. (a) 58. (c) 59. (a) 60. (a) 61. (a)
62. (b) 63. (d) 64. (b) 65. (b) 66. (b)
67. (b) 68. (b) 69. (a) 70. (c) 71. (c)
72. (b) 73. (a) 74. (c) 75. (a) 76. (b)
77. (c) 78. (b) 79. (b) 80. (c) 81. (b)
82. (a) 83. (b), (c), (d) 84. (a), (b) 85. (d) 86. (a,b,c,d)
87. (b) 88. (b) 89. (a), (b) 90. (a) 91. (c)
92. (d) 93. (d) 94. (4) 95. (3) 96. (2)
97. (2)
CHAPTER TEST
1. (d) 2. (b) 3. (d) 4. (b) 5. (b)
6. (a,b,c) 7. (a,b) 8. (a,b,c) 9. (a,b,c) 10. (a,c)
11. (9) 12. (4) 13. (4) 14. (9) 15. (3)
16. (3) 17. (8) 18. (4) 19. (a) 20. (a)
21. (c) 22. (a)

HINTS AND SOLUTIONS

1. (d) Cyclohexane is less dense than water.
2. (b) HBr add according to Markovnikoff rule.
3. (d) As branching increases, boiling point decreases due to decrease in the surface area of the
molecule.
4. (b) Para derivative gives only one monobromo derivative.
5. (d) –CH3 is an activating group towards electrophilic substitution reaction. Whereas –COOH,
–NO2 are deactivating groups towards electrophilic substitution reaction.
6. (c) Reaction proceed with formation of cyclic brominium ion followed by attack with chloride ion to
bring an addition product.
7. (a) Excess of ethane in presence of chlorine.
8. (b) NO2 group is a meta directing group towards electrophilic aromatic substitution reaction. It also
decreases electron density on aromatic ring by means of resonance and inductive effect.
9. (d) –CN group deactivates the ring towards electrophilic substitution by means of withdrawing
electron from the ring through resonance and inductive effect.
10. (b) The dipole moment of trans isomer generally cancel out.
11. (b) The reaction is a Diels Alder reaction (Cyclo addition reaction).
12. (a) Conformers can be generated by means of rotation about C – C single bond.
13. (c) For hybridisation we count number of sigma bond and lone pair in a carbon atom.
14. (b) –NO2 group is a deactivating group towards electrophilic aromatic substitution reaction.
15. (b) Heptan-4-ol can be dehydrated to hept-3-ene because its a symmetrical alcohol.

16. (4) An asymmetric carbon has four different groups attached to it.
17. (5) Xylene derivative gives dicarboxylic acid on reaction with KMnO4. Whereas terminal alkenes
give CO2 on reaction with KMnO4 as one of the product.
18. (9) Degree of unsaturation is number of moles of hydrogen requried to make a compound saturated.
For a benzene ring, degree of unsaturation is four.
19. (3) 1,2-dibromopropane undergoes dehydrohalogenation in presence of NaNH2 followed by a removal

of acidic proton.
20. (4) Undergo substitution reaction at different carbon centre having different degree.
21. (9) Undergo substitution reaction at different carbon centre to generate dichloro product.
22. (2) Degree unsaturation is two. The product is a bicyclo compound.
23. (5) Double bond equivalent is 5. Because the formula of cubane is C8H8. To make it saturated five
moles of hydrogen is required.
24. (4) Number of stereoisomers is 4. (Geometrical isomers)
25. (8) Use the concept of degree of unsaturation.

26. (a,b) Periodic acid (HIO4) is an oxidising agent and bring about C-C bond cleavage.
27. (a,c,d) Following are the condition for aromaticity.

(a) Compound should be planar
(b) Follows Huckel rule (4n + 2)  electron. Where n = 0, 1, 2, 3....
(c) Complete delocalisation of electron.
28. (a,b,c) Apply the condition of aromaticity.
29. (a,c,d) Apply the condition of aromaticity.
30. (a,b,c,d) Self explanatory
31. (a,c,d) Undergo Diels Alder reaction. Its a concerted reaction of a diene with a dienophile.
32. (a,b) Addition of water by means of Markovnikoff Rule.
33. (b,c) Allylic substitution followed by electrophilic substitution.
34. (b,c) The compound which give more than 50% yield doesnot undergo any rearrangement.
35. (a,b,c) The reaction proceed with formation of dibromo compound followed by elimination
reaction.

36. A–(r),(s), B–(t), C–(p), (q), D–(r)
(A) Coupling reaction.
(B) Pinacol - pinacolone reaction.
(C) Reduction.
(D) Nucleophilic substitution reaction.
37. A-(r),(s),(t); B-(s),(p); C-(r),(s); D-(q),(r)
(A) Aldol condensation.
(B) Addition Grignard reagent followed by nucleophilic substitution.
(C) Formation of hemiacetal followed by dehydration.
(D) Electrophilic substitution reaction.

38. (d) Reaction proceed with formation of cyclic brominium ion followed by attack of water to give
anti-product.
39. (c) Reaction proceed with allylic substitution of bromine radical.
40. (d) Addition of water by Markovnikoff rule.
41. (b) Allylic substitution of bromine.
42. (c) Reaction proceed with formation of a stable benzyl radical.
43. (a)


Untitled

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Untitled

Uploaded by

Copyright:

Available Formats

Contents

Chapter 1: Nomenclature ............................................. 01 – 16

Chapter 2: General Organic Chemistry ....................... 17 – 108

Chapter 3: Hydrocarbons ........................................ 109 – 226

I. Common Name System

II IUPAC System of Nomenclature.

PRIORITY LIST (Table - A)

S.No. Functional group Formula Family name Substituted prefix/suffix

1. Sulphonic acid –SO3H Alkane Sulphonic acid Sulpho

3. Carboxylic acid –C–O–C– Alkanoic acid anhydride

8. Aldehyde * Alkanal Formyl. Aldo, Oxo

2. Subsidiary group : If the molecule contains C = C or C  C apart from Main functional

Main Functional group = –CONH2

Step-II: Identification of main chain:

Following points should be considered for choosing the main chain:

2. It must contain maximum number of subsidiary groups.

4. The main chain must contain maximum number of carbon atoms.

Use the above points for identifying the chain.

correct chain wrong chain

correct chain wrong chain

Reason same as above.

groups which is – C – group.

Step-III: Numbering the Main Chain

Numbering of the main chain is done according to :

(a) The main functional group gets the lowest number.

(b) The second lowest number is given to the subsidiary groups.

(Main functional group given lowest number)

1 2 3 4 5 Set - 1 (incorrect numbering)

Therefore, set - 2 is preferred.

Step - IV: Writing the name

Adjective String = 2-Bromo

Family Name = Alkenal

3' 2' 1' 2 1

Adjective String = 2-[2- Bromo Propyl]

Nomenclature of Specific Families (Few selected)

Term-1 Term-2 Term-3 Term-4

Set - 1 3, 4 (wrong numbering)

2. Esters: The name written is Alkyl alkanoate.

CH3 – C – O – CH3 Alkyl

1. CH3 – N – CH2 – CH3

2. CH3 – CH2 – C – NH – CH – CH3

N-(1-Methyl) ethyl propan amide

1. Compound is named as bicycloalkane corresponding to total number of C-atoms.

Bicyclo [3.1.0] hexane Bicyclo [3.3.0] octane Bicyclo [4.2.0] octane

3-Ethyl bicyclo [4.4.0] decane

Nomenclature of spiro compounds

ring first. For example

Spiro [4.5] decane 2,6-di(cyclopropyl)-spiro [3.4] octane

Nomenclature of unbranched identical hydrocarbon ring systems having NO common

3: ter 4 : quater 5: quinque 6: sexi 7: septi

1–1´, 3´ - 1´´-tercyclopropane 1, 1´, 2´, 1´´ - tercyclobutane

3´´ 2´´ 3´ 2´ 2 3 5´´ 2´´

p-terphenyl or 1, 1´, 4´, 1´´-terphenyl m-terphenyl or 1, 1´, 3´, 1´´-terphenyl

Amity Institute for Competitive Examinations : Phones: 24336143, 24336144, 25573111/12/13/14,95120-2431839/42 [ 10 ]

PREVIOUS YEAR QUESTIONS

1. The correct IUPAC name of the compound, is [IIT 1990]

(a) 5,6-Diethyl-8-methyldec-6-ene (b) 6-Butyl-5-ethyl-3-methyloct-4-ene

2. Choose the correct IUPAC name for

3. In compound, CH2=CH–CH2–CH2–CH, the C2–C3 bond is of the type [IIT 1999]

(a) Chlorophenyl ketone (b) Chloroaceto benzene

6. The number of structural isomers for C6H14 is [IIT 2007(P-1)]

Amity Institute for Competitive Examinations : Phones: 24336143, 24336144, 25573111/12/13/14,95120-2431839/42 [ 11 ]

10. The IUPAC name of the following compound is [IIT 2009]

(a) (b) (c) (d)