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HYDROCARBON

AROMATIC COMPOUND
ALCOHOL AND ETHER
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THEORY AND EXERCISE BOOKLET
CONTENTS

S.NO. TOPIC PAGE NO.

HYDROCARBON
THEORY WITH SOLVED EXAMPLES ............................................................. 5 59

EXERCISE - I (JEE Main) ................................................................................ 60 68

EXERCISE - II (JEE Advanced Objective) .................................................... 69 79

EXERCISE - III (JEE Advanced) ...................................................................... 80 83

EXERCISE - IV (JEE Advanced Previous Years)................ ......................... 84 92

ANSWER KEY................................................................................................. 93 94

AROMATIC COMPOUND
THEORY WITH SOLVED EXAMPLES ............................................................ 95 97

EXERCISE - I (JEE Main) ............................................................................... 98 118

EXERCISE - II (JEE Advanced Objective) .................................................. 119 126

EXERCISE - III (JEE Advanced) .................................................................... 127 135

EXERCISE - IV (JEE Main & JEE Advanced Previous Years) .................... 136 145

ANSWER KEY............................................................................................... 146 154

ALCOHOL AND ETHER


THEORY WITH SOLVED EXAMPLES .......................................................... 155 169

EXERCISE - I (JEE Main) .............................................................................. 170 175

EXERCISE - II (JEE Advanced Objective) .................................................. 176 183

EXERCISE - III (JEE Advanced) .................................................................... 184 186

EXERCISE - IV (JEE Main & JEE Advanced Previous Years) .................... 187 189

ANSWER KEY............................................................................................... 190 192


Page # 4 Chemistry ( Booklet-1 )

JEE SYLLABUS

HYDROCARBON
JEE - ADVANCED

Preparation, properties and reactions of alkanes: Homologous series, physical properties of alkanes
(melting points, boiling points and density); Combustion and halogenation of alkanes; Preparation
of alkanes by Wurtz reaction and decarboxylation reactions.
Preparation, properties and reactions of alkenes and alkynes: Physical properties of alkenes and
alkynes (boiling points, density and dipole moments); Acidity of alkynes; Acid catalysed hydration
of alkenes and alkynes (excluding the stereochemistry of addition and elimination); Reactions of
alkenes with KMnO4 and ozone; Reduction of alkenes and alkynes; Preparation of alkenes and
alkynes by elimination reactions; Electrophilic addition reactions of alkenes with X2, HX, HOX
(X=halogen) and H2O; Addition reactions of alkynes; Metal acetylides.

AROMATIC COMPOUND
JEE - ADVANCED

Reactions of benzene: Structure and aromaticity; Electrophilic substitution reactions: halogenation,


nitration, sulphonation, Friedel-Crafts alkylation and acylation; Effect of o-, m- and p-directing
groups in monosubstituted benzenes. Phenols: Acidity, electrophilic substitution reactions
(halogenation, nitration and sulphonation); Reimer-Tieman reaction, Kolbe reaction. basicity of
substituted anilines, preparation from nitro compounds, reaction with nitrous acid, azo coupling
reaction of diazonium salts of aromatic amines, Sandmeyer and related reactions of diazonium
salts; carbylamine reaction; Haloarenes: nucleophilic aromatic substitution in haloarenes and
substituted haloarenes (excluding Benzyne mechanism and Cine substitution).

ALCOHOL AND ETHER


JEE - ADVANCED
Alcohols: esterification, dehydration and oxidation, reaction with sodium, phosphorus halides,
ZnCl2/concentrated HCl, conversion of alcohols into aldehydes and ketones; Ethers:Preparation
by Williamsons Synthesis;

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ALKANE
Alkane are the saturated non polar hydrocarbon having general formula CnH2n+2.
Hydrocarbon Those organic compounds which contain only carbon and hydrogen atoms are known as
hydrocarbons.

1.2 General method of preparation

1.2.1 By catalytic reduction of alkenes and alkynes


H2,25C
R C C R R CH2 CH2 R
Ni,Pt or Pd

H 2,25C
R CH = CH R R CH2 CH2 R
Ni,Pt or Pd
Hydrogenation Addition of H2 to unsaturated bond.

Hydrogenation is of two kind


(a) Heterogeneous and (b) Homogeneous
(a) Heterogeneous It is two phase hydrogenation the catalyst is finely divided metal like Ni, Pt
or Pd and a solution of alkene.
(b) Homogeneous It is one phase hydrogenation both catalyst and alkenes are solution. In this
hydrogenation catalyst are organic complex of transition metal like Rh or Ir.
Hydrogenation is exothermic, qualitative and during the hydrogenation, total heat evolved to hydrogenate
one mole of unsaturated compound is called heat of hydrogenation. Heat of hydrogenation is the
measurement of stability of isomeric alkenes.
1
stability of alkene
Heat of hydrogenation

1.2.2 From alkyl halide

(A) From organometallic compound compound having bond. (M metal)


(i) By wurtz reaction
dry ether
2R X + 2Na R R + 2NaX
Na
R X + R X R R, R R, R R
ether (dry)

Mechanism Two mechanisms are suggested


(a) Ionic mechanism
2Na 2Na + 2e

R X + 2e R+X
(1, 2)
2
R+RX SN RR
(1 or 2)

Na + X NaX

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(b) Free radical mechanism

Na Na + e

RX+e R+X
R +R RR
Note : The alkyl halide should be 1 or 2, with 3 R X SN2 and free radical coupling is not possible
due to steric hinderance so in that case elimination or disproportionation is possible.

In the ionic mechanism alkyl sodium (R Na) gives R strong base as well as nucleophile which gives SN2

with R X, ether should be dry otherwise, if moisture is present then R forms R H instead of R R
with H2O.

RX Mg
(ii) By G.R. RMgX
1,2,3 ether
all active
RMgX + H containg RH
compound
H2O
RH + Mg (OH) X
ROH RH + Mg (OR) X
RMgX NH3
RH + Mg (NH2) X
R' C CH
RH + Mg C CR')
RSH RH + Mg (SR) X
R COOH RH + Mg (OCOR) X

(iii) By corey house alkane synthesis

R' X
RX 2Li CuX (1 > 2)
R Li R2CuLi R R'
(1,2,3) + Lithium dialkyl
LiX cuprate
(Gilman Reagent)

Mechanism

R2CuLi is the source of R


2
SN
R + R' X R R'
1 >> 2

R2 CuLi do not reacts with NO2, CN, > C = O etc.

Ex.1 CH3 Br Li CuI B Y


A C
if C is CH3 CH2 (CH2)5 CH3, than what is Y.
Ans. CH3 (CH2)6 Br

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CH3 CH3
Li CuI R'X
Q.1 CH3 C Cl A B CH 3 C CH2 R' is ?
CH3 CH3

(iv) By Franklande reagent


Ether
R X + Zn + R X R R + Zn X2
Mechanism

R
Zn RX
RX R Zn X RR
+
Organozinc ZnX2
compound

(B) By reduction of alkyl halides

(i) with metal-acid

e/H
RX R H + HX
1 Metal / acid
Reducing agent

Zn / acid, Zn Cu / H2O or Zn Cu + acid


Zn Cu / C2H5OH, Na Hg / acid, Al Hg / H2O etc.

Mechanism

Metal M+e

RX e M
R + X MX
1
acid

RH

(ii) With Metal hydrides

(a) TPH (Ph3SnH) : It reduces 1, 2 & 3 R X


RX Ph3SnH RH

NaBH4
(b) NaBH4 RX RX
1 & 2
LiAlH4 LiAlH4
(c) RX R H, RX Alkene
1 & 2 3

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1.2.3 By red P & HI


Red P & HI is strong reducing agent
Red P + HI
R COOH R CH3
Red P + HI
R C Cl R CH3
O

Red P + HI
R C OEt R CH3
O
Red P + HI
RX RH
Red P + HI
R OH R H + H2O

1.2.4 By soda lime Fatty acids are good source of hydrocarbon, correction, heating of sodium salt of
carboxylic acid (R COONa) with soda lime (NaOH CaO) gives hydrocarbon, which is known as
decarboxylation (e.g. replacement of COOH group by H) decarboxylation also takes place on heating
only, when compound is gem dicarboxylic acid or there is keto group or double bond on carbon.

CaO/NaOH
R + Na 2CO3
H2O

HOH

RH

COOH NaOH
Ex.2 A B
COOH
What are A and B

Ans. A is COOH , B is

O
H3C COOD

Q.2

Opticallyactive

Write the structure of A and mention its stereochemistry

1.2.5 By Kolbes electrolysis

Electrolysis
2RCOOK + 2HOH RR + 2CO2 + H2 + 2KOH
Electrolysis
e.g. 2CH3 COOK + 2H2O CH3CH3 + 2CO2 + H2 + 2KOH.
If n is the number of carbon atoms in the salt of carboxylic acid, the alkane formed has 2(n 1) carbon
atoms.

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1.2.6 Reduction of aldehydes, ketones :

(a) By Clemmensens reduction : with Zn Hg / conc. HCl

Zn Hg /conc. HCl
R CHO RCH3 + H2O

O
Zn Hg /conc. HCl
R C R' RCH2R + H2O

Zn Hg /conc. HCl
e.g. CH3 CHO CH3CH3 + H2O

O
Zn Hg /conc. HCl CH3CH2C2H5 + H2O
CH3 C C2H5 + 4[H]

Clemmensen reduction is not used for compound which have acid sensitive group.

(b) By Wolff-kishner reduction with NH2NH2 / KOH

NH2NH 2 / KOH
RCHO RCH3

NH2NH 2 / KOH
RCO R RCH2R

Wolff-kishner reduction is not used for compounds which have base sensitive groups.

1.3 Physical Properties of Alkanes :

3.3.1 Physical State :


The first four members (C1 to C4) are gases : the next thirteen members, (C5 to C17) are liquids while
the higher members are waxy solids.

1.3.2 Boiling points :

The boiling points of n-alkanes increase regularly with the increase in the number of carbon atoms

650 Bolling point

500
Temperature, K

350

200

50
0 4 8 12 16 20
Number of carbon
atoms per molecule

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Among the isomeric alkanes, the branched chain isomers have relatively low boiling points as compared
to their corresponding straight chain isomers. Greater the branching of the chain, lower is the boiling
point. This is due to the fact that branching of the chain makes the molecules more compact and
brings it close to a sphere, so the magnitude of vander wall forces decreases.

1.3.3. Melting Points

It is the evident that the increase in melting point is relatively more in moving from an alkane having
odd number of carbon atoms to the higher alkane with even no. of C while it is relatively less in moving
from an alkane with even number of carbon atoms to the higher alkane.
Explanation : The alkanes with even no. of C atoms are more closely packed.

320

260
Temperature, K

200

140

80
0 7 11 15 19 23

Number of carbon
atoms per molecule

1.3.4 Solubility

In keeping with the popular rule like dissolves like hydrocarbons are insoluble in polar solvent like
water because they are predominantly non-polar in nature.

1.3.5 Density

The densities of alkanes increase with increasing molecular weight but become constant at about 0.8
g cm3. This means that all alkanes are lighter than water so they floats over water.

1.4.1 Chemical Reaction of Alkanes :

Characteristic reaction of alkanes are free radical substitution reaction, these reaction are generally
chain reactions which are completed in three steps mainely.
(i) chain initiation (ii) chain propagation, (iii) chain termination

Examples of free radical substitution reaction


UV Light or
R H + X2 R X + HX
250 400C

Cl2 Cl2 Cl 2 Cl 2
Exp. CH4 CH3Cl CH2Cl 2 CHCl3 CCl 4
hv hv hv hv
+ + +
HCl HCl HCl
When equimolar amount of methane and Cl2 are taken, a mixture of four possible products are formed,

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but if we take excess of CH4 then yield of CH3Cl will be the major product.
Reactivity of X2 : F2 > Cl2 > Br2 > I2
Reactivity of H : 3H > 2H > 1H

with F2 alkanes reacts so vigorously that, even in the dark and at room temp, reactant diluted with an
inert gas.
Iodination is reversible reaction, since HI formed as a by-product is a strong reducing agent and
reduces alkyl iodide back to alkane. Hence iodination can be done only in presence of strong oxidizing
agent like HIO3, HNO3 or HgO
R H + I2 R I + HI
HI + HIO3 H2O + I2

Mechanism of halogenation of CH4

(i) Chain initiation it is a endothermic step


UV or temp
X2 2X
250 400C

(ii) Chain propagation


X+RH R + HX


R+XX RX+X

(iii) Chain termination it is always exothermic



X+X X2

R+R RR

R+X RX

Each photon of light cleaves one chlorine molecule to form two chlorine redicals, each chlorine atom
starts a chain and on an average each chain contains 5000 repetitions of the chain propagating cycle
so about 10,000 molecules of CH3Cl are formed by one photon of light.

Some reagent affects the rate of halogenation : For example

Q.3 In the given ways which is feasible



CH 3 + HCl (1)

CH4 + Cl

CH 3Cl + H (2)

Q.4 Which of the following reaction has zero activation energy



(A) CH4 + Cl CH3 + HCl (B) Cl2 2 Cl

(C) CH + CH CH3 + CH3 (D) CH3 + Cl Cl CH 3 + Cl + Cl
3 3

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Q.5 If the Eact for a forward reaction is given



CH3 H + Cl CH3 + HCl
the Eact for backward reaction will be
(A) 1 kcal (B) 4 kcal (C) 4 kcal (D) 3 kcal

Halogenations of higher alkane :

Cl2
(i) CH3 CH2 CH3 CH3 CH CH3 + CH3 CH2 CH2 Cl
light, 25C
Cl 45%
55%

Cl 2
(ii) CH3 CH2 CH2 CH3 CH3 CH2 CH CH3 + CH3 CH2 CH2 CH2 Cl
light, 25C
28%
Cl
72%

CH 3
Cl 2
(iii) CH3 CH CH3 CH 3 CH CH2 Cl + CH3 C CH 3
light, 25C
CH3 Cl
CH3
64% 36%

Br2
(iv) CH3 CH2 CH3 CH3 CH 2 CH 2 Br + CH 3 CH CH 3
light, 127C
3% Br
97%

CH3
Br2
(v) CH3 CH CH3 CH3 CH CH2 Br + CH3 C Br
light, 127C
CH3 CH 3 CH3
trace over 99%

Relative amounts of the various isomers differ remarkably depending upon the halogen used from the
above reaction, it is observed that chlorination gives mixture in which no isomer greatly dominates
while, in bromination gives mixture in which one isomer dominates greatly (97% 99%).

Factors determining the relative yields of the isomeric products.


(i) Probability factor This factor is based on the number of each kind of H atom in the
molecule.
(ii) Reactivity of hydrogen The order of reactivity is 3 > 2 > 1

1.4.2 Aromatisation:
CH3

CrO3 + Al 2O5
CH3 (CH2)5 CH3 + 4H2
600C

Toluene

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CH2 CH3 CH3


CH 3
CH3 (CH2)6 CH3 + + 4H 2

ortho-xylene
CH3
CH 3
CH3 (CH2)4 CH CH3
CH3
meta-xylene
CH3
CH3
CH3 (CH2)3 CH CH2 CH3

CH3

para-xylene
1.4.3 Combustion : (i.e. complete oxidation)

3n 1 combustion
CnH2n 2 O nCO2 + (n + 1) H2O (Hcombustion = ve)
2 2

y combustion y
C xHy x O xCO2 + HO
4 2 2 2

combustion
C5H12 + 8O2 5CO2 + 6H2O

Heat of combustion : Amount of heat i.e. liberated when 1 mole of hydrocarbon is completely burnt into
CO2 & H2O.

Heat of combustion as a measure of stability of alkane :


Combustion is used as a measurements of stability.
More branched alkanes are more stable and have lower heat of combustion.

CH3
e.g. (I) CH3 CH2 CH2 CH3 (II)
CH3 C CH 3

H
stability : II > I
Hcomb. : I > II
More branched alkane has more no. of primary C H bonds. (therefore it has more bond energy).
Homologues : Higher homologues have higher heat of combustion.
Isomers : Branched isomer has lower heat of combustion.
(i) Initiators they initiate the chain reaction, initiators are R2O2, Peresters etc.
hv
ROOR RO
or
temp

hv
RCOOCR RCO
or
O O temp
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(ii) Inhibitors A substance that slow down or stop the reaction are known as inhibitors
For example O2 is a good inhibitor

R + O2 ROO+R ROOR
all reactive alkyl free radicals are consumed so reaction become stop for a period of time.

Relative reactivity of halogen toward methane


Order of reactivity is F2 > Cl2 > Br2 > I2 which can be explained by the value of H (energy change)

Steps of halogenation, value of H for each step. (Kcal/mole)


F Cl Br I
(i) X2 2X + 38 + 58 + 46 + 38

(ii) X + CH4 CH3 + HX 32 + 1 + 16 + 33

(iii) CH3 + X CH3X + X 70 26 24 20

Ex.3 Explain why the chain initiating step in thermal chlorination of CH4 is

Cl2
Cl and not CH4 CH 3 + H
Ans. Because Eact of Cl2 is less than Eact of CH4
Potential energy

Eact of Cl2 Eact of CH4

Progress of reaction

Ex.4 Chlorination of CH4 involves following steps :



(i) Cl2 2 Cl

(ii) CH + Cl CH3 + HCl
4


(iii) CH 3 + Cl
CH3Cl
Which of the following is rate determining ?
(A) Step (i)
(B) Step (ii)
(C) Step (iii)
(D) Step (ii) and (iii) both
Ans. (B)
Reactivity of hydrogen 3 > 2 > 1
Because formation of alkyl free radical is Rds so, that H is more reactive which produce more stable
free radical (less Eact)

order of stability of F.R.



Ph3C > Ph2CH > Ph CH2 > CH2 = CH CH2 > 3 > 2 > 1 > CH3

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ALKENE

1. INTRODUCTION

Alkenes are hydrocarbons with carboncarbon double bonds, Alkenes are sometimes called olefins, a
term derived from olefinic gas, meaning oil forming gas. Alkenes are among the most important
industrial compound and many alkenes are also found in plants and animals. Ethylene is the largest
volume industrial organic compound, used to make polyethylene and a variety of other industrial and
consumer chemicals.

2. Structure and bonding in Alkenes

(1) Alkenes are unsaturated hydrocarbons having at least one double bond.
(2) They are represented by general Formula (G.F.) CnH2n (one double bond)
(3) In Ethene C = C bond length is 1.34
(4) Its bond energy is 146 kcal.mol1
(5) The hybridization of (C = C) alkenic carbon is sp2
(6) The e cloud is present above and below the plane of bonded skeleton.
(7) They are also known as olefins since ethene, the first member of the homologous series forms
oily liquid substance when treated with halogens.
(8) Compounds may exist as conjugated polyenes or as cumulated polyenes or as isolated polyenes

Note : That angle a > b since repulsion due to electrons (double bond - single bond repulsion > single
bond single bond repulsion according to VSEPR theory.

Ex.1 Write IUPAC names of

CH3
CH3
(a) (b)

Ans. (a) 2, 3-Dimethylcyclohexene


(b) 1-(2-butenyl) cyclohex 1ene

Ex.2 Give the structure for each of the following


(a) 4-Methyl-1, 3-hexadiene
(b) 1-Isopropenylcyclopentene

Ans. (a) (b)

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3. Physical Properties of Alkenes / Hydrocarbons


Table : III

Physical properties Homologus series Isomers

1. Physical state C1 C3 gases


C4 C20 liquids
>C20 : solids

2. cis > trans

3. Polarity cis > trans (for Cab = Cab type of alkenes

4. Melting point increases with M.W. trans > cis


(due to more packing capacity)
5. Boiling point increases with M.W. cis > trans
# branching decreases B.P.
C

CC=C<CC=CC
Polarity increases, boiling point
increases
6. Solubility Practically insoluble cis > trans
in water but fairly Polarity increases, solubility in polar
soluble in nonpolar solvents increases.
solvents like benzene
petroleum ether, etc.

7. Stability trans > cis


(cis isomers has more Vander Waals
repulsion)

4. Laboratory test of Alkene


Table - IV

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5. Methods of preparation of alkenes


(I) BY PARTIAL REDUCTION OF ALKYNES
(a) By Catalytic Hydrogenation of Alkynes in presence of poisoned catalyst (A Syn Addition
of Hydrogen : Synthesis of cis-Alkenes : This is performed by)

(i) Lindlars catalyst : Metallic palladium deposited on calcium carbonate with lead acetate
and quinoline.

(ii) P-2 catalyst (Ni2B nickel boride)

H 2Pd / CaCO3
(Lindlar's catalyst) R R
General Reaction RCCR C=C
quinoline H H

Mechanism of hydrogenation :

(1) (2) C=C


HH+C=C+HH HH C=C HH H H
H H
metal surface
adsorption desorption

Steps : The reactant alkyne molecules and hydrogen molecules get adsorbed at the surface of metal
catalyst. It is chemical adsorption (chemisorption).
In this state, the reactants lie very close to each other and so the hydrogen atoms start forming
bond with carbon. Two hydrogen atoms are added to two triply bonded carbon atom from the same
side of bond and a cis or syn addition product is formed. The product alkene now escapes away
from the surface of the catalyst. Quinoline occupies the metal surface inhibiting further reduction to
alkanes Quinoline therefore is called catalyst poison and palladium is called deactivated catalyst or
poisoned catalyst.

H2/Ni2B(P-2) CH3CH 2 CH 2CH 3


or H2 /Pd/CaCO3 C=C
e.g. CH3CH2C = CCH2CH3
(syn addition) H H
3-Hexyne (Z)-3-Hexene
(cis-3-hexene)
(97%)

(b) Birch Reduction : (Anti Addition of Hydrogen : Synthesis of trans-Alkenes)

R H
Na / Li
General Reaction RC CR C=C
Liq. NH3 H R

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+
Mechanism : Reagents Na(or Li, K) + liq NH3 Na + e (solvated electron)

R R H
Na H NH2
RC=CR C=C C=C
R R
Na

R H R H
H2N H
NaNH 2 + C=C C=C
H R Na R
(100%)
(trans alkene)

Na / NH3 ( l) CH3CH2 H
e.g. CH3 CH2 C = C CH2 CH3 C=C
H CH2CH 3
trans
hex-3-ene
Note : This process of reduction is not eligible when terminal alkynes are taken. (R C CH)
because terminal alkynes form sodium salt with Na metal.
CH3 C = CH + Na / NH3 CH3 CH = C Na+ + [H]+

Ex.3 Identify the reagent for following synthesis.

O O
?
CH2 C C CH2CH3

(A)
cis Jasmone

Ans. H2 / Lindiars catalyst.


H2
A cis - Jasmone
Lindlar's catalyst

Ex.4 Identify the products in the following reaction :

Na / NH3

CH2 C CCH3

CH2 H
Ans.
C=C
H CH3

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(II) BY DEHAL OGENATION OF VICINAL DIHALIDES

There are two types of dihalides namely gem (or geminal) dihalides in which the two halogen atoms
are attached to the same carbon atom and vicinal dihalides in which the two halogen atoms are
attached to the adjacent carbon atoms.
Dehalogenation of vicinal dihalides can be effect either by NaI in acetone or zinc in presence of
acetic acid or ethanol.
General Reaction

Br
NaI
(i) CC C=C
or Zn. CH3COOH
Br

Br
Zn
:

Mech. CC C C C = C + ZnBr2

Br Br

Zn dust
(ii) CH3 CHBr CH2Br CH3 CH = CH2
CH 3COOH or
C2H5OH as solvent

Mech.

With NaI in acetone :

I X:

CC C=C + IX

It involves an antielimination of halogen atoms

Remarks
(1) Both are E2 elimination.
(2) Both are stereospecific anti elimination.

(III) DEHYDRO HALOGENATION OF ALKYL HALIDES

Dehydro halogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an
alkene.

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Dehydro halogenation can take place by E1 and E2 mechanism.

(i) Hot alcoholic solution of KOH EtO / EtOH (ii) NaNH2


(iii) t-BuOK+ in t-BuOH

(i) Dehydrohalogenation by the E2 mechanism : Second-order elimination is a reliable


synthetic reaction, especially if the alkyl halide is a poor SN2 substrate. E2 dehydrohalogenation
takes place in one step, in which a strong base abstracts a proton from one carbon atoms as the
leaving group leaves the adjacent carbon.

General reaction :

alcohol
C C + KOH C = C + KX + H2O

H X

B:H

CC C=C +BH +X
Mechanism
X

Undergo elimination of hydrogen halide (HX) leading to the formation of alkenes.

CH3
Heat CH3 C = CH2 + KBr + H2O
e.g. CH3 C Br + alc. KOH
CH3 CH3

Here H is eliminated by base hence called elimination following Saytzeff rule.


i.e, (Highly substituted alkene is major product). It also involves an anti elimination of HX.

e.g.
(minor)
Br
(less stable alkene)

Cl CH3 CH3
CH3
e.g. alc. KOH +
(major) (minor)

Cl H
H (CH3)3CO K
e.g. H
H H
Chlorocyclooctane Cyclooctene
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CH 3
CH3
e.g. CH3 C Br + OH H2C = C + H2O + Br
CH3
CH3

(ii) Formation of the Hoffmann product


Bulky bases can also accomplish dehydro halogenation that do not follow the saytzeff rule.
Due to steric hindrance, a bulky base abstracts the proton that leads to the most highly
substituted alkene. In these cases, it abstracts a less hindered proton, often the one that
leads to formation of the least highly substituted product, called the Hoffmann product.

H CH3
OCH2CH3 H3C CH3 CH3 H 2C H
CH3 C C CH2 C=C + C=C
CH3CH2OH H CH3 H 3C H
H Br H 71% 29%
Saytzeff product

H CH3
OC(CH3)3 H3C CH3 CH3 H 2C H
CH3 C C CH2 C=C + C=C
(CH3)3COH H CH3 H H
H Br H 28% 72%
less
hindered

Stereospecific E2 reactions
The E2 is stereospecific because it normally goes through an anti and coplanar transition state. The
products are alkene, and different diastereomers of starting materials commonly give different
diastereomers of alkenes.

Ph Ph Base H
Ph Ph H
Br S H
H R CH3
H CH3 Ph
Ph CH3
Br H

Br

Ph H CH3

Ph Ph
CH3 Ph
H

Ex.5 What alkyl halide would yield each of the following pure alkene on reaction with alcoholic KOH ?

CH3
(i) CH 3 C = CH 2 (ii) CH3 CH2 CH2 CH = CH2 (iii) CH 3 CH 2 C = CH 2
CH3
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CH3

Ans. (i) CH3 C CH 3 (ii) CH3CH2CH2CH2CH2Cl (iii) CH3CH2CHCH2Cl


Cl CH3

CH3
CH3
Ex.6 What are the various product due to loss of HBr from
Br

CH3 CH3 CH3


CH3 CH3 CH2
Ans.

(major) (minor) (minor)

(IV) DEHYDRATION OF ALCOHOLS

Alcohols when heated in presence of following reagents undergo loss of water molecule and form
alkenes. The elimination is elimination.
(i) H2SO4 / 160C
(ii) H3PO4 /
(iii) P2O5 /
(iv) Al2O3 / 350C undergo loss of water molecule and form alkenes

P2O5 or conc. H2SO4 or Al2O 3


General Reaction RCHCH2OH R CH = CH2 + H2O

CH2OH CH2 CH3

P2O5 or conc. H2SO4 or Al2O3


e.g. +

(I) (II)
Minor Major

Q.1 If the starting material is labelled with deuterium as indicated, predict how many deuterium will be
present in the major elimination product ?

HO CD3 HO CD3
D D
(a) (b) D D
H2SO4 H2SO4

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CH3 CH2OH CH 3 CH2

Conc. H2SO4
Q.2 +

Major Minor

Explain the mechanism ?

(V) BY PYROLYSIS OF ESTERS


Thermal cleavage of an ester involves formations of a six membered ring in the transition state
leading to the elimination of an acid leaving behind an alkene.

H H H
R2C O R2C O R2C o
500C +
H2C C c
H2C C H2C
Me o Me
O Me O

As a direct consequence of cyclic transition state, both the leaving groups namely proton and
carboxylate ion are eliminated from the cis position. This is an example of syn elimination.

(VI) BY HOFMANN ELIMINATION METHOD

Alkenes can be prepared by heating quaternary ammonium hydroxide under reduced pressure at a
temperature between 100C and 200C.
Less substituted alkenes are formed as major product in this case, which are defined as Hofmann
alkenes.

CH3

CH3 N CH2 CH 2 H + OH (CH 3)3N + CH 2 = CH2 + H2O

CH 3

CH3 CH 2 CH2 CH3 CH3 CH2 CH2 CH 3



OH
CH3 CH CH2 N CH2 CH2 CH2 = CH 2 + CH 3 CH CH2 N

CH3 H CH 3
less crowded 'H'

(VII) BY WITTIG REACTION


The aldehydes and ketones are converted into alkenes by using a special class of compounds called
phosphorus ylides, also called Wittig reagents.
The Triphenyl group of phosphorane has a strong tendency to pull oxygen atom of the aldehyde or
ketone via a cyclic transition state forming an alkene.

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Page # 24 HYDROCARBON

R'' R''
C=O CO
R'' R'' R
R''
C=C + Ph3P = O
R C PPh3 R'' R'
R C PPh3
R'
ylide
R'

(R, R, R and R may be hydrogen or any alkyl group)

Me
C=O
Me
e.g. Ph3P: + CH3 Br [Ph3P CH3] Br Bu-Li
Ph3P CH 3
Methyltriphenyl Ylide
phosphorium salt

Me
Ph3P = O + C = CH2
Me
Product alkene

Ex.7 Complete the following reaction :

H (i) Ph3P
C = PPh3 + O=C
H CH = CH 2 (ii) :B

Ans.
H
C=C H
H C=C
H H
1-Phenyl-1, 3-butadiene

Ex.8 Identify the (X), (Y), and (Z) in the following reactions
O
(i) Ph3P
(i) PhCH2Br + CH3 C CH3 (X)
(ii) :B
(i) Ph3P
(ii) CH3I + PhCOCH3 (Y)
(ii) :B

(i) Ph3P
(iii) PhCH2Br + PhCH = CHCHO (Z)
(ii) :B
Ans. (X) = Ph CH = C(CH3)2
(Y) = Ph C(CH3) = CH2
(Z) = Ph CH = CH CH = CH Ph

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Q.3 Complete the following reactions

(i) Ph3P
(i) CH3I +
(ii) :B

(i) Ph 3P
(ii) C2H5Br +
(ii) :B

6. Chemical reactions of alkenes


(I) CATALYTIC HYDROGENATION OF ALKENES : (HETEROGENEOUS HYDROGENATION)
Hydrogenation : The function of catalyst
Hydrogenation of a alkene is exothermic reaction (H = 120 kJ mol1)
Ni
R CH = CH R + H2 R CH2 CH2 R + heat

As a consequence ,both hydrogen atoms usually add from the same side of the molecule. This mode
of addition is called a syn addition.
Hydrogenation of an alkene is formally a reduction, with H2 adding across the double bond to give
an alkane.
The process usually requires a catalyst containing Pt, Pd or Ni.

Pt
e.g. CH3 CH = CH CH3 + H2 CH3 CH2 CH2 CH3

D H
H2 D
e.g.
Pt D
D H

Ex.9 Complete the following reactions :


Pd,Pt or Ni
CH3CH = CH2 + H2 ?
Sol. CH3CH2CH3

(II) ELECTROPHILIC ADDITION REACTIONS :


Mechanism
Step 1 : Attack of the electrophile on bond forms a carbocation.

C=C +E CC
E

Step 2 : Attack by a nucleophile gives the product of addition

C=C + Nu: CC
E E Nu

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(i) Acid-Catalyzed Hydration of Alkenes


Alkenes add water in the presence of an acid catalyst to yield alcohols. The addition takes place
with Markovnikov regioselectivity. The reaction is reversible, and the mechanism for the acid-
catalyzed hydration of an alkene is simply the reverse of that for the dehydration of an alcohol.
The carbocation intermediate may rearrange if a more stable carbocation is possible by hydride or
alkanide migration. Thus, a mixture of isomeric alcohol products may result.

H CC
General Reaction C=C + H2O
H OH
(Markovnikov
orientation)

Mech.
Step 1 : Protonation of the double bond forms a carbocation

H H

:
C=C +HOH CC+ + H2O :

Step 2 : Nucleophilic attack by water


H
H
H
OH
C C + + H2O
CC

Step 3 : Deprotonation to the alcohol

H
H H
:

OH :OH
:

CC + H2O: C C + H3O

+
H2O, H
e.g. CH3CH = CH2 CH3CHCH3
Propene
OH
Isopropyl alcohol

CH 3 CH3 H
50% H2SO4
e.g. CH3 C CH = CH 2 CH3 C C CH3

CH 3 OH CH3
3, 3-Dimethyl-1-butene 2, 3-Dimethyl-2-butenol
(major product)

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Ex.10 Identify the product in following reaction

CH 3
D2O / D
CH3 C = C CH3

CH3 H

Ans. CH3 C C CH 3

OD D

(ii) (a) Oxymercuration - Demercuration


Alkenes react with mercuric acetate in a mixture of water and tetrahydrofuran (THF) to produce
(hydroxyalkyl) mercury compounds. These can be reduced to alcohols with sodium borohydride and
water :
Oxymercuration
OH O
O
THF
General Reaction C=C + H2O + Hg C C O + CH3 COH
OCCH3
2
Hg OCCH 3
OH O
C C O + OH + NaBH4 C C + Hg + CH3CO (Demercuration)
Hg OCCH3 HO H
In the oxymercuration step, water and mercuric acetate add to the double bond; in the
demercuration step, sodium borohydride reduces the acetoxymercury group and replaces in with
hydrogen. Then net addition of H and OH takes place with Markovnikov regioselectivity and
generally takes place without the complication of rearrangements.

OH

e.g. Hg(OAc)2 NaBH4


H2C = CHCH2CH3 CH3 CHCH2CH3
H2O
1-butene 2-butanol

(b) Alkoxymercuration - demercuration

OR OR
ROH NaBH4
General reaction C=C + Hg(OAc)2 C C C C
HgOAc H
(Markovnikov
orientation)

e.g. CH2 = CH CH2 CH3 (i) Hg(OAc)2, CH3OH


CH3 CH CH2 CH 3
1-butene (ii) NaBH 4
OCH3
2-Methoxy butane

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Ex.11 Supply the structures for (X) and (Y) in the following two step reaction :
Hg(OAC) 2 NaBH4 / NaOH
(X) (Y)
C3H7CH = CH2
THF / H2O
Sol. (X) = C3H7CH(OH)CH2HgOAC (Y) = C3H7CH(OH)CH3
(An organomercurial alcohol)
Ex.12 Identify final product in the following :

Hg(OAC)2 NaBH 4
(a)
CH3OH

OH
Hg(OAC)2 NaBH4
(b)
NaOH

Ans. (a) (b) O

OCH 3

Q.4 Identify the product in the following reaction

CH3
Hg(OAc)2, H2O NaBH4
CH3 C CH = CH2
CH3
3, 3-Dimethyl - 1- butene

(iii) Hydroboration-oxidation (SYN ADDITION)

ROH H2O2, OH
General Reaction C=C + BH3.THF C C C C
H BH H OH
anto-Markovanikov
orientation
H (syn stereochemistry)

An alkene reacts with BH3 : THF of diborane to produce an alkylborane. Oxidation and hydrolysis of
the alkylborane with hydrogen peroxide and base yields an alcohol.

CH3
BH3 ; THF H
e.g. CH3 + enantiomer + dialkyl-and trialkylborane
anti-Markovnikov and
syn additon
H
B
H H H
Oxidation

CH3 H2O2, HO CH3


H H
Boron group is + enantiomer
replaced with
H retention of H
B configuration OH
H H

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In the first step, boron and hydrogen undergo syn addition to the alkene in the second step,
treatment with hydrogen peroxide and base replaces the boron with OH with retention of
configuration. The net addition of H and OH occurs with anti Markovnikov regioselectivity and syn
stereoselectivity. Hydrogboration oxidation therefore, serves as a useful regiochemical complement
to oxymercuration demercuration.

CH3
(i) BH3, THF H
e.g. H
(ii) H2O 2, OH
OH
e.g.

CH3 CH3 CH3


+
H (dil. H2SO4) CH3 shift
CH3 C CH = CH2 CH 3 C CH CH3 CH3 C CH CH3
3 carbocation
CH3 CH3 CH3
H 2O
2carbocation (H )
CH3 OH CH3
Hydroboration
CH3 C CH2 CH2OH CH3 C CH CH3
oxidation
CH3 CH 3
CH3 OH
Hg(OAc) 2
CH3 C CH CH3
NaBH 4
CH3

(i) Hydration with dil. H2SO4 proceeds via carbocation rearrangement


(ii) Hydration with Hg(OAc)2, H2O, following by NaBH4 proceeds via Markonikovs rule
(ii) Hydration with (BH3)2 followed by H2O2 / OH proceeds via Anti Markonikovs rule

Q.5 Identify x, y, z and w in the following reaction :

HBr H2SO4 (i) BH3/THF HBr


(W) z (X) (Y)
(ii) H 2O2/OH

Also select pair of isomers if any

(iv)Addition of hydrogen halides

General Reaction C=C + HX C C


(HX = HCl, HBr, or HI) H X
Markovniko
orientation
(anti-Markovnikov with
HBr and peroxide)

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HBr (dark)
CH 3CHBrCH 3 Markovnikov addition
2-Bromopropane
(Isopropyl bromide)
CH3CH = CH2

peroxides
CH3CH2CH2Br
HBr (light) 1-Bromopropane Anti - Markovnikov addition
(n-Propyl bromide)

Note : (1) Anti Markovnikov addition is valid only for HBr in presence of
peroxide and light only.
(2) HF, HCl and HI give only polar addition and give Markovnikov product only.

HI CH3CHICH3
e.g. CH3CH = CH2
Propene 2-Iodopropane
(Isopropyl iodide)

CH3 CH3 CH 3 CH3


H Br
H Br H Br H
H H H H
product
positive charge
on less substituted carbon
less stable ; not formed

H H
CH 2 C
H
e.g. + HI I

+ HCl

H
Cl H
H

Ex.13 Predict the major products of the following reactions and propose mechanism to support your
predictions.
CH3 O O
(A)
H3C C = CH2 + HBr + CH3 C O O C CH3

CH3

(B) + HBr + CH3 CH2 O O CH2 CH3

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CH 3 CH 3

(C) HC = CH CH3 + HBr + H3C C O O C CH3

CH3 CH 3

CH3
CH 3
Br
Sol. (A) H3C CH CH2Br (B) (C) H2C CH CH3
Br

Ex.14 Identify the products in the following reactions :


(a) F3C CH = CH2 + HCl
(b) O2N CH = CH2 + HCl
(c) CH3O CH = CH2 + HCl
(d) PhCH = CHCH3 + HCl

(e)
+ HCl
H3C CH2CH3

Q.6 Give the products of the following reactions :

CH3
CH3 C CH = CH2 HBr
CH3
3, 3-dimethyl - 1 - butene

Q.7 Give the reactant (alkene) of the following products.

CH3
Br CH3
Br
X Y

1-bromo-1-methyl 2-bromo-1-methyl
cyclohexane cyclohexane

(v) Addition of halogen


Halogen add to alkenes to form vicinal dihalides.

X
C=C + X2 C C
General Reaction X
usually anti addition

(X2 = Cl2, Br2)


The nucleophile attacks the electrophilic nucleus of one halogen atom, and the other halogen serves
as the leaving group, departing as halide ion. Many reactions fit this general pattern.

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Page # 32 HYDROCARBON

Note : (i) F2 is not added because F+ is never generated. Morever reaction is explosive giving CO2 &
H2O
(ii) I2 is not added because reaction is reversible with equilibrium in backward direction.
(iii) Reaction with bromine is basis for test of alkenes.
(iv) Halogen addition is stereospecific anti addition
(v) Halogens can also be added in presence of sun light and give free radical addition.
(Reactivity of halogen addition in sunlight is F2 (explosive) > Cl2 > Br2 > I2)

Mech.
Step-1 Formation of a halonium ion

: :
:X:
: :

: :
C=C + : X X: C C +

Halonium ion

Step-2 Opening of the halonium ion


:

: :
:X:
X
C C C C
:X:
:
: :

:X:

X attacks from the back side of halonium ion.

Br2 in CCl 4
e.g. CH 3CH = CH2 CH3CHBrCH2Br
Propene 1,2-Dibromopropane
(Propylene) (Propylene bromide)


:Br back side
e.g. H attack H Br + enantiomer

+
H H Br Br H
trans
Br Br

Ex.15 Give the product of the following reaction.


Me2C = CH2 + ICl ?
Sol. Cl is more electronegative than I making I the E+ that, according to the Markovnikov rule, adds to
the C with the greater number of Hs. The product is 2-chloro-1-iodo-2-methylpropane,
(Me2CClCH2I).

Ex.16 What are the products and (type of isomers) when Br2 adds to : -

Br2
(a) (b) Br2

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Br
& enantiomer & enantiomer
Ans. (a) (b)
Br Br

(vi) Hydroxylation of Alkenes


(a) Syn Hydroxylation : (Reaction with Bayers reagent, (cold dilute alkaline KMnO4 solution).
Both OH groups are added from same stereochemical side. This addition is example of syn addition

General Reaction C=C + KMnO4 + OH, H 2O


C C
(or OsO 4, H2O2)
OH OH
(syn addition)

e.g.


OH + MnO2 + H2O
H H H H
H2O
H H O O OH OH
cis-glycol
O O Mn

O O
Mn
O O

The same function of syn addition of 2 - OH groups is performed by OsO4 / H2O2

O O
2H2O H H + H2OsO4
+ Os H H
O O OH OH
H H O O
Os

O O

H
OsO4.H2O2 OH
e.g.
OH
H
Cyclohexene Cis-Cyclohexane-1,2-diol

(b) Anti hydroxylation

OH
+
H , H2O
General Reaction C=C + R C OOH C C C C
O O
OH
(anti addition)
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O H
+ OH
e.g. H C OOH, H3O
H
OH
Cyclohexene
Trans-Cyclohexane-1,2-diol

Ex.17 Identify the product in the following reaction :

KMnO 4
(x)
Cold

OH
Ans.
OH

Ex.18 Identify the product (X) in the following reaction :


CH = CH2
C6H5CO3H
CHCl3 at 298K

CH = CH2
Ans. (x) : O

Since C = C bond in ring is more substituted than that in open chain.

(vii) Addition of carbenes to Alkenes :


Methylene is the simplest of the carbenes : uncharged, reactive intermediates that have a carbon
atom with two bonds and two nonbonding electrons. Like borane (BH2), methylene is a potent
electrophile because it has an unfilled octet. It adds to the electrons rich pi-bond of an alkene to
form a cyclopropane.

C H C H
General Reactions + :C C
C H C H

Heating or photolysis of diazomethane (CH2N2) gives nitrogen gas and methylene.

H
Heat or ultraviolet light
N = N = CH2 N = N CH2 N2 + C
H
diazomethane Methylene

There are two difficulties with using CH2N2 to cyclopropene double bonds. First, it is extremely toxic
and explosive. A safer reagent would be more convenient for routine use. Second, methylene
generated from CH2N2 is so reactive that it inserts into C H bonds as well as C = C bonds.

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H 3C H
C=C CH2 N = N; shv
e.g.
H H
Propene

H3C H H3C H H CH 2 H 3C H
CC + C=C + C=C
H H H CH2 H H H
CH2

H3C H
+ C=C
H CH2 H

Ex.19 Identify the product in the following reactions


light
CH3CH = CHCH3 + CH2N2
(a)
2-Butene Diazomethane

(b) + CHBr3 NaOH /H2O

Br
Ans. (a) CH 3CH CHCH3 + N 2 (b)
Br
CH2
1,2-Dimethylcyclopropene

(III) EPOXIDATION OF ALKENES :


An alkene is converted to an epoxide by a peroxyacid, a carboxylic acid that has an extra oxygen
atom in a O O (peroxy) linkage.

O O
O
General Reaction C=C +RCOOH C C + R C O H (acid)
Epoxide (Oxirane)

The epoxidation of an alkene is clearly an oxidation, since an oxidation, since an oxygen atom is
added Peroxyacids are highly selective oxidizing agents. Some simple peroxyacids (sometimes called
per acids) and their corresponding carboxylic acids are shown below :

O O
RCOOH COOH

a peroxyacetic acid
Peroxy benzoic acid

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Page # 36 HYDROCARBON

Mech.

O R R O R
C O C C O C C
O C
H O O +
C O C H O
C
H
transition state Acid
Alkene peroxyacid

e.g.

O H
O
Cl C O
O H3C CH 3
MCPBA O Cl C H
CH3 CH3 O
C=C +
H H
Cis CH2Cl2
H H
Cis

H CH3
CH3 H O
C=C
H CH3
Trans
H3C H
Trans

Ex.20 Complete the following reaction

+ C OOH (X) + (Y)

O
Cyclohexene Cl

Ans. (X) O (Y) C OH

Epoxycyclohexane Cl O

Ex.21 Predict the product, including stereochemistry where appropriate, for the m-chloroperoxy-benzoic
acid expoxidations of the following alkenes.

H H H CH2CH2CH3
(a) CH C = C (b) C=C
3 CH2CH2CH3 CH3 H

(c) Cis-cyclodecene (D) Trans-cyclodecene

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(IV) HALOHYDRIN FORMATION

General Reaction C = C + X2 + H2O C = C + HX (X 2 = Cl2, Br2)

X OH

X and H2O are generated as attacking species from X2 + H2O

Cl2, H2O
e.g. CH3CH = CH2 CH3CH CH2
Propylene OH Cl
(Propene)
Propylene chlorohydrin
(1-Chloro-2-propanol)

Ex.22 Predict the product in the following reactions

H
Br2 H2O
(a)
Anti addition
H (Markovnikov Orientation)
Cyclopentene

H2O
(b) + Br2 Anti addition
(Markovnikov Orientation)

H CH3
Br OH
Ans. (a) (b)
Br Br
H
H
trans-1,2-dibromocyclo
pentane (92%)

(V) OXIDATIVE CLEAVAGE OF ALKENES

(i) Cleavage by permanganate

In a KMnO4 hydroxylation, if the solution is warm or acidic or too concentrated, oxidative cleavage
of the glycol may occur. Mixtures of Ketones and carboxylic acids are formed, depending on whether
there are any oxidizable aldehydes in the initial fragments. A terminal = CH2 group is oxidized to CO2
and water.

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R R' KMnO4 R R'


General Reaction C=C C=O + O=C
R H Warm R H
conc.
Glycol Ketone Aldehyde
(Stable) (Oxidizable)

R'
O=C
OH

O OH
e.g. KMnO4
+
Warm C
O
conc.

KMnO4
e.g.
Warm + CO2
conc. COOH
O COOH

Ex.23 What is the main utility of this reaction and why is it superior to KMnO4 cleavage for this purpose
Sol. It locates the position of C = Cs in molecules. KMnO4 cleavage is more vigorous and can oxidiz
other groups, i.e., OH.

Ex.24 Give the products of the following reactions : -

H H
or KMnO4 (aq.)
+ KMnO4 X C=C Y
(i) (aq.base) OsO 4 in (ii) or
H2O2 H3C CH3 OsO4 in H 2O2

H3C H
KMnO4 (aq.)
C=C Z
(iii) or
H CH3 OsO4 in H2O 2

Sol. X = Cis-1, 2-Cyclopentanediol Y = meso - CH3 CHOH CHOH CH3


Z = rac CH3CHOHCHOHCH3

Q.8 Complete the following reactions

CH3
hot KMnO4 hot KMnO4
(a) (X) (b) Y
(or K2Cr 2O7) (or K2Cr 2O7)
CH3

1,2-dimethylcyclobutene

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(ii) Ozonolysls : Like permanganate ozone cleaves double bonds to give ketones and aldehydes.
However, ozonolysis is milder, and both ketones and aldehydes can be recovered without further
oxidation.

R R'
R R' C C
General Reaction C=C + O3
R H R H

Ozonide

(CH 3)2S

R R'
C=O + O=C
R H
Ketone

Mech.

C O C
O
C O C

Monozonide (Primary ozonide)

C
C
O O
O
C C

Ozonide

O
R' R R'
R
CH 3 S CH3 C=O + O=C + CH S CH
C C 3 3
H dimethyl sulfide R H
R Dimethyl sulfoxide
(DMSO)

H H
O3 H2O, Zn
e.g. CH3CH2CH = CH2 CH3CH2C = O + O = CH
1-Butene

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(i) O3
e.g. CH3CH2CHO + CH3(CH2)4CHO (65%)
3 - nonene (ii) (CH3)2 S

CH 3 CH3 H
O3 H2O, Zn
e.g. CH3 C = CH2 CH3C = O + O = CH

(VI) HALOGENATION, ALLYLIC SUBSTITUTION

(500-600C)
X C C = C

General Reaction H C C = C X2 = Cl2, Br 2


NBS or NCS
X C C = C

(allyl halide)

O
NBS = N-Bromosuccinimide N Br

O
NCS = N-Chlorosuccinimide N Cl

Cl2, 600C
e.g. CH3CH = CH2 Cl CH2CH = CH 2
Propylene allyl chloride
(Propene) (3-Chloro-1-propene)

Ex.25 CH2 = CHCH2CH = CH2 NBS (X), (X) is

(A) CH2 = CH CHCH = CH2 (B) CH2 = CHC = CHCH2Br

Br

(C) CH2 = CHCH2CH = CHBr (D) CH2 = CHCH2C = CH2

Br

Ans. A

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Ex.26 Assertion (A) : Propene (CH3CH = CH2) undergoes allylic substitution.

Reason (R) : CH2 = CHCH2 (allylic) free radical is stabilised by resonance.

Ans. (A)

Q.9 Identify the product (X) in the following reaction

+ NBS (X)

Cyclohexene

Ex.27 Identify the product in the following reactions


H
(i) O3
(i) O3
(a) (ii) (CH3)2 S (b)
(ii) (CH3)2 S
H

H
H
C
Ans. (a) O (b) CHO
H C CHO
H O O

Ex.28 Identify the products (x, y) of following reaction : -

CH3 CH3
O3 /H2O, Zn
CH3 C = CHC CH3 (X) + (Y)

CH3

CH3 O CH3

Ans. (X) : CH3 C = O (Y) : H C C CH 3


CH3

Q.10 Predict the major product of the following reaction

(i) O3
+
(ii) (CH3)2 S

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(VII) ADDITION OF FREE RADICALS

peroxides
General Reaction C = C + Y Z CC
or light
Y Z

BrCCl3 peroxides
e.g. n C6H13CH = CH2 n C6H13CH CH2 CCl3
1-Octene Br
3-Bromo-1,1,1-trichlorononane

HBr/R2O2
n C6H13CH CH2 Br

Ex.29 Which of the following reactions are correct ?

peroxides
(a) C6H13CH = CH2 + BrCCl3 C6H13CHCH2CCl3

Br

peroxides
(b) RCH = CH2 + BrCCl3 RCHCH 2CCl3

Br

(A) only (a) (B) only (b) (C) both are correct (D) None of these
Ans. (C)

+HBr
Ex.30 Isobutylene product is :
peroxides

(A) Tertiary butyl bromide (B) Isobutyl bromide


(C) Tertiary butyl alcohol (D) Isobutyl alcohol

Ans. (B)

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ALKYNES
1. Introduction
A triple bond gives an alkyne four fewer hydrogen atoms than the corresponding alkane. There fore the
triple bond contributes two degree of unsaturation (DU).
Alkynes are not as common in nature as alkenes, but some plants do use alkynes to protect themselves
against disease or predators. Acetylene is by far the most important commercial alkyne. Acetylene is
an important industrial feedstock but its largest use is as the fuel for the oxyacetylene welding torch.

2. Structure and Bonding in Alkynes


(1) Alkynes are hydrocarbons that contain carbon -carbon triple bond.
(2) Alkynes are also called acetylenes because they are derivatives of acetylene.
(3) The general formula is : CnH2n2. (one triple bond)
(4) In alkyne C C bond length is 1.20 .
(5) Its bond energy is 192 kcal. mol 1
(6) The hybridization of carbon atoms having triple bond (C C) in alkynes is sp
(7) Overlapping of these sp hybrid orbitals with each other and with the hydrogen orbitals gives the
sigma bond framework which is linear (180) structure.
(8) Two bonds result from overlap of the two remaining unhybridized p orbitals on each carbon atom.
These orbitals overlap at right angles (90) to each other, forming one bond with electron density
above and below the C C sigma bond, and the other with electron density in front and in back of the
sigma bond. This result in a cylindrical electron cloud around bonded structure

1.20 1.06

180
H C C H HCCH

Note : Any type of stereoisomerism does not arise in acetylenic bond due to linearity of C C bond.

Ex.1 Cis-trans isomerism is not possible in alkynes because of :


Ans. 180 bond-angle at the carbon-carbon triple bond.

Ex.2 Draw the geometrical isomers of hept -2-en-5-yne?


MeC CCH2 H MeC CCH2 Me
C C C C
Ans. H Me H H
(trans) (Cis)

Q.1 C6H10 (alkyne) is optically active. What is its structure?

Q.2 C5H8 (alkyne) has three-degree of unsaturation. What is the structure ? What is the isomerism show?

3. Physical Properties of Alkynes


(1) Alkynes are relatively nonpolar (w.r.t. alkyl halides and alcohols) and are nearly insoluble in water
(but they are more polar than alkenes and alkanes). They are quite soluble in most organic solvents,
(acetone, ether, methylene chloride, chloroform and alcohols).
(2) Acetylene, propyne, and the butynes are gases at room temperature, just like the corresponding
alkanes and alkenes. In fact, the boiling point of alkynes are nearly the same as those of alkanes and
alkenes with same number of carbon atoms.

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4. Table

Relative density
Name Formula M.p.,C B.P., C
(at 20C)

Acetylene HC CH 82 75
Propyne HC CCH3 101.5 23
1-Butyne HC CCH2CH3 122 9
1-Pentyne HC C(CH2)2CH3 98 40 0.695
2-Butyne CH3C CCH3 24 27 0.694
2-Pentyne CH3C CCH2CH3 101 55 0.714
3-Methyl-1-butyne HC CCH(CH3)2 29 665

5. TABLE - COMPARATIVE STUDY OF ALKANES, ALKENES, ALKYNES


o.
.N Properties Alkanes Alkenes Alkynes
S

1. Bond length 1.54 (C C) 1.32 (C = C) 1.20 (C C)

-1
2. Bond energy (KJmol ) 415 (C C) 615 (C = C ) 835 (C C)
3 2
3. Hybridization sp sp sp

4. % s character 25% 33% 50%

5. pKa 50 44 25

6. Electronegativity of 'C' Increases

7. Polarity Increases

8. Rate of hydrogenation less more

9. Rate of electrophilic more less


addition reaction

10. Heat of combustion C2H6(-373) C2H4(-337k cal) C2H2(-317kcal)

3
11. Density (g/cm ) C3H8(-373) C3H6(0.52k cal) C3H4(0.67)

10928'
121.2
H H H H 180
CC C C
12. Structure HC CH
H H
H H
H H 1.06
1.09 1.08
ethene ethyne
ethane

13. Shape Tetrahedral Planar Linear

Ex.3 Which has a longer carbon-methyl bond, 1-butyne or 2-butyne. Explain?


Ans. The bond from the methyl group in 1-butyne is to an sp3-hybridised carbon and so is longer than the
bond from the methyl group in 2-butyne, which is to an sp-hybridised carbon.

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CH3CH2C CH CH3C C CH3


sp3 sp3 sp3 sp
Ex.4 Arrange the following bond-lengths in increasing order.
(e)
H3C (c) C C CH3
(a) (d)
C C
H (b) H
Ans. (d) < (b) < (c) < (e) < (a)

Q.3 Arrange C H bond -lengths (,,) in increasing order as shown :


H H H
HC CC=CCH
H
6. Laboratory test of Alkyne

Functional Reagent Observation Reaction Remarks


Group

(1) Bayer's HC CH + H2O + O alk. KMnO4


Pink Colour
Reagent OHC CHO Hydroxylation
disappears
alk.dil.cold KMnO4

C C (2) Br 2/H2O Red Colour Br2 + HC CH Bromination


decolourises

(3) O 3 (ozone) O3
Acid Formed R C C R' RCOOH + Ozonolysis
RCOOH

7. Laboratory test of terminal alkynes


When triple bond comes at the end of a carbon chain. The alkyne is called a terminal alkyne.
acetylenic hydrogen

HC C CH2CH 3
1-Butyne, terminal alkyne

Functional Reagent Reaction


Group

(1) Cuprous chloride RC CH + CuCl NH4OH


+NH4OH Red ppt. R C C Cu (red)

+
RC CH + Ag
RC CH (2) AgNO3 + NH4 OH White ppt
R C C Ag (white)

(3) Na in ether Colourless HC CH + 2Na


gas
Na C C Na + H2

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8. Acidity of Terminal Alkynes


Terminal alkynes are much acidic than other hydrocarbons due to more electronegative sp hybridised
carbon. The polarity (acidity) of a C H bond varies with its hydridization, increasing with the increase
in precentage's character of the orbitals.
sp3 < sp2 < sp
Weakest
acid
o.
.N Compound Conjugate Base Hybridization of C %Character
S

1. H H H H
3
sp 25% 50
HCCH HCC
H H H H

H H H 2
sp 33% 44
2. C C C C
H H H H


3. NH 3 NH 2

sp 50% 25
4. HC CH HC C

16-18
5. R OH R O

Stronger
acid
The hydrogen bonded to the carbon of a terminal alkyne is considerably more acidic than those bonded
to carbons of an alkene and alkane (see section). The pKa values for ethyne, ethene & ethane
illustrate this point
H H
H H
HC CH C C HCCH
H H
H H
pKa = 25 pKa=44 pKa=50
The order of basicity of their anions is opposite to that of their relative acidity:
Relative Basicity
CH3CH2: > H2C = CH: > HC C:
Relative acidity
H OH > H OR > H C CR > H NH2 > H CH=CH2 > H CH2CH3
pKa 15.7 16-17 25 38 44 50

Relative Basicity

OH < OR < C CR < NH2 < CH = CH2 < CH2CH3


9. General methods of preparation :
(I) By dehydro halogenation of gem and vic dihalide:

H H
2NaNH2
General Reaction: RCH = CHR + Br2 R C C R R C C R + 2NaBr
Br Br
A vic - dibromide
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The dehydrohalogenations occur in two steps, the first yielding a bromoalkene and the second alkyne.
Mechanism :
Step 1

H H
+ R H
HN+ RCCR C C + H N H + Br
Br R
H Br Br H
Amide ion Vic-Dibromide Bromoalkene Ammonia Bromide
(The strongly ion
basic amide ion
brings about an
E2 reaction.)

Step 2
R H
C C + NH RC C R + H N H + Br
Br R
H H
Bromoalkene Amide ion Alkyne Ammonia Bromide
(A second E2 reation ion
produces the alkyne)

Br2 NaNH2
e.g. CH3CH2CH = CH2 CCl4
CH3CH 2CHCH2Br CH3CH2C CH
mineral oil
110-160C
Br

CH3CH2CH=CHBr
+
e.g. CH3CH2C = CH2 NaNH2
[CH3CH2C CH] NaNH2
CH3CH2C CNa
mineral oil
Br 110-160C

NaNH2
CH3CH2C C:Na+ CH3CH2C CH + NH3 + NaCl

O Cl
CH
C C CH3 C
CH3 PCl 5 PCl5
Cl
General Reaction 0C 0C
(-POCl3) (-POCl3)
Cyclohexyl methyl A gem-dichloride Cyclohexylacetylene
Ketone (70-80%) (46%)

Ex.5 Give the structure of three isomeric dibromides that could be used as starting materials for the
preparation of 3,3-dimethyl-1-butyne.
CH3 CH3 CH 3 Br
Sol. (I) CH3CCH2CHBr2 (II) CH3C CH CH 2 (III) CH3C C CH3
CH3 CH3 Br Br CH 3 Br

Ex.6 Show the product in the following reaction


CH3
CH3
EtOK C CH
CH CH2 ? Sol.
EtOH
Br Br
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Q.4 1,1-dibromopentane on reaction with fused KOH at 470 K gives 2-pentyne


Br
fused KOH
Br-CHCH2CH2CH2CH3 CH3CH2C CCH3
470 K
1,1-dibromo pentane 2-pentyne
Give the mechanism of this rearrangement.

(II) By Dehalogenation of Tetrahaloalkane:


X X
2 Zn dust
General Reaction R C C R' RC C R' + 2Zn X2
Alcohol,
X X
(III) Replacement of The Acetylenic Hydrogen atom of terminal Alkynes.

NaNH2
General Reaction R C CH RC C + R' X RC C R'
Sodium ethynide and other sodium alkynides can be prepared by treating terminal alkynes with sodium
amide in liquid ammonia.
liq. NH3 +
HC CH H + NaNH2 HC C Na + NH3
liq. NH3 +
CH3 C CH H + NaNH2 CH3C C Na + NH3

RC C: Na + R'CH2 Br RC C CH2R' + NaBr


Sodium Primary Mono or disubstituted
alkynide alkyl halide acetylene
(R or R' or both may be hydrogen)

The following example illustrates this synthesis of higher alkyne homologues.

liq. NH3
CH3CH2C C: Na + CH3CH2 Br CH3CH2C CCH2CH3 + NaBr
6 hours 3-Hexyne
(75%)

2
SN
RC C + R'X RC CR' + X

(R'X must be an unhindered primary halide or tosylate)

The unshared electron pair of the alkynide ion attacks the back side of the carbon atom that bears the
halogen atom and forms a bond to it. The halogen atom departs as a halide ion.
2 eq. + + 2 moles (CH3X)
e.g. HC=CH Na C = C Na CH3C = C CH3
NaNH2
R' MgX R' X
e.g. RCCH RC C Mg X R C C R'
+ R' H

(i) NaNH2
C CH (ii) ethyl bromide
C C CH2CH3
e.g.
Ethynylcyclohexane 1-Cyclohexyl-1-butyne
(ethylcyclohexyl acetylene)

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Addition of acetylide ions to carbonyl groups

Nu C=O Nu C O

R' R'
R' H2O (or H3O)
RC C + C=O RC CCO RC C C OH
R'
R' R'
O OH
e.g. H2O
HC C + CH3CH2 C H HC C CH CH2CH3
Sodium Propanal 1-Pentyn-3-ol
acetylide
CH 3 CH3 Ph
(i) NaNH2
e.g. CH3 CH C CH CH3 CH C C CH OH
(ii) PhCHO
+
(iii) H 3O

3-Methyl-1-butyne 4-Methyl-1-Phenyl pent-2-yne-1-ol

O OH
(i) NaC CH
e.g. +
C CH
(ii) H 3O

Cyclohexanone 1-Ethynylcyclohexanol(3)

Ex.7 Show how to synthesize 3-decyne from acetylene along with necessary alkyl halides.
(i) NaNH2
Sol. HCCH (ii) CH3(CH2)5Br H3C (CH2)5 C C H
1-Octyne
(i) NaNH2
H3C (CH2)5 C C H (ii) CH3(CH2)5Br CH3 (CH2)5 C C CH2CH3
1Octyne 3Decyne

Q.5 Show how you would synthesize the following compound, beginning with acetylene and any necessary
additional reagents.
OH
CHC CCH2CH3

(IV) By Kolble's Electrolytic synthesis.


+
CHCOO K CH
Electrolysis
+
+ H2O + 2CO2 + 2KOH + H2
Current CH
CHCOO K

(V) By Hydrolysis of carbides

CaC2 + 2HOH C2H2 + Ca(OH)2

MgC2 + 2HOH C2H2 + Mg(OH)2

Mg2C3 + 4HOH CH3 C CH + 2Mg(OH)2

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10. Chemical reactions of Alkyne


(I) Reduction to alkenes
(a) By Lindlar's reagent

R R
Pd/BaSO4, quinoline C=C
General Reaction R C R' + H2 (syn addition)
H cis H

(b) By Brich reduction

R H
Na + NH3 C=C
General Reaction R C C R' (anti addition)
H Trans R

CH3CH2 CH2CH3
H2Pd/BaSO4
CH3CH2C CCH2CH3 quinoline
C C
H H
cis-3-hexene

e.g. Na + NH3
CH 3CH 2 H
C C
H CH2CH3
trans-3-hexene

(c) By hydroboration reduction


R R'
(i) BH3THF
General Reaction R C C R' (ii) CH3COOH
C C
H H
Ex.8 Identify (X) and (Y) in the following reaction
BH3.THF CH 3COOD
(Y)

CH3CH2 C CH
BH3.THF CH3COOH
(X)

CH3CH 2 H CH 3CH2 H
Ans. (X) : C C (Y) : C C
H H H D

Q.6 Use two methods to convert 2-butyne to (z) 2,3-dideutero-2-butene

Q.7 From 1butyne, synthesize


(a) (E) 1-deutero-1-butene and
(b) 2-deutero -1-butene

Q.8 Write the equation for the reduction of 2-butyne with Na with EtOH.

(II) Addition of Halogen (X2=Cl2, Br2)


X X
X2 X2 R C C R' (Anti-addition)
General Reaction R C C R' R CX = CX R'
X X

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Ex.9 Explain why alkynes are less reactive than alkenes toward addition of Br2.
Sol. The three memebered ring bromonium ion fromed from the alkyne (A) has a full double bond causing it
to be more strained and less stable than the one from the alkene (B).
HC = CH H2C CH 2
(A) (B)
Br Br
(A) less stable than (B)
Also, the C's of A that are part of the bormonium ion have more s-character than those of B, further
making A less stable than B.

(III) Addition of Hydrogen halides (Were HX = HCl, HBr, HI)

H X
HX
General Reaction R C C R' HX R CH = CX R' R C C R'
(Markovnikov addition)
H X

CH3-CH2 H Cl
HCl HCl
e.g. CH3CH2 C CH C C CH3CH2CCH3
1-Butyne Cl H
2-Chloro-1-butene Cl
2,2-dichlorobutane

Br H H Br
e.g. CH3C C CH2CH3 + HBr CH3C = C CH2CH3 + CH3C = C CH2CH3

H H Br
CH2CH 2CH3
HBr HBr
e.g. H C C CH2CH2CH3 C C H C C CH2CH 2CH 3
H Br
H Br

Ex.10 Identify the product when one equivalent of HBr reacts with 1-pentene-4-yne

H
Ans. CH2 = CHCH2C CH CH3 C HCH2C CH Br
CH 3CHCH2C CH
Br
stable 2
alkyl carbocation
H
CH2 = CHCH2C CH CH2=CHCH2 C =CH2
less stable vinyl carbocation
(It is not formed)

Ex.11 CH3C CH 2HBr (X) + (Y)


Idntify (X) and (Y) in the above reaction.

Ans. After first HBr molecule is added, product is CH3C = CH2 : Second addition CH3CCH3 and CH 3CCH2.
Br Br Br
(2) (1)

Br
Since 2 carbocation ion is more stable than 1, hence final product is CH 3CCH3 Y is CH3CH2CHBr2
Br
(X)
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(IV) Addition of water


(a) Mercuric ion catalyzed hydration:

Dil. HgSO4
General Reaction R C C H + H2O Tauto.
Dil. H2SO4

(Martkovnikov rule) Vinyl alcohol Ketone


(unstable) (stable)

Electrophilic addition of mercuric ion gives a vinyl cation, which reacts with water and loses a proton to
give an organomercurical alcohol. Under the acidic reaction condition, Hg is replaced by hydrogen to
give a vinyl alcohol, callled an enol.

OH OH H
+2 + H H + O
Hg H2O/H H H
Mech. RC CH RC=CH C C C C CCH
+
Alkyne R Hg R H H
+2 Vinyl alcohol H
Hg methyl Ketone
(enol)
Vinyl cation (Keto)

O
Dil. HgSO4
e.g. CH3 C C H + H2O CH3 C CH3
Dil. H2SO4
Propanone (acetone)

Dil. HgSO4
Ex.12 CH3 C CH + H2O Dil. H2SO4
X
Identify the (X) in the above reaction
Sol. (X) = CH3CCH3 Acetone (a ketone) stable

Ex.13 When 2-heptyne was treated with aq. H2SO4containing some HgSO4, two products, each having the
moleuclar formual C7H14O, were obtained approximately in equal amounts. What are these two
compounds?
O
Dil. HgSO4
Ans. CH3CH2CH2CH2C CCH3 Dil. H2SO4 +
2-Heptanone O
3-Heptanone

Q.9 From which alkyne could each of the following compound be prepared by acid-catalysed hydration?
O O O
(a) CH3CCH 2CH2CH 3 (b) (CH 3)3CCCH3 (c) CH3(CH 2)3C(CH2) 4CH 3

(b) Hydroboration-oxidation
In alkyne, except that a hindered dialkylborane must be used to prevent addition of two molecules of
borane across the triple bond.

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General Reaction

H2O2 NaOH

O
(1) BH3, THF
e.g. CH3C C H (2) H2O2, NaOH
CH3CH2CH
Propanal

Ex.14 Compare the results of hydroboration oxidation and mercuric ion-catalysed hydration for
(a) 2-butyne (b) Cyclohexyl-actylene
Ans.
Product by
Reactant 2+
Hydroboration oxidation Hg ion-catalysed hydration

O O
(a) CH3C CCH3
CH3CCH2CH3 CH3CCH2CH3
O
(b) C CH CH 2CHO
CCH3

(V) Formation of Alkylide anions (Alkynides)


Sodium, lithium and magnesium alkynide

General Reaction R C C H + NaNH2 R C C: +Na + NH3

R C C H + R' Li R C CLi + R' H

R C C H + R'MgX R C CMgX + R'H

(VI) Alkylation of alkylide ions


General Reaction R C C: + R' X R C C R'
(R' X must be an unhindered primary halide or tosylate)
e.g. CH3CH2 C C + Na + CH3CH2CH2 Br CH3CH2C C CH2CH2CH3
sodium butynide 1-bromopropane Hept-3-yne

(VII) Reactions with Carbonyl Groups


General Reaction

R C C: +

e.g.

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Ex.15 Give the products of the following reactions.


(a) CH3C C: + CH3CH = O H2O X
(b) CH3C C: + (CH3)2C = O H2O Y

(c) CH3C C: + O H2O Z

Sol. (a)

(b)

(c)

Q.10 What are the products of the following reactions:

(a) (b) CH3C CH +

(c) HC CD + CH3CHO

Q.11 Identify 'X' in the following reaction

(VIII) Oxidation of -Dlketones


If an alkyne is treated with aqueous KMnO4 under nearly neutral conditions, an -diketone results.

General Reaction

KMnO4. (neutral)
e.g. CH3 C C CH2CH3 CH3 C C CH2CH3
(or, O3 & Zn/H2O)
2-Pentyne
O O
Pentane-2,3-dione

Ex.16 Give the product of the following reactions.


KMnO4
H3C H2C C C CH2CH2CH3 Neutral
X
KMnO4
H3C H2C C C CH2CH2CH3 acidic higher temp
Y
Sol. X = CH3CH2C CCH2CH2CH3 Y = CH3CH2COOH + HOOCCH2CH2CH3
|| ||
O O
( diketone)
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HYDROCARBON Page # 55

(IX) Oxidative Cleavage


If the reaction mixture becomes warm or too basic the diketone undergoes oxidative cleavage. The
products are the salts of carboxylic acids, which can be converted to the free acids by adding dilute
acid.

General Reaction

e.g.

e.g.

Ex.17 Give the products of the following reactions


KMnO4
(i) (CH3)2CHC CCH2CH2CH3 X
KMnO4
(ii) CH3CH2C CCH2CH3 Y
KMnO4
(iii) HC CCH2CH2CH3 Z
KMnO4
(iv) CH3C CCH2CH2C CCH2CH3 W
Sol. X: (CH3)2CHCOOH + HOOCCH2CH2CH3
Y: 2CH3CH2COOH, symmetrical internal alkynes give one acid
Z: CH3COOH + HOOCCH2CH2COOH + HOOCCH2CH3

Q.12 C5H8 on KMnO4 oxidation gives CO2 and isobutyric acid. Identify C5H8.

(X) Ozonolysis
(i) O3
General reaction R C C R' (ii) H2O R COOH + R' COOH
(i) O3
e.g. CH3 C C CH2CH3 (ii) H2O CH3COOH + CH3CH2COOH

Ex.18 C8H10 (A) O3.H2O Acid (B) Identify (A) and (B) in the above reaction

Sol. (A) C C (B) COOH

Ex.19 A certain hydrocarbon has the formula C16H26. Ozonation followed by hydrolysis gave CH3(CH2)4CO2H
and succinic acid as the only product. What is hydrocarbon
Sol. DU = 4
Hydrocarbon C16H26 is CH3(CH2)4 CCH2CH2C C(CH2)4CH3

Solution Unsolved problems


1. It means there is chiral carbon, hence structure is
H

CH3CH2 C CH

CH3

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Page # 56 HYDROCARBON

2. Alkyne (C C) has unsaturation hence C5H8 has also one ring of three or four carbon atoms.

(a) (b)
HC C CH 3 C CH
(a) Exists as cis-and trans-isomer

H H HC C H
HC C CH3 H CH3
(cis) (trans)

3. ( C H) < ( = C H) < ( C H )

Hence < <

4. As the S-character of the orbital that binds carbon to another atom increases, the pair of electrons in
that orbital is more strongly held and it requires more energy for homolytic cleavage of both the C H
and C C bonds.

5. Mech.

6. We need to add two groups to acetylene and ethyl group and a six-carbon aldehyde (to form the
secondary alcohol). If we formed the alcohol group first, the weakly acidic OH group would interfere
with the alkylation by the ethyl group. Therefore, we should add the less reactive ethyl group first, and
add the alcohol group later in the synthesis.
(i) NaNH2
HCCH (ii) CH 3CH 2Br H C C CH2CH3
The ethyl group is not acidic and it does not interefere with the addition of the second group

H C C CH2CH3 NaNH2 Na C C CH2CH3

Reason : Electron donating groups such as R's make the -bond more electron - rich and more reactive.
Conversely, electron - withdrawing groups such as halogens make the -bond more electron-poor and
less reactive.

CH3 CH3
D2/Lindlar's catalyst BD3
7. CH3 C C CH3 C C CH3COOD
CH3 C C CH3
D D

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REACTION CHART FOR ALKANES


GMP

H2 , Ni X2 , h or UV light or 400 C
(1) RC CH (1) RX
200 300C
or
R CH = CH2 Sabatier senderens Reed reaction
(2) SO2 + Cl2 RSO2Cl
reaction h
Zn Cu HCl
(2) RX
Re d P Hi, LiAlH4
AlCl3 / HCl
(3) branched alkanes
HOH or ROH Isomerisation
(3) RMgX

or NH3 or RNH2
RH Pyrolysis
Na, dry ether or (4)
Alkenes + CH4 or C2H6
(4) RX 500 700 C
Wurtz reaction RR
or
(5) Re d P / HI
R C Cl or ROH CnH2n+2

O
or
R C R or RCHO

Zn Hg / Conc. HCl
(6) RCR
Clemension' s reduction
O

2 2 H N NH ,HO ,
(7) R C R

Wolf / Kishner reduction
O
or

(RCH2CH2)3B H O
2

(8) RCOONa NaOH CaO


(9) Kolbe' s electrolytic synthesis


RCOONa

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Page # 58 HYDROCARBON

REACTION CHART FOR ALKENES


GMP GR
conc.H SO4 H2 , Ni
(1) RCH2CH2OH 2

H2O
(1) RCH CH
2 3
200 300 C

alc. KOH X2
(2) RCH2CH2X (2)
RCHXCH2X
HX

HX
(3) RCHXCH3

Zn dust RCH=CH2
(3) RCH2CH or
for higher alkene
CnH2n HBr , Peroxide
(4)
X2 RCH2CH2Br

HOCl
(5)
(4) R CH CH2 Zn dust RCH(OH)CH2Cl


X X
dil. H2SO4
(6) RCH (OH)CH
H2O 2 3
Ni, H2
(5) RC CH

200 300C
BH3
(7) (RCH2CH2)3B
RCH COOK Kolbe' s electrolytic synthesis
(6)
RCH COOK O2
(8)
CO + H O
2 2

(7) (C2H5)4N+OH

OS O4
(9) R CH CH2
(8) RCOCH2CH2R Pyrolysis
OH OH
O
Bayer reagent
(10) R CH CH2
1% alkaline KMnO 4
OH OH

R H
O3 H2O C+C
(11)
Ozonolysis H H
O O

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Exercise - I OBJECTIVE PROBLEMS (JEE MAIN)

H
CH3
Br
CH 3
Br2,hv
1. Major Product
Na (A)
H 3.
H D.E
H

CH 3 CH3
| | Br
(A) CH3CHCH2Br (B) CH 3CBrCH 3
Br
| (A) (B)
(C) CH3CH 2CH2Br (D) CH 3CHCH3
Sol.

(C) (D)

Sol.

Br

Na (A) Major product (A) is :


2. Br
D.E
Na (A)
4.
D.E
(A) (B) Cl

(A) (B)
(C) (D)
Sol.

(C) (D)

Sol.

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Br O
Na (A) se (B)
5. N2H4 KOH
D.E
7. (A) (B)
Br
Product (B) will be :
Product (B) will be :

(A) (B)
(A) (B)

Br
OH
CH3
(C) (D)
(C) (D)

Sol.
Sol.

CH3 Zn(Hg)
6. (A)
HCl

Cl2
8. (A). Product (A) will be :
(Major) Product (A) will be : hv
CH3
Cl

(A) (B)
(A) (B)

OH

(C) (D) (C) (D)

Sol.
Sol.

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Page # 62 HYDROCARBON

Cl2 Sol.
9. n-Pentane (A)
hv
(A) 2 (B) 3
(C) 4 (D) 5
Sol.

Cl
Na
13. Dry ether ?
Cl2 Cl
10. CH3CHCH2CH2CH3
| hv
CH3
(A)
Mono-chloro product (inculding steroisomers)
are :
(A) 6 (B) 7
(C) 8 (D) 9
Sol. (B)

(C)

11. CH 3 CH3 ?
Na
Cl
Dry ether
Cl Cl
CH3
CH 3 CH3
(D)
(A) CH3 (B)
Cl
CH3 Sol.
CH3
(C) (D)

CH3
Sol.

14. Methyl cyclohexane react with Br2 in pres-


ence of u.v. light major product will be

Br
Na (A) (B)
12. CH3 Cl + CH3 CH2 Cl
Dry ether Br
products.
Which of the following is not the free radical
combination product in wurtz process. Br
(C) (D)
(A) CH3 CH3
(B) CH3 CH2 CH3
(C) CH3 CH2 CH2 CH3 (D) CH4
Br

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Sol.
Na
16. * Cl ?
Dry ether

Possible prodcuts are :(C = C14)

(A) * *

Br2 Na
15. (A) (B)(B) is (B)
h.v. DMF

* *

(C) *

(A) *
(D) All of these
Sol.

(B)
Na
17. (i) Br
D.E

(ii) Na
F
D.E

(iii)
Na
Cl
D.E

(iv) Na
I
(C) D.E
Correct order of rate of reaction will be
(A) iv > iii > i > ii (B) iii > iv > i > ii
(C) iv > i > iii > ii (D) None of these
Sol.
(D) None of these
Sol.

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Page # 64 HYDROCARBON

+ electrolysis
20. X 2, 3-dimethyl butane
Which of the following anion will be migrates
18.
towards anode to prepare 2, 3-dimethyl
butane in the given reaction.
O

(A)
CH3COOK O
+
Et COOK O
(B)
Which of the gases evolved on the surface of O
anode. O
(A) C2H6, H2 (C)
(B) C3H8, H2 O
(C) C2H6 + C4H6 + CO2 O
(D) C2H6 + C4H10 + CO2
Sol. (D) O
Sol.

O
21.
NH2NH2+OH/ Most stable
O O
confomer of product will be (across C2 C3
OH bond) :
19. (A) gauche (B) Anti
(C) Eclipsed (D) Partially eclipsed
Sol.
O

OH

Suitable reagent for following cenversion will O


be : Zn-Hg+HCl
(A) Zn Hg + HCl (B) Mg(Hg) 22. most stable
(C) HBr (D) All of these confomer of product will be :
Sol.
H H H
H H

(A) (B)
Et
H H H H H
Et
H H H

H H
(C) (D)
Me
H H H H H
Me

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Sol. Sol.

* O
ZnHg + HCl (excess)
26. O
14
(*C=C )
product will be :
* O
CH3 (A) (B)
H H *
H H H H H H
* O
(C) * (D)
23.
CH3 CH3 H H CH3 CH3 Sol.
H H CH3

(I) (II) (III)


Correct order of mono bromination of given
compound is :
(A) I > III > II (B) I > II > III (C) II > I > III
(D) III > II > I
Sol.
27. Rate of decarboxylation of following carboxy-
lic acid with sodalime will be in order
NaOH+CaO
CH3COOH
r1
NaOH+CaO
CH3CH2COOH
r2
O CH 3
| NaOH+CaO
+ CH3 CH COOH
ONa Electrolysis r3
24. major product
ONa
+
(A) r1 > r2 > r3 (B) r3 > r2 > r1
(C) r2 > r3 > r1 (D) r1 > r3 > r2
Sol.
O
will be
(A) 1-butyne (B) n-butane
(C) 2-butene (D) 2-butyne
Sol.

28. Benzoic acid Product will be


NaOH+CaO

(A) (B)

25. In kolbes electrolytic synthesis the pOH of


solution will be
(A) decreases (B) Increases
(C) Constant (D) None of these (C) (D)

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Page # 66 HYDROCARBON

Sol. Sol.

29. Number of required O2 mole for complete 33. e + CH3 Cl CH3 + Cl


combustion of one mole of propane- Above reaction is a step of wurtz reaction
(A) 7 (B) 5 electron will attack on which vacant orbital
(C) 16 (D) 10 of methyl chloride.
Sol. (A) p-orbital
(B) anti-bonding orbital
(C) s-orbital
(D) d-orbital of chlorine
Sol.

30. How much volume of air will be needed for


complete combustion of 10 lit. of ethane-
(A) 135 lit (B) 35 lit.
(C) 175 lit (D) 205 lit.
Sol.
34. Pick the correct statement for
monochlorination of R-secbutyl chlorine.
Me
Cl2
Cl H
300C
31. BrCH2 CH2 CH2Br reacts with Na in the Et
presence of ether at 100C to produce - (A) There are four possible products ; three
(A) BrCH2 CH = CH2 are optically active one is optically inactive
(B) CH2 = C = CH2 (B) There are five possible products ; three
are optically inactive & two are optically
(C) CH2CH 2
active
CH2 (C) There are five possible products ; two
(D) All of these are optically inactive & three are optically
Sol. active
(D) There are four possible products ; two
are optically active & two are optically
inactive
Sol.

O

32. H C O H + CO2
Driving force of above reaction is
(A) H = ve, S = +ve
(B) H = ve, S = ve
(C) H = +ve, S = ve
(D) H = +ve, S = +ve

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35. Reaction : 1 CH3CH2CH2CH2CH3 O


Cl 2
Optically active monochloro product 37. A
hv Ph C CH3 Ph CH2 CH3
(s) are (R)
A could be :
CH3 (A) NH2NH2, glycol/OH
H Cl Cl 2 (B) (ZnHg)/conc. HCl
Reaction : 2 (C) RedP/Hl
hv
Et
S-2-chlorobutane (D) CH2 CH2 ; Raney Ni H2 (mozingo)
| |
Optically active di-chloro product(s) are (S) SH SH
Sol.

Cl 2
Reaction : 3 Optically
hv
active di-chloro product(s) are (P)
Reaction : 4 2-methoxy propane
Cl 2
Optically active mono chloro
hv
product(s) are (Q)
sum of P + Q + R + S is
(A) 8 (B) 9 38. Which of the following is not produced as an
(C) 10 (D) 11 intermediate during the reation :
Sol.
Br

Na
+
Dry ether

Br

Multiple Choice Questions :



(A) CH2
NaOH
36. (X)
+
CaO
(X) will be (B)

(A) COONa (B)


COONa
(C)
COONa
(C) (D) COONa

Sol.
(D)

Sol.

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Page # 68 HYDROCARBON

True or False :

41. Clemenson reduction is not useful for reduc-


tion of acid-sensitive compound
Sol.

39. Possible product during the reation will be :


Na
2EtBr 42. Wolf-kishner reduction is used for reduction
Dry ether
of Base-sensitive compound.
(A) (B) Sol.
(C) CH3 CH3 (D)
Sol.

40. Which of the following acid salt does not give


alkene as an major product when it is
electroysed.
(A) Maleic acid (B) Oxalic acid
(C) Succinic acid (D) Adipic acid
Sol.

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Exercise - II
Single Choice Questions : 4. Which of the following will decolourise alkaline
KMnO4 solution ?
(A) C3H8 (B) CH4
D2 (C) CCl4 (D) C2H4
1. Product will be :
Pt Sol.

D H
(A) (B) H H

H D D D
Na
5. CH3 C C CH3 (A)
D D liq. NH3
(C) (D) B & C both
cold. KMnO4
(B)
H H (A) Meso (B) Racemic mixture
Sol. (C) Diastereomers (D) All
Sol.

H2
2. Which of the following reagent not gives syn 6. CH3 C C CH3 (A)
PdBaSO4
addition when react with alkyne.
(A) H2 + Pd (CaCO3 + Quinoline) Br 2
(B) P 2 catalyst (B)
CCl4
(C) Raney Nickel (D) Li/liq. NH3
Sol. (A) Meso (B) Racemic mixture
(C) Diastereomers (D) All
Sol.

H2
3. CH3 C C CH3 (A) alc.KOH
PdBaSO4 7.
cold. KMnO4
(B). Compound (B) is : Br
(A) Meso (B) Recemic mixture Total number of products.
(C)Diastereomers (D) All (A) 2 (B) 3
Sol. (C) 4 (D) 5
Sol.

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Page # 70 HYDROCARBON

HCl
8. Peroxide
(X) (Major product)

Structure of (X) will be


Cl
CH3
Cl
HBr
(A) (B) 10. Peroxide Major product will

be :
Cl CH3 CH3

(A) H (B) Br
(C) (D) Br H
Cl Br
Sol. CH3

(C) (D)
Br
Sol.

9. Major product for the reaction

Br2
is :
hv

O
H2
(A) Br 11. Ni
Me
Br Product of above reaction is
(A) Meso
(B) racemic
(B) (C) Distereomers
(D) Optically inactive mixture
Sol.
Br

(C)

(D)
Br
Sol.

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12. Suggest reagent and condition for the asym-


metric synthesis of the epoxide given.

O
H2
15. Pt

product of above reaction is


(A) Racemic (B) Diastereomers
(C) Enantiomer (D) Meso
Sol.
+
(A) H3O (B) H2O/HO
+
(C) CH3CO3H (D) CH3CO 2H/H
Sol.

O
16. CH3 C C CH2 CH = CH CH2 C Cl
(a) (b) (c)
Reactivity toward catalytic hydrogenation
O (A) a > b > c (B) b > a > c
(C) a > c > b (D) c > a > b
H2 Sol.
13. Ni

Me
product of above reaction is
(A) Meso
(B) Racemic
(C) Diastereomers 17. CH3 C C CH2 CH = CH2
(D) Optically active products. (a) (b)
Sol. Reactivity toward electrophilic addition
reaction.
(A) a > b (B) b > a
(C) a = b (D) Cannot predict
Sol.

D2
14. Pt

product of above reaction is 18. CH3 C C CH3


(A) Racemic (B) Diastereomers CH3 H
(C) Enantiomer (D) None
Sol. C=C
H CH3
Above conversion can be acheived by
(A) Na/ liq NH3 (B) Li / liqNH3
(C) Li / EtOH (D) All

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Page # 72 HYDROCARBON

Sol.

hv
21. + Br2 mixture of product.

Among the following which product will


formed minimum amount.
O
H2
19. (A), Product (A) Br (B)
PdC
Br
(A) is
Br
Br
(A)
(C) (D)

Sol.
OH

(B)

(C)

CH2OH
H2SO4 NBS
22. P (Major)
(D)
Q (Major). The structure of Q is
O
Sol. Br
Br Br
(A) (B)

Br

Br
(C) (D)
20. Which of following will reacts with Na / liqNH3
? Sol.

(A)

(B) CH3 C C CH3


(C) CH3 C C H
(D) All
Sol.

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Sol.
CH 3 H
18

(i) CH3COO OH
23. X.
+
(ii) H3O
H CH 3
The probable structure of X is 26. 1-Penten-4-yne reacts with 1 mol bromine at
-80C to produce :
CH3 CH3
(A) 4, 4, 5, 5-Tetrabromopentene
18 18
H OH H OH (B) 1, 2-Dibromo-1, 4-pentadiene
(A) (B) (C) 1, 1, 2, 2, 4, 5-hexabromopentane
H OH OH H (D) 4, 5-dibromopentyne
Sol.
CH3 CH3

CH3 CH3
18
H OH H OH
(C) (D) 18
H OH H OH
27. AntiMarkownikoffs addition of HBr is not
CH3 CH3 observed in -
Sol. (A) Propene
(B) But-2-ene
(C) Butene
(D) 1-Methylcyclohexene
Sol.

24. Ozonolysis of CH3CH=C=CH2 will give


(A) Only CH3CHO
(B) Only HCHO
(C) Only CO2
(D) Mixture of CH3CHO, HCHO & CO2
Sol.
28. Which alkene on heating with alkaline KMnO4,
solution gives acetone and a gas, which turns
lime water milky.
(A) 2-Methyl-2-butene
(B) isobutylene
(C) 1-Butene
25. O-xylene on ozonolysis will give (D) 2-Butene
Sol.
O
CHO
(A) | & CH3CCHO
CHO
O
CH3C = O
(B) | & CH3CCHO
CH3C = O
CH3C = O CHO
(C) | & |
CH3C = O CHO 29. Which is expected to react most readily with
bromine -
O
CH3C = O CHO (A) CH3CH2CH3 (B) CH2 = CH2
(D) | , CH3CCHO & | (C) CH CH (D) CH3 CH = CH2
CH3C = O CHO

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Page # 74 HYDROCARBON

Sol.
CH3

NBS
32. Major product will be :

Br
Br
A (A) (B)
30.

A can be
(A) Conc. H2SO4 (B) alcoholic KOH CH3
(C) Et3N (D) t-BuOK
Sol.
(C) (D) All

Br
Sol.

CH3
31.

(i) Hg(OAC) 2,H2O 33. Write mechanism best accounts for the
A.A is transformation in the brackets ?
(ii) NaBH4/NaOH/H2O
Cl
OH CH3
CH3
(A) (B) HCl Cl
OH ?
OH
OH
CH3 CH3
+
(C) (D) +

(A)
Sol.

+
+

(B)

(C)

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Sol.
+

+
+ 1,2-hydride
shift
+
ROH/H
35. P (major)

+ O
+
The product P is

(D) OR
(A) (B)

O OR O
+

OR

Sol.
(C) (D)
CH 3 O
O
Sol.
OR

34. Consider the following rearragement reaction:


Br
+
HBr + Br

CH3
+
Which of the following reaction coordinates H
36. Et (P) major
best represents the overall reaction ? (Note:
the units are arbitrary) OH
Br2
Products
CCl4
Products obtained at the end of the reaction
(A) (B) are
(A) Meso compound
(B) Racemic mixture
(C) Diastereomeric mixture
(D) Structural isomers
Sol.

(C) (D)

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Page # 76 HYDROCARBON

Sol.

HBr/40C
37.
Thermodynamically controlled product will be
:

(A) (B)
Br Br 40. The reaction of HBr with the following com-
pound would produce :

(C) (D)
Br Br OH
Sol.

OH
(A)

Br

Br
CH3
OH
Conc. H2SO4 (B)
38. (A) C4H10O CH 3 C = CH2
dil.H2SO4
(B) C4H10O
What is relationship between A & B ?
(A) A and B may be position isomer (B) A and
Br
B may be chain isomers (C)
(C) A and B may be stereoisomers
(D) All of the above Br
Sol.
Br
Br
(D)

Sol.

39. The product(s) of the following reaction can


best be described as :

HBr

(A) A racemic mixture


(B) A single enantiomer
(C) A pair of diasteromers
(D) An achiral molecule

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41. In which of the following reaction formation


of racemic mixture. Br2
43. Products obtained in this
Br2 CCl4
(A)
CCl4
Cold, KMnO4 Me
(B)
reaction are
(A) Diastereoismers
CH 3 (B) Enantiomers
H (C) Positional isomers
(D) Single meso compound
+ Sol.
H
(C)

OH

H
44. In the given reaction :
CH3
+
H Cold, KMnO4
(D)

OH
Sol. OH OH

(A) (B)

OH OH
OH

(C) (D) B and C both

OH
CH3 H Sol.
C=C Br2
42. (X) Prod-
CCl4
H CH3
ucts. Value of x is
(A) 4 (B) 1
(C) 2 (D) 3
Sol.

CH3 H
Br 2
45. C=C P; 'P' is :
CCl4
H Et
(A) Racemic mixture
(B) Diastereomer
(C) Mixture of Threo compounds
(D) Meso compound
Sol.

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Page # 78 HYDROCARBON

HCl
48. Me CH CH = CH Ph W, W is
|
Et
(A) Me CH CH2 CH Ph
| |
Et Cl
(B) Me CH CH CH2 Ph
| |
Et Cl
46. CH3 CH = CH2 dil.H2SO4 (A) .
(C) Me CH CH CH 2
Product (A) is | | |
Cl Et Ph
(A) OH
(D) Cl CH CH CH 2 Ph
(B) CH3 CH2 CH2 OSO2OH | |
Et Me
(C) CH3 CH CH3
| Sol.
O SO2OH
OH
(D)
Sol.

3O 3
49.
Zn+H2O

Products are
(A) CO2H (B) CO2H
| |
47. Which reaction condition would be perform CHO CO2H
the following transformations ?
(C) CHO (D) CH2OH
OMe | |
CHO CH2CH2OH
CH 3 Sol.

Br

(A) HOBr, CH3OH/H


(B) OsO4, HBr, NaOH, Mel
(C) Br2\ MeONa
(D) mCPBA, HBr, NaOH, Mel
Sol.

50. Gases libreated at the surface of anode and


cathode respectively in kolbe's electrolytic
syntheis will be :
(A) H2, CO2 (B) CO2, H2
(C) NaOH, H2 (D) Only CO2
Sol.

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Sol.
CH3

CH2
HBr
51. CCl4

Cl
What is sterochemistry of products
(A) Optically inactive (B) Meso product CH3
(C) Diastereomers (D) None of these SO2Cl2 PhSNa
54. (A) (B) .
Sol. hv

Product (B) is

S Ph Cl

+
H3O Cl SPh
52. (A) (B)
Shape of intermediate produced during this
reaction will be
(A) Square planer (B) tetrahedral
(C) Trigonal planer (D) Pyramidical Cl
Sol. SPh
(C) (D) None

Sol.

53. H+

OH
Which of the following is formed as an prod-
uct during the following reaction

(A)

OH2
+

(B)
O

(C)
+

(D)
OH

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EXERCISE III JEE ADVANCED


H2 D2
Single Choice Questions : 4. CH3 C C CH3 (A)
Pd-BaSO4 Ni
1. CH3 C C H CH3 C C CH3
Above conversion can be achieved by (B)
(A) NaNH2, CH3 I (B) NaH, CH3 I Product (B) of above reaction is
(C) Na, CH3 I (D) All
Sol. CH3 CH3
H D H D
H D D H
(A) (B)

CH3 CH3

2. Which of the following is most reactive toward H CH3


catalytic hydrogenation ? H D D H
O
(C) H D (D) H D
(A) R C Cl (B) R C C R
H Et

Sol.
(C) R CH = CH R (D)

Sol.

Na
5. Ph C C Ph
Liq. NH3 (A)
D2
(B) Product (B) is
Pt
(A) Racemic (B) Diastereomer
(C) Enantiomer (D) None
3. Which of the following is least reactive toward
Sol.
hydrogenation ?
(A) CH3 C C CH3
(B) CH3 C CH
(C) HC CH
(D) H2C = CH2
Sol.

HBr
6. C3H7C CH 'X' X is
(1eq.)
(A) C3H7CH CHBr (B) C3H7Br CH2
(C) C3H7CBr C Br (D) C3H7HC CBr2

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Sol.

HgSO4
9. CH3 C CH (A) ;
H2SO4
HgSO4
(1) H2/Pt CH3 C C CH3 (B)
7. CH3 C C CH3 X H 2SO4
(2) Br2
Relation between (A) and (B)
(A) (d)-2, 3-Dibromobutane
(A) Position isomer
(B) (l)-2, 3-Dibromobutane
(B) Functional isomers
(C) (dl)-2, 3-Dibromobutane
(C) Homologous
(D) meso-2, 3-Dibromobutane
(D) Metamers
Sol.
Sol.

Lindlar
10. B R C C R
Catalyst
HgSO4 Na/NH3
8. P, Products P is A
H2SO4
A and B are ge om et ri cal i s om ers
(R CH = CH R)
OH (A) A is trans, B is cis
(B) A and B both are cis
(A) (C) A and B both are trans
OH (D) A is cis, B is trans
Sol.
OH
OH
(B)

O
NaNH2/NH 3(liq.)
11. CH3CH2C CH
(C)
CH3CH2Br Li, NH3(liq.)
O
(A) CH3CH2CH = CHCH3
O (B) CH3CH2CH = CH2

CH3CH2 H
(D)
C=C
(C)
H CH2CH3
Sol.

CH3CH2 CH2CH3

(D) C=C
H H

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Page # 82 HYDROCARBON

Sol.

15. Li,/liq. NH3

Major product
given reaction is an example of
(A) catalytic hydrogenation
12. List I (B) Metal dissolved reduction
(A) CH3 C C CH3 cis-2-butene (C) Metal adsorbed reduction
(D) Non metal dissolved reduction
(B) CH3 C C CH3 trans-2-butene Sol.

(C) CH3C C CH3 1-Butyne

(D) CH3 CH3 C CH3 2-Butyne

List II
(1) Na/NH3()
(2) H2/Pd/BaSO4 16. What is the major organic product of the fol-
(3) alc. KOH, lowing reaction ?
(4) NaNH2,
Code : 2+
a b c d Hg
CH
(A) 2 1 3 4 H2SO4
(B) 1 2 4 3
(C) 1 2 3 4 O
(D) 2 1 4 3
(A)

H2(one mole)
13.
Pt H
Product will be
(B) OH
(A)
H
(B)
H
(C) (C)
(D) B and C both O
Sol.
H

H
(D)
HO
Li, C 2H5NH2 Sol.
14.
78C

Major product will be


(A) Z-3-Hexene (B) E-3 Hexene
(C) E-2-Hexene (D) A and B both
Sol.

Multiple Choice Questions :

17. Bromination can take place at

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HYDROCARBON Page # 83

5 2
NBS/hv
CCl4
4 3 O
(A) 1 (B) 2 NaHCO3
(C) 3 (D) 4 22. (i) COH y (gas)
Sol. 14

KH z (gas)
(ii) OH

Sum of molecular weight of gas (y) + mo-


lecular weight of gas (z) is
Sol.
18. Benzyl chloride (C6H5CH2Cl) can be prepared
from toluene by chlorination with :
(A) SO2Cl2 (B) SOCl2
(C) Cl2/hv (D) NaOCl
Sol.
23. Complete the following reaction with appropri-
ate sturcture of products/reagents
CH=CH2

Br2 (i) NaNH2(3 equi.)


19. An alkene on ozonolysis yields only ethanal. (A) (B)
(ii) CH 3I
There are an structural isomers of this which
on ozonolysis yields :
Sol.
(A) propanone (B) ethanal
(C) methanal (D) only propanal
Sol.

24. (a) HCl


H CH 2
NBS
20. CH2 = CHCH2CH = CH2 possible prod-
ucts can be CH3
(A) CH2 = CHCHCH = CH2 Total number of Markownikoff's products in
above reaction is ?
Br
(B) CH2 = CHCH = CH CH2Br (b) Br2
(C) CH2 = CH CH2 CH = CHBr CCl4
(D) CH 2 = CHCH 2C = CH 2

Br Me
Sol.
Number of products obtained in the above re-
action is ?
Cl2
(c)
CS2
21. Which of the following will same product with Total number of products obtgained in
HBr in presence or absence of peroxide this reaction is ?
(A) Cyclohexene Sol.
(B) 1-methylcyclohexene
(C) 1,2-dimethylcyclohexene
(D) 1-butene
Sol.

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EXERCISE IV PREVIOUS YEARS PROBLEMS

LEVEL I JEE MAIN


Q.1 The compound Q.4 On mixing a certain alkane with chlorine and
H3CC = CH CH2 CH3 irradiating it with ultraviolet light, it forms only
H3C Vigorous prod-
oxidation one monochloroalkane. This alkane could be -
uct, here product is [AIEEE-2002] [AIEEE-2003]
CH 3C CH3 (A) Isopentane (B) Neopentane
(A) CH3COOH & (C) Propane (D) Pentane
O
Sol.
CH 3C=O
(B) CH3 CH2 COOH &
CH3
(C) CH3 CH2 COOH only
CH 3C=CH3
(D) HCOOH & Q. 5 Butene-1 may be converted to butane by re-
O
Sol. action with [AIEEE-2003]
(A) Zn Hg (B) Pd / H2
(C) Zn HCl (D) Sn HCl
Sol.

Q.2 Reaction
HCCH + HOCl product, here product Q.6 During dehydration of alcohols to alkenes by
heating with conc. H2SO4 the initiation step is-
will be -
(A) Elimination of water [AIEEE-2003]
[AIEEE-2002]
(B) Formation of an easter
(A) CHCl2CHO (B) CHOCHO
(C) Protonation of alcohol molecule
(C) CHCl=CHCl (D) CHCl2CHCl2
(D) Formation of carbocation
Sol. Sol.

Q.7 Bottles containing C6H5I and C6H5CH2I lost their


Q.3 Acetylene does not react with - original labels. They were labelled A and B for
[AIEEE-2002] testing. A and B were separately taken in test
(A) NaNH2 (B) NaOH tubes and boiled with NaOH solution. The end
(C) Na metal (D) Ammonical AgNO3 solution in each tube was made acidic with
Sol. dilute HNO3 and then some AgNO3 solution was
added. Substance B gave a yellow precipitate.
Which one of the following statements is true
for this experiment ? [AIEEE-2003]
(A) B was C6H5I
(B) Addition of HNO3 was unnecessary
(C) A was C6H5I (D) A was C6H5CH2I

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HYDROCARBON Page # 85

Sol. Sol.

Q.8 Which one of the following has the minimum Q.11 Acid catalyzed hydration of alkenes except
boiling point ? [AIEEE-2004] ethene leads to the formation of
(A) n-Butane (B) 1-Butyne [AIEEE-2005]
(C) 1-Butene (D) isobutane (A) secondary or tertiary alcohol
Sol.
(B) primary alcohol
(C) mixture of secondary and tertiary alcohols

(D) mixture of primary and secondary alcohols


Sol.

Q.9 Amongst the following compounds, the opti-


cally active alkane having lowest molecular
mass is - [AIEEE-2004]
(A) CH3CH2CH2CH3
CH3
(B) Q.12 Alkyl halides react with dialkyl copper reagents
CH3CH2CHCH3 to give [AIEEE-2005]
H (A) alkyl copper halides (B) alkenes
(C) alkenyl halides (D) alkanes
(C) CH3C
Sol.
C2H5
(D) CH3CH2CCH
Sol.

Q.13 Elimination of bromine from 2bromobutane re-


sults in the formation of [AIEEE-2005]
Q.10 Reaction of one molecule of HBr with one mol- (A) predominantly 2butene
ecule of 1,3butadiene at 40C given predomi- (B) equimolar mixture of 1 and 2butene
nantly [AIEEE-2005] (C) predominantly 2butyne
(A)1bromo2butene under thermodynamically (D) predominantly 1butene
Sol.
controlled conditions
(B) 3bromobutene under kinetically controlled
conditions
(C) 1bromo2butene under kinetically con-
trolled conditions
(D) 3bromobutene under thermodynamically
controlled conditions

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Page # 86 HYDROCARBON

Me
Q.17 Which of the following reactions will yield 2, 2-
dibromopropane? [AIEEE 2007]
Me
Q.14 N (A) CH3 C CH + 2HBr
OH
n-Bu Et (B) CH3CH = CHBr + HBr
The alkene formed as a major product in the (C) CH CH + 2HBr
above elimination reaction is (D) CH3 CH = CH2 + HBr
[AIEEE 2006]
Sol.
Me
(A) CH2 = CH2 (B)

Me
(C) (D) Me
Sol.

Q.18 In the following sequence of reactions, the alk-


ene affords the compound B
H 2O
CH3CH = CHCH3 O
3 A B, The com-
Zn
pound B is [AIEEE 2008]
Q.15 Fluorobenzene (C6H5F) can be synthesized in (A) CH3COCH3
the laboratory - [AIEEE 2006] (B) CH3CH2COCH3
(A) from aniline by diazotisation followed by (C) CH3CHO
heating the diazonium salt with HBF4 (D) CH3CH2CHO
(B) by direct fluorination of benzene with F2 Sol.
gas
(C) by reacting bromobenzene with NaF solu-
tion
(D) by heating phenol with HF and KF
Sol.

Q.19 The treatment of CH3MgX with CH3CCH pro-


duces
[AIEEE 2008]
(A) CH3CCCH3
Q.16 Phenyl magnesium bromide reacts with metha-
nol to give - [AIEEE 2006] H H
(B) | |
(A) a mixture of benzene and Mg(OMe) Br CH3 C = C CH3
(B) a mixture of toluene and Mg(OH)Br (C) CH4
(C) a mixture of phenol and Mg(Me)Br (D) CH3CH=CH2
Sol.
(D) a mixture of anisole and Mg(OH) Br
Sol.

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HYDROCARBON Page # 87

Q.20 The hydrocarbon which can react with sodium


in liquid ammonia is - [AIEEE 2008] Q.23 2-Hexyne gives trans -2- Hexene on treat-
ment with - [AIEEE 2012]
(A) CH3CH2CCH
(A) Li/NH3 (B) Pd/BaSO4
(B) CH3CH=CHCH3 (C) LiAlH4 (D) Pt/H2
Sol.
(C) CH3CH2CCCH2CH3

(D) CH3CH2CH2CCCH2CH2CH3
Sol.

Q.24 Which branched chain isomer of the hydro-


carbon with molecular mass 72u gives only
one isomer of mono substituted alkyl halide ?
[AIEEE 2012]
(A) Neopentane
Q.21 Ozonolysis of an organic compounds gives form- (B) Isohexane
aldehyde as one of the products. This con- (C) Neohexane

firms the presence of : [AIEEE 2011] (D) Tertiary butyl chloride


Sol.
(A) two ethylenic double bonds
(B) vinyl group
(C) an isopropyl group
(D) an acetylenic triple bond
Sol.

Q.22 Ozonolysis of an organic compound A pro-


duces acetone and propionaldehyde in equimo-
lar mixture. Identify A from the following com-
pounds : [AIEEE 2011]
(A) 1 - Pentene
(B) 2 - Pentene
(C) 2 - Methyl - 2 - pentene
(D) 2 - Methyl - 1 pentene
Sol.

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Page # 88 HYDROCARBON

LEVEL II JEE ADVANCED


Q.1 Which one of the following alkenes will react
fastest with H2 under catalytic hydrogenation
condition [IIT 2000]
Q.4 In the presence of peroxide, hydrogen chloride
and hydrogen i odi de do not gi ve anti
(A) (B) Markonikoff addition to alkene because
[IIT 2001]
(A) both are highly ionic
(B) one is oxidising and the other is reducing
(C) one of the step is endothermic in both the
(C) (D) cases
(D) All the steps are exothermic in both cases
Sol. Sol.
7

Me H

Q.2 Propyne and propene can be distinguished by CH3C C C Me


Q.5
[IIT 2000]
(A) conc. H2SO4 (B) Br2 in CCl4 H H
Hydrogenation of the above compound in the
(C) dil. KMnO4 (D) AgNO3 in ammonia
presence of poisoned paladium catalyst gives
Sol.
[IIT 2001]
(A) An optically active compound
(B) An optically inactive compound
(C) A racemic mixture
(D) A diastereomeric mixture
Sol.

Q.3 Statement-1 : 1-butene on reaction


with HBr in the presence of a peroxide produces
1-bromobutane.
Statement-2 : It involves the formation
of a primary radical. [IIT 2000]
(A) Statement-1 is true, Statement-2 is true
Q.6 The reaction of propene with HOCl proceeds
and statement-2 is correct explanation for
via the addition of [IIT 2001]
statement-1
(A) H+ in first step
(B) Statement-1 is true, Statement-2 is true
(B) Cl+ in first step
and statement-2 is NOT the correct explanation
(C) OH in first step
for statement-1
(D) Cl+ and OH in single step
(C) Statement-1 is true, Statement-2 is false.
Sol.
(D) Statement-1 is false, Statement-2 is true.
Sol.

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HYDROCARBON Page # 89

Q.7 Statement-1 : Addition of bromine to


trans-2-butene yields meso-2, 3-dibromo
butane.
Statement-2 : Bromine addition to an
alkene is an electrophilic addition.[IIT 2001] Q.9 Identify a reagent from the following list which
(A) Statement-1 is true, Statement-2 is true can easily distinguish between 1butyne and
and statement-2 is correct explanation for 2-butyne- [IIT 2002]
statement-1 (B) State me nt -1 i s true , (A) bromine, CCl4
Statement-2 is true and statement-2 is NOT (B) H2, Lindlar catalyst
the correct explanation for statement-1 (C) dilute H2SO4, HgSO4
(C) Statement-1 is true, Statement-2 is false. (D) ammonical Cu2Cl2 solution
(D) Statement-1 is false, Statement-2 is true. Sol.
Sol.

Q.10 Identify the set of reagents/reaction conditions


Q.8 Consider the following reactions 'X' and 'Y' in the following set of transformation
[IIT 2002] X
CH3 CH2 CH2 Br Product

Y
H3C CH CH CH3 + Br 'X' + HBr CH 3 CH CH 3 [IIT 2002]

D CH3 Br
(A) X = dilute aqueous NaOH, 20C; Y = HBr/
Identify the structure of the major product X acetic acid, 20C
(B) X = concentrated alcoholic NaOH, 80C; Y
(A) H3C CH CH CH2
= HBr/acetic acid, 20C
D CH3 (C) X = dilute aqueous NaOH, 20C; Y = Br2/
CHCl3, 0C
(D) X = concentrated alcoholic NaOH, 80C; Y
(B) H3C CH C CH 3
= Br2/CHCl3, 0C
D CH3 Sol.

(C) H3C C CH CH 3
D CH3

(D) H3C CH CH CH3

CH3 HgSO4
Q.11 C6H5CCCH3 A
Sol. H2SO4

[IIT 2003]

(A) (B)

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Page # 90 HYDROCARBON

[IIT 2004]
(C) C 6H5 C CHCH3 (D) C 6H5 CH C CH3 (A) 2 (B) 4
| | (C) 6 (D) 8
OH OH
Sol.
Sol.

H x Q.16 1bromo3chlorocyclobutane when treated


Q.12 Br2
(mixture)
H2O with two equivalents of Na, in the presence of
5 compounds of molecular formula C4H8Br2 ether which of the following will be formed?
Number of compounds in X will be: [IIT 2005]
[IIT 2003]
(A) 2 (B) 3
(C) 4 (D) 5 (A) (B)
Sol.

(C) (D)
Sol.

Q.13 2hexyne can be converted into trans2


Q.17 Cyclohexene is best prepared from cyclohexanol
hexene by the action of : [IIT 2004]
by which of the following [IIT 2005]
(A) H2Pd-BaSO4 (B) Li in liq. NH3
(A) conc. H3PO4 (B) conc. HCl/ZnCl2
(C) H2PtO2 (D) NaBH4
(C) conc. HCl (D) Conc. HBr
Sol.
Sol.


Q.14 2-phenyl propene on acidic hydration, gives Q.18
H ,

(i) O
X 3 Y..
(ii) Zn / CH COOH
[IIT 2004] 3

(A) 2-phenyl-2-propanol
Identify X and Y. [IIT 2005]
(B) 2-phenyl-1-propanol
Sol.
(C) 3-phenyl-1-propanol
(D) 1-phenyl-2-propanol
Sol.

Q.19 CH3CH=CH2 + NOCl P Identify the adduct.


[IIT 2006]
(A) CH3 CH CH2 (B) CH3 CH CH2
Q.15 How many chiral compounds are possible on | | | |
mono chlorination of 2-methyl butane ? Cl NO NO Cl

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HYDROCARBON Page # 91

(B) alcoholic KOH followed by NaNH2


NO (C) aqueous KOH followed by NaNH2
|
(C) CH3 CH2 CH (D) CH2 CH2 CH2 (D) Zn / CH3OH
| | | Sol.
Cl NO Cl
Sol.

CH3
Cl2, hv Q.24 The correct stability order for the following
species is [IIT 2008]
H3C
Q.20 N(isothermeric
CH3 O
fractional distillation (I) (II)
p roduct s) C 5 H 1 1 C l
M(isomeric products). What are N and M ?
[IIT 2006]
(A) 6, 6 (B) 6, 4 O
(C) 4, 4 (D) 3, 3 (III) (IV)
Sol. (A) II > IV > I > III (B) I > II > III > IV
(C) II > I > IV > III (D) I > III > II > IV
Sol.

Q.21 The number of structural isomers for C6H14 is


[IIT 2007] Q.25 In the following carbocation, H/ CH3 that is
(A) 3 (B) 4 most likely to migrate to the positively charged
(C) 5 (D) 6 carbon is [IIT 2009]
Sol.
H H
1 2 + 4 5
H3CCCCCH3
3

Q.22 The number of stereoisomers obtained by HO H CH3


bromination of trans-2-butene is (A) CH3 at C-4
[IIT 2007] (B) H at C-4
(A) 1 (B) 2 (C) CH3 at C-2
(C) 3 (D) 4 (D) H at C-2
Sol. Sol.

Q.26 Intermediate produced when propene react with


HCl in presence of peroxide [IIT 2009]
(A) CH 3 CH 2 CH2
Q.23 The reagent(s) for the following conversion,
[IIT 2007] (B) CH CH CH
3 3
?

H H (C) CH 3 CH2CH2
is / are (D) CH 3 CH CH 3
(A) alcoholic KOH

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Page # 92 HYDROCARBON

Sol.

Q.27 The total number of cyclic isomers possible for


a hydrocarbon with the molecular formula C4H6
is [IIT 2010]
Sol. Q.31 What would be the major product in each of
the following reactions?[IIT 2000]

H2
CH3 Lindlar catalyst

Sol.

Q.28 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

H, (i) O 3
Q.32 X Y
Q.29 Carry out the following transformation in not (ii)Zn/CH3COOH
more than three steps.[IIT 1999]
Identify X and Y. [IIT 2005]
O Sol.

CH3CH2CCH CH3CH2CH2CCH3
Sol.

Q.33 The total numb er al kenes p ossi bl e by


d ehyd robrom i nat i on of 3-b romo-3-
cyclopentylhexane using alcoholic KOH is .
[IIT 2011]
Sol.
Q.30 CH2 =CH C
is more basic than HC
[IIT 2000]
Sol.

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HYDROCARBON Page # 93

Answers
Exercise-I

1. B 2. A 3. B 4. C 5. B 6.B 7. A
8.A 9. C 10. C 11. D 12. D 13. C 14. C

15. B 16. D 17. C 18. D 19. A 20. B 21. B


22. C 23. A 24. D 25. A 26. A 27. A 28. A
29. B 30. C 31. C 32. A 33. B 34. C 35. B

36. C D 37. ABCD 38. C D 39. ACD 40. ABD 41. T 42. F

Exercise-II

1. D 2. D 3. A 4. D 5. B 6. B 7. B
8. A 9. D 10. A 11. C 12. C 13. C 14. D
15. D 16. D 17. B 18. D 19. C 20. D 21. C
22. C 23. A 24. D 25. D 26. D 27. B 28. B
29. D 30. A 31. C 32. A 33. C 34. D 35. A
36. B 37. B 38. A 39. C 40. B 41. C 42. B
43. B 44. D 45. A 46. A 47. A 48. A 49. C
50. B 51. C 52. C 53. B 54. B

Exercise-III
1. D 2. A 3. D 4. A 5. A 6. B 7. C
8. D 9. C 10. A 11. C 12. D 13. C 14. B

15. B 16. A 17. A,C,D 18. A,C 19. A.C 20. A,B 21. A,C

22. 44 + 2 = 46
Br

CH CH2Br
23. (A) 3NaNH2(liq.) CH3I
(B)

24. (a) 2 (b) 2 (c) 2

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HYDROCARBON Page # 94

Exercise-IV (PREVIOUS YEARS PROBLEMS)

Level-I (JEE MAIN)

1. B 2. A 3. B 4. B 5. B 6. C 7. C
8. D 9. C 10. A 11. A 12. D 13. A 14. A
15. A 16. A 17. A 18. C 19. C 20. A 21. B

22. C 23. A 24. A

Level-II (JEE ADVANCED)

1. A 2. D 3. C 4. C 5. B 6. B 7. B
8. B 9. D 10. B 11. A 12. B 13. B 14.A

O
15. B 16. D 17. A 18. (x) = , (Y) = CH 3 C (CH2) 4 CH = O
CH3

19. A 20. B 21. C 22. A 23. B 24. D 25. D


26. B 27. 5 28. B 29. (1) NaNH2, (2) Me I (3) HgSO4 dil H2SO4
30. higher electronegativity of sp carbon
31. In presence of Lindlar's catalyst (Pd and CaCO3 in quinoline) partial hydrogenation takes place and cis
isomer is obtained.

H2 CH3
CH3 Lindlar catalyst

32. (X)
CH3

O
(Y) CH3 C (CH2)4 CH = O

33. 5

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AROMATIC COMPOUNDS Page # 95

AROMATIC COMPOUND
some important aromatic compounds with their common names.
Formula Name Formula Name
CH3 CHO
Toluene Benzaldehyde
(bp 111 C) (bp 178 C)

OH COOH
Phenol Benzoic acid
(mp 43 C) (mp 122 C)

NH2 CN
Aniline Benzonitrile
(bp 184 C) (bp 191 C)

O
CH3
C Acetophenone Ortho-xylene
CH3 (mp 21 C) (bp 144 C)
CH3
IUPAC Name of Substituted phenol and benzoic acid.
OH O
1
Br Br
6 2
Cl C
OH
5 3
4
2,6-Dibromophenol m-chlorobenzoic acid
Electrophilic Aromatic Substitution Reaction
H H H
H H H H H E
+ +
+ E E + H
H H H H H H

H H H
-complex
A reaction energy diagram for the electrophilic bromination of benzene. The reaction occurs in two
steps and releases energy.

H Br
H
Eact H Br
Br
Addition
-complex (does NOT occur)

Br
+ Br2
+ HBr

Substitution

Reaction progress

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Page # 96 AROMATIC COMPOUNDS
Some Electrophilic Aromatic substitution reactions:

C
X R

NO2 R
Acylation
Halogenation
SO3H
Alkylation
Nitration

Sulfonation

(i) Ortho- and para-directing activators : Groups like OH ad NH2 present on a ring direct an electrophile,
E+, to ortho or para position and they react faster than benzene.
(ii) Ortho- and para-directing deactivators : Helogens present on a ring direct an electrophile, E+, to
ortho or para positions, and they react slower than benzene.
(iii) Meta-directing deactivators : Groups containing a carbonyl (C = O) or a CN group direct an
electrophile, E+, to the meta positions, but they react slower than benzene.
No meta-directing activators are known. Figure 5.8 shows how the directing effects of the groups
correlate with their reactivities. All meta directing grops are deactivating and most ortho-and para-
directing groups are activating. The halogens are unique in being ortho and para directing and
deactivating.

O O
NO2 SO3H COH CH Br F OCH3 NH2

Reactivity

C N O O I Cl H CH3 OH
CCH3 COCH3 (alkyl)

Meta-directing Ortho-and Ortho-and


deactivators para-directing para-directing
deactivators activators

Figure Substituent effects in electrophilic aromatic substitutions. All activating groups are ortho-and
para-directing, and all deactivating groups other than halogen are meta-directing. The halogens are
ortho and para-directing deactivators.

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AROMATIC COMPOUNDS Page # 97

CONCEPT MAP

Electrophilic Aromatic Substitution

involves reaction
between

An aromatic ring An electrophile


and
is is
can be

Activated towards Deactivated towards


electrophilic substitution electrophilic substitution X
+

+
NO2
by by SO3
R+
RCO+
Electron-donating Electron-Withdrawing
groups groups

lower raise
the the

Energy of activation (Eact)


for arenium ion formation

Increase Decrease
reaction rate reaction rate

stabilize destabilize
An arenium ion

is a loses a proton to form the

Cyclohexadienyl cation Aromatic substitution product

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Page # 98 AROMATIC COMPOUNDSE

EXERCISE I OBJECTIVE PROBLEMS (JEE MAIN)


Sol.
Single Choice Questions :

NO2
Nitrating
1. Mixture 5. Which of the following compound gives poor
yield in friedel-craft reaction

Given reaction is an example of NO2 NH2


(A) Substitution electrophilic aromatic (SEAr)
(B) Substitution nucleophilic aromatic (SNAr) (A) (B)
(C) Electrophilic addition reaction (EAR)
(D) Bi molecular nucleophilic substution (SN2)
Sol. CF3

(C) (D) All of these

E Nu Sol.
2.

6. Most reactive towards nitration reaction (Sub-


Name of intermediate produced during given
stitution electrophilic aromatic)
reaction will be
(A) Arenium ion
NH2
(B) -complex/wheeland intermediate
(A) (B)
(C) Nonaromatic cyclohexa dienyl carbocation
(D) All of these
Sol.
O

NH
3. Which of the following reagent is best when
friedel craft Halogenation takes place (C)

(A) HO (B) AlCl3 (anhyd.)


(C) AlCl3 (hydrated) (D) All of these
Sol.

N
4. WHat is the name of electrophile when ben-
zene goes nitration
(D)
(A) Nitrosonium ion (B) Nitronium ion
(C) Halonium ion (D) Alkyl carbocation

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AROMATIC COMPOUNDS Page # 99

Sol. OCH3

7. Which of the following compound gives ben- 9. Nitration Major product


zoic acid when it reacts with hot KMnO4 fol-
lowed by acidification.
F

OCH3
(A) OCH3

NO2
O H
(A) (B)
CH3
NO2
(B) (C) F
F
(C) Mixture A and B (D) None of these
(D) All of these Sol.
Sol.

CF3 NH2

Conc. HNO3
NaNO2 H2O
8. + Major product 10. (A) (B)
2HCl Boil
Conc.H2SO4

CF3 Product (B) will be :


CF3
NO2 OH
(A) (B)
NO2 (A) (B)

CF3
+
N2Cl Cl

(C) (D) A and C both


(C) (D)
NO2
Sol.
Sol.

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Page # 100 AROMATIC COMPOUNDSE

O 13. Ease of ionization to produce carbocation and


bromide ion under the treatment of Ag will be
maximum in ?
11. + AlCl3 (A)
O

O
O
Zn(Hg)
(B)
conc.H2SO4 (A) (B)
HCl (C) (Major prod-
uct)
Br
C will be : Br

(A) (B)
(C) (D)

O
Br Br

Sol.
(C) (D)
O

Sol.

Cl
14. 2SbCl5
P ; P will be
Cl


(A) 2 (B) 2+ 2SbCl6

12. How many electron are there in the follow-


ing speices :
(C) (D) Mixture of A & B

Sol.

(A) 2 (B) 4 15. Which order is correct for the decreasing re-
(C) 6 (D) 8 activity to ring monobromination of the fol-
Sol. lowing compounds :
(I) C6H5CH3 (II) C6H5COOH
(III) C6H6 (IV) C6H5NO2
(A) I > II > III > IV (B) I > III > II > IV
(C) II > III > IV > I (D) III > I > II > IV
Sol.

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AROMATIC COMPOUNDS Page # 101

16. Which of the following order is correct for the Sol.


decreasing reactivity to ring monobromination
of the following compounds :

CH 3 COOH

(I) (II) 19. Which of the following will form tri-bromo de-
rivative of phenol ?

COOH NO2 OH OH

(III) (IV) Br2 Br2


(A) (B)
HO 2 H2O

(A) I > II > III > IV (B) II > III > IV > I
(C) I > III > II > IV (D) III > I > II > IV
OH OH
Sol.
Br2 Br2
(C) (D)
CS 2 H2O


17. Electrophile N O2 attacks the following :
Sol.
CCl3 NO2

(I) (II)

CHO O

(III) (IV) Ph

20. HBF4
Ph OPh Product of this

In which cases N O2 will attack at meta posi-
Ph
tion
reaction is :
(A) II and IV (B) I, II and III
OH
(C) II and IV (D) I only Ph
Sol.
(A) Ph H+

Ph
OH
18. Increasing order of the following for electrophile Ph
substitution reaction as -
(B) + Ph OH
(I) CH3 (II)
Ph

(III) COOH

(A) I > II > III (B) III > II > I


(C) II > III > I (D) I > III > II

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Page # 102 AROMATIC COMPOUNDSE

Ph Sol.

(C) Ph OH +

Ph 23. Benzene reacts with n-propyl chloride in the


presence of anhydrous AlCl3 to give predomi-
Ph
nantly :
Ph OH (A) n-Propylbenzene
(D) (B) Isopropylbenzene
Ph (C) 3-Propyl-1-Chlorobenzene
Sol. (D) No reaction
Sol.

NO2

(1)NaOH
(A), Product (A) is 24. In the sulphonation, acetylation and formylation
21.
(2)H3O of benzene the group of effective electrophiles
I
would be :
Br

(A) SO3+, CH3C O+, H C O
NO2
NO2

(B) SO3, CH3 C O+, H C O

(A) (B) (C) SO3, CH3CHO, CO + HCl


OH
I (D) HSO3, CH3CO, HCO
Br
OH Sol.
OH NO2

OH

(C) (D) 25. p-Nitrotoluene on further nitration gives :


I I

Br Br CH3
CH3
Sol. NO2
(A) (B)

NO2
22. For preparing monoalkyl benzene, acylation NO2
NO2
process is preferred than direct alkylation be-
cause
(A) In alkylation, a poisonous gas is evolved CH2OH CH3
NO2 NO2
(B) In alkylation, large amount of heat is evolved
(C) (D)
(C) In alkylation, pollyalkylated product is
formed O2N

(D) Alkylation is very costly NO2

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AROMATIC COMPOUNDS Page # 103

Sol. 27. The major product formed in the reaction is :

+
OCH3 + E
(electrophile)

26. The major product formed on monobromination


of phenylbenzoate is : OCH3
(A)

Br E

O (B) E OCH3
(A)
O
OCH3
(C)
E

O OCH3
Br
(B) (D)
O E
Sol.

Br

O
(C)
O 28. The major product formed in the reaction is :

OMe
AlCl3
+ (CH3)2 CHCH2Br

O
OMe
(D)
O (A)
Br CH2CH(CH 3)2
OMe
Sol.
(B)
(CH3)2CHCH2

OMe

(C)
C(CH3)3
OMe

(D)
(CH3)3C

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Page # 104 AROMATIC COMPOUNDSE

Sol. 31. In the reaction the major product formed is :


O

Br2 (1mole)
N
Fe

O
29. In the sulhponation of benzene, the active elec-
Br
trophilic species is :
(A) N
(A) SO2 (B) SO3
(C) SO42 (D) HSO4
O
Sol.
N
(B)

Br
O

N
30. Which one of the following compounds under- (C)
goes bromination of its aromatic ring at the
fastest rate ? Br
O

(A) (B) (D) N Br


N
| Sol.
H

NH
(C) (D)
NH
O
Sol.

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AROMATIC COMPOUNDS Page # 105

Sol.
32. HNO3 / H2SO4
(A) Ma-

MeO
jor product :
34. What combiantion of acid chloride or anhy-
NO2 dride and arene would you choose to prepare
NO2 given compound ?
(A)
MeO

NO2
(B)
CCH2CH2CO2H
MeO
O

NO2
(C)
O O
MeO
AlCl3
(A) + ClCCH2CHCCl

CH3
(D)
MeO NO2

Sol. O

(B) + AlCl3
O

33. Increasing order of rate of reaction with Br2/


O
AlBr3 is :

OCH3 OCH3 (C) + AlCl3


O

(I) (II) O

O
O OCH3
(D) + AlCl3
O
(III) (IV)
O

(A) III < I < II < IV (B) III < II < I < IV Sol.
(C) II < IV < III < I (D) IV < II < III < I

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Page # 106 AROMATIC COMPOUNDSE

35. Which position will be attacked most rapidly


+
by the nitronium ion (NO2 ) when the com-
37. Which of the following is most reactive toward
pound undergoes nitration with HNO3/H2SO4 : SNAr :

(I) (II) (III) (IV)


H2C Cl Cl
OCH3 NO2
H3C
(A) (B)
(A) I (B) II
(C) III (D) IV NO2 NO2
Sol.

Cl
Cl
O2N NO2
36. Identify (C) in the reaction(s)
(C) (D)
CH3 NO2
NO2
NaNO2 / HCl H2O,
(A)
0C Sol.

NH2

(i)CHCl ,KOH, Cl
(B) 3 (C)
(ii)dil.HCl

HNO3 CH3ONa
38. (A) (B) Major,,

CH3 CH3
CHO Cl
Product (B) is
(A) (B)
CHO Cl Cl
OH OH

(A) (B)
CH3 NO2 OCH3
OCH3 Cl
(C) (D) None of these OCH3 Cl
H3
CHO OC
Cl
(C) (D)
NO2 NO2
Sol.
Cl Cl

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AROMATIC COMPOUNDS Page # 107

Sol.
41. Which chloroderivative of benzene among the
following would undergo-hydrolysis most
readily with aq. NaOH to furnish the corre-
sponding hydroxy derivative.

NO2
39. The major product formed in the reaction is :
(A) O2N Cl

NO2
conc.H2SO4
+ HNO3

(B) O 2N Cl

NO2

(A) (B)
NO2 (C) Me2N Cl

NO2
(D) Cl

(C) (D)
Sol.
NO2

Sol.

42. Chloral + Cl conc.H2SO4


prod-

40. CrO2Cl2
C6H5CH3 H2O
A B
uct. The produt is :

The functional group present in B and name of (A) Lindane (B) DDT
the reaction would be (C) Caprolactum (D) Nylon-6

(A) CHO, Gattermann aldehyde synthesis Sol.


(B) CHO, Etard reaction
(C) COCH3, Fridel Crafts reaction
(D) CHO, Oxo reaction
Sol.
43. AlCl3
C6H6 + A C6H5CONH2

A in the above reaction is :


(A) NH2CONH2 (B) ClCONH2
(C) CH3CONH2 (D) CH2(Cl)CONH2

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Page # 108 AROMATIC COMPOUNDSE

Sol. Sol.

47. The mixture of the following four aromatic com-


pounds on oxidation by strong oxidising agent
CH3COCl Zn Hg
44. C6H6 AlCl
A B gives :
3 HCl

The end product in the above sequence is : CH3 C2H5


(A) Toluene (B) Ethyl benzene
(C) Both the above (D) None
Sol.

CH2OH CHO

and

45. AlCl3
+ CH3CH2CH2CH2Cl (A) Mixture of C6H5CH2OH+C6H5COOH

(B) Mixture of C6H5CHO + C6H5COOH
hydrocarbon (X) major product X is (C) C6H5COOH
(D) None of the above
Sol.
(A) CH2CHCH3

CH3

CH3

(B) CCH3
48. Methyl group attached to benzene can be
CH3 oxidised to carboxyl group by reacting with :
(A) Fe2O3 (B) AgNO3
(C) KMnO4 (D) CrO3

(C) CH2CH2CH2CH3 Sol.

(D) None of correct


Sol.

CH=CH2

Br2
46. Reaction of SO3 is easier in : 49. A
CCl
KMnO4 /
B
4

(A) Benzene (B) Toluene


(C) Nitrobenzene (D) chlorobenzene
Compound A and B respectively are :

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AROMATIC COMPOUNDS Page # 109

(A) o-Bromostyrene, benzoic acid


(B) p-Bromostyrene, benzaldehyde
(C) m-Bromostyrene, benzaldehyde (C) (D)
(D) Styrene dibromide, benzoic acid
Sol. Sol.

50. The number of benzylic hydrogen atoms in 53. Which of the following is/are produced when a
ethylbenzene is : mixture of benzene vapour and oxygen is
(A) 3 (B) 5 passed over V2O5 catalyst at 775 K ?
(C) 2 (D) 7 (A) Oxalic acid (B) Glyoxal
Sol. (C) Fumaric acid (D) Maleic anhydride
Sol.

51. The highest yield of m-product is possible by


the el ec trop hi l i c subs ti tuti on of the 54. Which of the following is the least reactive in
following : the case of bromination ?
(A) C6H5CH3 (A) Phenol (B) Aniline
(B) C6H5CH2COOC2H5 (C) Nitrobenzene (D) Anisole
(C) C6H5CH(COOC2H5)2 Sol.
(D) C6H5C(COOC2H5)3
Sol.

F
55. Above compound undergoes
NO2

(A) SN1
(B) SN2
Ni,High temp.
52. + H2 (A). Which of
high pressure (C) Elimination
(D) Nucleophilic aromatic substitution
the following can be isolated as the product Sol.
of this reaction.

(A) (B)

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Page # 110 AROMATIC COMPOUNDSE

56. Benze ne on re ac ti on w i t h A form s


O

which on reaction with (C) (D)

Sol.
B forms A and B are:

(A) Zn (Hg) + conc. HCl, Cl


59. Which of the following is most reactive to-
O
wards sulphonation ?
(B) , LiAlH4
Cl (A) m-Xylene (B) o-Xylene

O (C) Toluene (D) p-Xylene


(C) , NaBH4 Sol.
Cl
O
(D) , Zn(Hg) + conc.HCl
Cl
60. When sulphonilic acid (p-H2NC6H4 SO3H) is
treated with excess of bromine water the prod-
+ AlCl3
uct is:
Sol.
(A) tribromo product
(B) dibromo product
(C) monobromo product
(D) tetrabromo product
Sol.

57. In a reaction of C6H5Y, the major product


(>60%) is m-isomer, so the group Y is :
(A) COOH (B) Cl
(C) OH (D) NH2
61. Ring nitration of dimethyl benzene results in
Sol. the formation of only one nitro dimethyl ben-
zene. The dimethyl benzene is :
CH3

CH3
(A) (B)
58. Which of the following will undergo sulphonation CH3
CH3
at fastest rate ?
CH3

(C) (D) None of these


(A) (B)

CH3

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AROMATIC COMPOUNDS Page # 111

Sol. 64. Identify the correct order of reactivity in elec-


trophilic substitution reactions of the follow-
ing compunds:
C2H5

(I) (II)

62. if p-methoxy toluene is nitrated, the major Cl NO2


product is : Cl NO2
CH3 CH3 (III) (IV)

NO2 (A) I > II > III > IV (B) IV > III > II > I
(A) (B) NO2 (C) II > I > III > IV (D) II > III > I > IV
Sol.
OCH3 OCH3
CH3NO2

(C) (D) No reaction

OCH3
CARBENE
Sol.
65. The orbital picture of a singlet carbene (:CH2)
can be drawn as

p
H
(A)
C

H sp2
63. For the electrophilic substitution reaction in-
volving nitration, which of the following se- p
quence regarding the rate of reaction is true ? H
(B)
(A) KC6H6 KC6D6 KC6T6 C

H sp2
(B) KC6H6 KC6D6 KC6T6

py
(C) KC6H6 KC6D6 KC6T6
pz
(D) K C6H6 KC6D6 K C6T6
(C)
C H
Sol.

H
(D) none of these
Sol.

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Page # 112 AROMATIC COMPOUNDSE

66. The orbital picture of a triplet carbene can be philic substitution on highly reactive phenox-
drawn as ide ring The electrophilic reagent is dichloro
carbene :CCl2.

p O
H

(A) C + :CCl2
2
H sp

O O OH
O
CHO CHO
CHCl 2
H OH H
+

CCl2
py
p pz o-product is major product because :
H
H
(i) There are two o-positions available as com-
(B) C (C) C pared to one para.
H sp2 (ii) o-product is more stable due to the forma-
H
tion ofsix membered chelate formation.

(D) none of these Na


O O
Sol.
CH

If 1 amines (aliphatic and aromatic) react with


Question No. 67 to 69 (3 questions) DCC in basic medium it yield isocyanide or
It is believed that chloroform and hydroxide carbyl amine. The reaction is known as
ion react to produce an electron deficient in- carbylamine reaction.
termediate dichlorocarbene : CCl2 (DCC)
H H
| Cl
Cl Cl |
RN:+CCl2 RN CCl2 R N C Cl
: CCl
OH + H CCl Fast
H 2O + | |
H H
H H
Cl Cl
Slow
: CCl2 + Cl R N = C Cl + Cl

Treatment of phenol with DCC in basic medium H H


introduces an aldehyde group, onto the aro-
matic ring. This reaction is known as Reimer
Tiemann reaction.

OH OH OH
H2O OH

CHO
(i)OH
+
+
(ii):CCl2,(iii)H

Phenol R N = C Cl OH
CHO
H
The Reimer-Tiemann reaction involves electro-

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AROMATIC COMPOUNDS Page # 113

69. If CCl4 is used in place of CHCl3 during Reimer


+
Tiemann reaction, the product formed is:
The product is known as isocyanide & it is a
foul smelling substance. OH OH
67. Step marked by * is : Cl CHO
(A) Aromatization reaction (A) (B)
(B) intramolecular acid base reaction
(C) both of the above
(D) none of the above OH OH
Sol. CCl3 COOH
(C) (D)

Sol.

OH

68. If is used instead of during

Reimer Tiemann reaction the product formed


is : 70. CHF 2 Br OH

(A) [Inte rme d i ate ]
Trans 2 butene
(B)
Cl Cl
in this reaction B is :
CHO
(A) (B) Br Br F
F
CH3 CH3 CH3 H

(A) (B)
OH

H H H CH3
(C) (D)
F F F F
H CH3 CH3 CH3
CHO
Sol.
(C) (D)

CH3 H H H

Sol.

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Page # 114 AROMATIC COMPOUNDSE

O Sol.
Ag2O
71. Ph C CHN 2 (A); product (A)
14 HO2

is:
(A) Ph 14CH2 CO2H
(B) Ph CH2 14CO2H
(C) Ph 14CO2H
(D) Ph CO2H I
Sol. Ph
Ph EtOK HBr
74. PhCHCl A B

EtOK
C
correct presentation of C is :

Ph I Ph OEt

72. Which of the following wil not give carbylamine


(A) (B)
reaction
(A) t-butly amine Ph Ph Ph Ph
(B) aniline Ph Ph Cl
(C) sec. butylamine
(D) N-methyl methanamine
(C) Br (D)
Sol.
Ph Ph Ph Ph

Sol.

OH
F
(i) CHCl3 / KOH 75. + CH Cl
MeOK
?
73. (A) Product (A) will
(ii) H Br
F
CH3
be (A)

OH OH F
(B)
Cl
(A) (B)
CHO Cl

CH3 CHO (C)


Br
OH OH Br
CHO
(D)
(C) (D)
Sol.
CH3 CH3

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AROMATIC COMPOUNDS Page # 115

76. Intermediate produced during reimer tiemanns


formlylation will be Cl Cl

(A) :CCl2 (B) :CH2 (A) (B)


..
(C) CCl3 (D) CHCl3

Sol. Cl

(C) (D)
Cl

Sol.

77. Which of the following compound doesnt gives


Hoffmanns carbyl amine test ?

(A) .. (B) ..
NH NH2

NH2
NH2
(C) (D)
NITRENE
Comprehension (Q.80 to Q.82) (3 Questions)
Sol.
Hoffmann Rearrangment:
It involves conversion of a carboxylic acid amide
into an amine with a loss of a carbon atom on
treatment with aqueous sodium hypobromite.
THus Hoffmann result in shortening of a car-
bon chain.

O
78. CH3 NH2 + CHCl3 + KOH major product Br
2
will be : R C NH2 NaOH
R NH + NaBr +
2

(A) CH3 C N (B) CH3 NH CH3 Na2CO3


(C) CH3 N+ C (D) NH3 Mechanism of the reaction is
Sol. O
NaOH

R C NH2
O

R C = NH + Br Br
79. What is the product of the following reaction
?

MeOK in chloroform
?

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Page # 116 AROMATIC COMPOUNDSE

Product (A) is :
O

R C NH Br
NH2 NH2
OH (A) (B)
H H H H
O
H2O
Na2CO3 + RNH2 O=C=NR R C N Br

NH2 NH2
O (C) (D)
HH H H
C NH2 Br
2
80. (A) (Major)
KOH Sol.

Product (A)
(A) PhNH2 (B) PhCH2NH2
(C) PhNHCH3 (D) Ph N (CH3)2
Sol.
Beckmann Rearrangment:
The gi ven i s mechani sm of Beckmann
rearrangment.

R + R
H
C=N C=N
(I)
81. Which of the following will not given Hoffmann R' OH R' OH
bromamide rection ? H

O (II) H2O
O
(A) CH C NH (B) C NH Br R'C = N R
3 2

(III) H2O

O O
O OH
(C) C NH2 (D) C NH CH3 (IV)
R'C NH R R'C = N R

Sol.
83. Reagent cannot be used in Beckmann rear-
rangement is
(A) H2SO4 (B) BF3
(C) SO3 (D) OH

O Sol.

C NH2 Br KOH
2
82. A (Ma-

H H

jor)

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AROMATIC COMPOUNDS Page # 117

84. Rate determining step in the Beckmann rear-


O
rangement is
(A) I (B) II C NH 2
(C) III (D) IV 86. KOBr
(A)
Sol.
(A) Ph CH2 NH2 (B) Ph NH2
(C) Ph CO2H (D) Ph NH CH3
Sol.

85.

C CH3 H
2SO 4
(X) . Prod-

N OH
uct (X) is 87.

(A) NH Br2
C NH CH3 (A) Product (A) will
KOH

O be

(B) CO2 CO2


NH C CH3
(A) (B)
NH 2 CO2
NH2 NH 2
O (C)

(C) NH 2
NH 2C H (D)

Sol.

O
(D)
C NH 2

Sol.

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Page # 118 AROMATIC COMPOUNDSE

88. Give the major organic product of the follow- 90. Which of the following reaction represent in-
ing reaction : correct major product.
(A)
O O

KOBr
CH3 NH2
CH 3 C NH CH 3
CF
3CO
3H
Major
OH
O
O ( i ) O 2 / hv
O (B)
+
( ii ) H 3 O
O
O
(A) (B)
Cumene
O
O
O O
O H 2SO4
(C) (D) (C) NH
2OH
(A) (B)
caprolactum

Sol.
O O

(D CH3O C
CH3CO3H
O C
CH3O

Sol.

O
89. CH
2N2

CH 3 C CH 3
(X) CF
3CO
3H
Major Product (Y) is
O

(A) CH 3 C O CH 3

(B) CH 3 C O CH 2 CH 3
O

(C) CH
3 CH 2 C O CH 3
(D) CH3 CH2 CH2 O CH3
Sol.

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AROMATIC COMPOUNDS Page # 119

Exercise - II (One or more than one option correct)


3. Which of the following carbocations is expected
1. An aromatic compound of molecular formula to be most stable ?
C6H4Br2 was nitrated which gives three iso-
NO2 NO2
mers of formula C6H3Br2NO2 were obtained. The
original compound is : +
(A) o-dibromobenzene (A) (B)
+
(B) m-dibromobenzene
H Y H Y
(C) p-dibromobenzene
NO2 NO2
(D) both A and C
+ H
Sol. Y
(C) (D)
H
+ Y
Sol.

N
4. Which of the following species expected to
2. + Ph N2+Cl (A) major product A have maximum enthalpy in an electrophilic aro-
matic substitution reaction ?
will be
H E

N
N (I) + E+ (II)

N = N Ph
H E H E
(A) (B)

(III) (IV)
N = N Ph
N N
E

(C) (D) (V)

Ph Cl
(A) Species (II) (B) Species (III)
Sol.
(C) Species (IV) (D) Species (V)
Sol.

5. Which of the following structures correspond


to the product expected, when excess of C6H6
reacts with CH2Cl2 in presence of anhydrous
AlCl3 ?

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Page # 120 AROMATIC COMPOUNDSE

Cl 7. Which of most reactive towards nucleophilic


aromatic substitution.
(A) CH
F F

(B) CHCl2
(A) (B)

Cl
CH3 NO2
C
(C) Cl I
Cl

CH2 (C) (D)


(D)

Sol. NO2 NO2

Sol.

6. Conjugation of electron withdrawing groups,


O O
e.g., CHO, C R , C OR , C N,
NO 2 act i v at es nuc l e op hi l i c at tack i n
8. Statement-1 : Nitro benzene reacts with
halobenzene. The order of reactivity of these
group towards nucleophilic aromatic substitu- O
tion.
Me C Cl , Al Cl 3 to p rod uc e
O m-nitroacetophenone.
O O
(A) NO2 > C N > CH > C R > C OR Statement-2 : NO2 group attached to the ring
is a meta directing during SE.
O O O (A) Statement-1 is true, statement-2 is true
and statement-2 is correct explanation for
(B) CH > C R > C OR > C N > NO2
statement-1
O O O (B) Statement-1 is true, statement-2 is true
and s tate me nt -2 i s NOT correc t
(C) C N > NO2 > CH > C R > C OR
explanation for statement-1

O (C) Statement-1 is true, statement-2 is false


O O
(D) CH > NO2 > C N > C OR > C R (D) Statement-1 is false, statement-2 is true
Sol.
Sol.

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AROMATIC COMPOUNDS Page # 121

9. Statement-1 : Rate of nitration is C6H6 ~ C6D6 Sol.


~ C T
6 6

Statement-2 : Formation of wheland inter-


mediate is rate determining step in nitration of
benzene, not the breaking of CH or CD bond.
(A) Statement-1 is true, statement-2 is true
and statement-2 is correct explanation for
statement-1
(B) Statement-1 is true, statement-2 is true
and s tate me nt -2 i s NOT correc t
explanation for statement-1
(C) Statement-1 is true, statement-2 is false
(D) Statement-1 is false, statement-2 is true 12. Which aromatic compound is obtained when n
- octane undergoes catalytic hydroforming
Sol. (Aromatization ) on heating with Al2O3 + Cr2O3.
(A) ethyl benzene (B) m-Xylene
(C) o-Xylene
(D) p-Xylene
Sol.
10. 2 Na
(A) Product (A) is

+
(A) (B)
+
+
(C) (D) 13. Benzoic acid may be prepared by the oxida-
tion of:
Sol. CH 2CH 3 CH2OH

(A) (B)

COCH3 OH
CH2CH3 CH3

2Na (C) (D)


11. (A) Product

(A) is
Sol.

(A) (B) 2

(C) +2 (D) All

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Page # 122 AROMATIC COMPOUNDSE

14. Isopropylbenzene can be prepared by : Sol.


(A) Benzene + CH3CH = CH2 H 2SO 4

(B) Benzene + CH3 CH CH3 AlCl


3

Cl
Cl
(C) Benzene + AlCl3

OH

(D) Benzene + H

Sol. 17. Which of the following reactions of bezene


proves the presence of three carbon - carbon
double bonds in it:
(A) Formation of a triozonide
(B) Hydrogenation of bezene to cyclohexane
(C) Formation of C6H6Cl6 by addition of chlo-
rine
(D) Formation of nitrobenzene on heating ben-
zene with a mixture of concentrated
nitirc acid and sulphuric acid
15. In w hi ch of the fol l ow i ng re ac ti on t - Sol.
butylbenzene is formed:
(A) Benzene + iso-butyl chloride,AlCl3
(B) Benzene + (CH3)2C = CH2 BF
3 .
HF

(C) Benzene + t-butyl alcohol H
2SO 4


(D) Benzene + (CH3)2C = CH2 H

Sol.

18. Electrophile NO2 attacks the following in


which cases NO2 will be at meta position:
CCl3 NO2
Cl
* NaOH H O
2
16. Product is:
395C
(A) (B)

* OH *
(A) (B) +
OH NMe3 O

Cl HO Cl
(C) (D)
(C) (D)
HO

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AROMATIC COMPOUNDS Page # 123

Sol. Sol.

19. The reaction of replacement of a hydrogen


atom in benzene by alkyl group can be brought
about with the following reagents:
(A) Alkyl chloride and AlCl3
(B) Alkene and BF3,HF 22. Which of the following can be used in Friedel
(C) Alkanol and alkali Crafts reaction when benzene used with AlCl3
(D) Alkanol and acid Cl
Sol.

(A) (B) CH2 = CH Cl

(C) CH3CH2Cl (D) CH2= CHCH2Cl


Sol.

20. Which of the following statements is correct:


(A) Bromination of toluene occurs faster than
that of benzene
(B) Nitration of toluene is faster than that of
ethylbenzene
(C) The bromonium ion is a good nucleophile
(D) Effective nitrating agent is nitrate ion
Sol.
23. The good method for converting benzene into
n-propyl benzene is:
(A) C6H6 + CH3CH2CH3Cl + Anhyd.AlCl3
(B) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and then
treatment with Zn/Hg/HCl
(C) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and then
treatment with H2Ni
21. Which of the following gives Friedel Crafts re-
action? Cl
NH 2
(D) C6H6 + , AlCl3

(A) (B) Sol.

+
NO2 NMe3

(C) (D)

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Page # 124 AROMATIC COMPOUNDSE

24. Which of the following will undergo nitration


slower than benzene ?

NH2

(A)

(B)

Cl NHCOCH3
26. The structure of the compound that gives a
tribromo derivative on treatment with bromine
(C) (D) water is:

CH3
Sol. CH 3

(A) (B)

OH
OH

SO3H
COOH

OH
(C) (D)

OH
25. Which of the following is ortho-para directing
group
Sol.
(A) CF3 (B) CCl3

(C) CH = CH COOH(D) N C
Sol.

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AROMATIC COMPOUNDS Page # 125

27. Amongst the following the moderately acti- (A) PhSR (B) Ph S R
vating group is-
(A) NHR (B) NHCOCH3
(C) NR2 (D) CH3
Sol.
(C) Ph S R (D) Ph S OR

Sol.

28. Which of the following is ortho para directing


30. Which of the following group(s) activate the
benzene ring towards electrophilic substitu-
tion reaction.
C NH CH 3 NH C CH3

(A) (B)
(A) Cl (B) N

O
(C) (D) C N
O C CH3
C
Sol.
OCH3 CH3
(C) (D)

Sol.

31. Choose the best method to prepare given com-


pound :

H3C
H3C NO2
H3C

O (1)HNO3 H2SO4
(A)
(2)Me3CCl / AlCl3
29. Of the species PhSH,Ph S R, phSR andPh S

O
(1)Me3CCl / AlCl3
OR the meta- substituted product is obtained (B)
(2)HNO3 H2SO4
from

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Page # 126 AROMATIC COMPOUNDSE

33. The cumulative effect of their fluorine acti-


CH3
| vate the rings of penta and hexa fluorobenzene
(1)CH C H CH Cl / AlCl
(C) 3
2
3
toward nucleophilic aromatic substituiton. What
(2)HNO3 H2SO 4
i s comp ound X i n the fol l ow i ng
synthesis ?
(1)HNO H SO
CH3
2 4


(D) 3
|
(2)CH3 C H CH2Cl / AlCl 3
F

F F
Sol.
HOCH CH OH K2CO3
2
(A)
2 (X) (C8H4F4O2)
F F NaOH,

32. W hi ch is the be st s ynthes i s of F O CH = CH2


(A)

CH3O NO2 ? F OH

F
NO2
F

F OCH2CHO
Br2 HNO3 HNO
3
(A)
FeBr3 H2SO4 H2SO4 (B)
F H
NaOCH
3

CH3OH F

F
HNO
3 HNO
3 Br2
(B) F O
H2SO4 H2SO4 FeBr3

(C)
NaOCH
3
F O
CH3OH
F

HNO
3 Br2 3 HNO F
(C)
H2SO4 FeBr3 H2SO4
F O
NaOCH
3
(D) CH3

CH3OH F O

F
HNO3 Br2 NaOCH3
(D) Sol.
H2SO4 FeBr3 CH3OH

3HNO

H2SO4

Sol.

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AROMATIC COMPOUNDS Page # 127

EXERCISE III SUBJECTIVE PROBLEMS (JEE ADVANCED)


Sol.
1. What prod uc t i s forme d when 2-
methylpropene is added to a large excess of
benzene containing HF and the Lewis acid BF3?
By what mechanism is it formed?
Sol.

4. Show two different Friedel-Crafts acylation


reactions that can be used to prepare the
following compound.

CH3

C CH 3
2. Predict the product of the following reaction
and give the curved-arrow mechanism for its
formation. (Hint: Friedel-Crafts alkylations can
be used to form rings.) CH3

Sol.
H3C CH2CH2CH2 Cl AlCl3


(a compound C10H12+HCl)
Sol.

5. The following compound reacts with AlCl3 fol-


lowed by water to give a ketone A with the
formula C10H10O. Give the structure of A and a
curved -arrow mechanism for its formation

3. Give the structure of the product expected


from the reaction of each of the following com-
pounds with benzene in the presence of one
equivalent of AlCl3, followed by treatment with H3C CH2CH 2 C Cl
water.

Sol.
(A) (CH3)2CH C Cl

(B) C Cl

lsobutyryl chloride
benzoyl chloride

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Page # 128 AROMATIC COMPOUNDSE

6. Predict the product(s) of Sol.


(A) Fri ede l -Crafts acyl ati on of ani sol e
(methoxybenzene) with acetyl chloride in the
presence of one equivalent of AlCl3 follwed by
H2O.
(B) Friedel-Crafts alkylation of a large excess
of ethylbenzene with chloromethane in the
presence of AlCl3.
Sol.

9. Explain why the nitration of anisole is much


faster than the nitration of thioanisole under
7. Biphenyl (phenylbenzene) undergoes the
the same conditions.
Friedel-Crafts acylation reaction, as shown by
the follwoing example. ..
OCH3
..
1)AlCl3
+ Cl C CH3 C CH3 + HCl
2)H 2O

..
biphenyl SCH
.. 3

p-phenylacetophenone anisole thioanisole


On the basis of this result, what is the direct-
ing effect of the phenyl group ? Sol.

Sol.

8. Predict the predominant products that would


result from bromination of each of the follow-
ing compounds. Classify each substituent group 10. Which should be faster bromination of ben-
as an ortho, para director or a meta director. zene or bromination of N,N - dimethylaniline?
and explain your reasoning Explain your answer carefully.

.. ..
(A) NH C CH 3 N (CH3)2

CF3 N,N - dimethylaniline


(B)
Sol.

+
(C) N(CH3)3

(D) C(CH3)3

..
(E) O
..

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AROMATIC COMPOUNDS Page # 129

11. Outline a synthesis of m-nitroacetophenone


from benzene: explain your reasoning.
14. When the following compound is treated with
H2SO4 the product of the resulting reaction
has the formula C15H20 and does decolorize Br2
C CH3 in CCl4. Suggest a structure for this product
and give a curved - arrow mechanism for its
formation.

NO2 OH
CH3
Sol.
H 2SO4
?

Sol.

12. Give the products expected(if any) when


ethylbenzene reacts under the following con-
ditions.
(A) Br2 in CCl4 (dark)
(B) HNO3 ,H2SO4
(C) conc. H2SO4

(D) C2H5 C Cl,AlCl3(1.1 equiv.) then H2O


15. Write the principal organic product in each of
(E) CH3Br,AlCl3 the following reactions:
(F) Br2,FeBr3 Cl
Sol.
NO2

(i) + C6H5 CH2SK A

CH3
Cl
13. Give the products expected (if any) when ni-
trobenzene reacts under the following condi- NO2
tions.
(A) Cl2,FeCl3, heat
(B) fuming HNO3,H2SO4 (ii) H
2 NNH 2
B
triethylene
glycol

NO2
(C) H3C C Cl,AlCl3(1.1 equiv.) then H2O CF3
Sol.

(iii) ( i ) HNO 3 , H 2SO 4


C
(ii ) NaOCH3 , CH3OH

Cl

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Page # 130 AROMATIC COMPOUNDSE

16. Complete the following reactions?


Cl NH 2 (A) b enze ne (l arg e ex ce ss )

+ClCH2 CH 2Cl AlCl


3
(iv) (
i ) NaNO 2 , HBr
D
(ii ) CuBr

O CH2CH 2CH Cl
(v) Br OCH3
(B) AlCl
3
CH3 CH3
(a compound with ten carbons)
(i) NBS,Benzoylperoxide,CCl4 .heat
E
(ii) NaSCH 3

Cl
Cl C C C Cl
(C) +
NO2
H3C CH3

(vi) + CH3CH2ONa F 1
) AlCl3
(three products, all
2) H 2O

naphthalene
NO2 -dimethylmalonyl

dichloride
Cl
isomers with formula C15H12O2)

NO2 H
2SO 4

(D) + HNO3 0 C
(vii) + C6H5CH2SNa G

NO2

Sol. 1
) AlCl3

(E) ferrocene + H 3 C C Cl 2) H 2O
(C12H12OFe)

(F) CH 3O SO3H HNO3 Br2,Fe

Sol.

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AROMATIC COMPOUNDS Page # 131

Sol.
OH

Br2
17. Product A and B is
H O 2

Br2
B
CS2 20. Column I
(A) CO2 is evolved from
Sol. (B) Libbermann nitroso test is given by
(C) Compounds gives yellow oily

(D) When reacts with CHCl



3

HO
Column II
OH

(P)

l3 A
/ AlC
Cl 2 NaHCO3 by the reaction of
CO2H
18. Cl
2 /
hv
B
(Q)
Product A and B is
Sol.
(R) R NH R
liquid on reaction with NaNO2 + HCl

S
(S) Ph OH
Match the following
19. Substituent on phenyl ring. salicy ladehyde will form
(A) CH2 CH3
(P) o/p - directors Sol.

(B) O S CH3 (Q) meta directors

(C) NH C CH3 (R) Activating group


(D) S CH3 (S) Deactivating group

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Page # 132 AROMATIC COMPOUNDSE

21. Compounds
(R) Electropile would
Substituent on phenyl attack on ortho or para
(C) position
N

(A) (P) Activating group


S Et

(D) (S) Rate of electrophilic


substitution is less than
that of bnzene
Sol.

(B) (Q) Deactivating group


23. Match th column :

X OCH3
O CH = CH 2

(C) (R) o/p director CH


3ONa


NO2 NO2
S Et
X = halogen
relative reactivity toward (SNAr)
(D) (S) meta- director (A) F (P) 312
(B) Cl (Q) 1
(C) Br (R) 0.8
Sol. (D) I (S) 1
Sol.

22. Column I Column II


(A) Cl (P) Group attached to
benzene ring is a + M
group here

24. Matrix : Reaction


Product
CH3
F

(B) (Q) Group attached to CHCl3


benzene ring is a M (A)
KOH,
group here

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AROMATIC COMPOUNDS Page # 133

Cl Ph OH
(S) C=N PCl
5
CH 3
(B) CHFCIBr
carbon increases
KOH ,
Sol.

Br

(C) CHCI
2 Br

KOH ,

26. Column-I Column-II (Reagent used)


OH OH
CHBr2 CI
(D)
CHO
KOH ,

(A)
Sol.

+
NH 2 NC

(B)

25. Column-I
NH 2
(A) Caprolactum formation take place in (C) PhNH2
(B) Beckmann rearrangement is
(C) Schmidt reaction is
(D) Reaction in which number of
Column-II
N OH

(D) Ph C Ph Ph C NH Ph
(P) HN
3
H 2SO 4
Column-II
(P) CHCl3 / KOH
(Q) Br2 / KOH
N OH
(R) H2SO4
(S) PCl5
H Sol.
(Q)

OH

(R) (
i ) CHCl3 / HO


( ii ) H

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Page # 134 AROMATIC COMPOUNDSE

27. Matrix Column-II


Column-I (P) Ph CHO is product
(Q) Etard reaction
(R) Stephon reduction
(A) HNO
3 (S) Gattermann Koch reaction
H 2SO 4 (T) Ph CO2H

Sol.

Cl
(B)
AlCl 3

OH
Comprehension - 3 (29 to 31)
It is not always easy to predict the position of
Br2
(C) attack on multiply substituted benzene. If the
H2O
benzene ring bears different group ortho/ para
directing group at the 1 and 4 positions, the
position of further substitution is not immedi-
ately clear.
Br2 29. Which of the following synthesis could be done
(D)
Fe in the single step ?

OH OH
Column - ll
(P) Carbocation is intermediate
(Q) Carabanion is intermediate
(R) Electrophilic substitution reaction
(S) Rearrangement takes place (A)
Sol.
CH3 Br

OH OH

28. Column-I Br Br

(B)
(A) + CO + HCl AlCl
3
CH3 Br
SnCl2 / HCl
(B) Ph C = N H
O

2

CH3 OH OH
CrO2 Cl2
(C)
Br
H2O

(C)

(D) Ph C N H
3O

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AROMATIC COMPOUNDS Page # 135

NH2 NH2 OH
OH Br Br

Br2
(D) (D)
CS2 , 0C

CH3 Br Br

Sol. Sol.

30. Which of following is the incorrect major prod-


uct ?

OCH3 OCH3 CH3


31. Which of the following side chain reaction/s
can be used to reduce the activity of strongly
activating groups like OH
CH 3
( CH 3 ) 2 CHBr
(A)

AlCl 3 ,15 25 C

(A) benzoylation
CH3 CH3 Ph C

(B)

CH3 CH3
(B) acetylation CH3 C

CH3 (C) both of the above


(D) none of the above
CH 3 C Cl Sol.
AlCl3,CS 25C
H3C CH3 H3C CH3

(C)

NH2 NH2

Br Br

OH Br
2
H 2O

40 , 50 C

Br OH

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Page # 136 AROMATIC COMPOUNDSE

EXERCISE IV PREVIOUS YEARS PROBLEMS

LEVEL I JEE MAIN


Q.4 The electrophile, E attacks the benzene ring
Q.1 Fluorobenzene (C6H5F) can be synthesized in
to generate the intermediate -complex. Of
the laboratory - [AIEEE 2006]
the following, which -complex is of lowest
(A) from aniline by diazotisation followed by
heating the diazonium salt with HBF4 energy ?
(B) by direct fluorination of benzene with F2 gas [AIEEE 2008]
(C) by reacting bromobenzene with NaF solution NO
H H
(D) by heating phenol with HF and KF
(A) + E (B) E
+
Sol.

NO
NO

+
(C) + H (D)
E H E
Q.2 Phenyl magnesium bromide reacts with metha-
nol to give - [AIEEE 2006] Sol.
(A) a mixture of benzene and Mg(OMe) Br
(B) a mixture of toluene and Mg(OH)Br
(C) a mixture of phenol and Mg(Me)Br
(D) a mixture of anisole and Mg(OH) Br
Sol.

Q.5 Toluene is nitrated and the resulting product


is reduced with tin and hydrochloric acid. The
product so obtained is diazotised and then
heated with cuprous bromide. The reaction
mixture so formed contains - [AIEEE 2008]
(A) mixture of o and p-dibromobenzenes
(B) mixture of o- and p-bromoanilines
(C) mixture of o- and m-bromotoluenes
Q.3 The reaction of toluene with Cl2 in presence
(D) mixture of o- and p-bromotoluenes
of FeCl3 gives predominantly - [AIEEE 2007]
Sol.
(A) benzoyl chloride
(B) benzyl chloride
(C) o-and p-chlorotoluene
(D) m-chlorotoluene
Sol.

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AROMATIC COMPOUNDS Page # 137

Q.6 pcresol reacts with chloroform in alkaline


medium to give the compound A which adds CH3
CH3
hydrogen cyanide to form, the compound. B
The latter on acidic hydrolysis gives chiral (C) (D)
carboxylic acid. The structure of the carboxylic
OH
acid is - [AIEEE-2005] OH

CH3 CH3 Sol.


CH(OH)COOH

(A) CH(OH)COOH (B)


OH OH

CH3 CH3
Q.9 Phenol, when it first reacts with concentrated
CH2COOH CH2COOH
sulphuric acid and then with concentrated nitric
(C) (D) acid, gives - [AIEEE 2008]
OH OH (A) o-nitrophenol
(B) p-nitrophenol
Sol. (C) nitrobenzene
(D) 2, 4, 6-trinitrobenzene
Sol.

OH ONa+
Q.7 + CHCl3 + NaOH .
CHO
The electrophile involved in the above
reaction is : [AIEEE 2006]
(A) dichlorocarbene (:CCl2) Q.10 The major product obtained on interaction of
phenol with sodium hydroxide and carbon
(B) trichloromethyl anion ( C Cl3 ) dioxide is - [AIEEE 2009]
(A) salicylaldehyde (B) salicyclic acid
(C) formyl cation ( C HO ) (C) phthalic acid (D) benzoic acid

(D) dichloromethyl cation ( C HCl 2 ) Sol.

Sol.

Q.11 Which one of the following undergoes reaction


with 50% sodium hydroxide solution to give
the corresponding alcohol and acid ?
Q.8 The structure of the compound that gives a [AIEEE-2004]
(A) Phenol (B) Benzaldehyde
tribromo derivative on treatment with bromine
(C) Butanal (D) Benzoic acid
water is - [AIEEE 2006]
Sol.
CH3
CH2OH OH
(A) (B)

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Page # 138 AROMATIC COMPOUNDSE

Q.12 Picric acid is [AIEEE-2002] Sol.


COOH COOH

(A) (B)
NO2 OH

OH
NO2 NO2 COOH

(C) (D)
NO2 NH2

Sol. Q.15 In the chemical reactions.


[AIEEE-2010]

The compounds A and B respectively are


(A) nitrobenzene and chlorobenzene
(B) nitrobenzene and flurobenzene
(C) phenol and benzene
(D) benzene diazonium chloride and flurobenzene
Sol.

Q.13 Consider the acidity of the carboxylic acids :


[AIEEE-2004]
(a) PhCOOH
(b) o NO2C6H4COOH
(c) p NO2C6H4COOH
(d) m NO2C6H4COOH
Which of the following order is correct ?
(A) a > b > c > d (B) b > d > c > a Q.16 In the chemical reactions [AIEEE-2011]
(C) b > d > a > c (D) b > c > d > a NH2
Sol.
NaNO2 CuCN B,
A
HCl,278 K

the compounds A and B respectively are :


(A) Benzene diazonium chloride and benzonitrit
(B) Nitrobenzene and chlorobenzene
(C) Phenol and bromobenzene
(D) Fluorobenzene and phenol
Sol.

Q.14 The compound formed as a result of oxidation


of ethyl benzene by KMnO4 is
[AIEEE-2007]
(A) benzophenone (B) acetophenone
(C) benzoic acid (D) benzyl alcohol

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AROMATIC COMPOUNDS Page # 139

LEVEL II JEE ADVANCED


Sol.
1. Statement -1 Phenol is more reactive than
benzene towards electrophilic substitution re-
action.
Statement -2 In the case of phenol the inter-
mediate carboation is more resonance stabi-
lized.
(A) Statement -1 is true Statement -2 is true
and Statement -2 is correct explanation for
Statement -1
(B) Statement -1 is true Statement -2 is true F NO2 (
CH3 )2 NH
A
4.
and Statement -2 is not correct explanation DMF
for Statement -1
(C) Statement -1 is true Statement -2 is false (i) NaNO 2 HCl 05 C
B [JEE 2003]
(D) Statement -1 is false Statement -2 is true (ii) H 2 Catalytic Re duction

[JEE 2000]
Sol.
(A) O2N NH 2

H3C
(B) N NH 2
H3C
2. Amongst the following the strongest base is
[JEE 2000] H2C
(A) C6H5NH2 (B) p-O2NC6H4NH2 N NO2
(C) m-O2NC6H4NH2 (D) C6H5CH2NH2
H2C
Sol. (C)

NH2

H3C
(D) N NO2
H3C
3. ldentify the correct order of reactivity in elec-
trophilic substitution reactions of the following Sol.
compunds : [JEE 2002]
CH3

(I) (II)

Cl NO2 NH
Me Me
Br2
(III) (IV) 5.
Fe

(A) I>II>III>IV (B) IV>III>II>I Major product of above reaction is:


(C) II>I>III>IV (D) II>III>I>IV [JEE 2004]

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Page # 140 AROMATIC COMPOUNDSE

Sol.
NH
Me Me
(A)

Br

NH 7. + Cl CH 2 CH 2 CH3 AlCl
3 P
Me Me
(
i) O 2 /
Q + Phenol P and Q are respectively
( ii ) H 3O
(B)
[JEE 2006]
Br

NH
(A) + CH3CH2CHO
Me Me
(C)

Br (B) + CH3COCH3

NH
Me Me

(D)
(C) + CH3COCH3

Br
Sol.

(D) + CH3CH2CHO
6. Which of the following is obtained when 4-
Methylbenzenesulphonic acid is hydrolysed with
excess of sodium acetate ? [JEE 2005]
Sol.
+
(A) CH3 COONa

(B) CH3 + SO3

Comprehension Type : (Q.8 to Q.10)


Reimer -Tiemann reaction introduces an
+
(C) CH3 SO3Na + CH3COOH aldehyde group on to the aromatic ring of
phenol, ortho to the hydroxyl group. This
reaction i nvolves el ectrophi li c aromatic
substitution. This is a general method for the
(D) CH3 SO2O.COCH3 + NaOH synthesis of substituted salicyladehydes as
depicted below. [JEE 2007]

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AROMATIC COMPOUNDS Page # 141

OH ONa ONa
ONa
CHO CCl3 CH2OH

I (II)
(I) aq
.HCl
(C) (D)

CH3 CH3 CH3 CH3


OH Sol.
CHO

(III)

CH 3
8. Which one of the following reagents is used in
the above reaction?
(A) aq NaOH + CH3Cl 11. In the following reaction
(B) aq NaOH + CH2Cl2
(C) aq NaOH + CHCl3
(D) aq NaOH + CCl4
Sol. ..
N con. HNO3
X
H con. H 2SO 4

the structure of the major product X is

9. The electrophile in this reaction is


NO2
(A) :CHCl (B) CHCl2 N
+ (A)
H
(C) :CCl2 (D) CCl3
Sol.

O2N

(B) N
H

10. The structure of the intermediate I is

N
ONa ONa (C) H
CH 2Cl CHCl 2
NO2

(A) (B)

O2N N
CH3 CH3 (D) H

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Page # 142 AROMATIC COMPOUNDSE

Sol. Sol.

12. Statement-1: p- Hydroxybenzoic acid has a


lower boiling point than o- hydroxybenzoic acid. 15. The compounds P,Q and S [JEE 2010]
[JEE 2007]
Statement-2: o-Hydroxybenzoic acid has in-
tramolecular hydrogen bonding.
COOH
(A) Statement-1 is True Statement-2 is True
Statement-2 is a correct explanation for State-
ment-1 (P)
(B) Statement-1 is True Statement-2 is True HO
Statement-2 is Not explanation for Statement-1
(C) Statement-1 is True Statement-2 is False OCH3
(D) Statement-1 is False Statement-2 is True
Sol.
(Q)
H3C

13. Statement-1: Bromobenzene upon reaction


with Br2 / Fe gives 1,4-dibromobenzene as the
major product. [JEE 2008] C
Statement-2: in bromobenzene the inductive (S)
effect of the bromo group is more dominant
than the mesomeric effect in directing the in-
coming electrophile.
(A) Statement-1 is True Statement-2 is True were separately subjected to nitration using
Statement-2 is a correct explanation for State- HNO3 / H2SO4 mixture.The major product formed
ment-1 in each case respectively is
(B) Statement-1 is True Statement-2 is True
Statement-2 is Not explanation for Statement-1
(C) Statement-1 is True Statement-2 is False
COOH OCH3
(D) Statement-1 is False Statement-2 is True
Sol.

(A) HO H3C

14. Statement-1 : Aniline on reaction with NaNO2 NO2 NO2


/HCl at 0C followed by coupling with
- naphthol gives a dark blue coloured pre-
cipitate. [JEE 2008]
Statement-2 : The colour of the compound C
formed in the reaction of aniline with NaNO2 /
HCl at 0 followed by coupling with naphthol
is due to the extended conjugation. O2N
(A) Statement-1 is True Statement-2 is True
Statement-2 is a correct explanation for State-
ment-1
(B) Statement-1 is True Statement-2 is True
Statement-2 is Not explanation for Statement-1
(C) Statement-1 is True Statement-2 is False
(D) Statement-1 is False Statement-2 is True

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AROMATIC COMPOUNDS Page # 143

16. Amongst the compounds given the one the


OCH3
would form a brilliant colored dye on treatment
COOH with NaNO2 in dil. HCl followed by addition to
an alkaline solution of - naphthol is
(B) H 3C
[JEE 2011]
HO NO2
NO2 N(CH3)2 NHCH 3

(A) (B)

C
NH 2 CH 2NH 2

NO 2 (C) (D)
H3 C
COOH
Multiple Choice Question:
OCH3
Sol.

(C) HO
H3C NO2
NO2
OH
NO2

C 17. In the reaction NaOH


( aq ) / Br2
the in-

termediate (s) is (are) [JEE 2010]


OO
O
Br
COOH

(A) (B)

(D) HO Br Br
Br
NO2 OO
OO

C (C) (D)
NO2
Br
Br
O2N Sol.
Sol.

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Page # 144 AROMATIC COMPOUNDSE

18. What would be the major product in the fol- 21. Give reasons for the following:
lowing reaction? [JEE 2000] [JEE 2000]
(i) tert-butylbenzene does not give benzoic
F acid on treatment with acidic KMnO4
(ii) Normally benzene gives electrophilic sub-
stitution reaction rather than electrophilic ad-
dition reaction although it has double bond.
Sol.
NaOCH
3

NO2

Sol. 22. How would you synthesis 4 methoxyphenol from


bromobenzene in NOT more than five steps?
State clearly the reagents used in each step
and show the structures of the intermediate
compounds in your synthetic scheme.
[JEE 2001]
Sol.

19. How would you bring about the following con-


version (in 3 steps)? [JEE 2000]
Aniline Benzylamine
Sol. 23. Write structures of the products A,B,C D and
E in the following scheme
[JEE 2002]

CH2CH2CH3

Cl
20. What would be the major product in the fol-
lowing reaction ? [JEE 2000] Cl2 / A Na
FeCl 3
Hg B
/
HCl

HNO3/H2SO4

D
CH 2 HCH 2 ONa , H 2 O C
N Br
2 /
Fe(1eq )

H2/Pd/C
Sol. E
Sol.

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AROMATIC COMPOUNDS Page # 145

24. Carry out the following conversions. Sol.


[JEE 2003]
(i) Phenol to aspirin
(ii) Benzoic acid to meta - fluorobenzoic acid
in not more than three steps.
Sol.

27. Convert

25. There is a solution of p-hydroxybenzoic acid


and p-amino benzoic acid. Discuss one method NO2 NO2
by which we can separate them and also write
down the confirmatory test of the functional
group present. [JEE 2003]
Sol.
OH
in not more than four steps. Also mention the
reaction conditions and temperature.
[JEE 2004]
Sol.

26. Which of the following is more acidic and why


? [JEE 2004]

+
NH3
+
NH3

F
(I) (II)

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AROMATIC COMPOUNDS Page # 146

Answers
Answer ExI OBJECTIVE PROBLEMS (JEE MAIN)

1. A 2. D 3. B 4. B 5.D 6. D 7. D
8. B 9. B 10. A 11. A 12. C 13. B 14. B
15. B 16. C 17. B 18. A 19. D 20. D 21. B
22. C 23. B 24. B 25. A 26. D 27. C 28. D
29. B 30. B 31. D 32. C 33. A 34. B 35. D
36. A 37. D 38. A 39. B 40. B 41. A 42. B
43. B 44. B 45. D 46. B 47. C 48. C 49. D
50. C 51. D 52. A 53. D 54. C 55. D 56. D
57. A 58. B 59. A 60. A 61. C 62. B 67. C
64. C 65. A 66. C 67. C 68. A 69. D 70. C
71. B 72. D 73. C 74. C 75. A 76. A 77. A
78. C 79. C 80. A 81. D 82. D 83. D 84. B
85. B 86. B 87. A 88. C 89. B 90. A

Answer ExII OBJECTIVE PROBLEMS (JEE ADVANCED)


1. B 2. B 3. D 4. A 5. D 6. A 7. B

8. D 9. A 10. B 11. B 12. A,C 13. A,B 14. A,B,C,D

15. A,B,C,D 16. A,B 17. A,B,C 18. A,B,C 19. A,B,D 20. A,B 21. A

22. C,D 23. B 24. C 25. C 26. B,C,D 27. B 28. B,D

29. C,D 30. B, C 31. B 32. A 33. C

Answer ExIII SUBJECTIVE PROBLEMS (JEE ADVANCED)

1. 2.

O
CH(Me)2

3. (A) (B)
Ph Ph

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Page # 147 AROMATIC COMPOUNDSE

Cl
Cl

4. (i) + AlCl
3 (ii) + AlCl
3

5.

OCH3
OCH3

6. (1) + (b)

7. o , p - directing

CF3
8. (A) (o/p) Br NH (B) (meta)
Br

C(Me)3

N+(Me)3
(C) (meta) (D)
Br(o/p)
Br

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AROMATIC COMPOUNDS Page # 148

(E)
Br(o/p)

9. Due to effecive delocalization of 2p-2p in comparison to 2p-3p, thats why anisole is more reactive
towards nitration.

Mix
10. NMe2 group is + M effecting group 11. Benzene
AlCl3 HNO3+H 2SO4

12. (a) No reaction. (b) NO2(o/p) (c) SO 3H(o/p)

(d) (o/p) (e) Me(o/p) (f) Br(o/p)

NO2 NO 2

13. (1) (B) (C) No reaction

Cl NO2

14.

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Page # 149 AROMATIC COMPOUNDSE

C6H5CH2S H2NNH CF3

NO2 NO2

15. (i) (ii) (iii) (iv)


O2N

CH3 NO2 OCH3

Cl Br

Br OCH3
(v)
CH 2SCH 3

OCH2CH 3 SCH2C6H5

NO2 NO2

(vi) (vii)

NO2 NO2

16. (a) CH2 CH 2 (b)

(c)

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AROMATIC COMPOUNDS Page # 150

OMe
+
Br NO2

+2
(d) (e) Fe (f)
NO2
(o,p)
+ SO3H

OH OH

Br Br OH

Br
17. and

Br Br

Cl

Cl
18. and

Cl

(1) (B)

19. A P , R ; B P, R ; C P , R ; D P , S
20. A Q , S ; B P , R ; C R ; D P
21. A P ,R ; B P , R ; C P , R ; D P , R
22. A P ,R ,S ; B P , R ; C Q ,S D Q, R, S

23. A P ; B Q ; C R ; D S

24. A Q;B P ;C Q;D Q

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Page # 151 AROMATIC COMPOUNDSE

25. A P,Q ; B Q , S ; C P ; D R

26. A P ; B P, ; C Q, ; D R , S

27. A P, R B P, R, S ; C Q, R ; D P , R

28. A P , S ; B P, R, ; C P ,Q ; D,, T

29. C 30. D 31. C

Exercise-IV (level-1)

1. A 2. A 3. C 4. A 5. D
6. A 7. A 8. D 9. A 10. B
11. B 12. C 13. D 14. C 15. D
16. A

Exercise-IV (level-2)

1A 2. D 3. C 4. B 5. D
6. C 7. C 8. C 9. C 10. B 11. B 12. D
13. C 14.D 15. C 16. C 17. A,C

F OCH3

18. CH
3ONa

+ NaF
heat

NO2 NO2

Nucleophilic aromatic substitution occur which is assisted by electron withdrawing NO2 group from para
position.

19. C6H5NH2 NaNO


2 C6H5N+2Cl CuCN C6H5CN LIAlH
4 C6H5 CH2NH2
HCl / C or H 2 . Ni

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AROMATIC COMPOUNDS Page # 152

N Br2

20. Fe N Br
(activated)
(deactivated)

CH3

C CH 3
21. (i) + KMnO4 No oxidation takes place
CH3

tert butyl benzene


(no. a H)

(ii) Pi - electrons of double bonds are involved in aromatic delocalisation (aromaticity). However
electrophilic addition do not ocour as it would distroy aromatic stability however electrophilic substitution do
not destroy asomaticity

OMe

Br ONa OMe

NaOH
MeSO4
22. high Pr essure
( Benzyne mech ) (SN2)
conc
. H 2SO 4
NaOH

SO3H

OMe OMe


H
3O

ONa OH
Alternative rout

Br Br Br
Br

conc
. H 2SO 4
NaOH


Me 2SO 4

SO3H ONa OMe

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Page # 153 AROMATIC COMPOUNDSE

OMe OMe

NaOH

high Pr essure H
3O

ONa OH

C
C CH2CH2CH 3
CH 2CH2CH 3 Cl 2

23. FeCl3
Cl
Cl
Cl
NO2
CH2CH2CH 2CH 3
CH2CH2CH 2CH 3

A Na
Hg
Cl HNO
3
HCl H 2SO 4
Cl
Cl
Cl
NO2 NO2

H
2 C CH CH 2 ONa
Cl H
2 / Pd / C
Cl

O CH2 CH = CH2 O CH2CH 2CH3

OH O OH

COO COOH
NaOH
24. (i) CO2
H

Kolbes reaction
OCOCH3

COOH

CH3CO 2 O

heat

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AROMATIC COMPOUNDS Page # 154

aspirin

COOH COOH COOH

(ii) HNO
3 Sn
/ HCl
NaNO
2 HCl

H 2SO 4 HBF4

NO2 NH 2
COOH

F
meta - fluorobenzoic acid

25.
+
COOH COOH HOOC NH3Cl(aq)

aq. HCl
+

OH NH2 HO COOH
(ether layer)

dissolve in diethyl ether

COOH COOH NC

aq. FeCl3 violet + CHCl3


colouration +KOH

OH NH2 COOK
foul smell

26. II is more acidic due to I effect of F.

NO2 NO2

HNO3 NH4HS
27. H2SO4
heat NO2

NO2 NO2 NO2

NaNO2 NaOH
HCl/0C H2O
NH 2heat N2Cl OH

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ALCOHOLS & ETHERS Page # 155

ALCOHOL

Introduction

O O
H
H H C H
104.5 108.9
water H
H
methyl alcohol
Physical Properties
(1) Boiling point :
(a) Alcohols show increase in boiling point with increase in molecular weight amongst homologues.
(b) Alcohols have higher boiling point than hydrocarbons of the same molecular weight. The reason
for higher boiling point is the intermolecular H-bonding present in alcohols.
HO HO HO
R R R
Intermolecular H bonds in alcohol
(2) Solubility in water :
As molecular weight increases solubility in water decreases. The lower alcohols are miscible with water.
This is due to intermolecular hydrogen bonding between alcohol and water molecules.
HO HO HO HO
H R H R
Intermolecular H bond between water & alcohol molecules
Preparation of alcohols
(1) From alkenes
(a) By acid catalyzed hydration of alkenes : Formation of carbocation intermediate (Markovnikov
addition, rearrangement possible)
conc.H SO
General reacion RCH=CH2 RCHCH3
2 4 Boiling H O
2
RCHCH3
Markonikoff 's addition
Alkene
OSO3H OH
Alcohol

H

HSO4 Boiling H2O
e.g. CH3CH=CH2 CH3CHCH3 CH 3CHCH3
OSO3H
H2SO4+CH3CHCH 3

OH

(b) By Oxymercuration - demercuration process :


(1) Oxymercuration involves an electrophilic attack on the double bond by the positively charged
mercury species. The product is a mercurinium ion, an organometallic cation containing a
three-membered ring.
(2) In the second step, water from the solvent attacks the mercurinium ion to give (after
deprotonation) an organomercurial alcohol.
(3) The third step is demercuration to remove the Hg. Sodium borohydride (NaBH4, a reducing
agent) re-places the mercuric acetate fragment with hydrogen.

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Page # 156 ALCOHOLS & ETHERS

General reaction
H H
O
H H THF
C=C + H2O + Hg RCCH + CH 3COOH
R H O C CH3 2 O
OH Hg(OCCH3)

H H H H O

RC CH + OH + NaBH4 RC CH + Hg + CH 3CO
O
OH Hg(OCCH 3) OH H

OH
Hg(OAc ) CH3CHCH3
CH3CH=CH2 CH3CHCH22
e.g. THF / H O NaBH 4
2

Prop-1-ene OH Hg(OAc) OH
Propan-2-ol
(c) By Hydroboration - oxidation process : (Forms anti-markovnikov alcohol, no rearrangement)
(i) BH .THF
General reaction RCh=CH2 ( RCH2CH2OH
ii) H O , NaOH
3

2 2

CH3H
H3C CH 3 (i) BH3 .THF
e.g. C=C H3CCCCH 3

(ii) H2 O2 , NaOH
H3C H
H OH

Ex. Give the major product of the following reaction

(a) dil H2SO4

CH3CHCH=CH 2 (b) (i) Hg(OCOCH 3)2 / H2O


CH3 (ii) NaBH4 / OH
3-Methyl-1-butene (c) (i) BH3.THF
(ii)H2O2 / OH
Ans. Major product is
CH3
(a) CH3CCH2CH3 because 3o carbocation is more stable.

OH
CH3
(b) CH3CHCHCH3

OH
CH3
(c) CH 3CHCH 2CH2OH

(2) From alkyl halides : By nucleophilic substitution reactions


(a) By SN2 mechanism (second-order substitution) : It is given by primary (and some
secondary) halides
KOH
General reaction : RCH2Br RCH2OH

H2 O

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ALCOHOLS & ETHERS Page # 157

KOH
e.g. (CH3)2CHCH2CH2Br (CH3)2CHCH2CH2 OH

H2 O

H Br HO H
C KOH
C
e.g. CH3 CH2CH3
CH3 CH2CH3
SN2

(S)-2-Bromobutane (R)-2-utanol
100% inverted configuration
(b) By SN1 mechanism : It is given by tertiary and some secondary halides
R' R'
Acetone / water
General reaction : RCR" RCR"
Heat

Cl OH

CH3 CH3
acetone / water / heat
e.g. CH3CCH3 CH3CCH3

SN 1

Cl OH
Tert-butyl chloride Tert-butyl alcohol

(3) From Grignard reagents

(a) From air


A Grignard reagent may be used to synthesize an alcohol by treating it with dry oxygen and decomposing
the product with acid :
O RMgX H O
General reaction RMgX RO2MgX
2
2ROMgX 2ROH 3

O H O C 2H5MgX
e.g. C2H5MgBr C2H5O2MgX 2C2H5OMgX
2
2C2H5OH + MgBr(OH) 3

(b) From ethylene oxide


Addition of Grignard reagent to ethylene oxide gives a primary alcohol (with two carbon atoms added)

CH 2
HO
General reaction O + RMgX RCH2CH2OMgX
RCH2CH2OH + MgX(OH)
3

CH 2
CH2
HO
e.g. O + C2H5MgBr C2H5CH 2CH 2OH + MgBr(OH)
C2H5CH2CH2OMgX 3

CH2 Butyl alchohol

MgBr

O CH 2CHOH
(1) CH2CHCH3
Cyclohexylmagnesium bromide
CH3
(2) H3O

(c) From carbonyl compounds : Nucleophilic addition to the carbonyl groups by Grignard reagent

O O MgX OH
H 3O
General reaction C + R MgX C
ether C + Mg(OH)X

R R

adduct

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Page # 158 ALCOHOLS & ETHERS

(i) Addition of formaldehyde gives a primary alcohol


H Ether
H OMgX H O
General reaction C = O + RMgX C RCH2OH
3

H H R

(ii) Addition to an aldehyde (other than formaldehyde) gives a secondary alcohol


O
Ether
R OMgX H O
R OH
General reaction RCH + R'MgX C
3
C
H R' H R'
(sec-alcohol)
O H
(1) ether solvent
e.g. MgBr + CH3CH COH
(2 ) H3 O
acetaldehyde CH3
Phenylmagnesium bromide
1-phenylethanol
(iii) Addition to a ketone gives a tertiary alcohol
R
R (1) ether
General reaction C=O + RMgX RCOH + MgX(OH)
(2 ) H3 O
R'
R
ketone

O OH
(1) ether
e.g. CH3CH2MgCl + CH2CH 3
(2 ) H3 O

Cyclohexanone 1-Ethylcyclohexanol

(iv) Addition to an acid halide or an ester gives a tertiary alcohol


Esters on treatment with Grignard ragent first form ketones which then react with second
molecule of Grignard reagent and form tertiary alcohol.
General reaction

O O MgX O
OR'
RC OR+ RMgX RCOR RCR+ Mg
X
R

R
R H2O / H
C=O + RMgX
RCR
R
OH
tertiaryalcohol


O O MgX O
RCX + RMgX RCX RCR+ MgX2 OH
RMgX X
R RCR+ Mg
OH
R'

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ALCOHOLS & ETHERS Page # 159

(4) By reduction of carbonyl compounds


(a) Catalytic hydrogenation of aldehydes and ketones
General reaction RCHO H2 / Ni
RCH2OH
o
Aldehyde 1 Alcohol
H2 / Ni
R2C=O R2CHOH
o
Ketone 2 Alcohol
H / Ni
e.g. CH3CHO + 2H CH3CH2OH 2

Ni
CH 2=CHCHO + 4H CH3CH2CH2OH
Catalyst
(Acrolein)
O H
+ 4H Ni OH

(b) Lithium aluminium hydride reduction of aldehydes and ketones


LiAlH
General reaction (i) RCHO RCH2OH 4

Aldehyde 1oAlcohol
(ii) R2C=O
LiAlH 4
R2CHOH
o
Ketone 2 Alcohol
LiAlH
(iii) RCOOH + 4H RCH2OH + H2O 4

LiAlH
(iv) RCCl + 4H RCH2OH + HCl 4

O
LiAlH
(v) RCOR' RCH2OH + ROH
4

O
O
LiAlH
e.g. CH 3COH CH3CH2OH 4

C2H5CCl + 4H C2H5CH2OH + HCl

(c) By NaBH4 (sodium borohydride) : It is insoluble in ether and is used in aqueous ethanolic
solution to reduce carbonyl compounds. It does not reduce esters and acids.
O
NaBH
RCH RCH2OH 4

O
NaBH
e.g. CH 4
CH2OH

benzaidehyde benzyl alcohol


NaBH
CH3 CH=CHCHO + 4H CH3CH=CHCH2OH 4

(ii) Reduction of a ketone gives a secondary alcohol


O H
NaBH
4 OH

Cyclohexanone Cyclohexanol

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Page # 160 ALCOHOLS & ETHERS

(d) Bouveault-Blanc reduction : The reduction of aldehydes, ketones or esters by means of excess
of sodium and ethanol or n-butanol as the reducing agent.
General reaction
Na
(i) Aldehyde RCHO RCH OH
EtOH 2

Na
(ii) Esters RCO2R RCH OH + ROH
EtOH 2

Na
(iii) Ketones R2CO R CHOH
EtOH 2

The Bouveault-Blanc reduction is believed to occur in steps involving transfer of one electron at a
time.
Mechanism

Na EtOH Na
RCOEt RCOEt RCHOEt RCHOEt
O O O O

EtOH Na EtOH Na
RCH2OH O RCH2O RCH2O RCO RCH=O+OEt

Na
e.g. CH3CHO + 2H CH3CH2OH
EtOH

Na
CH3COOC2H5 + 4H 2CH3CH2OH
EtOH

CH 3
Na
CH 3CCH3+2H CHOH
EtOH
CH 3
O

Ex. Identify (X) in the following reaction


O
LiAlH 4
CH3CHCH 2CH X

OH
Ans. X=CH3CHCH 2CH2OH
OH

Ex. What are the product A, B, C, D and E in the following reactions?


O NaBH4
O O B
OEt LiAlH 4 CH4OH
A
LiAlH4
O C
O
O
OEt NaBH 4 NaBH 4
D E
CH3OH CH3OH
O O

OH
Ans. A: OH + (EtOH)

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ALCOHOLS & ETHERS Page # 161

O O
B: Ester part is not affected by NaBH4

OH

OH OH
C: Ester part and keto parts are affected by LiAlH4

OH
O
OEt
D:
O

E:
OH

(5) By reaction of nitrous acid on aliphatic primary amines


NaNO2 / HCl
General reaction RNH2+HONO ROH + N2 + H2O
Mech.
HNO2
RNH2 (R N2 )
H2O
ROH+ N2+ H
e.g. (i) C2H5NH2 + HNO2 C2H5OH + N2 + H2O
CH3 CH3
NaNO2 / HCl
(ii) CH3CH2 CCH3 + HONO CH3CH2 CCH3 + N2+H2O
NH2 OH
Mech.
CH3 CH3 CH 3
HONO H O
CH3CH2 CCH3 CH3CH2 CCH3 2 CH3CH2 CCH3
NH2 OH

(6) Hydroxylation : Forms vicinal diols (glycols)


Converting an alkene to a glycol requires adding a hydroxy group to each end of the double bond. This
addition is called hydroxylation of the double bond.
(a) Syn hydroxylation, using KMnO4 / NaOH or using OsO4/H2O2
General reaction :
OsO4,H2O2
C=C C=C
or KMnO4,OH
(cold, dilute) HO OH

H CH2CH3
CH2CH3
C
OH
e.g. H
KMnO4

C cold
( dilute ) H OH
H CH2CH3 CH2CH3
cis-3-hexene

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Page # 162 ALCOHOLS & ETHERS

H
OH
OsO4 / H2O2


OH
Cyclopentene H
cis-Cyclopentane-1, 2-diol

(b) Anti hydroxylation, using per acids

H

OH
RCOOH, H

H2O

Cyclopentene H
OH
trans-Cyclopentane-1, 2-diol

Chemical reactions of alcohols


1. Reaction with hydrogen halides

General reaction :
R OH + HX R X + H2O (R may rearrange)
Reactivity of HX : Hl > HBr > HCl
Reactivity of ROH: allyl, benzyl > 3o > 2o > 1o

Mechanism H
R OH R

OH2

X RX
X
R
cons. HBr
e.g. CH3CHCH3 CH3CHCH3
or NaBr,H 2SO4
OH reflux Br
Isopropyl alcohol Isopropyl bromide

HCl, (anhydrous) ZnCl2


Lucas reagent
e.g. CH 3CH2CH2CH2CH2OH CH3CH2CH2CH2CH2Cl
heat n-Pentyl chloride
n-Pentyl alcohol

CH3 CH3
conc . HCl
e.g. CH3CCH3 CH3CCH3
room temp .

OH Cl
tert- Butyl alcohol tert-Butyl chloride

2. Reaction with Phosphorus trihalides


(1) Several phosphorus halides are useful for converting alcohols to alkyl halides. PBr3, PCl3, & PCl5
work well and are commercially available.
(2) Phosphorus halides produce good yields of most primary and secondary alkyl halides, but none
works well with ter. alcohols. The two phosphorus halides used most often are PBr3 and the
P4 / I2 combination.
General reaction :
(PX 3 PCl3 , PBr3 , Pl3 )
3R OH + PX3 3R X + H3PO3
Mechanism
The mechanism for the reaction involves attach of the alcohol group on the phosphorus atom, displacing
a bromide ion and forming a protonated alkyl dibromophosphite (see following reaction).

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ALCOHOLS & ETHERS Page # 163



RCH 2OPX2 + X



RCH 2OH + X P X



X H
Protonated
alkyl dibromophosphite
In second step a bromide ion acts as nucleophile to displace HOPBr2, a good leaving group due to the
electronegative atoms bonded to the phosphorus.

X + RCH2 OPX2
RCH2X + HOPX2

A good leaving group

CH3 CH3
PBr3
e.g. CH3CH 2CHCH2OH CH3CH2CHCH2Br
2Methyl1butanol 2Methyl1bromobutane
P I2
CH3CH 2OH CH 3CH 2I
Ethyl alcohol Ethyl iodide

3. Reaction with thionyl chloride


O
Heat
RCl+SO2+HCl
ROH+ClSCl

4. Dehydration of alcohols

acid
C = C + H2O
C C (Rearrangement may occur)
H OH
Mechanism

CH 3 H CH 3 H

Step 1 :

CH3 C O H + H O

CH3 C O

H+HO
CH 3 H CH 3 H
Protonated alcohol
or alkyloxonium ion

CH3 H CH 3
C H
Step 2 : CH3 C
O H +
CH3 CH3 OH

CH3
A carbocation

H CH2
HCH H C H

Step 3 : C + OH CH3 CH3 + H O H


CH3 CH3 2-Methylpropene
Reactivity of ROH : 3 > 2 > 1

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Page # 164 ALCOHOLS & ETHERS

5. Reaction with metals



ROH+M RO M + H 2 M=Na, K, Mg, Al, etc
Reactivity order of ROH: o o
CH3OH > 1 > 2 > 3
o


e.g. CH3CH2OH Na
CH3CH2O M + H 2
Ethyl alcohol Sodium ethoxide

CH 3 CH 3
3
CH3COH
Al
(CH3CO)3Al + H2
2
H H
Isoporpyl alcohol Aluminium Isopropoxide

CH3 CH3

CH3COH CH3CO K
K


CH3 CH3
tertButyl alcohol Potassium tert-butoxide

6. Ester formation

General reaction

O O
RC + R'OH H RC + H2O
OH Alcohol OR'
Acid Ester

O
O
H
e.g. CH3CH2O H + CH3C CH 3C + H2O
OH OC2H5
Acetic acid Ethyl acetate

O H2SO4 O
CH2CH2CH2C + C2H 5OH CH2CH2CH2C +H2O
OH reflux OC2H5
Ethyl alcohol
-Phenyl butyric acid (8 moles) Ethyl -phenyl butyrate
(1 mole) (85-88% yield)

7. Oxidation reactions
(a) oxidation of primary alcohols
Oxidation of a primary alcohol initially forms an aldehyde. obtaining the aldehyde is often difficult, since
most oxidizing agents are strong enough to oxidize the adehydes formed. CrO3 acid generally oxidizes a
primary alcohol all the way upto the carboxylic acid
(b) oxidation of secondary aldohols
Sec. alcohols are easily oxidized to give excellent yields of ketones. The chromic acid reagent is often
best for laboratory oxidations of secondary alcohols. The active species in the mixture is probably
chromic acid,

H2CrO4, or the acid chromate ion, HCrO4

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(c) Resistance of tertiary alcohols to oxidation


Oxidation of ter-alcohol is not an important reaction is organic chemistry. Ter-alcohols have hydrogen
atoms on the carbinol carbon atom, so oxidation must take place by breaking CC bonds. These
oxidations require severe conditions and result in mixtures of products.

H
C2H5NHCrO3Cl
RC=O
Primary RCH2OH An aldehyde
KMnO4
RCOOH
A carboxylic acid

R R

K Cr O7 or CrO3 / H
Secondary RCHOH 22 RC = O
A ketone

R
KMnO4
Tertiary RCOH no reaction

H
C5H5NHCrO3Cl
e.g. CH3CH2CH2OH CH3CH2C=O
n-Propyl alcohol Propionaldehyde
(1)

CH3 CH3
KMnO4
CH3CH2CHCH2OH CH3CH2CHCOOH
2-Methyl-1-butanol 2-Methylbutanoic acid
(1)


CrO3 / H
CH 3CH2CHCH2CH 3 CH 3CH2CCH2CH 3

OH O
3-Pentanol 3-Pentanone
(2)

OH

CrO3
Ex. A
H2SO4
acetone

Identify A

OH O

CrO3
Ans.
H2SO4
acetone

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Page # 166 ALCOHOLS & ETHERS

ETHER
Structure of ether

Compound Hybridization Bond angle

O 104.5
H H sp3
O O O water
H H
O
C 110 C H 104.5 H (CH3)3C 132 C(CH3)3 R H sp3 108.5
H H Water Di-ter.butyl ether Alcohol
H H O
R R
dimethyl ether sp3 111.7
Ether

Classificaion of Acyclic ethers


S.No. Type Example Name
CH3OCH3 Methoxy methane
1 Simple ether
CH3CH2OCH2CH3 Ethoxy ethane
2 Mixed ether CH3OCH2CH3 Methoxy ethane

IUPAC Nomenclature of ether Alkoxy Alkane


S.N. Compound IUPAC Name

1. CH3CHOCH 3 2-Methoxy propane

CH3

2. ClCH2OCH3 Chloromethoxy methane

OCH 3
3. Methoxy benzene (Anisole)

CH 3 CH 3

4. 3-Ethoxy-1, 1-dimethyl cyclohexane


H
OCH2CH3
Cl

5. H trans-1-Chloro-2-methoxy cyclobutane
OCH 3

H
CH2OH
6. 2-Ethoxy ethan-1-ol
CH2OCH2CH 3

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ALCOHOLS & ETHERS Page # 167

Method of Preparation of Ether


(1) Williamson synthesis
General reaction
RX + R OR
nPr Br
e.g. (i) n-PrOH CH3CH 2CH2O CH2CH2CH 3
Di-n-propyl ether

Na PhCH2Br
(ii) MeOH Me O CH2OCH3

Benzylmethyl ether

Na EtBr
(iii) t-BuOH t-Bu O t-Butyl ethyl ether
(This reaction produces a poor yield of ether because of the bulkiness of t-BuO)

2. Williamsons Continuous Etherification process or by Dehydration of Alcohols



(i) ROH + H RO H2
S2

ROH + R OH2
N
R2OH + H2O ROR + H3O


(ii) ROH + H ROH2 R .... S1N

ROH + R ROR ROR

H2SO4
o CH 2=CH 2
180 C Ethene

e.g. CH3CH2OH

H2SO4
o CH3CH2OCH2CH3
140 C Diethyl ethene

Mechanism
H

Step-1: CH3CH2O H + H OSO3H CH3CH2O H + OSO3H

This is an acid-base reaction in which the alcohol accepts a proton from the sulfuric acid
H

Step-2 : CH 3CH 2O H + CH3CH 2 OH

Another molecule of the alcohol acts as a nucleophile and attacks the protonated alcohol in an S2N
reaction.

H H H

Step-3 : CH3CH2O CH2CH3 + OH CH3CH2OCH2CH3 +HOH

Another acid-base reaction converts the protonated ether to an ether by transferring a proton to a
molecule of water (or to another molecule of the alcohol).

Only one combination of alkythalide and alkoxide is appropriate for the preparation of each of the
following ethers by Willianson ether synthesis. What is the correct combination in each case ?

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Page # 168 ALCOHOLS & ETHERS

3. Form alkenes
(a) By addition of alcohols in alkenes
When alcohol is added to alkenes in presence of acid, we get ethers.

General reaction
H2SO4
(I) C=C carbocation

(II) Carbocation + alcohol ether



e.g. (I) Me2C = CH2 + H (H2SO4) Me3 C

H
(II) Me3 C + EtOH Me3COEt Me3COEt
H
(b) Alkoxymercuration - demercuration

Hg(OAc)2 NaBH4
C=C CC C C
ROH
AcOHg O H H OR


mercurial ether

e.g.
(i) Hg(OCOCF3 )2
(i) RCH=CH2+ROH RCH(OR)CH3
(ii) NaBH 4

CH 3 CH 3
(i) Hg(OCOCF3 )2
(ii) CH2=CHCH3+CH3CH(OH)CH3 CH3CHOCHCH3
(ii) NaBH 4

CH3 CH3
(i) Hg(OCOCF3 )2
(iii) CH3CH=CHCH3+CH3CH(OH)CH2CH3 CH3CH2CHOCHCH2CH3
(ii) NaBH 4

Reactions of ethers
1. With HX
General reaction

X H H
HX
XR + OR' XR + XR
R

ROR'

+HX R O R

alkyl halide
HBr
e.g. (i) CH3CH2CH2CH3 2CH3CH2Br

2. Reaction with sulphuric acid


Ethers dissolve in concentrated solutions of strong inorganic acids to from oxonium salts, i.e. ether
behave as bronsted Lowry bases.
conc.H2SO4

R2O + H2SO4 (R O R)HSO4
ROH + ROSO 2OH
alkyl hydrogen
H sulphate
When heated with dilute H2SO4

R2O + H2SO4
2ROH
H O
e.g. C2H5OC2H5 + H2SO4
C2H5OH + C2H5OHSO4 2 C2H5OH + H2SO4

3. Autoxidation of ethers :
When ethers are stored in the presence of atmospheric oxygen, they slowly oxidize to produce
hydroperoxides and dialkyl peroxides, both of which are explosive. Such a spontaneous oxidation by
atmospheric oxygen is called an autoxidation.

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General reaction
OOH
excess O2
ROCH2R' ROCHR' + ROOCH2R'
(Slow )
ether Hydroperoxide dialkl peroxide

OOH
H3C CH3 H3C H3C CH3
excess O2
Ex. (i) C=C CHOCCH3 + CHOOCH
( weeks or months)
H3C CH3 H3C H3C CH3
CH3 Diisopropyl peroxide
Hydroperoxide

OOH
h
(ii) CH3CH2OCH2CH3 CH3CHOCH 2CH3
Diethyl ether 1-Ethoxyethyl hydroperoxide

4. Reaction with acid chlorides and anhydrides


Reagent : ZnCl2, AlCl3 etc.
AlCl3
General reaction (i) ROR + RCOCl RCl + RCOOR

Mech.
RCOCl + AlCl3 RCO+ + AlCl4
+ AlCl
R'O + RCO+ R'O COR RCOOR + R" 4 RCl + AlCl3
R" R"
Anhydous
ZnCl
e.g. C2H5OC2H5 + CH3COCl 2 C2H5Cl + CH3COOC2H5
ZnCl2
(ii) R2O + (CH 3CO) 2O 2CH3COOR
acid anhydride
anhydrous
AlCl3
e.g. C2H5OC2H5 + (CH3CO)2O 2CH3COOC2H5

5. Reaction with carbon monoxide :


Ether react with CO at 125-180oC and at a pressure of 500 atm, in the presence of BF3 plus a little
water.
BF3
500 atm
R2O + CO
RCOOR
125 180 C

6. Reaction with halogens :


When treated with chlorine or Br, ether undergo substitution, the extent of which depends on the
conditions.
Cl2 Cl2
CH3CH2OCH2CH3
hv
CH3CHClOCH2CH3
hv
CH3CHClOCHClCH3

in presence of light
Cl2
(C2H5)2O (C2Cl5)2O
hv
Perchloro
diethyl ether
Mech.
The reaction proceeds by a freeradical mechanism, and substitution occurs readily because of
resonance stabilization of the intermediate radical
Cl
Cl2
R'OCH 2R" R'OCHR" R'O=CHR R'OCHClR" + Cl , etc.

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Page # 170 ALCOHOLS & ETHERS

EXERCISE I OBJECTIVE PROBLEMS (JEE MAIN)


1. O
+
CH2OH (i). Mg/Hg H
3. CH3 CH3 (A) (B)
CHO C=O
(ii) HOH
H OH HO H
HO H XHIO 4 H OH YHIO4 Product (B) is -
(A) H OH (B) H OH
H OH O O
CH2OH
CH 2OH (D-glucose) (A) (B)
(D-glucose) CH 3
O
x & y are moles of HIO4 consumed is above
reaction. O

(i) Value of x inabove reaction is - (C) CH (D)


3
OH OH OH
(A) 2 (B) 3
(C) 4 (D) 5 Sol.
(ii) Sum of x + y is -
(A) 8 (B) 9
(C) 10 (D) 11
(iii) Mole of HCHO formed in (A) is -
(A) 1 (B) 2 O
(C) 3 (D) 4
PCl5
Sol. 4. O (A); Product (A) is -

O O
CCl CCl
(A) (B)
CH2OH
xHIO4 COH CCl
C=O
2. O
O
CHOH
CH2OH
Cl O
Cl
x is moles of HIO4 consumed C CCl
(A) x = 3 (B) x = 2 Cl
(C) x = 4 (D) x = 1 (C) (D)
Sol. CO2H CH2Cl

Sol.

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ALCOHOLS & ETHERS Page # 171

H2 CHO
|
5. 7. 2HIO4
CH OH , Products obtained in the
PtO2 or Ni
|
Product of above reaction is obtained by CH2 OH
(A) racemic mixture above reaction are -
(B) Diastereomers (A) HCHO, HCO2H
(C) Meso (B) HCHO, 2HCO2H
(D) Optically-active product (C) CO2, 2HCO2H
Sol. (D) CO2, HCHO, HCO2H
Sol.

CHO
6. The structure of the product formed in the |
8. (CH OH)3 + 4HIO4 , Products obtained are
reaction given below is - |
CH2 OH
H+
Aldo pentose
H2O
(A) 4HCO2H, HCHO (B) 4CH2O, HCO2H
OH OH (C) CO2, 4HCHO
(D) CO2, 3HCO2H, HCHO
Sol.
(A)

(B)
O 9. Which of the following compound gives 2HCHO,
CO2, 2HCO2H when oxidisized by periodic acid
(C) CHO OH COH
| |
(A) (CH OH)2 (B) (CH OH)2
O | |
CH2 OH CH2 OH

(D) CH2 OH CHO


| |
O CO CO
| |
Sol. (C) (CH OH)2 (D) CH OH
| |
CH2 OH CH2 OH

Sol.

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Page # 172 ALCOHOLS & ETHERS
12. In the given reaction :
MeCH
OH OH
CHOH | |
HIO4
CH3 CH C CH3
xHIO4 (a) + (b)
10. CHOH , W hat is the |
CH3
CHOH (a) and (b) respectively be -
HC (A) CH3CHO and CH3CHO
(B) CH3COCH3 and CH3CHO
CH2OH (C) CH3COCH3 and CH3COCH3
(D) CH3COOH and CH3COCH3
maximum value of (x) ? Sol.
(A) 1 (B) 2
(C) 3 (D) 4
Sol.

O
CCH3
Zn(Hg)
CHOH (A)
2 13. HCl ; Identify the
O
CHOH
2 LiAlH4 HO
3
(A) (B) (C)
H+ HO
11. CHCOEt
2
A.
CH3
CH2CH3
O
(A) (A)
CH 2CHOH
HO
CH3
O
(B) (B)
CHCH 2OH
Cl
CH3
O
(C) OH OH
CCH3
(C) (D)
CH3
O Cl

(D) Sol.
CH 2CH 2OH
Sol.

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ALCOHOLS & ETHERS Page # 173

14. PhCH 2 Cl KCN H O


(A) 3 (B) OH
18
CH3 O H, conc.H2SO4 ,
(C) CH3CO2H(1mole)
17. (A) product
product (C) is - H

18 OH
O
|| (A) is -
(A) PhCH2 C OCH3
O
O
|| OCH 3 OCCH3
(B) Ph C O CH3
18

O (A) (B)
||
(C) PhCH2 C O CH3 OH
18 CH3 OH
O18
|| H OH
(D) PhCH2 C OCH3
Sol. (C)
O

OCCH3

O
O O
|| || H OCCH3
H O
15. Ph C CH2 C OEt 3 (A)
(B)

Product (B) is - (D)
O O
|| || H OH
(A) Ph C H (B) Ph C CH3
Sol.
O
||
(C) PhCH2 C OH (D) PhCO2H
Sol.

CH 3O CO2 Et
CHO
3 CO2Et

O O 18. H3O/strong heated ; Product (A)
|| ||
H
16. R C OH+R1OH R
C OR, (A)
In above esterification reaction rate of reactin
is maximum, when R1OH is - is -
(A) 1 alcohol O
(B) 3 alcohol
(C) 2 alcohol
(D) CH3OH (A) O (B)
Sol.
CO2H
O
CO2H
(C) CO2H (D)

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Page # 174 ALCOHOLS & ETHERS
Sol. Product (C) of above reaction is -

O18 O
|| || 18
(A) CH3 C OCH3 (B) CH3 C O CH3

O18 O
|| 18 ||
O O (C) CH3 C O CH3 (D) CH3 C OCH3
|| H3O ||
19. R1 C OH + R OH R1 C OR+H+H2O Sol.
In above esterification reaction rate of reaction
maximum when -
(A) R1 = CH3 (B) R1=CH2CH3

CH3
CH3 |
(C) R1 = CH (D) R1= C CH3 O O
CH3 | || ||
23. CH 3 C CH 2 C OEt NaOEt
CH3 (A)

Sol. 3 H O
CH3I
(B)

(C)

Product (C) is -
O O
(A) Ph (B)

O
O
|| 18 H3O (C) (D)
O
20. Ph C C CH3
Sol.
O18 is present in -
(A) Carboxylic acid (B) Alcohol
(C) Water (D) Cannot predict
Sol.

24. RCCl+ROH
(d & l) (d) Pyridine
racemic

Product of above reaction is -


O
|| (A) Enantiomer (B) Racemic
21. Ph C OCH3 H2O / HO (C) Diastereomers (D) Meso

Above reaction is known as - Sol.
(A) Esterification (B) saponification
(C) Transesterification (D) Acidic hydrolysis
Sol.

O
||
25. Ph C OH+CH3O18H (X) + H2O
18 Na O
22. CH3 O H (A) + B (gas) ||
(A) X = Ph C O18CH3 (Trans esterification)
O
|| O
CH3 C OCH3 (A) (C) ||
(B) X = Ph C O18CH3 (esterification reaction)

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ALCOHOLS & ETHERS Page # 175
28. Which of the following compound reduces by
O
|| NaBH4 ?
O
(C) X = Ph C O18CH3(Saponification) ||
(A) CH3 C OH (B) CH3NO2
O O O
|| || ||
(D) X=Ph C OCH3 (Hydrolysis) (C) CH3 C OEt (D) CH3 C Cl
Sol.
Sol.

29. Which of the following compounds not reacts


O with NaOH ?
CH 2OH
CHCCl (A) HCCH (B) EtOH
3
26. Et (A) (major) (C) H2C=CH2 (D) All
N Sol.

O O O
|| ||
CH2OCCH 3 CH 2OH 30. EtOH+CH3 C O C CH3
(A) Et (B) Et In above reaction molecular weight of alcohol
increases by
N N
(A) 22 (B) 32
H COCH3 (C) 42 (D) 52
CH 2 COCH3 Sol.
(C) (D) Et
N N

H H
31. N-Ethyl pthalimide oin hydrolysis gives -
Sol.
(A) Methyl alcohol (B) Ethyl amine
(C) Dimethyl amine (D) Diethyl amine
Sol.

27. Which of the following compound reduces by


DIBAL-H ? 32. Which of the following is acetylation reaction

O H
|| (A) EtOH

(A) CH3 C OH (B) CH3CN
O O
O || ||
|| (B) EtOH + CH3 C O C CH3
(C) CH3 C OEt (D) All
Sol. (C) EtOH + H CL
(D) EtO + CH3 CH2 Cl
Sol.

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Page # 176 ALCOHOLS & ETHERS

EXERCISE II OBJECTIVE PROBLEMS (JEE ADVANCED)


3. AC7H14O optically active alcohol is oxidized by
CH2 CH2
jones reagent to an optically inactive (achiral)
SOCl2 Mg O
Product ketone. Which of the following compounds
pyridine, (C2 H5 )2 O H+
1. meets these facts ?
O CH2 OH
(X) OH
Product of the reaction is - (A) (B) OH

(A)

O CH2CHCH 3
(X)
OH (C) OH (D)

(B) OH
Sol.
O CH2CH2CH2OH

(C)

O CH 2CH2OH 4. Glycol on treatment with Pl3 mainly gives -


(A) Ethylene (B) Ethylene iodide
(D) (C) Ethyl iodide (D) Ethane
Sol.
O CH2CH2OCH2CH3
Sol.

5. Ethanol on reaction with acetic anhydride gives


(A) Acetic ester (B) Formic ester
O OH (C) Ethaoic acid
(D) Acetic ester and Ethanoic acid both
CH3 l2/NaOH
+
H Sol.
2. A, A is

-
O O
O
COH 6. A compound X with molecular formula C3H8O
(A) (B) can be oxidised to a compound Y with the
molecular formula C3H6O2, X is most likely to
be -
O O (A) Primary alcohol
COH C (B) Seconary alcohol
OCH3 (C) Aldehyde
(C) (D)
(D) Ketone
Sol.
Sol.

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ALCOHOLS & ETHERS Page # 177
7. Phenol with Hinsbergs reagent gives - Sol.
(A) Sulphone (B) Sulphanilic acid
(C) Sulphonic ester (D) Sulphonal
Sol.

CH3
CH3OH 18
H2O
11. B CH3CCH2 A, A and
CH3ONa H
KHSO4 LiAH4
8. Glycerol A , A and B are O

(A) Acrolein, allyl alcohol B are -


(B) Glycerl sulphate, acrylic acid CH3 CH3
(C) Allyl alcohol, acrolein
(D) Only acrolein (B is not formed) (A) CH 3C CH 2 , CH3C CH2
Sol. OH OH OH OCH3
18

CH3 CH3

(i) NaOH H / H O
2
(B) CH3C CH2 , CH3C CH2
9. Phe nol A B
(ii) CO2 / 140C
OH18 OH OH OCH3
18
Al2O3
C
CH3COOH CH3 CH3
In this reaction, the end product C is - (C) CH3C CH2 , CH3C CH2
(A) Salicylaldehyde (B) salicylic acid 18
(D) Phenyl acetate (D) aspirin 18 OH OH 18 OH OH
Sol.
CH3 CH3
(D) CH3C CH2 , CH3C CH2
18
18 OH OH OMe OH

CH 3 cold Sol.
CrO3
10. A B, A
alkaline KnO 4 AcOH

and B are -

CH3 CH3
OH OH CH2CH3 CH=CH2
(A) , 12. OH C
OH O
B A
CH3
CH3
CHCH3 CH 2CH 2OH
OH O
(B) , OH
OH O

CH3 CH3 Select schemes A, B, C out of -


OH I. acid catalysed hydration
(C) , II. HBO
OH OH
III. Oxymercuration-demercuraton
(A) I in all cases (B) I, II, III
(D) no formation of A and B
(C) II, III, I (D) III, I, II
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Page # 178 ALCOHOLS & ETHERS
Sol. Alc. KOH
15. H Cl Major product
O
is -
13. CH3MrBr (A) H O (B) H O
+ O
H
+
HO HBr Mg/ether
A B C (C) H O
3
(D)
+

O HCHO H3O
O
Sol.
D

HI

E
E is -
CH OH CH OH
3
16. (A) 3
(B) A
H SO
2 4
CH3O
(A) (B)
O CH3
I
CH 2CH3 & B are -
CH3 CH2I

H CH3 H OCH3
(C) (D) (A) &
I I
H3CO OH OH CH3
CH3 CH3

Sol.
H OH H OCH3
(B) &

H3CO CH3 HO CH3


O
H+
Q.14 ?
H2O OH
OMe CH3 H
(C) &
O
OH O OH H OH MeO CH 3
(A) (B)

CH3 H H CH 3
O OH (D) &
O
(C) (D) H 3CO OH H3CO OH

Sol.
OH
Sol.

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ALCOHOLS & ETHERS Page # 179

MnO2 Sol.
17. CH2 = CHCHCH2CH2OH A, A is -
|
OH

(A) CH2 = CHCCH2CH2OH


||
O

(B) CH2 = CHCCH2CHO 19. What will be the chief productg from the
| following reaction sequence ?
OH
(i) H3PO4150C
(C) CH2 = CHCCH 2CHO OH ?
|| (ii) C6H5CO3H
O

(D) CH2= CHCCH 2COH (A) O (B) OH


|| ||
O O O
Sol. H
(C) (D) O
H
O
Sol.

CH3CH2OH
18. CH=CH2 find out the
H2SO4
product : 20. A chiral C7H16O2 diol is oxidized by PCC in
CH2Cl2 to an achiral C7H12O2 compound. Which
CH2CH3 of the following wuld satisfy these facts?
(A)
OCH2CH 3
OH OH
(B) CH2CH3 (A) (B)
OH OH
OCH2CH 3
CH2CH3 OH OH

(C) (C) (D)


OH OH

OCH2CH 3 Sol.
H3CCH 2

(D)

OCH2CH 3

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Page # 180 ALCOHOLS & ETHERS
21. Which of the following is the product from 24. A water soluble C6H14O2 compound is oxidized
ethanol addition to dihydropyran (shown on the by lead tetraacetate (or periodic acid) to a
left below) ? single C3H6O carbonyl compound. Which of the
following would satisfy this fact ?
C2H5 OH (A) meso-2, 3-dimensthoxybutane
+
H (B) 1,2-diethoxyethane
O (C) meso-2,5-hexanediol
OC2H5 (D) meso-3,4-hexanediol
(A) (B) Sol.

O O OC2H5
OC2H5
OC2H5
(C) (D) OC2H5
O OC2H5 25. A racemic mixture of () 2-phenyl propanoic
acid on esterificaton with (+) 2-butanol gives
Sol. two esters. Mention the sterochemistry of two
esters formed -

Me H O Et Me H O Et
(A) Ph Me , Ph Me
H H
O O
(+) (+) () (+)
22. What product (s) are expected from the
following reaction ?
Me H O Me Me H O Et
O HI(excess) (B) Ph Et , Ph Me
? H H
& heat O O
(+) (+) (+) ()
O

(A) 2CH3CH2l (B) 2ICH2CH2OH Me Me


H O Me H O Me
(C) 2iCH2CH2
(D) CH3CH2l + CH3CH2OH (C) Ph Et , Ph Et
H H
Sol. O O
() () (+) (+)

Me H O Me Me Ph Me
O
(D) Ph Et , H Et
H H
O O
23. Which of the following reagents would be best () (+)
(+) ()
for oxidizing a 1-alcohol to an aldehyde ?
(A) H3PO4 Sol.
(B) PCC in CH2Cl2
(C) Jonews reagent (H2CrO4)
(D) OsO4
Sol.

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ALCOHOLS & ETHERS Page # 181
26. Compound which gives alcohol on reduction is/ 29. Which of the following alcohol can not be
are (When reacts with LiAH4) oxidized by KMnO4 :
(A) Me C Cl (B) Me C NH2 OH
|| || (A) (B) OH
O O
OH
O O
|| || (C) (D)
(C) Me CHCH 2 (D) Me C O C Me OH
Sol. O Sol.

27. Which of following compound undergo acidic 30. Which of the following reaction esterification ?
hydrolysis. (A) EtOH + Acetic anhydride

O H
|| (B) EtOH + CH3CO2H

(A) CH3CN (B) CH3 C OEt
O
O O O ||
|| || || (C) EtOH CH3 C Cl
(C) CH3 C Cl (D) CH3 C O C CH3 (D) None
Sol. Sol.

28. Which can be cleaved by HIO4 ?


O O 31. CH 3
|| ||
(A) CH3CH2 C CH2 C CH3 CH 3C C CH3l H2/Pd/BaSO4
CHCH2 (X) (Y) (Z)

OH O O
| ||
(B) CH3 CH CCH2CH3 Identify X, Y, Z :

(A) Y is CH3 CH CH2C CCH3


|
O CH3
(C)
(B) Y is CH3CH2 CHC CCH3
OH OH |
O O CCH3
|| ||
(D) CH3 CCH2 CHCH2 CCH3
|
(C) Z is CH3 CH CH2 CH=CHCH5
OH |
O CH3
Sol.

(D) X is CH3 CHCH2C CCH3


|
O

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Page # 182 ALCOHOLS & ETHERS
Sol.
34. PBr
OH 3 (X)

CH3

(i) CH3CHCHO
Mg / Et O
32. Which is/are corect statement ? 2 (Y) (Z)
(ii) H2O+
CH3 CH3
CH3/OH (A) X is Br
(A) C C
H2SO4
H O CH3
(B) Y is MgBr
nucleophile attacts here when epoxy linkage is cleaved

OH CH3
CH3 CH3
NaOH (C) Z is CCCH 3
(B) C C
CH3OH H H
H O CH3 H CH3

nucleophile attacts here when epoxy linkage is cleaved


(D) Z is CCCH 3

(C) This is only affected in reduciton to 2 alcohol H OH


Sol.
O

NaBH4

O CH3OH

O CH=CHCHCH3
KMnO 4/ SOCl2
H H X+Y
O 35. OH
+
H
(D) R RCOH+HOR D OH
Identify the product X and Y.
These bonds undergo cleavage in the reaction O
Sol. ||
(A) X is Cl C C CH2Cl
||
O

COCl
(B) X is
33. 3-methyl-3-hexanol can be prepared by -
(A) CH3Mgl and 3-hexanone, followed by D O
hydrolysis D O
(B) C2H5 Mgl and 2-Pentanone, followd by
CH2CCl
hydrolysis (C) Y is
(C) C3H7Mgl and 2-butananone, followd by
hydrolysis
D O
(D) C4H9 Mgl and propanon, followed by
hydrolysis (D) Y is ClCO C CH3
||
Sol. O
Sol.

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ALCOHOLS & ETHERS Page # 183
36. Which one of the following alcohols can be O
oxidised by K2CrO4 ? OH +
(A) Ethanol (B) Tert butyl alcohol H
+ (Q)
(C)
(C) Isopropyl alcohol (D) Allyl alcohol Acetone
Sol. OH
cis-1,2-Cyclohexanediol
38. Product P is -
OEt OEt
(A) (B) OEt
OEt
37. Asparmatge, an artificial sweetener is a peptide
and has the following structure. Which of the OMe OMe
following is correct about the molecule ? OPr
O (C) (D)
C6H 5 OPr
OH Sol.
O

H2N NH
O O

CH 3
(A) It has four functional groups
(B) It has three functional groups 39. Product Q is -
(C) on hydrolysis it produces only one amino
acid O
(D) on hydrolysis it produces a mixture of amino (A) (B)
acids O
Sol.
O
(C) (D)
O
Sol.
Comprehansion : (Q.38 to Q.40) :
Al dehydes and ketones react with oi ne
molecule of analcohol to form compounds called
hemiacetals, in which there is one hydroyl group
and one either-like group. Reaction of a
hemiacetal with a second molecule of alcohol
gives an acetal and a molecule of water. We 40. Product R is -
study this reaction
O
ROH OH ROH OR
O + O O
H OR H
+
OR
A hemiacetal An acetal
(A) (B)
The carbonyl O
group of an (has anCH and (has twoOR
aldehyde or ketone anOR group to groups to the
the same carbon) same carbon)
Draw structural formulas for the hemicetal and
acetal formed from these reagents. The
stoichiometry of each reaction is given in the (C) (D)
problem.

H+ Sol.
(A) O+2CH3CH2OH (P)

Cyclohexanone Ethanol

+
H (R)
(B) O+HOCH 2CH2OH

Cyclohexanone Ethylene glycol

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Page # 184 ALCOHOLS & ETHERS

EXERCISE III OBJECTIVE PROBLEMS (JEE ADVANCED)


1. How can you convert PhCH = CHCH3 to - Sol.
(i) PhCH=CHCO2H
(ii) PhCH=CHCH2CH3
(iii) PhCH2CH2CH2CH3
(iv) PhCH=CHCH(OH)CH3 7. t-butyl alcohol reacts less rapidly with metallic
(V) PhCH2CH2COCH3 sodiumthan thepriamry alcohol. Explain why ?
Sol. Sol.

2. What reagents could you use for the following 8. Diethyl ether behaves as base. Why ?
Sol.
conversions
(a)MeCO(CH2)2CO2Et MeCHOH(CH2)2CO2Et
(b) HO2C(CH2)4COCl HO2C(CH2)4CH2OH
(c) O2N(CH2)2CN O2N(CH2)2CH2NH2
(d) O2N(CH2)2CH=CH2 H2N(CH2)2CH=CH2 9. Sometimes explosion occurs during distillation
(e) Me2CHCOCl Me2CHCHO of ether sample. Give the reason.
(f) O2N(CH2)3CHO O2N(CH2)3CH2OH Sol.
(g) O2N(CH2)2CH=CH2 O2N(CH2)3CH3
Sol.

10. Ethyl alcohol reacts with HI but not with HCN.


3. Outline a mechanism to account for different Explain why ?
Sol.
isomer formed when Me2 C CH 2 reacts with

O
CH3OH in acidic and in basic medium. 11. Write the structure of the principal organic
Sol. product formed in the reaction of 1-propanol
with each of the following reagents :
(i) Potassium dichromate (K2Cr2O7) in aqueous
sulfuric acid, heat
O
||
4. Differentiate : (ii) Acetic acid CH3 C OH in the presence of
(a) 1-Hexanol and 1-chlorohexane
(b) Diethyl ether and n-butanol disolved hydrogen chloride.
(c) Diethyl ether and n-pentane
Sol. (iii) CH 3 SO 2Cl in the presence of
pyridine
O O
5. Complete the following equations & comment || ||
(iv) C6H5 CO CC6 H5 in the presence of pyridine
HI
(i) MeOEt Na
? (ii) Et2O
O
Sol.

(v) O in the presence of pyridine

6. Complete the following equations :


(i) nC3H7CO2HnC4H9OH O
Sol.
H
(ii) Me2CO + EtMgl ? ?
HO
(iii) EtCO2Et+2MeMgl ? 2
?
? MnO 2
(iv) CHCO2Et CHCH2OH ?

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ALCOHOLS & ETHERS Page # 185
12. Column-I Column-II 14. Match the following :
Column-I Column-II
O
(A) (P) Reduces by LAH OH
CH 3 CH3 O
+
(A) + H (P) Product formed is
O
known as Acetal
(B) (Q) Reduce by NaBH4 OH
CH3 OCH3
OH
H+
O (B) O+ (Q) Product reacts with
||
(C) CH3 C OH (R) Positive Iodoform OH Nametalto evolve
H2 gas
(D) OH (S) Reacts with Na to H+
(C) O+2 EtOH (R) Product when reacts
evolve H2 gas with H2| Ni
Sol. formation of alkane
OH H
+ takes place
(D) CH3OH (S) Product when
OCH3
reacts with LAH
No-reaction takes
place
2EtSH
(E) O
13. Match the following X, yZ (C5H12O) are isomeric H
Sol.
alcohols on oxidation X gives a given, Y gives
acid and Z is not oxidised X gives positive I2/
OH test. The activity order with HBr is Z > X
> Y.
CH3
(X) (i) CHCHCHCHOH
3 2 2

CH3 15. Column-I Column-II

(Y) (ii) CHCHCHCH


3 3
O OH

CH3
(A) (P) H2/Ni
CH 3

(Z) (iii) CHCCHCH


3 2 3

OH O
CH 3

(iv) CH3 CH
2 CH CHOH
2 2
(B) (Q) PCC
CH3

(v) CH
3 CCHOH
2
OH
CH3
(C) (R) H3PO4/
Sol.

OH Cl

(D) (S) conc. HCl

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Page # 186 ALCOHOLS & ETHERS
Sol. 18. Column-I
O
|| Pyridine
(A) EtOH + CH3 C Cl

16. Column-I
O O
(A) Ph CH CH3 Ph C CH3 || || H
(B) EtOH + CH3 C O C CH3
| ||
OH O
O
(B) PhCH2CH2OH PhCH2CO || H
(C) EtoH + CH3 C OH
(C) PhCH2CH2OH PhCH2CO2H

(D) Ph CH CH3 Ph CO2H H
(D) EtOH + EtOH
|
OH
Column-II
Column-II (Reagent used) (P) Esterification reaction
(P) hot alk.KMnO4 (Q) Acetylation reaction
(Q) Cold. KMnO4 (R) Molecular formulaof alcohol increases by
(R) CrO3/CH2Cl2 C2H2O
(S) Cu/300C (S) Molecular weight of alcohol increases by28.
Sol. Sol.

17. Column-I 19. Column-I


(A) RCN
OH OH
O
RO COEt
(A) (B)
(B)

CH2OH OH
O O O
|| || ||
(C) (D) (C) Ph C NH2 (D) R C O C R
Column-II
(P) When reacts with H3O, carboxylic acid
Column-II will form
(P) When reacts with CrO3H2SO4 carboxylic (Q) When reacts with LiAlH4, 1 alcohol will
acid will form. form.
(Q) Give positive test with FeCl3. (R) When reacts with LiAlH4, 1 amine will
(R) When reacts with HBr alkyl bromide will form.
(S) When undergo alkaline hydrolysis salt of
formed.
carboxylic will form
(S) When reacts with K2Cr2O7 ketone will form. Sol.
(T) CrO3 in anhydrous form (CH3Cl2) gives
aldehyde
Sol.

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ALCOHOLS & ETHERS Page # 187

EXERCISE IV PREVIOUS YEARS PROBLEMS

LEVEL I JEE MAIN


Q.1 Maximum dehydration takes place that of Q.6 In the following sequence of reactions,
[AIEEE-2002] Mg
CH3CH2OH P A ether
I2
B HCHO
C

H
2O
D, then compound D is -
O O [AIEEE 2007]
OH
(A) butanal (B) n-butyl alcohol
(A) (B) (C) n-propyl alcohol (D) propanal
OH
Q.7 A liquid was mixed with ethanol and a drop of
O CH3 concentrated H2SO4 was added. A compound
(C) (D)
with a fruity smell was formed. The liquid was
[AIEEE 2009]
OH (A) HCHO (B) CH3COCH3
OH
(C) CH3COOH (D) CH3OH
Q.2 When CH2=CHCOOH is reduced with LiAlH4,
the compound obtained will be
[AIEEE-2003] Q.8 From amongst the following alcohols the
(A) CH3CH2CH2OH (B) CH3CH2CHO one that would react fastest with conc, HCl
(C) CH3CH2COOH (D) CH2=CHCH2OH and anhydrous ZnCl 2 , is [AIEEE 2010]
(A) 1- Butanol
Q.3 Among the following compounds which can be
dehydrated very easily is - [AIEEE-2004] (B) 2- Butanol
(A) CH3CH2CH2CH2CH2OH (C) 2- Methylpropan -2-ol
OH (D) 2- Methylpropanol
(B) CH3 CH2 CH2 Q.9 The main product of the following reaction is
CHCH 3
C 6 H 5 CH 2 CH(OH)CH(CH 3 ) 2 conc
.H2SO4
?
CH3

(C) CH3CH2C CH2 CH3 [AIEEE 2010]


OH H5C6CH2CH2
(A) C = CH2
CH H3C
(D) CH3 CH2 CH2 CH2OH
CH 3 H5C6 H
(B) C=C
Q.4 For which of the following parameters the H CH(CH3)2
structural isomers C2H5OH and CH3OCH3 C6H5CH2 CH3
would be expected to have the same values (C) C= C
? (Assume ideal behaviour) [AIEEE-2004] H CH3
(A) Heat of vaporization C6H5 CH(CH3)2
(D) C= C
(B) Vapour pressure at the same temperature H H
(C) Boiling points
(D) Gaseous densities at the same temperature
and pressure Q.10 Consider the following reaction :
C2H5OH + H2SO4 Product
Q.5 HBr reacts with CH2 = CH OCH3 under Among the following which one cannot be
anhydrous conditions at room temperature
to give - [AIEEE 2006] formed as a product under any conditions ?
(A) BrCH2CHO and CH3OH [AIEEE 2011]
(B) BrCH2 CH2 OCH3 (A) Ethylene (B) Acetylene
(C) H3C CHBr OCH3
(D) CH3CHO and CH3Br (C) Diethyl ether
(D) Ethyl-hydrogen sulphate

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Page # 188 ALCOHOLS & ETHERS

LEVEL II JEE ADVANCED


1. 1-propanol & 2-propanol can be best
distinguished by - [JEE 2001] OCOCH3
(A) oxidation with alkaline KMnO4 followed by Acidic
4. P Product
reaction Fehling solution Hydrolysis
(B) Oxidation with acedic dichromate OCOCH3
followed by reaction with Fehling solution Q
(C) Oxidation by heating with copper
followed by reaction with Fehling solution formed by P & Q can be differentiated by :
(D) Oxidatioin with concentrated H2SO4 [JEE 2003]
followed by reaction with Fehling (A) 2, 4 DNP
Sol. (B) Lucas reagent (ZnCl2) conc. HCl
(C) NaHSO3
(D) Fehlings solution
Sol.

2. Identify the correct order of boiling point of


the following compounds : [JEE 2002]
CH3CH2CH2OH CH3CH2CHO
1 2
5. Reactn of entainomerically pure acid with 1
chiral carbon and racemic alcohol with 1
CH3CH2CH2COOH chiral carbon gives an ester which is -
3
[JEE 2003]
(A) 1 > 2 > 3 (B) 3 > 1 > 2
(A) Meso
(C) 1 > 3 > 2 (D) 3 > 2 > 1
(B) Optically active mixture
Sol.
(C) Racemic mixture
(D) Enationmerically pure
Sol.


C2H5O Na
3. OH+C2H5I
C2H5OH(anhydrous )

AlCl3
[JEE 2003] 6. + Cl CH2CH2CH3 P

(i) O /
(A) OC2H 5 (B) I 2 Q + Phenol [JEE 2006]
The major products P and Q are -
(C) C6H5OC6H5 (D) C2H5OC2H5
Sol.

(A) and CH3CH2CHO

(B) and CH3COCH3

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ALCOHOLS & ETHERS Page # 189

9. Mention two esters produced when a racemic


(C) and CH3COCH3 mixture of 2-phenyl propanoic acid is treated
with () 2-butanol. What is the stereochemical
relationship between these esters ?
[JEE 2003]
Sol.

(D) and CH3CH2CHO

NaNO2 .HCl
10. (X)C5H13N (Y) (Tertiary alcohol
N2
Sol.
+ other products)
(Optically active)
Find X and Y. Is Y optically active ? Write the
intermediate steps. [JEE 2005]
Sol.

7. Satement-1 : p-Hydroxybenzoic acid has a


lower boiling point than o-hydroxybenzoic
acid.
because
Statement-2 : o-Hydroxybenzoic acid has 11. Column-I [IIT 2009]
intramolecular hydrogen bonding. (A) CH3CH2CH2CN
[JEE 2007] (B) CH3CH2OCOCH3
(A) Statement-1 is true, Statement-2 is True; (C) CH3CH=CHCH2OH
Statement-2 is a correct explanation for (D) CH3CH2CH2CH2NH2(s)
Statement-1 Column-II
(B) Statement-1 is True, Statement-2 is (P) Reduction with Pd-C/H2
True; Statement-2 is NOT a correct (Q) Reduction with SnCl2/HCl
explanation for Statement-1. (R) Development of foul smell o n treatment
(C) Statement-1 is True, Statement-2 is with chloroform and alcoholic KOH
false. (S) Reduction with diisobutylauminium hydride
(D) Statement-1 is False, Statement-2 is (DiBAL-H)
True. (T) Alkaline hydrolysis
Sol. Sol.

8. Cycl obutyl bromi de on treatment wi th


magnesium in dry ether forms an organometallic
A. The organometallic reactw with ethanal to
give an alcohol B after mild acidification.
Prolonged treatment of alcohol B with an
equivalent amount of HBr gives 1-bromo-
methylcylopentane (C). Write the structures
of A, B and explain how C is obtained from B.
[JEE 2001]
Sol.

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ALCOHOLS & ETHERS Page # 38

Answers
Exercise-I

1.(i) D (ii) C (iii) A 2. (A) 3. (B) 4. (B) 5. (C) 6. (C) 7. (B) 8. (A)

9. (C) 10.(B) 11.(B) 12.(B) 13.(B) 14.(C) 15.(B) 16.(D) 17.(B) 18.(B)

19.(A) 20.(B) 21.(B) 22.(B) 23.(C) 24.(C) 25.(B) 26.(B) 27.(D) 28.(D)

29.(D) 30.(C) 31.(B) 32.(B)

Exercise-II

1.(B) 2.(A) 3.(C) 4.(A) 5.(D) 6.(A) 7.(C) 8.(A) 9.(D) 10.(A) 11.(A) 12.(C)

13.(D) 14.(B) 15.(D) 16.(B) 17.(A) 18.(A) 19.(D) 20.(B)

21.(B) 22.(A) 23.(B) 24.(D) 25.(A)

26.(A,C,D) 27.(A,B,C,D) 28.(B) 29.(B,D) 30.(A,B,C) 31.(A,C,D) 32.(A,B,C,D)

33.(A,B,C)34.(A,B,C) 35.(B,D) 36.(A,C,D) 37.(A,D) 38.(B) 39.(B)

40.(B)

Exercise-III

1.(i) I2 + NaOH (ii) WKR (iii) Zn/Hg-HCl (iv) not LiAH4 (v) N2H2

2.(a) NaBH4 (b) NaBH4 (c) Na + C2H5OH (d) LiAlH4 (e) H2Pd/BaSO4 (f) NaBH4 (g) N2H2

OCH3 OCH3
| |
3. In acidic medium Me2 C CH2 and in basic medium Me2 C CH2
| |
OH O

4. (a) 1-hexanol reduces organ red CrO3 to green Cr3+; while 1-chlorohexane gives white ppt. of AgCl on
warming with ethanolic AgNO3.
(b) n-Butanol gives a positive test with CrO3 in acid and evolves H2 with sodium; while dry ethyl ether is
negative to both tests.
(c) Unlike n-pentane, diethyl ether is basic and dissolves in conc. H2SO4.
(C2H5)2 O + H2SO4 (C2H5)2 OH+ + HSO4

5. (i) Mel + EtOH due to SN2 mechanism (ii) No reaction

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Page # 191 ALCOHOLS & ETHERS
LiAlH 4
8. (i) n-C3H7CO2H nH OH
or B2H6 9

OMgI

(ii) Me2CO + EtMgl M2C H
Me2C(OH) Et
Et
IMgO Me

(iii) EtCO2Et + 2MeMgl C H O


2 EtCMe2OH
Et Me
LiAlH MnO
(iv) CHCO2Et
4
CHCH2OH
2
CHCHO

7. The +I.E. of three methyl groups on ce ntral C-atom of tert-butyl alcohol makes is partially negative with
the result that it pushes the electron pair of OH bond towards H-atom and thus H-atom is not replaced
easily.
CH3 H

CH3 C O H CH 3CH 2CH 2 C O H

CH3 H
(less partial + ve charge) (more partial +ve charge)

8. Oxygen atom is diethyl ether molecule has two ione pair of electron available for co-ordination. Therefore
ether behave as Lewis base forming oxonium salts.
R
O+HCl R2IO+Cl (dialkyl oxonium chloride)
R

9. Due to formation of explosive peroxide by oxidation.

10.Ethanol being very weak Lewis base and thus reacts with stronger acid HI

11.(i) CH3CH2COOH (ii) CH3COOCH2CH2CH3 (iii) MePhSO2OCH2CH2CH3

(iv) PhCOOH + PhCOOCH2CH2CH3 (v) OCH2CH2CH3


OH

12.A P; B Q,R; C S 2. X (ii), Y (i), (iv), (v), Z (iii)

13.A (ii), Y (i), (iv), (v), Z (iii)

14.A P, S; B P, S; C P, S; D P, S, E R

15.A P; B Q; C R; D S

16.A Q, r, S ; B R, S; C Q ; D P

17.A R; B R, S ; C P, R, T ; D Q

18.A P, Q, R; B P, Q, R; C P, Q, R; D S

19.A P, Q, R; B P, Q, R; C P, Q, R; D S

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ALCOHOLS & ETHERS Page # 192

Exercise-IV (LEVEL-I)

1. B 2. D 3. C 4. D 5. D 6. C 7. C 8. C 9. B 10.B

Exercise-IV (LEVEL-II)

1. (C) 2. (B) 3. (A) 4. (D) 5. (B) 6. (C) 7. (D)

8.

Br Me
MgBr BrMgOCHMe HOCHMe
+
Mg MeCHO H3O HBr
Et2O
(B) (C)
(A)
Mechanism
+
HOCHMe H2O CHMe CHMe
+
H H 2O

Br Me
Me Me Br

2carbonium 3carbonium

H
Ph H |
( )CH3CH2 C OH
Ph H H
| | | | | |
CH3
9. CH3 C COOH CH3 C COOH CH3 C C O C CH2CH3 +CH3 C O C CH2CH3
conc. H2SO 4 ,
| | | || | | |
H Ph H O CH3 Ph CH3
(recemic mixture)
during esterification reaction onlyCOOH and OH participates. Tehre is no effect on structure of configuration
of catrbon adjacent of these group. So when () acid reacts with pure (+) alcohol two esters are
produced whinc are diastereoisomers of each other.

OH
|
10.X : C C C C Y : C C C C
| | |
C NH2 C

11.A Q, S, T ; B S, T; C P., D R
Y is optically inactive.

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