JEE

CONTENTS
4.0 INTRODUCTION
4.1 CONFORMATIONAL ISOMERISM
4.2 GEOMETRICAL ISOMERISM
4.2.1 Geometrical Isomerism Concept
4.2.2 Geometrical Isomerism in Alkene
4.2.3 Geometrical Isomerism in Oxime
4.2.4 Geometrical Isomerism in Azo Compounds
4.2.5 Properties
4.2.6 E and Z nomenclature of geometrical isomers
4.3 OPTICAL ISOMERISM
4.3.1 Optical Isomerism Concept
4.3.2 Types of Symmetry
4.3.3 Chiral Compound
4.3.4 Projection Formula of Chiral Molecules
4.3.5 Enantiomers
4.3.6 Diastereomerism
4.3.7 D-L System (Relative configuration)
4.3.8 Absolute Configuration (R, S configuration)
4.3.9 Meso isomers
4.3.10 Calculation of number of optical isomers
4.3.11 Stereochemical Formula
4.3.12 Pseudo Chiral Centre
4.3.13 Optically active compounds having no asymmetric carbon
4.3.14 Difference between Racemic mixture and Meso compound
4.3.15 External compensation
4.3.16 Internal compensation
4.3.17 Optical Purity

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 Stereochemistry

4.0 INTRODUCTION
Isomers that have the same structural formula but have a different relative arrangement of atoms or
groups in space are called stereo isomers and the phenomenon is known as stereo isomerism. It is
of three types:
(i) Conformational isomerism (ii) Optical isomerism
(iii) Geometrical isomerism
Stereoisomers

Configurational Conformational
(Inter-convertible
(non-interconvertible non-resolvable)
resolvable

Geometrical diastereomers Optical Isomers

(non-mirror image isomers)

Enantiomers Optical
(Mirror Image stereoisomers) (non-mirror image
optical isomers)

4.1 CONFORMATIONAL ISOMERISM

The different arrangement of atoms in space that result from the free rotation arround C—C bond
axis are called conformations. The phenomenon is called conformational isomerism
 Some Important Terms :
(i) Dihedral or Torsional angle : Angle between bonds of two adjacent atoms is knows as dihedral
or Torsional angle.
(ii) Staggered Conformation : Conformations which have 60° or 180° dihedral angle are known
as staggered conformations.
(iii) Eclipsed Conformation : Conformations which have 0° or 120° dihedral angle are known as
eclipsed conformations.
(iv) Skew Conformation : All other conformations are known as Skew Conformations.
 Conformers of ethane [CH3—CH3]:
HH
H
H H H H
H
H H
H
H H
C C H 60° H 60°

H H
H H H H H H H H H H
H H
H
(I) (II) (III) (IV)
(Saw-horse projection) (Newman projection)
I = III (Eclipsed form) in this form distance between 2C–H bonds is minimum so maximum repulsion
or minimum stable.
II = IV (Staggered form) in this form distance between 2C–H bonds is maximum so minimum
repulsion so maximum stable.
There are infinite conformers possible between eclipsed and staggered forms which are called as
skew forms
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Stability order: Staggered > Skew > Eclipsed

The variation of energy with rotation about the C–C bond in ethane has been shown in figure below:
H H
1 2
 Conformation of Ethane: [CH3—CH3] C C
H H H H

HH H H H H
H H H H

60° 60° 60°

H H H H H
H H H
H H H H H H
Eclipsed Staggered Eclipsed Staggered
 Stability order: Staggered > Eclipsed
 Energy order: Eclipsed > Staggered

3 Eclipsed E E
Potential Energy (P.E)

0 Staggered S S

60 120 10 240 300 360

dihedral angle ( )
The difference in the energy of various conformers constitutes an energy barrier to rotation. The
energy required to rotate the ethane molecule about carbon-carbon single bond is called torsional
energy. But this energy barrier is not large enough to prevent the rotation. Even at ordinary temperature
the molecules possess sufficient thermal and kinetic energy to overcome the energy barrier through
molecular collisions. Thus, conformations keep on changing form one form to another very rapidly
and cannot be isolated as separate conformers.
1 4
CH 3 CH3

 Conformation of Butane: [CH3—CH2—CH2—CH3] 2 3

C C
H H H H

Me Me Me Me Me Me
H Me H H

60° 60° 60°

H H H H H H H H
H H H H H Me
Fully eclipsed gauche partially eclipsed Anti
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 Stereochemistry

Me H Me Me Me
Me H

60° 60° 60°

Me H H
H H H
H H H H H
partially eclipsed Gauche Fully eclipsed
 (Fully eclipsed form): In this form distance between 2 methyl groups is minimum so maximum
repulsion or minimum stable.
 (Anti or antistaggered): In this form distance between 2 methyl groups is maximum so minimum
repulsion or maximum stable.
 Stability order: Anti > gauche > partially eclipsed > Fully eclipsed
 Energy order: Fully eclipsed > partially eclipsed > gauche > Anti
(i) Angle of rotation to get minimum stable to maximum stable form in butane is 180°.
(ii) Angle of rotation to get maximum stable to minimum stable form in butane is 360° or 0º.
(iii) The energy profile diagram for the conformation of butane is given below along with the difference
of energy between various conformation of butane.
(Eclipsed)

P.Eclipsed Eclipsed
P.E
Potential Energy (P.E)

Gauche Gauche
Anti

60 120 180 240 300 360

(Dihedral angle)
Energy changes that arises from rotation about the C2–C3 bond of butane
 Conformational analysis of cyclohexane:
(i) Chair form : Experimental evidences show that cyclohexane is non-planar. If we look to the
models of the different conformations that are free of angle strain first there is chair conformation.
If we sight along each of the carbon-carbon bonds in turn we see in every case perfectly staggered
bonds.
5 1
6
6 1 3 2
4 3 5
2 4
Chair conformation Chair conformation(all staggered bonds)
The conformation is thus free of all the strains, it lies at energy minimum and is therefore a
conformational isomer. The chair form is the most stable conformation of cyclohexane.
 Conformers of cyclohexane:
HA
HA 5 1 5 2 4 2 4 2
1 2 HB HA 3
3 4 1 5 HA
2 HB 3
4 6 HB HA 6 1
4 6 3 6 3 6 5
5 1 HB
chair half-chair twist-boat HB chair
half-chair
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conformational changes during the inversion of cyclohexane

half-chair half-chair
43
true boat

energy/kJ mol–1 25
21
twist-boat twist-boat

chair-A chair-B
Reaction coordination
(1) Order of Energy: Half chair > boat > Twisted boat > chair
(2) Order of stability: chair > Twisted boat > boat > Half chair
 Cyclohexnane is optically active in twisted boat form as there is no plane of symmetry and
centre of symmetry.
 Axial and equatorial bonds in chair form of cyclohexane:
HH
H
H H H H
H H H H

H H H H
H H H
H
HH H
Axial C–H bonds Equatorial C–H bonds Axial & Equatorial
bonds together
The 12 hydrogen atoms of chair conformation of cyclohexane can be divided into two groups.
Six of the hydrogens, called axial hydrogens, hence their bonds parallel to a vertical axis that
passes through the rings centre. These axial bonds are directed up & down on adjacent carbons.
The second set of six hydrogens called equatorial hydrogens are located approximately along the
equator of the molecule.
(ii) Boat form: Another conformation which is known as boat conformation has exactly eclipsed
conformations.
Flagpole
hydrogens

1
4 1 6 H H
4 2 H H
5 6 eH He
5 3
3 2 eH He
Boat conformation Boat conformation
(all eclipsed bonds) HH HH
a a a a
In boat form of cyclohexane 6 hydrogens are equatorial, 4 hydrogens are axial and two hydrogens
are flagpoles. It is an unstable conformation of cyclohexane due to torsional strain among axial
hydrogens and due to van der waals strain caused by crowding between the "flagpole" hydrogens.

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 Stereochemistry
 Conformational inversion (Ring flipping) in cyclohexane:
Like alkanes cyclohexane too is conformationally mobile. Through a process known as ring inversion,
Chair-chair interconversion, or more simple ring flipping one chair conformation is converted to
another chair.

6 1
5 6 5
4
1 2
3 2 3
4

axial
a a'
equatorial
a a'
4 3 2
5 6
56 2 3
b b' 4
1
equatorial b b'
axial
By ring flipping all axial bonds convert to equatorial and vice-versa. The activation energy for
cyclohexane ring inversion is 45 kJ/mol. It is a very rapid process with a half-life of about 10–5 sec at
25°C.
 Conformational analysis of monosubstituted cyclohexanes:
In ring inversion in methylcyclohexane the two chair conformations are not equivalent. In one chair
the methyl group is axial ; in the other it is equatorial. At room temperature 95% of the
methylcyclohexane exist in equatorial methyl group whereas only 5% of the molecule have an axial
methyl group.

CH3
H CH3
(95%)
(5%) H

 1, 3-diaxial repulsion: A methyl group is less crowded when it is equatorial than when it is axial.
The distance between the axial methyl groups at C-1 and two hydrogens at C-3 and C-5 is less than
the sum of their vander waal radii which causes vander waal strain in the axial conformation this type
of crowding is called 1,3-diaxial repulsions. When the methyl group is equitorial, it experience no
significant crowding.

H H
H C H H
H H 6
H 5
5 H 1 C
H 6 2 H
H 1
3 H
4 H H
H 2
Vander waals strain between No vander waals strain between
hydrogen of axial CH3 and axial hydrogen at C-1 and axial
hydrogens at C-3and C-5 hydrogens at C-3and C-5

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JEE

MID LEARNING EXERCISE (MLE)-17

Q.1 Which of the following shows conformational isomerism ?
H H H H
O O
(a) H C (b) C (c) (d) H C C H
H H
H H
H H H H H
H H H

(e) H C C C H
H H H
(A) b, d, e (B) a, b, c, e (C) b, c, d (D) c, d, e
Q.2 Most stable conformation of butane is:
(A) Partial eclipsed (B) Full eclipsed (C) Staggered (D) Gauche
Q.3 What is dihedral angle in staggered form of ethane ?
(A) 30° (B) 45° (C) 75° (D) 60°
Q.4 The pair of structures represents:

Me Me
H Me H H

H H H H
Cl CH 2Cl
(A) Enantiomers (B) Position isomers (C) Conformers (D) None
Q.5 Rotational angle require to get maximum stable conformer from minimum stable conformer in n-
butane is :
(A) 360° (B) 180° (C) 120° (D) 240°
Q.6 Which conformation of butane will have the minimum energy ?
(A) Gauche (B) Anti/staggered (C) Eclipsed (D) None
Q.7 In the following the most stable conformation of n-butane is:

CH3 CH3 CH3 CH3

H H CH3 H H CH 3

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

H H H H
H H H
CH 3 H CH3 H
Q.8 Which of the following conformers for ethylene glycol is most stable ?

OH OH OH OH
OH H H OH H H

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

H H HO H H H H H
H H H H H OH
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 Stereochemistry
Q.9 Give sawhorse representation for following compound
CH3
H OH
H OH
CH3

H H CH 3 OH
OH OH H CH 3
CH3 CH 3 H HO
(A) CH3 (B) CH3 (C) OH (D) H
HO H H OH HO CH 3 CH3 H
Q.10 Which one of the following is the most stable conformation of 2, 3-butanediol ?

OH OH OH OH
H OH H CH3 HO CH3 HO CH3

(A) H CH3 (B) (C) (D)

H CH3 H3C H H CH3
CH 3 OH H H
Q.11 What is the value of p & q of following conformer of 2,3-dimethyl butane?
p
H3C CH 3

H CH 3
q
(A) p = H, q = H (B) p = CH3, q = CH3
(C) p = CH3, q = H (D) p = H, q = CH3
Q.12 Which of the following is least polar and most stable conformer as compared to its other conformers?

CH3 CH3 Br CH3

H OH H H H H
H H
(A) (B) (C) (D)
H OH H H H H H H
CH3 NO2 F Cl
Q.13 Identify the compound and find the relation between them.

OH COOH
H COOH H C2H5

H C2H5 H CH 3
CH3 OH
(A) Conformational isomers or identical (B) Configurational diastereomer
(C) Configurational enantiomers (D) Constitutional isomers

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Q.14 Newmann projection representation of CH3  CH 2  CH  Et about C2—C3 is

|
CH3
H
H Y

X H
Me
Then X & Y are respectively :
(A) Me, Et (B) H, Et (C) Et, H (D) Et, Me
Q.15 In the given four conformational isomers which of the following has minimum torsional strain and
minimum steric strain.

OH CH 3
H H3C H

(A) (B) H CH 3
H3C CH3
H CH 3 CH 3

CH3 CH3
CH 3 H CH3

(C) H (D) H CH3

H CH3
CH 3 CH3
Q.16 Which of the following statement is not true?
(A) The different arrangements formed by rotation about a single bond are called conformations.
(B) The repulsion felt by the bonding electrons of one substituents as they pass close to the bonding
electrons of another substituent is called steric strain.
(C) The strain arises due to repulsion between electron clouds of the interacting atoms or groups is
called steric strain.
(D) The investigation of the various conformations of the compound and their relative stabilities is
called conformational analysis.
Q.17 What is the type of isomerism in following pairs?
H
H
H
H CH3

H and
CH 3 H H H
H3C
CH3
(I) (II)
(A) Conformational isomers (B) Position isomers
(C) Chain isomers (D) Geometrical isomers

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 Stereochemistry

4.2 GEOMETRICAL ISOMERISM

4.2.1 Geometrical Isomerism Concept :
A (pi) bond is always formed by sideways overlapping of unhybridised p-orbitals of two carbon
atoms above and below the plane of C atoms. A double bond consists of a  bond and a  bond as
shown below.

Ha Ha
C C
Hb Hb

If any one carbon atom of the double bond is rotated with respect to the other, the ‘p’ orbitals will not
overlap and  bond should break. The  bond dissociation energy is 251 KJ mole–1 and is not
provided by the collisions of molecules at room temperature. Therefore, the rotation about the C = C
(that is, carbon-carbon double bond) is not free but restricted, or a  bond prevents the free rotation
of carbon atoms of the double bond with respect to each other. Due to this hindered rotation the
relative positions of atoms or groups Ha and Hb attached to carbon atoms of the double bond get fixed
up and cannot exchange their positions. As a result, the substituted alkenes can exist in two distinct
isomers which differ from each other only in the relative position of atoms or groups in space around
the double bond. For example, maleic acid and fumaric acid.
H COOH H COOH
C C
C C
H COOH and HOOC H
Maleic acid Fumaric acid
(cis) (Trans)
4.2.2 Geometrical Isomerism in Alkene:
The isomer in which similar groups are present in the same direction (on the same side of the double
bond) is called ‘cis’ isomer and the one in which similar groups are in opposite direction is ‘trans’
isomer. For example, cis and trans 2-butene.
H H H CH3
C=C and C=C
CH3 CH3 CH3 H
cis-isomer trans-isomer
Such isomers that have the same structural formula but differ in relative spatial arrangement of
atoms or groups around the double bond are called geometrical isomers and the phenomenon is
called geometrical isomerism. It is a type of stereoisomerism.
It should be noted that all compounds with a carbon-carbon double bond do not show geometrical
isomerism. The necessary conditions are:
(i) That the molecule must have a double bond, and each of the two carbon atoms of the double
bond must have different substituents which may be the same or different.
For example:

a a a b
C=C and C=C
b b b a
(cis) (trans)
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 JEE
a d
C=C a c
b c C=C
(Z ) b d
(E)
(If groups a and d have
higher priority as explained (If groups a and d have
in subsequent paragraphs) higher priority)
(ii) This isomerism is not possible if one or both carbon atoms have two similar substituents. In such
a case, the two isomers will be the same.
a c a d
C=C C=C
a d a c
It is for this reason that alkenes like propene and 1-butene do not show geometrical isomerism

CH3 H CH3CH2 H CH3 H

C=C C=C C=C
H H H H CH3 H
Propene But-1-ene 2-methylprop-1-ene
Note: All geometrical isomers have the same molecular structure but differ only in the relative
positions of atoms or groups in space and so these are also called stereoisomers. However, note that
these stereoisomers are not optical isomers since their molecules are not chiral.
4.2.3 Geometrical Isomerism in Oxime:
Besides alkenes, the compounds having C = N and N = N bonds also exhibit geometrical isomerism.
However, in these, the terms ‘syn’ and ‘anti’ are used for ‘cis’ and ‘trans’. Cyclic compounds and
dienes also show geometrical isomerism. Consider the examples given below.

C6H5 C 6 H5 OH



C=N aldoxime C=N

H OH H



(syn) (anti)
(It is also possible in ketoxime if R1 and R2 are different).
R1 R2
C
Ketoxime N


OH
4.2.4 Geometrical Isomerism in Azo Compounds:
 = N
Azo compounds have – N  – so are capable of exhibiting geometrical isomerism


   C6 H 5  

N=N N=N
C6H 5 C6H5 

C6 H 5
(syn) (anti)
A few other examples of cyclo compounds where restricted rotation is possible, can exhibit geomerical
isomerism.
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 Stereochemistry

OH OH H H H H3C

CH 3 CH 3 CH3 H
OH OH
(trans) (cis 1,2-dimethyl (trans 1,2-dimethyl
(cis)
cyclohexane) cyclohexane)

Cl Cl
H Cl H H
H H
H H H Cl
(cis 1,2-dichloro (trans 1,2-dichloro
cyclopropane) cyclopropane)

MID LEARNING EXERCISE (MLE)-18

Q.1 Which of the following shows Geometrical isomerism?

H Cl H Me
H
Me
(a) H H (b) Cl Cl (c) Cl Br (d)
Cl Cl Me
H H
Cl Br
Me
(A) a, b, d (B) a, c, d (C) a, b, c (D) b, c, d
Q.2 Geometrical isomers differ in
(A) Position of atoms (B) Length of carbon chain
(C) Spatial arrangement of atoms (D) Position of functional group
Q.3 Which is a pair of geometrical isomers?
Cl Br Cl Br Cl CH3 H Br
C C C C C C C C
H Br H CH3 Br Me Cl CH 3
(I) (II) (III) (IV)
(A) (I) and (II) (B) (I) and (III)
(C) (II) and (IV) (D) (III) and (IV)
Q.4 Which of the following show geometrical isomersm ?
(a) CH3 – CH2 – CH = N – OH (b) H2C = N – OH

(c) CH3  C  CH3 (d) CH3  C  CH 2 CH 3

|| ||
N  OH N  OH
(A) a, c (B) c, d (C) a, d (D) b, c
Q.5 Which of the following can show geometrical isomerism ?
(A) 1, 1–Diphenyl–1–butene (B) 1, 1–Diphenyl–2–butene
(C) 2, 3–Dimethyl–2–butene (D) 3–Phenyl–1–butene

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JEE
Q.6 Which compound shows cis-trans isomerism ?
(A) 1-butene (B) 2-propene (C) 2-butene (D) Benzene
H3C CH3 H3C H
Q.7 C C and C C exhibit which isomerism
H H H CH3
(A) Position isomerism (B) Geometrical isomerism
(C) Chain isomerism (D) Functional isomerism
Q.8 Which of the following does not show geometrical isomerism ?
(A) 1, 2-dichloro-1-pentene (B) 1, 3-dichloro-2-pentene
(C) 1, 1-dichloro-1-pentene (D) 1, 4-dichloro-2-pentene
Q.9 Which of the following will show geometrical isomerism ?
(A) CH3CH = CHCH3 (B) (CH3)2C = C(CH3)2
(C) (CH3)2C = CH2 (D) CH3 CH = C(CH3)2
Q.10 Which compound does not show geometrical isomerism ?
(A) 2-butene (B) 2-pentene
(C) 2,3-dibromo-2-butene (D) 2-methyl propene
Q.11 Geometrical isomerism is shown by-
(A) 2-butene (B) 2-butyne (C) 2-butanol (D) Butane
Q.12 Geometrical isomers are possible for-
(A) 3-butenoic acid (B) 2-phenylpropenoic acid
(C) 3,3-diphenylpropenoic acid (D) 3-phenypropenoic acid
Q.13 Which of the following compounds can show geometrical isomerism?
(A) 1-Methylcyclobutanol (B) 2,2-Dimethylcyclobutanol
(C) 3,3-Dimethlcyclobutanol (D) 1, 3-Dimethylcyclobutanol
Q.14 Geometrical isomers are possible for
(A) CH3CH 2  C  CH 2 CH 3 (B) CH3  CH 2  C  CH3
|| ||
NOH O

(C) CH 3 CH 2  C  CH 3 (D) C6 H5  C  C6 H5
|| ||
NOH NOH
Q.15 Which of the following pairs of compounds are geometrical isomers?
I Cl F I Br F Cl I
(A) C=C and C=C (B) C=C and C=C
F Br Cl Br Cl I Br F
I F Br I I Cl Br I
(C) C=C and C=C (D) C=C and C=C
Br Cl F Cl F Br Cl F
Q.16 Which among the following compounds will show geometrical isomers?
(A) CH3 – CH = CH2 (B) CH3  C  CH 2
|
CH3

(C) CH 3  C  CHD (D) CH3 – CH = CHD

|
CH3
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 Stereochemistry
4.2.5 Properties:
Geometrical isomers differ in physical properties and also in some chemical properties.
The cis form is comparatively less stable due to mutual repulsion in groups. The trans form being
symmetrical in most of the cases has a zero dipole moment. Even in cases where the trans form is
not symmetrical, it has a low dipole moment as compared to the cis form. Since the trans form is
less polar, it is less soluble in water. The cis form is polar and has a comparatively higher boiling
point; however, the melting point of trans is more because of better packing due to symmetry in the
molecule.
4.2.6 E and Z nomenclature of geometrical isomers:
Sometimes, it becomes difficult to assign cis or trans form to an isomer.
For example:
Cl F Cl I
C=C or C=C
Br I Br F
The following rules are observed in such a case.
(i) The priority of the two attached groups is individually decided. It is decided as mentioned in
the discussion of R and S configuration.
(ii) If the higher priority groups are on the same side of double bond, then it is Z isomer and if the
higher priority groups are attached on the opposite side to the double bond, then it is E isomer.
In the above case
(2) (2) Cl I (1)
Cl F (2) C=C
C=C or (1) Br F (2)
(1) Br
(Z) I (1) (E)
In maleic (cis) and fumaric (trans) acids, we have

(2) H COOH (1) (2) H COOH (1)

C C
C C
(2) H COOH (1) and
(1) HOOC H (2)
Z-(cis) E-(Trans)
Normally, ‘Z’ isomer is ‘cis’ and ‘E’ is ‘trans’; however, it is not always necessary.
In compounds like ‘oximes’ having C = N the N is attached to only one group and its other
direction is unattached, and this unattached direction is given a low priority. In benzaldoxine
(2)
(1) C6H5 (1) C6H5 OH (1)
C=N C=N
(2) H OH (1) (2) H (2)
syn-benzaldoxine anti-benzaldoxine
E-isomer Z-isomer
 Geometrical Isomerism in cycloalkenes:
The cycloalkenes donot show geometrical isomerism upto seven numbered ring.
H
, , , ,
H
only single isomer exist
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JEE
A ring of 8-carbon can show cis-trans isomerism. But its trans form is very less stable

H H Trans form
(cis-form cyclooctene)
so ring having 8-carbon or more than 8-carbon can show geometrical isomerism

H
H

H H
cis Form Trans form

MID LEARNING EXERCISE (MLE)-19

Q.1 Which of the following will not show geometrical isomerism ?

Me Me
(A) (B) Me (C) Cl (D)

Q.2 cis–trans isomerism is shown by-

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

Q.3 Which of the following will form geometrical isomers?

Cl
(A) (B) CH3CH = NOH (C) (D) All of these
Cl
Q.4 Geometrical isomerism is possible in-

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

Q.5 Which of the following compounds does not have any geometrical isomer?
Cl Cl Cl
Cl Cl Cl Cl
(A) (B) (C) (D) Cl
Cl Cl Cl Cl
Q.6 Which of the following pairs are geometrical isomers?
H 3C CH3 H3C H
(A) C C C C and C C C C
H H H CH3

H 3C CH3 H3C H
(B) C C C and C C C
H H H CH 3
(C) Both (A) and (B) (D) None of the above

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 Stereochemistry

Q.7
(I) (II) (III)
Which of these compounds will exhibit geometrical isomerism?
(A) I (B) II (C) III (D) None of these
Q.8 The correct IUPAC name of Br is

(A) 7–Bromo–2Z, 5E–Heptadiene (B) 1–Bromo–2Z, 5E–Heptadiene

(C) 1–Bromo–2E, 5E–Heptadiene (D) 1–Bromo–2E, 5Z–Heptadiene
Q.9 Which of the following represents (E)–3,6–dichloro–6–methyl–3–heptene?
Cl Cl
(A) (B)
Cl Cl
Cl
(C) (D)
Cl Cl Cl
Q.10 According to CIP sequence rule, the correct arrangement in order of decreasing priority is-
(A) –OH > –CH2OH > –CHO > –COOH (B) –OH > –COOH > –CHO > –CH2OH
(C) –COOH > –OH > –CHO > –CH2OH (D) –COOH > –CHO > –CH2OH > –OH
Q.11 Applying the sequence rule, which of the following priority arrangements is correct in determining
the E/Z configuration of
(A) –C6H5 > –CH = CH2 > –CHO > –COOH (B) –COOH > –CH = CH2 > –CHO > –C6H5
(C) –COOH > –CHO > –C6H5 > –CH = CH2 (D) –COOH > –C6H5 > –CHO > –CH = CH2
Q.12 The total number of isomers having the molecular formula C2BrClFI is
(A) 3 (B) 4 (C) 5 (D) 6
Q.13 The total number of geometrical isomers of 2,4–hexadiene is
(A) 2 (B) 3 (C) 4 (D) 5
Q.14 The total number of geometrical isomers of 2,4–hexadienoic acid is
(A) 2 (B) 3 (C) 4 (D) 5
Q.15 Which of the following would exhibit cis-trans isomerism?
(A) CH 3CH 2 CH  CH 2 (B) ClCH  CHCl
(C) ClCH  CCl 2 (D) CH 2  CH  COOH

4.3 OPTICAL ISOMERISM

4.3.1 Optical Isomerism Concept:
Compounds which have same molecular and structural formula but have different optical activity are
known as optical isomers.
 Optical activity:
Certain substances possess the property to rotate the plane of polarized light. Such substances are
called optically active substances and this phenomenon is called optical activity.
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 JEE
Light has vibrations occur in all planes at right angles to the line of propagation. In plane polarized
light the vibrations take place only in one plane. Plane polarized light can be obtained by passing
ordinary light through a Nicol prism.

detector
light
source sample analyzer
compartment
polarizer

Certain organic compounds, when their solutions are placed in the path of a plane polarized light,
have the remarkable property of rotating its plane through a certain angle which may be either to the
left (or) to the right. This property of a substance of rotating the plane of polarized light is called
optical activity and the substance possessing it is said to be optically active.
The observed rotation of the plane of polarized light [determined with the help of polarimeter] produced
by a solution depends on :
(a) The amount of the substance in tube
(b) On the length of the sample tube
(c) The temperature of the experiment and
(d) the wavelength of the light used
The instrument used to measure angle of rotation is called polarimeter. The measurement of optical
rotation is expressed in terms of specific rotation []Dt ; this is given by the following relation :

 obs
[ ]tD  [where  = observed angle of rotation]
C
[ ]tD = specific rotation determined at t°C, using D-line of sodium light.
 = length of solution in decimeters
C = concentration of the active compound in grams per millilitre.
The sign attached with the angle of rotation signifies the direction of rotation. Negative sign (–)
indicates that the rotation is towards anti-clockwise, while positive (+) sign means that the direction
of rotation is toward right clockwise.
If the substance rotates plane-polarised light to the right i.e. in clockwise direction it is called
dextrorotatory and indicated by ‘d’ or (+)
If the substance rotates plane-polarised light to the left i.e. in anti clockwise direction it is called
laevorotatory and indicated by ‘l’ or (–)
 Condition of Optical Activity
Compound must not contain plane of symmetry and centre of symmetry.
4.3.2 Types of Symmetry:
(i) Plane of symmetry (POS):
An imaginary plane which bisects any object or molecule into two equal parts which are mirror
images of each other is known as POS.

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 Stereochemistry

H Me

Cl H OH
H H H
H OH
Cl Me Me Me
Plane of symmetry Plane of symmetry Plane of symmetry

MID LEARNING EXERCISE (MLE)-20

Q.1 Which dimethylcyclobutane does not contain plane of symmetry ?
(A) trans 1, 2 (B) cis 1, 2 (C) trans 1, 3 (D) cis 1, 3
Q.2 Total number of plane of symmetry (POS) in 1-bromo-3-chlorocyclobutane-
(A) 0 (B) 1 (C) 2 (D) 3
Q.3 Rotation of plane polarised light is measured by-
(A) Manometer (B) Polarimeter (C) Viscometer (D) Refractometer
Q.4 An organic compound exhibit optical isomerism, when
(A) It contains Centre of Symmetry (B) It contains Plane of Symmetry
(C) It contains Elements of Symmetry
(D) It doesn’t contains any Element of Symmetry
Q.5 Which of the following conformation of n-butane has a plane of symmetry?

CH 3 CH3
CH3 H 3C H
(A) H (B) H
H H
H H H

CH3 CH3
H CH3 H
(C) H (D) H
H H
H H CH3

Q.6 The property by virtue of which a compound can turn the plane polarised light is known as
(A) Photolysis (B) Phosphorescence (C) Optical activity (D) Polarization
Q.7 Which species exhibits a plane of symmetry?
COOH
CH3 H
H
(A) H
H H (B)
CH3
H H
H OH
Ph Ph
H COOH
H H H
H H HH
(C) (D) H
HOOC H
H H COOH COOH

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JEE
Q.8 How many plane of symmetry are present in following compound ?
Cl Cl
C C
H H
(A) 0 (B) 1 (C) 2 (D) 3
Cl

Q.9 Cl
Cl
Number of planes of symmetry in the above molecule is:
(A) 0 (B) 1 (C) 2 (D) 3
Q.10 How many planes of symmetry in the following compounds ?
H H
(a) C=C (b)
H H
(A) a - 1, b - 3 (B) a - 2, b - 5 (C) a - 3, b - 7 (D) a - 4, b - 9
Q.11 How many of the following posses plane of symmetry ?
CH 3 CO2 H CO2 H
H OH H OH H OH
HO OH HO H H OH
CH 2OH CO2 H CO2 H

CH3 H CH 3 CH3
NO2 NO2 H CH 3
H Cl
CH2BrCl
CH3 H
H CH 3 H H I I Cl H
(A) 2 (B) 3 (C) 4 (D) 5
Q.12 Determine the number of planes of symmetry of the given compound-

Cl
(A) 1 (B) 2 (C) 3 (D) 4
Q.13 Which of the following compound has centre of symmetry ?
Br
O
H2 C CH2 CH3
H NH – C
(A) (B) C – NH H
H2 C CH2 H3 C
O
Br
H3C H
Cl

(C) (D) All of these

Cl
H CH3
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 Stereochemistry
Q.14 Which of the following compound is achiral ?
Me
O

(A) O (B)

Me O

(C) H H (D) All of these

Cl Br Cl
Q.15 Which of the following compound is achiral ?

H2C CH2 H2 C CH2

(A) (B)
H2C CH2 H2 C CH2

CO2H HO2 C

H2C CH2
HO2C
(C) (D)
H2C CH2

HO2C
(ii) Center of Symmetry (COS): It is a point inside a molecule from which on travelling equal
distance in opposite directions finds same group at same distance.
CH3 COOH
Cl
R H
H H H H
H
•
H
C=C
H R
Centre of symmetry Cl
Centre of symmetry
COOH CH3
(iii) Axis of Symmetry (AOS) (Cn): Axis of symmetry is an axis such that if one rotates the
360 
molecule by , the new position of molcule is superimposable with the original one.
n

H3C CH 3 H3C CH 3
C C  C C
H H H H

180°
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 JEE
(iv) Alternate axis of Symmetry (AAOS): An imaginary plane around which rotation by angle x
360
gives its mirror image is known as AAOS. It is represented by Sn where n =
x

H3C H H CH 3
C C  C C
H CH 3 CH 3 H

180°
4.3.3 Chiral Compound:
Compound which is not super imposable on its mirror image is known as Chiral Compound. All
optically active compounds are Chiral.
 Asymmetric carbon (or) Chiral Carbon
If all the four bonds of a single carbon are satisfied by four different atoms/groups, it is chiral.
Chiral carbon is designated by an asterisk (*).
Br

Example : H C* Cl
I

MID LEARNING EXERCISE (MLE)-21

Q.1 How many chiral carbon atoms are present in following molecule ?
C 2 H5
|
CH 3  CH  CH  CH  CH 3
| |
Cl CH3
(A) 1 (B) 2 (C) 3 (D) 4
Q.2 Which of the following molecule has chiral carbon ?
Me C2H 5 Et Cl
(A) Cl CH3 (B) HO H (C) H Me (D) I Br
H C2H 5 H F
Q.3 Which one of the following contains asymmetric carbon atom ?

Cl Br H Cl H H H H
| | | | | | | |
(A) H  C  C  H (B) H  C  C  Cl (C) H  C  C  H (D) H  C  C  CH3
| | | | | | | |
H H H H H H Br OH
Q.4 Which of the following contains asymmetric centre ?
(A) 2-Butene (B) 2,2-Dimethylpropane (C) 2-Hexyne (D) Lactic acid
Q.5 Which of the following has chiral carbon ?
H
|
(A) CH 3  CH  CH 2 COOH (B) CH3 – CH = CH – CH3

CH3
|
(C) CH 3  CH  CH 2 OH (D) CH3 – CHOH – CH2CH3

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 Stereochemistry
Q.6 Which of the following molecule is chiral ?
(A) Isobutane (B) Neopentane (C) Sec-butylchloride (D) All
Q.7 Which one of the following shows optical activity ?

H H
| |
(A) HO  C  COOH (B) CH 3  C  COOH
| |
H Cl

CH3 CH3
| |
(C) CH3 – C – COOH (D) CH3 – C – COOH
| |
OH Cl
Q.8 Which of the following compounds is not chiral ?
(A) DCH2CH 2CH 2Cl (B) CH3CH2CHDCl
(C) CH3CHDCH2CH 2Cl (D) CH3CHClCH2D
Q.9 Which of these molecule is optically active ?
CH3
CH3 C2H 5
H Br
H Br H Br H Br
C2H 5 CH3 C2H5
(I) (II) (III)
(A) I (B) II (C) III (D) All of these
Q.10 Which is optically active ?
HO CH3
(A) H3C CH3 (B)
Cl
COOH
H OH
(C) (D)
H OH
COOH
Q.11 Total number of plane of symmetry (POS) and centre of symmetry (COS) in cis–1,3-
dichloroyclobutane-
(A) 0, 0 (B) 0, 1 (C) 1, 1 (D) 2, 0
Q.12 How many different chiral molecules can be obtained by the replacement of one hydrogen with
chlorine in cyclopropene, cyclobutene, cyclopentene and cyclohexene respectively ?
(A) 0, 2, 2, 4 (B) 0, 0, 1, 1 (C) 0, 0, 0, 1 (D) 1, 1, 1, 2
CH 3 H
HOOC
H H
Q.13 COOH
H CH 3
The above configuration has
(A) plane of symmetry (B) axis of symmetry
(C) centre of symmetry (D) not any type of symmetry
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 JEE
Q.14 How many chiral centres are present in cholesterol?

H3C

H3C H

H H
HO

(A) 7 (B) 8 (C) 9 (D) 5

H 3C H
Q.15 The compound C C shows-
COOH
H 3C C
H CH3

(A) Optical isomerism (B) Geometrical isomerism

(C) Tautomerism (D) Optical & Geometrical isomerism
Q.16 Which of the following conformation on n-butane has a centre of symmetry?

CH3 CH3 H H
CH3
(A) (B)
H H H H CH3
H H

CH3 H
H CH3 H H
(C) H (D) H 3C H
H
H CH3

4.3.4 Projection Formula of Chiral Molecules:

(i) Wedge-Dash Projection formula:
down

up

CH 3

C
Ex. (i) Butan-2-ol
H C 2H 5
OH
(ii) Ficher Projection formula:
Rules of writing Fisher Projection formula
(a) Groups at Vertical line are away from observer.

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 Stereochemistry
(b) Groups at Horizontal line are towards the observer.
(c) Central ‘C’ atom of the cross is chiral.
(d) High priority group lies at the top of vertical line (Numbering starts from top).

CH3 CH 3

H OH HO H

CH2CH 3 CH 2CH3
4.3.5 Enantiomers:
Stereoisomers which are non-superimposable mirror-image of each other are called enantiomers
(or) enantiomorphs.

CH3 CH 3

H OH HO H

CH2CH 3 CH 2CH3
 Enantiomer have same physical properties like melting point, boiling point refrective index, density,
solibility etc., but different optical rotation (same magnitude but different sign)
4.3.6 Diastereomerism:
The stereo isomers are not mirror images to each other are called diastereomers which may or may
not be optically active.
 All geometrical isomers are diastereomers
 diastereomers have different physical and chemical properties
Ex.:
CH3 CH3 CH3 CH3
H Cl Cl H H Cl Cl H
H Cl Cl H Cl H H Cl
CH2CH3 CH2 CH3 CH2 CH3 CH2CH3
(I) (II) (III) (IV)

I, II = Enantiomers, III, IV = Enantiomers

I, III = Diastereomers, II, IV = Diastereomers
II, III = Diastereomers, I, IV = Diastereomers

COOH COOH
H OH HO H
H OH HO H
Ex.: COOH (I) COOH (II)
Achiral
I and II are identical

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 JEE
4.3.7 D-L System (Relative configuration):
 Application on correct Ficher Projection Formula:
This method is used to relate the configuration of sugars and amino acids to the enantiomers of
glyceraldehyde. The configuration of (+)-glyceraldenyde has been assigned as D and the com-
pounds with the same relative configuration are also assigned as D, & those with (-) glyceraldehyde
are assigned as L.
CHO CHO
H OH HO H
(R)CH 2OH CH2OH (S)
D-(+)-glyceraldehyde L-(+)-glyceraldehyde
–OH group on right side –OH group on left side
Ex.:
COOH COOH COOH

NH2 H H NH2 H2 N H

CH3 CH2 OH CH2 CH2COOH

L-Alanine D-(+)-serine L-(+)-Glutamic acid
Sugars have several asymmetric carbons. A sugar whose highest numbered chiral centre (the penultimate
carbon) has the same configuration as D-(+)-glyceraldehyde (–OH group on right side) is designated
as a D-sugar, one whose highest numbered chiral centre has the same configuration as L-glyceralde-
hyde is designated as an L-sugar.
CH2 OH
CHO CHO
C=O
H OH CHO H OH
OH H
OH H OH H OH H
H OH H OH H OH H OH
e.g.,
H OH H OH H OH
CH 2OH
CH2 OH CH2 OH
CH2OH
D-(+)-Glucose D-(+)-Threose D-(+)-Fructose D-Mannose
4.3.8 Absolute Configuration (R, S configuration):
The actual three dimensional arrangement of groups in a molecule containing asymmetric carbon is
termed absolute configuration.
System which indicates the absolute configurastion was given by three chemists R.S. Cahn,
C.K. Ingold and V. Prelog. This system is known as (R) and (S) system or the Cahn–Ingold
system. The letter (R) comes from the latin rectus (means right) while (S) comes from the latin
sinister (means left).
 (R) (S) nomenclature is assigned as follows :
Step 1 : Assign priority to the groups which are attached with chiral carbon.
Step 2 : Bring the lowest priority group to dash by even simultaneous exchanges.
Step 3 : Draw an arrow from first priority group to second priority group till third priority group.
Step 4 : If the direction of arrow is clockwise the configuration is R and if anticlockwise it is S.
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 Stereochemistry
 RS Nomenclature in ficher formula :
Step 1 : Assign priority to the groups which are attached with chiral carbon.
Step 2 : Bring the lowest priority group to vertical line.
Step 3 : Draw an arrow from first priority group to second priority group till third priority group.
Step 4 : If the direction of arrow is clockwise the configuration is R and if anticlockwise it is S.

(1)
OH C2 H5
H
S
(2) C2H5 CH3 S
C C CH3 OH
H CH3 OH C2 H5
(4) (3) H

 Important:
Note that the designation of a compound as R or S has nothing to do with the sign of rotation. the
Cahn-Ingold rule can be applied to any three dimensional representation of a chiral compound to
determine whether it is R or S only. For example in above case (i.e. lactic acid), R configuration is
laevo rotatory is designated as R-(–)-lactic acid. Now the other configuration of it will have opposite
sign of rotation i.e. S-(+)- lactic acid.

MID LEARNING EXERCISE (MLE)-22

Q.1 Which one of the following structure is D-Glyceraldehyde?

CHO CHO OH CH2 OH

(A) H OH (B) HO OH (C) HOH2 C H (D) H OH
CH2 OH CH2 OH CHO CHO

Q.2 If optical rotation produced by the compound (A) is 52º, then that produced by the compound (B) is:

CH 3 CH3
Cl H H Cl
H Cl Cl H
CH 3 CH3
(A) (B)
(A) –52º (B) +52º (C) Zero (D) Unpredictable

CHO CHO
H OH H OH
Q.3 HO H and HO H are:
H OH HO H
CH2 OH CH2OH

(A) diastereomers (B) enantiomers (C) tautomers (D) conformers

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JEE
Q.4 Which of the following is the enantiomer of the compound shown below ?

H
Me Br
Br H
Me OH
Et

H H H H
Br Me Me Br Br Me Br Me
Br H H Br Br H H Br
(A) (B) (C) (D)
HO Me Me OH HO Me Et OH
Et Et Et Me

Br CH3 H CH3
Q.5 and are
H H Br H
(A) enantiomers (B) diastereomers (C) conformers (D) homologous
Q.6 How are the following compounds related?
H3C Br CH3
Br
Br
H Br H CH3
(A) Diastereomers (B) enantiomers (C) meso form (D) identical
Q.7 Which of the following pairs of compounds is a pair of enantiomers ?

Br Br

(A) (B)
Cl Cl

Cl Cl

(C) (D)

Cl Cl Cl Cl
Q.8 Which one of the following is threo?

CH2OH CH 2OH CH2OH

| | |
H — C — Br HO — C — H H — C — Br
| | |
(A) HO — C — H (B) H — C — OH (C) H — C — H (D) (A) and (B) both
| | |
CH3 CH 3 CH3

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 Stereochemistry
Q.9 Which of the following has ‘S’ configuration ?

F H
Et CH3
C H C F
(A) H F (B) (C) (D) F H
H3C H3C
Me CH 2CH3 CH 2CH3 CH2CH 3
Q.10 The configuration of the compound
Br
H
C
H3C Et
(A) R (B) S (C) Z (D) E
Q.11 (2R, 3R)-2, 3-Butanediol is -

CH3 CH 3 CH 3 CH3
HO H H OH H OH OH H
(A) H OH (B) HO H (C) H OH (D) OH H
CH3 CH 3 CH 3 CH3
Q.12 Among the following L-serine is-
COOH COOH NH 2 CH2OH
(A) H NH2 (B) HOH 2C H (C) H COOH (D) H2N H
CH 2–OH NH 2 CH 2OH COOH
Q.13 D & L Configuration is applied for -
(A) Amino acids (B) Carbohydrates
(C) Both (A) and (B) (D) None of these
Q.14 Erythro & Threo are the pair of -
(A) Enantiomers (B) Diastereomers (C) Identical (D) Meso compounds
Q.15 The following two compounds are

Cl Br
H F and F Cl

Br H

(A) Enantiomers (B) Diastereomers (C) Identical (D) Epimer

Q.16 Which of the following can show enantiomerism ?
CH3
|
(A) CH3  CH  COOH (B) CH2 = CHCH2CH2CH3

NH 2 NH 2
| |
(C) CH3  CH  CH3 (D) CH3  CH 2  CH  CH3

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 JEE
Q.17 Which of the following compounds can exist in optically active form ?
(A) 1-Butanol (B) 2-Butanol (C) 3-Pentanol (D) 4-Heptanol
Q.18 Which of the following is optically active ?
(A) Ethylene glycol (B) Oxalic acid (C) Glycerol (D) Tartaric acid

4.3.9 Meso isomers:

(i) Achiral compounds which have chiral centers but contains POS or COS are known as meso
compound.
(ii) They are achiral (optical rotation = 0).
(iii) They have [] = 0 due to internal compensation of optical rotation.
(iv) They are diastereomer of d- pair. So, it has different physical properties than d- pair.
(v) Presence of more than one asymmetric ‘C’ atoms.
(vi) They are non resolvable.
 Stereoisomerism in Tartaric Acid:
Tartaric acid exists in only three stereomeric forms. Two of them (1 and 2) are non superimposable
mirror images of each other so they are enantiomers of each other. The 3rd isomer is non mirror
image stereomers of (1) and (2) so it is diastereomer of (1) and (2). 3rd isomer containes plane of
symmetry so, it is optically inactive. It is known as meso tartaric acid.

COOH COOH COOH

HO H H OH H OH
H OH HO H H OH
COOH COOH COOH
(1) (2) (3)
Meso tartaric acid
4.3.10 Calculation of number of optical isomers:
The number of optical isomers of an organic compound depends on its structure and number of
asymmetric carbon atoms. Thus, the number of optical isomers may be determined from the knowledge
of the structure of the compound as follows :
(i) When the molecule is unsymmetrical

 T otal no. of optically active isomers = (a + m) = 2 n

No. of optically active isomers, a = 2n
Number of meso forms (m) = 0
2n
Number of enantiomeric pair, r = a/2 =
2
(ii) When the molecule is symmetrical and has even no. of asymmetric carbon atoms.

 Total no. of stereo isomers = (a + m) = 2n –1  2n/2–1

No. of optically active isomers, a = 2(n –1)
n
1
Optically inactive / No. of meso forms, m  2 2
n 1
No. of enantiomeric pair, r = a/2 = 2 2

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 Stereochemistry
(iii) When the molecule is symmetrical and has an odd no. of asymmetrical carbon atoms.

 Total no. of stereo isomer = (a + m) = 2(n–1)

n 1
no. of optically active isomers, a  2( n 1)  2 2

n 1
Optically inactive / No. of meso forms, m  2 2

Example Structural formula: CH 3  CH  CH CH 2  CH 3

| |
Cl Cl
Optical isomer = 2n = 22 = 4
4.3.11 Stereochemical Formula:

CH 3 CH3 CH3 CH 3
H Cl Cl H H Cl Cl H
;
H Cl Cl H Cl H H Cl
C2H 5 C2H5 C2H5 C 2H 5
(I) (II) (III) (IV)
[] = + x
o o o o
–x +y –y

Analysis:
I, II – Enantiomers III, IV – Enantiomers
I, III – Diasteromers I, IV – Diasteromers
II, III – Diasteromers II, IV – Diasteromers
4.3.12 Pseudo Chiral Centre:
A chiral center which becomes achiral on changing the configuration of one of its substituents and
vice versa

CH3
CH OH
Pseudo chiral center  CH Br
CH OH
CH3

MID LEARNING EXERCISE (MLE)-23

Q.1 Meso–tartaric acid is optically inactive due to the presence of –
(A) Geometrical isomerism (B) Two chiral carbon atoms
(C) Internal compensation (D) External compensation
Q.2 The process of separation of racemic modification into d– and l– enantiomers is called –
(A) Resolution (B) Dehydration
(C) Racemisation (D) Dehydrohalogenation

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JEE
Q.3 Which of the following compounds are meso forms?
CH 3 CH 3 CH3
H OH H OH
H OH H H
CH 3
C 2H5 C 2H5
(1) (2) (3)
(A) 1 only (B) 3 only (C) 1 and 2 (D) 2 and 3
Q.4 Among the following aldose which is D-threose
CHO CHO CHO CHO
H OH H OH HO H HO H
(A) HO H (B) H OH (C) HO H (D) H OH
CH 2OH CH 2OH CH 2OH CH 2OH
Q.5 Which of the following can be a meso compound?

(A) (B) (C) (D) All of these

Br
Q.6 Meso-tartaric acid and d-tartaric acid are
(A) positional isomers (B) enantiomers (C) Diastereomers (D) racemic mixture
Q.7 Which one of the following is a meso-compound?
COOH CH 3 COOH CH 2OH
H OH H OH HO H H Cl
(A) H OH (B) HO H (C) HO H (D) H Cl
CH 2OH CH 3 CH 3 CH 2OH
Q.8 Which of the following will have a meso isomer also
(A) 2,3-Dichloropentane (B) 2,3-Dichlorobutane
(C) 2-Chlorobutane (D) 2-Hydroxypropanoic acid
Q.9 Which of the following statement is incorrect?
(A) A meso compound has chiral centres but does not exhibit optical activity.
(B) If a molecule is dissymmetric, it rotate the plane of plane polarized light.
(C) A meso compound is optically inactive because the rotation caused by any molecule is canelled
by an equal and opposite rotation caused by another molecule that is the mirror image of the
first.
(D) The two disastereomers have same structure formula but different physical and chemical
properties.
Q.10 How many stereoisomers of shikonin (a drug for healing of wounds) are possible & how many of
them are optically active ?
OH O

OH O OH
(A) 4, 2 (B) 4, 4 (C) 8, 4 (D) 16, 4
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 Stereochemistry
Q.11 Which of the following compounds is a meso compound?
(A) (2R,3R)-dibromobutane (B) (2R,3S)-dibromobutane
(C) (2R,3S)-3-bromo-2-butanol (D) (2R,3R)-3-bromo-2-butanol
Q.12 Total number of stereoisomer of compound is :
CH3  CH  CH  CH  CH  CH  CH3
|
Cl

(A) 2 (B) 4 (C) 6 (D) 8

Q.13 How many stereoisomers are possible for following molecule ?

Cl Br

(A) 4 (B) 8 (C) 12 (D) 16

Q.14 Find out no. of sterogeniccentre in following compound:

NH2 H
N S

O N
HO O
COOH
(A) 4 (B) 5 (C) 3 (D) 6
Q.15 Number of streocentres and stereoisomers of the given compound will be-
CH3
OH

(A) 1 and 2 (B) 2 and 4 (C) 3 and 8 (D) 3 and 6

4.3.13 Optically active compounds having no asymmetric carbon:

(i) Allenes: An sp-hybridized carbon atom possess one electron in each of two mutually perpendicular
p orbitals. When it is joined to two sp2-hybridized carbon atoms, as in allene, two mutually
perpendicualr -bonds are formed and consequently the -bonds to the sp2-carbons are in
perpendicular planes. Allenes of the type abC=C=Cab (a  b) are therefore not superimposable
on their mirror images and despite the absence of any asymmetric atoms, exist as enantiomers
and several optically active compounds have been obtained.
(Ex. a = phenyl, b=1-naphthyl)

b b
a a
C C C C C C
b b
a a
(Optically active)
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 JEE
a
b
C C C
b
a
Optically inactive
(contains POS)
(ii) Alkylidene cyclo alkanes: The replacement of one double bond in an allene by a ring does not
alter the basic geometry of the system and appropriately substituted compounds exist in optically
active forms.
H CO2H
H
H 3C
Related compounds in which sp2-carbon is replaced by nitrogen have also been obtained as
optical isomers.
H OH
N
CO2 H
4.3.14 Difference between Racemic mixture and Meso compound:
A racemic mixture contains equimolar amounts of enantiomers. It is optically inactive due to external
compensation.
4.3.15 External compensation:
If equimolar amounts of d and -isomers are mixed in a solvent, the solution is inactive. The
rotation of each isomer is balanced (or) compensated by the equal but opposite rotation of the
other. Optical inactivity having this origin is described as due to external compensation. Such
mixtures of (+) and (–) isomer (Racemic mixtures) can be separated into the active components.
A meso compound is optically inactive due to internal compensation
4.3.16 Internal compensation:
In meso tartaric acid the inactivity is due to effects within the molecule and not external. The force
of rotation due to one of the molecule is balanced by the opposite and equal force due to the other
half. The optical inactivity so produced is said to be due to internal compensation. It occurs whenever
a compound containing two (or) more asymmetric carbon atoms has a plane (or) point of symmetry.
Since the optical inactivity of such a compound arises within the molecule, the question of separating
into active components does not arise.
Special Point:
(i) Chiral nitrogen containing tetra alkyl ammonium ion show optical isomerism.

R1 R1

N N
R4 R2 R2 R4
R3 R3
(I) (II)

I and II enatiomers
(ii) Chiral nitrogen containig tertiary amine do not show optical isomerism
Reason: Rapid umbrella inversion.

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 Stereochemistry

R2
R1 R3
N
N
Room temperature
R1 R3
R2
(I) (II)

(iii) Energy required for this interconversion is available at room temperature so I and II are enantiomers
and form a recemic mixture so overall solution is optically inactive.
(iv) Ortho substituted biphenyl compounds do not have any chiral carbon but due to chiral molecule,
they are optically active.

NO2 HOOC SO3H H3C

COOH O 2N CH 3 HO3S
Horizontal Vertical Optically active
plane plane
4.3.17 Optical Purity / Enantiomeric Excess:
Some times we deal with mixtures that are neither otpically pure nor racemic mixture. In these cases
we specify the optical purity of the mixture. It is defined as the ratio of its rotation to the rotation of
pure enantiomer.
observed optical rotation αobs
 Optical purity = optical rotation of pure enantiomer × 100 = ×100
αD
e.g. If we have some 2-butanol with observed rotation of +9.72, we compare this rotation with +13.5
rotation of the pure (+) enantiomer.
9.72
Optical purity = 100  72%
13.5
That means 72% is pure (+) 2-Butanol and 28% is ( mixture)
Total (+) isomer = 72 + 14 = 86%, (–) isomer = 14%
MID LEARNING EXERCISE (MLE)-24
Q.1 How many spatial orientations are possible in the following compound ?

I CH=CHCH 3

CHClCH 3 Br
(A) 2 (B) 8 (C) 6 (D) 4
Q.2 Total number of optical active stereoisomers of the following compound is :
CH3 – CH = CH – CHCl – CH = C = CH – CH = CH – CH3
(A) 8 (B) 6 (C) 16 (D) 10

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JEE
Q.3 A 1.20 gm sample of cocaine, []0 = –16o was dissolved in 7.50 ml of chloroform and placed in a
polarimeter tube having path length of 5.00 cm. Calculate the observer rotation?
(A) +1.3o (B) –2.6o (C) +2.6o (D) –1.3o
Q.4 Optical activity of an enantiomeric mixture is +12.6 and the specific rotation of (+) isomer is +30.
The optical purity of sample is -
(A) 17% (B) 29% (C) 42% (D) 68%
CH=NH
Cl Me

Q.5 How many stereoisomers are possible for I Et ?

OH
(A) 128 (B) 64 (C) 32 (D) 16
An optically pure compound X gave an   D  20.0o . A mixture of (X) and its enantiomer (Y) gave
25
Q.6

  25
D
 10.0o . Select the true (T)/false (F) statements regarding this mixture.
(i) It has 50% dextrorotatory isomer.
(ii) It has 25% laevorotatory isomer.
(iii) It has 50% optical purity
(A) TTF (B) FFT (C) FTT (D) TFT
Q.7 How many isomers are possible for the following molecule?

H
CH–CH=CHCOOH
CH 3
(A) 1 (B) 2 (C) 3 (D) 4
Q.8 Stereoisomer possible for following compounds:
CH=CH–CH 2CH 3

CH=CH 2
(A) 8 (B) 16 (C) 32 (D) 64
Q.9 Number of stereoisomers of the given compound
OH
|
CH 3  CH  CH  CH  CH 3

(A) 2 (B) 4 (C) 3 (D) 6

Q.10 Calculate total number of stereo isomers in following compound:
CH 3  CH  CH  CH 3
| |
OH OH

(A) 4 (B) 3 (C) 2 (D) 1

Q.11 Number of optical isomers of lactic acid are
(A) 1 (B) 2 (C) 3 (D) 4
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 Stereochemistry
Q.12 The maximum number of stereoisomers possible for 2-hydroxy-2-methyl butanoic acid is
(A) 1 (B) 2 (C) 3 (D) 4
Q.13 The number of enantiomeric pairs of the compound CH3CHBrCHBrCOOH is
(A) 2 (B) 1 (C) 3 (D) 4
Q.14 Total number of stereoisomers for compound?
CH 3  CH  CH  CH  CH  CH  C 2 H5
|
CH 3

(A) 2 (B) 4 (C) 6 (D) 8

Q.15 Calculate the total number of stereoisomers when alkene having trans configuration:

(A) 2 (B) 3 (C) 4 (D) 8

*****

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JEE

QUICK RECAP
 Asymmetric carbon: The carbon which is attached with four different groups of atoms is called
asymmetric carbon.
 Asymmetric molecule : If all the four substituents attached to carbon are different, the resulting
molecule will lack symmetry. Such a molecule is called asymmetric molecule. Asymmetry of molecule
is responsible for optical activity in such organic compounds.
 Achiral molecule : A molecule that is superimposable on its mirror image. Achiral molecules lack
handedness and are incapable of existing as a pair of enantiomers.
 Chiral molecule : A molecule that is not superimposable on its mirror image. Chiral molecules have
handedness and are capable of existing as a pair of enantiomers.
 Chirality : The property of having handness.
 Conformation : A particular temporary orientation of a molecule that results from rotations about its
single bonds.
 Conformer : A particular staggered conformation of a molecule.
 Dextrorotatory : Those substances which rotate the plane of polarisation of light towards right are
called dextrorotatory. Currently, dextro and laevo rotations are represented by algebraic signs of (+)
and (-) respectively.
 Enantiomers : Stereoisomers that are non superimposable mirror images of each other. enantiomers
rotate the plane of polarised light to the same extent but in opposite direction.
 Levorotatory : A compound that rotates plane polarized light in a counterclockwise direction.
 Meso compound : An optically inactive compound whose molecules are achiral even though they
contain tetrahedral atoms with four different attached groups. A meso-compound is optically inactive
due to internal compensation.
 (R-S) System : A method for designating the configuration of tetrahedral stereogenic centres.
 Racemisation : The process of conversion of an enantiomer into racemic mixture is known as an
racemisation.
 Retention : If in an optically active molecule that relative configuration of the atoms groups around
a chiral centre remains the same before and after the reaction, the reaction is said to proceed with
retention of configuration.
 Relative configuration : The relationship between the configuration of two chiral molecules. Molecules
are said to have the same relative configuration when similar or identical groups in each occupy the
same position in space. The configuration of molecules can be related to each other through reactions
of known stereochemistry, for example through reactions that cause no bonds to a stereogenic
center to be broken.
 Resolution : The process by which the enantiomers of a racemic form are separated.
 Ring flip : The change in a cyclohexane ring (resulting from partial bond rotations) that converts one
ring conformation to another. A chair-chair ring flip converts any equatorial substituent to an axial
substituent and vice verse.
 Specific rotation : Specific rotation is defined as the number of degrees of rotation observed when
the concentration of optically active substance is 1 g cm-3 and length of polarimeter tube is 1
decimetre (dm) for D-line of sodium vapour lamp at 25°C.
 Stereogenic center : An atom bearing group of such nature that an interchange of any two groups
will produce a stereoisomer.
*****
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 Stereochemistry

SOLVED EXAMPLES
Example 1. A and B are enantiomer of each other. Specific rotation of A is 20o. Rotation of mixture of A and
B = –5o what is the percentage of racemic part?

5
Solution: Optical purity =  100 = 25%
20
Recamic mixture = 100 – 25 = 75%
Example 2. How many stereoisomers of 1,2,3-cyclohexantriol ?

HO OH
OH
Solution: No. of Chiral carbon = 3 (identical) symmetrical
n = odd
total stereoisomers = 2n – 1 = 23 – 1 = 4
Mesoform is optically inactive due to internal compensation and recemic mixture is optically
inactive due to external compensation.
Example 3. Find total isomers obtained by dichlorination of n-butane.

Cl
Solution: C–C–C–C (1)
Cl

C – C – C – C – Cl
| (2)
Cl

C – C –C – C
| | (1)
Cl Cl

C – C – C – C – Cl (2)
|
Cl

Cl
|
C – C –C – C (1)
|
Cl

 
C–C–C–C
| | (3) (2 optically + 1 meso)
Cl Cl

Total isomers = 10 (6 optically active + 1 meso + 3 structural)

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 JEE
Example 4. Find total isomers obtained by dichlorination of cyctopentane.

Cl Cl
Cl Cl
Cl
Solution:

Cl

Cl Cl

   

Cl Cl
(2 optically active +1 meso) (2 optically active +1 meso)

Total isomers = 3 + 3 + 1 = 7
Optically active isomers = 6
Example 5. Give the correct order of initials T or F for following statements. Use (T) if statement is true and
(F) if it is false.
I. Me–CH=C=C=CH–Br is optically active.
II. All optically active compound are chiral.
III. All chiral pyramidal molecules are optically inactive.

IV. CH3–CH2–CH2–COOH and CH 3  CH  CH 3 are positional isomers.

|
COOH
(A) TTTF (B) FTFT (C) FTFF (D) TFTT
Answer: (C)
Solution: (II) Cyclic chiral pyramidal molecules are optically active.

(IV) CH3–CH2–CH2–COOH and CH 3  CH  CH 3 are chain isomers.

|
COOH
Example 6. Which pairs of the salts should have identical solubilities in methanol?

(I) (II)

(III) (IV)

(A) I & IV (B) I & III (C) I & II (D) II & IV

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 Stereochemistry
Answer: (A)
Solution: I & IV are enantiomers, enantiomers have identical solubility

Example 7. An optically pure compound X gave an []25

D = + 20.0°. A mixture of X and its enantiomer Y

gave []25
D = +10°. The ratio of X to Y in the mixture is
(A) 2 : 1 (B) 1 : 3 (C) 3 : 1 (D) 1 : 2
Answer: (C)
10
Solution: Optical purity = × 100 = 50% i.e., amount of X
20
Hence optical impure = 100 – 50 = 50%

Total 'X' = 50 + 25 = 75%

Total 'Y' = 25%
Hence, Ratio of X & Y = 75 : 25 = 3 : 1
Example 8. Pick the correct statement for monochlorination of R-secbutyl chloride.

Cl

2
300C

(A) There are four possible products ; three are optically active one is optically inactive
(B) There are five possible products ; three are optically inactive & two are optically active
(C) There are five possible products ; two are optically inactive & three are optically active
(D) There are four possible products ; two are optically active & two are optically inactive
Answer: (C)

Solution:

Example 9. Which of the following statements regarding the projections shown below is true ?

(a) (b)
(A) both (a) & (b) are optically active (B) (a) & (b) are identical compounds
(C) only (a) is optically active (D) only (b) is optically active
Answer: (D)
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 JEE

Solution:   Meso (erythro, inactive)

  (threo, active)

Example 10. Out of the following which are chiral

H3C H3C Cl H3C CH3

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

H3C CH3
CH 3 CH3 H3C CH3
(A) I, II, III (B) I, III, IV (C) II, III (D) II, III, IV
Answer: (C)
Solution: I  Plane of Symmetry , Centre of Symmetry
II  unsymmetrical
III  unsymmetrical
IV  Plane of Symmetry , Centre of Symmetry
Example 11. Which of the following is a meso compound.

Cl Cl COOH CH2CH3
H OH H Et
(A) (B) HOOC H (C) H Et (D) All of these
H H
OH CH2CH3
Answer: (B)
Cl Cl

Solution: (A) no chiral carbon so not meso

H H

COOH COOH
H OH H OH
(B) HOOC H is H OH so meso
OH COOH

CH2–CH3
H Et
(C) Et
No chiral carbon so not meso.
H

CH2–CH3
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 Stereochemistry
Example 12. Select the correct configuration for this compound:

OH

CH 2
O O

O O
O
O

(A) 1R, 3S (B) 1R, 3R (C) 1S, 3R (D) 1S, 3R

Answer: (A)

1
OH
3 R 2

4
CH2
O 4 O
2 1
Solution: S
O O
O
3
O

Example 13. What can be said about the magnitude of the equilibrium constant K for the following process?

(A) K = 1 (B) K > 1

(C) K < 1 (D) No estimate of K can be made
Answer: (C)
Solution: Since, bulky group is more stable on equatorial position, hence flipping is restricted.
So, K < 1

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 JEE
Example 14. Four Newman projection formula of compound CH2OH–CHOH–CHOH–CHO are shown below:

(I) (II)

(III) (IV)

Which of the above represents erythro isomer?

(A) I and IV (B) I and II
(C) II and IV (D) I and III
Answer: (A)
Solution: Fischer projection representation of I & IV are

Example 15. The following pair of compounds represents:

(A) same compound (B) diastereomers

(C) enantiomers (D) structural isomers
Answer: (D)

Solution: I compound is CH3 –CH 2 –CH–CH3 : 2–chlorobutane and

|
Cl

II compound is CH 3 –CH 2 –CH 2 –CH 2 : 1 – chlorobutane

|
Cl

 They are structural isomers.

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 Stereochemistry
Example 16. Out of the following which is relatively the most stable conformer of Erythro-2,3-Pentandiol.

(A) (B)

(C) (D)

Answer: (A)
Solution: (B) and (C) are not erythro while. In (D) there is not intramolecular H-bonding.
Example 17. Select the correct one
Compound Number of geometrical isomers
(A) 6
(B) 6
Cl
(C) Cl 4
H

(D) 8

Answer: (C)
Solution: Compound Number of geometrical isomers
(A) 21 = 2
(B) 23 = 8
Cl
(C) Cl 22 = 4
H

(D) 22 = 4

****

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 JEE

EXERCISE # 1(A)(Level 1 – Beginner)

1. Geometrical isomers arise due to
(A) free rotation about a bond (B) restricted rotation about a bond
(C) different connectivity of atoms (D) same spatial arrangement of atoms and groups

H3C CH3 H3C H

2. C C and C C are configurational isomers because
H H H CH3
(A) they can be interconverted only if -bond is cleaved.
(B) they can be interconverted without cleaving the -bond.
(C) they are mirror image of each othe
(D) their physical and chemical properties are same.
3. Which of the following pairs of isomers represents a pair of conformational isomers?

CH3 CH3
and
(A) (B) H Cl and Cl H
C2H5 C2H5
H3C H H3C H
Cl
H H H Cl
(C) (D) and
and
Cl Cl Cl H
Cl Cl Cl
4. All alkenes do not exhibit geometrical isomerism. For an alkene to exhibit geometrical isomerism,
which of the following conditions is required?
(A) Two atoms or groups bonded with each C of C = C bond should be same.
(B) Two atoms or groups bonded with each C of C = C bond should not be same.
(C) C = C bond should bear at least three identical groups.
(D) C = C bond should bear all four atoms or groups identical.
5. Which of the following compounds will exhibit geometrical isomerism?
(A) CH  CH  CH  CH  C  CH (B) CH 2  CH  C  C  C  CH
(C) CH 2  CH  CH  CH  CH  CH 2 (D) Both (A) and (C)

6.
I II III
Which of the cycloalkenes will exhibit geometrical isomerism ?
(A) I (B) II (C) III (D) All of these
7. Among these groups, which of the following orders is the correct priority order in accordance with
sequence rule?
CH3
CH3
CH C CH3 CH CH2 CH CH
CH3
CH3 III IV
I II
(A) II > I > IV > III (B) IV > III > II > I (C) IV > II > III > I (D) II > IV > III > I
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 Stereochemistry

2 4 6 8
1 3 5 7
8.
Cl
This compound can be named as
(A) 3-chloro-6-methyl-(3E,5Z)-octadiene (B) 3-chloro-6-methyl(3Z,5E)-octadiene
(C) 3-chloro-6-methyl(3Z,5Z)-octadiene (D) 3-chloro-6-methyl(3E, 5E)-octadiene
CH3
CH3
9. ,
CH3
CH3
How many geometrical isomers of this compound are possible ?
(A) 0, 1 (B) 2, 2 (C) 3, 2 (D) 4, 3
10. CH3  CH  C  C  CH  CH3
| |
Br Cl
How many geometrical isomers of this compound are possible ?
(A) 2 (B) 3 (C) 4 (D) 6
11. CH 3  CH  CH  CH  CH  CH  CH  CH3
How many geometrical isomers of this olefine are possible ?
(A) 4 (B) 5 (C) 6 (D) 8
CH3 H3C
12. , ,
CH3 H3 C
How many geometrical isomers of this cyclodecene are possible ?
(A) 0, 1, 0 (B) 2, 0, 2 (C) 3, 2, 2 (D) 4, 2, 0
13. Which of the following compounds has asymmetric centre?
O O O

(A) (B) O (C) Br (D)

OH OH Br
14. Which of these molecules is optically inactive ?
CH3 CH3 CH3
H OH H OH H Br
H OH H OH H OH
CH3 CH3 H Br
CH3
I II III
(A) I (B) II (C) III (D) I and III
15. Which of these molecules is optically inactive ?
CH3
OH Br
Br
OH Br
I II CH3
III
(A) I (B) II (C) III (D) I and II
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 JEE
16. Which of the following statements is true about these molecules?
CH3 CH3 CH3
H OH HO H H OH
H OH HO H HO H
CH3 CH3 CH3
I II III
(A) I and III are nonsuperimposable mirror image of each other
(B) I and II are superimposable mirror image of each other
(C) I and II are identical
(D) Both (B) and (C)
17. Which of the following statements is true about these molecules?
CH3 C2H5 CH3
S S R
H Br H Br Br H
R R R
H Br H Br H Br
C2 H5 CH3 C2 H5
I II III
(A) I and II are nonsuperimposable mirror image of each other
(B) I and III are nonsuperimposable mirror image of each other
(C) I and II are identical
(D) Both (A) and (C)
18. CH3  CH  CH  CH 2  CH3
| |
OH OH
CH3  CH  CH  CH3
| |
OH OH
CH3  CH  CH  CH  CH3
| | |
OH OH OH
How many optical isomers are possible in this compound?
(A) 4, 3, 4 (B) 4, 4, 4 (C) 4, 3, 2 (D) 2, 4, 3
19. Enantiomers have
(A) all physical properties same except their action on plane polarized light which is equal in magnitude
but opposite in direction
(B) all chemical properties same, except when reagent is chiral. In that case, reactivity of enantiomers
will be different
(C) both (A) and (B)
(D) none of these
20. Which of the following statments is true about these isomers?
CH3 CH3 CH3 CH3
H OH HO H H OH HO H
H OH HO H HO H H OH
C2H5 C2H5 C2 H5 C2 H5
I II III IV
(A) I and II is a pair of enantiomers (B) III and IV is a pair of enantiomers
(C) II is the diastereomer of III and IV (D) all of these
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 Stereochemistry
21. Which of the following statements is true about these molecules?

H Br H D Cl Br

D Cl Cl Br H D
I II III
(A) I and III are identical (B) I and II are a pair of enantiomers
(C) I and II are a pair of diastereomers (D) Both (A) and (B)
22. Which of the following statements is true about these molecules?

H CH3 H CH3 H CH3

I II III
(A) I and II are a pair of enantiomers (B) III is the diastereomer of I and II
(C) III is not stereoisomer of I and II (D) Both (A) and (C)
23. Which of the following biphenyls is optically active?

I
NO2

Br I I I I I
(A) (B) (C) (D)
Br I Br Br Br Br

I
Br
24. Which of the following compounds is optically active?

CH–CH3
CH–Me CH–CH3
CH3
(A) (B) (C) (D) All of these
CH3 Me

(D) All of these

25. % optical purity of a sample containing two enantiomers can be expressed by?
(obs) 2 (obs)
(A)  100 (B)  100
[ ] [ ]
(obs)
(C)  100 (D) none of these
2[ ]

*****

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 JEE

EXERCISE # 1(B)(Level 2 – Learner)

1. Meso-tartaric acid and d-tartaric acid are
(A) positional isomers (B) enantiomers
(C) diastereomers (D) racemic mixture
2. The number of isomers of C3H5Br3 is
(A) 4 (B) 5 (C) 6 (D) 7
3. The number of optically active compounds in the isomers of C4H9Br is
(A) 1 (B) 2 (C) 3 (D) 4

4.

The compound with the above configuration is called:

(A) (2S, 3S)-2-chloro-3-pentanol (B) (2S, 3R)-2-chloro-3-pentanol
(C) (2R, 3R)-2-chloro-3-pentanol (D) (2R, 3S)-2-chloro-3-pentanol

5. The full name of the compound is

(A) (2R,3R)-3-chloro-2-pentanol (B) (2R,3S)-3-chloro-2-pentanol

(C) (2S,3R)-3-chloro-2-pentanol (D) (2S,3S)-3-chloro-2-pentanol
6. The structure of (2R, 3R)C2H5CH(CH3)CH(D)CH2D is

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

7. How many stereoisomers can exist for the following acid

H  C(OH).CO 2 H
|
H  C.CO 2 H
|
H  C(OH).CO 2 H

(A) Two (B) Four (C) Eight (D) Sixteen

8. How many stereoisomers of the following molecule are possible?
HOOC.CH=C=CH.COOH
(A) two optical isomers (B) two geometrical isomers
(C) two optical and two geometrical isomers (D) None

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 Stereochemistry
9. The structures shown here are related as being:

(I) (II)
(A) confermers (B) enantiomers (C) geometrical isomers (D) diastereoisomers
10. Observe the given compounds and answer the following questions.

Which of the above formulae represent identical compounds?

(A) I and II (B) I and IV (C) II and IV (D) III and IV
11. Which species exhibits a plane of symmetry?

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

12. Increasing order of stability among the three main conformation (i.e. eclipse, anti, gauche) of ethylene
glycol is :
(A) Eclipse, gauche, anti (B) Gauche, eclipse, anti
(C) Eclipse, anti, gauche (D) Anti, gauche, eclipse
13. Number of stereoisomers of D-glucose are
(A) 10 (B) 14 (C) 16 (D) 20
14. The total number of isomeric optically active monochloro isopentane is:
(A) two (B) three (C) four (D) one
15. On chlorination of propane number of products of the formula C3H6Cl2 is
(A) 3 (B) 4 (C) 5 (D) 6
16. The number of optically active isomers observed in 2,3-dichlorobutane is:
(A) 0 (B) 2 (C) 3 (D) 4
17. What observed rotation is expected when a 1.5 M solution of (R)-2-butanol is mixed with an equal
volume of a 0.75 M solution of racemic 2-butanol and the resulting solution is analysed in a sample
container that is 1 dm long? The specific rotation of (R)-2-butanol is –13.9°ml gm–1dm–1.
(A) +0.77° (B) –0.77° (C) +0.35° (D) –0.35°

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 JEE
18. The two compounds given below are-

(A) enantiomers (B) identical (C) optically inactive (D) diastereomers

19. A pure sample of 2-chlorobutane shows rotation of PPL by 30° in standard conditions. When above
sample is made impure by mixing its opposite form, so that the composition of the mixture becomes
87.5% d-form and 12.5% l-form, then what will be the observed rotation for the mixture.
(A) –22.5° (B) +22.5° (C) +7.5° (D) –7.5°
20. When an optically active compound is placed in a 10 dm tube is present 20 gm in a 200 ml solution
rotates the PPL by 30°. Calculate the angle of rotation & specific angle of rotation if above solution
is diluted to 1 Litre.
(A) 16° & 36° (B) 6° & 30° (C) 3° & 30° (D) 6° & 36°
21. Which of the following will not show optical isomerism.
(A) Cl–CH=C=C=CH–Cl (B) Cl–CH=C=C=C=CH–Cl

COOH
H OH
(C) HO H (D)
COOH

22. The R/S configuration of these compounds are respectively.

HO H
CF3 H NH2 H CH3
HS CHO
COOH

(A) R,R,R (B) R,S,R (C) R,S,S (D) S,S,S

23. Which of the following combinations amongst the four Fischer projections represents the same absolute
configurations?

(A) (II) and (III) (B) (I) and (IV) (C) (II) and (IV) (D) (III) and (IV)
24. Predict stereochemistry of product when d and -amine reacts with -acid:
(A) Diastereomers (B) Meso (C) Racemic (D) Pure Enantiomer

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 Stereochemistry
25. How many geometrical isomers are possible for the above compound ?

(A) 3 (B) 4 (C) 6 (D) 8

CH3

26.

Br
How many geometrical isomers are possible for the above compound ?
(A) 0 (B) 2 (C) 3 (D) 4

27. CH3  CH  C  C  CH  CH3

| |
Br Cl
How many geometrical isomers are possible for the above compound ?
(A) 2 (B) 3 (C) 4 (D) 6

28. CH3  CH  C  C  CH  CH3

| |
Br Br
How many geometrical isomers are possible for the above compound ?
(A) 2 (B) 3 (C) 4 (D) 6

Cl Cl Cl Cl

29.

Br Br Br Br
(A) (B)

Relationship between above pair (A) & (B) is :

(A) Enantiomer (B) Diastereomers
(C) Identical (D) Structural isomer

*****

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 JEE

EXERCISE # 2(A)(Adept – JEE Main PYQs)

1. Among the following four structures I to IV
CH3 O CH3
| || |
(i) C3H 5  CH  C3H 7 (ii) C 2 H5  C  CH  C 2 H 5

H CH3
| |
(iii) H  C  CH 3 (iv) C2 H5  CH  C 2 H5
|
H
It is true that - (JEE Main 2003)
(A) Only (iii) is a chiral compound (B) Only (ii) and (iv) are chiral compounds
(C) All four are chiral compounds (D) Only (i) and (ii) are chiral compounds
2. Which of the following will have a mesoisomer also ? (JEE Main 2004)
(A) 2-Chlorobutane (B) 2, 3-Dichlorobutane
(C) 2,3-Dichloropentane (D) 2-Hydroxypropanoic acid
3. Which of the following compounds is not chiral? (JEE Main 2004)
(A) 1-chloropentane (B) 2-chloropentane
(C) 1-chloro –2–methyl pentane (D) 3-chloro-2-methyl pentane
4. Which types of isomerism is shown by 2,3-dichlorobutane ? (JEE Main 2005)
(A) Optical (B) Diastereo (C) Structural (D) Geometric
5. Increasing order of stability among the three main conformations (i.e. Eclipse, Anti, Gauche) of 2-
fluoroethanol is (JEE Main 2006)
(A) Gauche, Eclipse, Anti (B) Eclipse, Anti, Gauche
(C) Anti, Gauche, Eclipse (D) Eclipse, Gauche, Anti
6. Which of the following molecules is expected to rotate the plane of plane-polarised light?
(JEE Main 2007)
CHO H2N NH2 COOH
(A) HO H (B) (C) H H (D) H2N H
SH Ph Ph
CH2OH H
7. Which one of the following conformations of cyclohexane is chiral ? (JEE Main 2007)
(A) Twist boat (B) Rigid (C) Chair (D) Boat
HO 2C CO 2H

8. The absolute configuration of is (JEE Main 2008)

HO H H OH
(A) R, R (B) R, S (C) S, R (D) S, S
9. Out of the following, the alkene that exhibits optical isomerism is- (JEE Main 2010)
(A) 2-methyl-2-pentene (B) 3-methyl-2-pentene
(C) 4-methyl-1-pentene (D) 3-methyl-1-pentene
10. How many chiral compounds are possible on monochlorination of 2–methyl butane ?
(JEE Main 2012)
(A) 6 (B) 8 (C) 2 (D) 4
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 Stereochemistry
11. Which branched chain isomer of the hydrocarbon with molecular mass 72 u gives only one isomer of
mono substituted alkyl halide ? (JEE Main 2012)
(A) Neohexane (B) Tertiary butyl chloride
(C) Neopentane (D) Isohexane
12. How many cyclic structures are possible for C4H6 :- (JEE Main 2012)
(A) 3 (B) 5 (C) 4 (D) 6
13. Maleic acid and fumaric acids are :- (JEE Main 2012)
(A) Tautomers (B) Chain isomers
(C) Geometrical isomers (D) Functional isomers
14. The optically inactive compound from the following is- (JEE Main 2015)
(A) 2-chloropropanal (B) 2-chlorobutane
(C) 2-chloro-2-methylbutane (D) 2-chloropentane
15. Which ofthe following compounds will exhibit geometrical isomerism? (JEE Main 2015)
(A) 2-Phenyl-1-butene (B) 1, 1 -Diphenyl-1-propane
(C) 1-Phenyl-2-butene (D) 3-Phenyl-1-butene
16. The absolute configuration of: (JEE Main 2016)
CO2H
H OH
H Cl
CH3
(A) (2R, 3R) (B) (2R, 3S) (C) (2S, 3R) (D) (2S, 3S)
17. Which of the following compounds will show the maximum enol content? (JEE Main 2019)
(A) CH3COCH 2COCH 3 (B) CH3COCH 3
(C) CH3COCH2CONH2 (D) CH 3COCH 2COOC2H 5
18. Which of these factors does not govern the stability of a conformation in acyclic compounds ?
(A) Torsional strain (B) Angle strain (JEE Main 2019)
(C) Steric interactions (D) Electrostatic forces of interaction
19. In the following skew conformation of ethane, H'–C–C–H" dihedral angle is: (JEE Main 2019)
H
H H' 29º
H

H" H
(A) 120º (B) 58º (C) 149º (D) 151º
20. Which of the following compounds shows geometrical isomerism? (JEE Main 2020)
(A) 2-methylpent-1-ene (B) 4-methylpent-1-ene
(C) 2-methylpent-2-ene (D) 4-methylpent-2-ene
21. Arrange the following conformational isomers of n-butane in order of their increasing potential
energy: (JEE Main 2021)
CH3 CH3 CH 3 H
H H CH3 H CH 3 H

H H H H
H H H H H3C
H H CH 3
CH3 H
(I) (II) (III) (IV)
(A) II < III < IV < I (B) I < IV < III < II
(C) II < IV < III < I (D) I < III < IV < II
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 JEE
22. The number of stereoisomers possible for 1,2 dimethyl cyclopropane is: (JEE Main 2021)
(A) One (B) Four (C) Two (D) Three
23. Which of the following molecules does not show stereo isomerism ? (JEE Main 2021)
(A) 3,4 -Dimethylhex-3-ene (B) 3-Methylhex-1-ene
(C) 3-Ethylhex-3-ene (D) 4-Methylhex-1-ene
24. Staggered and eclipsed conformers of ethane are: (JEE Main 2021)
(A) Polymers (B) Rotamers (C) Enantiomers (D) Mirror images
25. Which of the following conformations will be the most stable ? (JEE Main 2022)
Me Me Me Me
H H Me H Me H

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

H H H H H H H Me
Me H H H H H
26. The isomeric deuterated bromide with molecular formula C4H8DBr having two chiral carbon atoms
is- (JEE Main 2022)
(A) 2-Bromo-1-dcuterobutane (B) 2-Bromo-2-dcuterobutanc
(C) 2-Bromo-3-dcuterobutanc (D) 2-Bromo-1-dcutero-2-mcthylpropane
27. In the following structures, which one is having staggered conformation with maximum dihedral
angle? (JEE Main 2022)

CH3 CH3 CH3 CH3

H CH3 H H H CH 3

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

H H H H H H
H H CH 3 CH 3 H H
28. The incorrect statement regarding conformations of ethane is: (JEE Main 2024)
(A) Ethane has infinite number of conformations
(B) The dihedral angle in staggered conformation is 60º
(C) Eclipsed conformation is the most stable conformation.
(D) The conformations of ethane are inter-convertible to one-another.

*****

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 Stereochemistry

EXERCISE # 2(B)(Scholar – JEE Main PYQs)

1. The number of chiral carbons present in the molecule given below is (JEE Main 2020)

O
H

C
CH3 CH3
HO

N
2. The number of acyclic structural isomers (including geometrical isomers) for pentene are
(JEE Main 2021)
3. The total number of chiral compound/s From the following ___ is- (JEE Main 2022)
Ph
COOH
OH OH
(A) O O Cl (B) OH
COOH
COOH
OH
HO CH 2
OH

(C) (D)
HO OH
HO 2C COOH
OH
4. Testosterone, which is a steroidal hormone, has the following structure- (JEE Main 2022)
OH
CH 3
CH 3

HO
Testosterone
The total number of asymmetric carbon atoms in testosterone ____ is-
5. Total number of possible stereoisomcrs of dimethyl cyclopentane ____ is (JEE Main 2022)
6. Observe structures of the following compounds (JEE Main 2022)
NH2
Cl OH OH
H2N
OH
O
O
The total number of structures/compounds which possess asymmetric carbon atoms is
7. The number of chiral alcohol(s) with molecular formula C4H10O is ____ . (JEE Main 2022)
8. Optical activity of an enantiomeric mixture is +12.6° and the specific rotation of (+) isomer is +30°.
The optical purity is ____ % (JEE Main 2022)
9. The dihedral angle in staggered form of Newman projection of 1, 1,1 -Trichloro ethane is __ degree.
(Round off to the nearest integer) (JEE Main 2022)
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 JEE

EXERCISE # 3(A)(Proficient – JEE Advanced Level Questions)

1. The correct structure of trans–2–hexenal is -
CHO CHO CHO
(A) (B) (C) CHO (D)
2. Which of the following compounds is not chiral ?
(A) DCH2CH 2CH 2Cl (B) CH3CHDCH2Cl
(C) CH3CHClCH2D (D) CH3CH2CHDCl
3. The total number of stereoisomers of 2,3–dibromobutane is -
(A) 2 (B) 3 (C) 4 (D) 5
4. In the structure:

CH 3
H OH
H Br
CH 3
The configurations at the chiral centres are :
(A) 2R, 3R (B) 2S, 3R (C) 2R, 3S (D) 2S, 3S
5. Which of the following compound contains a pseudo-asymmetric carbon atom
(A) CH 3 CH CH CH 2 (B) CH 3 CH  CH  CH CH 3
| | | | | |
Br Br Br Br OH Br

(C) CH3 CH CH CH CH3 (D) CH3 CH CH CH CH 3

| | | | | |
OH Br Br Br OH Cl
6. Consider the following structures (A), (B), (C) and (D)-

CH 3 C2H 5 Cl Cl
(i) Cl Br (ii) Cl Br (iii) CH 3 Br (iv) C2H5 CH 3
C2H 5 CH 3 C2H5 Br
Which of the following statements is not correct ?
(A) B and C are identical (B) A and B are enantiomers
(C) A and C are enantiomers (D) B and D are enantiomers
7. The interchange of two groups (Br and CH3) at the chiral centre of the projection formula (A) yields
the formula (B), while the interchange of another set of two groups (C2H5 and Cl) of (A) yields the
projection formula (C)-
CH3 Br CH 3

Cl Br Cl CH 3 C2H5 Br
C2H5 C2H5 Cl
(A) (B) (C)
Which of the following statements is not correct about the structures (A), (B) and (C)-
(A) B and C are identical (B) A and C are enantiomers
(C) B and C are enantiomers (D) A and B are enantiomers
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 Stereochemistry
8. How many meso stereoisomers are possible for 2, 3, 4-pentanetriol ?
(A) 1 (B) 2 (C) 3 (D) None of these
9. The total number of stereoisomers of the compound CH 3CH  CH  CH  CH  CH  CH 3 is -
|
OH
(A) 2 (B) 3 (C) 4 (D) 8
10. Which of the following molecules is/are identical with that represented by ?

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

11. The IUPAC name of the compound-

(A) (2E, 4E, 6Z)-octa-2,4,6-triene (B) (2E, 4E, 6E)-octa-2,4,6-triene

(C) (2Z, 4E, 6Z)-octa-2,4,6-triene (D) (2Z, 4Z, 6Z)-octa-2,4,6-triene
12. Which of the following will show optical isomerism or geometrical isomerism ?

(A) (B)

(C) (D)

13. Which of the following statements is/are correct?

(A) A meso compound has chiral centres but exhibits no optical activity
(B) A meso compound has no chiral centres and thus are optically inactive.
(C) A meso compound has molecules which are superimposable on their mirror images even though
they contain chiral centres
(D) A meso compound is optically inactive because the rotation caused by any molecule is cancelled
by an equal and opposite rotation caused by another molecule that is the mirror image of the first.
14. Which of the following statements is/are not correct for D-(+) glyceraldehyde?
(A) The symbol D indicates the dextrorotatory nature of the compound
(B) The sign (+) indicates the dextrorotatory nature of the compound
(C) The symbol D indicates that hydrogen atom lies left to the chiral centre in the Fischer projection
diagram
(D) The symbol D indicates that hydrogen atom lies right to the chiral centre in the Fischer projection
diagram.
15. Select the optically inactive compound among the following :

NH H3C COOH H3C CH3 HN NH

(A) HN (B) H3C COOH (C) HOOC COOH (D) OC CO

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 JEE
16. The S-ibuprofen is responsible for its pain reliveing property. Which one of the structure shown is
S-ibuprofen ?
O
Me C–OH
C Me H
(A) Me (B)
CH3 Me C
H C – OH
CH3 O
CH3 O
Me ||
Me C – OH
Me C H
(C) (D) Me C H
C – OH
O CH3

CH3
17. Which of the following operations on the Fischer formula H OH does not change its absolute
C2H5
configuration?
(A) Exchanging groups across the horizontal bond
(B) Exchanging groups across the vertical bond
(C) Exchanging groups across the horizontal bond and also across the vertical bond
(D) Exchanging a vertical and horizontal group
18. Which of the following statements for a meso compound is/are correct?
(A) The meso compound has either a plane or a centre of symmetry
(B) The meso compound has at least one pair of similar stereocenters
(C) The meso compound is achiral
(D) The meso compound is formed when equal amounts of two enantiomers are mixed
19. Which of the following states are correct ?
(A) Any chiral compound with a single as ymmetric carbon must have a positive optical rotation if
the compound has the R configuration
(B) If a structure has no plane of symmetry it is chiral
(C) All asymmetric carbons are stereocentres.
(D) Alcohol and ether are functional iosmers
20. Which of the following pairs of compound is/are identical?

(A) (B)

(C) (D)

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 Stereochemistry
21. Which of the following compounds are optically active?
(A) CH3.CHOH.CH2.CH3 (B) H2C=CH.CH2.CH=CH2
HOOC NO2

(C) (D)
NO2 COOH

22. Which of the following pairs can be resolved ?

(A) (B)

(C) (D)

23. Which of the following are D sugars:

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

24. Concider the following structure and pick by the right statement :

H O
NH2 C
F OH
C C
H CH2OCH3
H CH2OCH3
CH3 OH III
I II

(A) I and II have R-configuration (B) I and III have R-configuration

(C) only III has S-configuration (D) I and III have S-configuration
25. Which of the following is a 'threo' isomer ?

CHO CH3 COOH

COOH
H OH Br H H Cl
NH2
(A) H OH (B) H (C) H OH (D) H
OH H OH
CH2OH CH3 CH3
CH3
*****

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 JEE

EXERCISE # 3(B)(Amateur - Variety of JEE Advanced Level Questions)

Paragraph # 1 for (Ques. 1 to 2)
S(+) Mono Sodium Glutamate (MSG) is a flavour enhancer used in many foods. Fast foods often
contain substantial amount of MSG and is widely used in Chinese food. If one mole of above MSG
was placed in 845 ml solution and passed through 200 mm tube, the observed rotation was found to
be + 9.6°.
+
COO¯Na
¯OOC—CH2—CH2—C

NH3 H

MSG
1. Find out the specific rotation of (–) MSG:
(A) +24° (B) +56.8° (C) –48° (D) None of these
2. Find out the approximate percentage composition of (–) MSG in a mixture containing (+) MSG and
(–) MSG whose specific optical rotation is –20°.
(A) 83.3 % (B) 16.7% (C) 91.6% (D) 74%

Paragraph # 2 for (Ques. 3 to 6)

Geometrical isomerism is a kind of stereoisomerism which is present in the compounds containing a
double bond (C=C, C=N, N=N) and arise due to the restricted or frozen rotation about the double
bond. The atoms or groups attached to the doubly bonded carbons must be different. In aldoximes,
the isomer is named as syn if hydrogen and hydroxyl groups are on the same side of C=N bond and
if these are on opposite sides, the isomer is named as anti. In ketoximes, the prefixes syn and anti
indicate which group of ketoxime is syn or anti to hydroxyl group.
3. Which of the following does not show geometrical isomerism ?
(A) 1,2-Dichloropent-1-ene (B) 1,3-Dichloropent-2-ene
(C) 1,1-Dichloropent-1-ene (D) 1,4-Dichloropent-2-ene
4. On treating with NH2OH, which can form two products ?
(A) Acetaldehyde (B) Acetone
(C) Formaldehyde (D) Benzophenone
5. Number of stereoisomers of the compound 2-chloro-4-methylhex-2-ene is/are
(A) 1 (B) 2 (C) 4 (D) 16
6. The geometrical isomerism is shown by -
CH2 CHCl
CH2 CHCl
(A) (B) (C) (D)

Paragraph # 3 for (Ques. 7 to 9)

Different spatial arrangements of the atoms that result from rotation about a single bond are conformers.
n-Butane has four conformers eclipsed, fully eclipsed, gauche and anti. The stability order of these
conformers are as follows:
Anti > gauche > Partial eclipsed > Fully eclipsed
Although anti is more stable than gauche but in some cases gauche is more stable than anti.
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 Stereochemistry
7. Which one of the following is most stable conformer :

Cl Cl Cl Cl
H3C H Cl CH3 H Cl Cl
H
(A) (B) (C) (D) H
H CH3 H CH3 H CH3
Cl H CH3
H H3C CH3

8. Which one of the following is the most stable conformer ?

CH3 CH3 CH3

HO H OH
H CH3 H OH H CH3
(A) H (B) (C) (D)
OH H OH H OH H CH3
CH3 OH CH3 OH
9. Number of possible conformations of n-butane is :
(A) 2 (B) 4 (C) 6 (D) infinite

Matrix Match Questions :

10. Match the column.
Column-I Column-II
CH3 H
H CH2OH H3C CH2NH2
(A) and (P) Structural
NH2 OH

CH3 Cl
H Cl H CH3
(B) and (Q) Identical
Et Et

CH3 H
H H3C Et
OH
(C) and (R) Enantiomers
Et OH

H3C2 H3C2
(D) and (S) Diastereomers
OH H H OH

11. Column-I Column-II

Compound Number of optically
active isomer
(A) Unsymmetrical compound with ‘n’ chiral carbon (P) 2n–1
 n 1 
n –1  
(B) Symmetrical molecule with ‘n’ chiral carbon when n is even (Q) 2 – 2 2 
(C) Symmetrical molecule with ‘n’ chiral carbon when n is odd (R) 2n

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 JEE
12. Match Column-I, Column-II and Column-III.
Column-I Column-II Column-III
CH3 H
CH3
Br H
(A) HO H (I) HO C–C H (i) (2R, 3R)
CH3 CH3 Br

CH3 H
CH3
HO H
Br C–C OH
(B) Br H (II) (ii) (2S,3S)
CH3 H CH3

CH3 H
CH3
H OH
C–C
(C) Br H (III) HO Br
(iii) (2S,3R)
CH3
CH3 H

CH3 H
CH3
HO H
Br C–C OH
(D) H Br (IV) (iv) (2R, 3S)
CH3
CH3
H

13. Match Column I with Column II.

Column-I Column-II

O O
|| ||
(A) CH 3  C  O  C3H 7 & Et  C  O  Et (P) Enantiomer

(B) & (Q) Positional isomers

(C) & (R) Metamers

(D) & (S) Tautomers

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 Stereochemistry
14. Match the Column.
Column-I Column-II

COOH COOH
H OH H OH
;
(A) A pair of metamer (P) HO H H OH
COOH COOH
(B) tautomerism (Q) CH3OC3H7 ; C2H5OC2H5

CH3 CH3
H OH ; HO H
(C) A pair of geometrical isomer (R)
COOH COOH

CH3 CH3 H3 C H
(D) A pair of distereomers (S)
C=C ; C=C
H H H CH3

O
||
(E) A pair of optical isomer (T) CH 3CH 2CH 2CH ; CH3CH2CH=CH–OH

15. Match the column I with column II.

Column-I (Reaction) Column-II (Stereoisomers)
(A) CH3—CH CH—CH N—OH (P) 2

(B) (Q) 4

(C) CH3—CH CH—CH CH—CH CH—CH3 (R) 6

(D) CH3—CH CH—CH CH—CH CH—Ph (S) 8

Integer Type Questions :

16. Calculate the total number of stereoisomers in the following compounds.

(I) (II) (III)

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 JEE
17. Find out the total number of cyclic isomers of C6H12 which are optically active?

18. How many pair(s) of geometrical isomers are possible with C6H12 (only in open chain structures)

19. Calculate the number of chiral center in the molecule Ethyl 2,2-dibromo-4-ethyl-6-methoxy
cyclohexane carboxylate.

20. How many monochlorinated products of methyl cyclohexane are optically active.

21. How many cyclopentane structures (including stereo) are possible for C7H14.

2H
22. X 
2 
Pt

Find out structures of X.

23. How many enantiomers are possible on monochlorination of isopentane.

24. Calculate the total number of cyclic isomeric carbonyl compounds of molecular formula C5H8O
which can't show geometrical isomerism.

25. (a) The number of diastereoisomers (excluding optical) for 1-bromo-2-chloro-3-iodocyclopropane

(b) Minimum number of carbon atoms required for an alkane to show any kind of isomerism.

*****

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 Stereochemistry

EXERCISE # 4(A)(Expert – JEE Advanced PYQs)

1. Isomers which can be interconverted through rotation around of single bond are-
(JEE Adv. 1997)
(A) Conformers (B) Diastereomers
(C) Enantiomers (D) Positional isomers
2. The number of possible enantiomeric pairs that can be produced during monochlorination of 2-methyl
butane is : (JEE Adv. 1997)
(A) 2 (B) 3 (C) 4 (D) 1
3. Tautomerism is not exhibited by : (JEE Adv. 1998)

(A) CH=CH–OH (B) O O

O
(C) (D) O
O
O
4. Rotation of polarised light can be measured by : (JEE Adv. 1998)
(A) Monometer (B) Galvanometer (C) Polarimeter (D) Viscometer
5. The optically active tartaric acid is named as D–(+) tartaric acid because it has a positive :
(JEE Adv. 1999)
(A) optical rotation and is derived from D–glucose
(B) pH in an organic solvent
(C) optical rotation and is derived from D–(+)– glyceraldehyde
(D) optical rotation only when substituted by deuterium
6. The enol form of acetone, after treatment with D2O gives (JEE Adv. 1999)
OD O OH OH
(A) CH3–C=CH2 (B) CD 3–C–CD 3 (C) CH2–C=CH2D (D) CD2=C–CD3
7. Which of the following compound will exhibits geometrical isomerism : (JEE Adv. 2000)
(A) 1-phenyl-2-butene (B) 3-phenyl-1-butene
(C) 2-phenyl-1-butene (D) 1, 1-diphenyl-1-propene
8. The number of isomers for the compound with molecular formula C2BrCIFI is: (JEE Adv. 2000)
(A) 3 (B) 4 (C) 5 (D) 6
9. Which of the following exhibits stereoisomerism– (JEE Adv. 2000)
(A) 2-Methylbutene-1 (B) 3-Methylbutyne-1
(C) 3-Methylbutanoic acid (D) 2-Methylbutanoic acid
10. Which of the following has the lowest dipole moment : (JEE Adv. 2002)
CH3 CH3
(A) C=C (B) CH 3–C  C–CH 3
H H
(C) CH3CH2CCH (D) CH2=CH–CCH

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 JEE
11. If C2 in below compound is rotated by 120º angle in anticlockwise direction along C2–C3, which of
the following form will be produced : (JEE Adv. 2004)
1
CH3
H H
2
3

H H
CH3
4

(A) Partial eclipsed (B) Perfectly eclipsed

(C) Perfectly staggered (D) Gauche conformation
CH3
Cl2/hv Fractional distillation
12. CH3–CH–CH2–CH3 N (no. of isomers)   (F), (N) and (F) are:

(JEE Adv. 2006)
(A) 6, 4 (B) 4, 4 (C) 6, 6 (D) 3, 3
13. The number of structural isomers of C6H14 is :
(A) 3 (B) 4 (C) 5 (D) 6
14. Statement-I : Molecules that are not superimposable on their mirror images are chiral
Because Statement-II : All chiral molecules have chiral centres. (JEE Adv. 2007)
(A) Statement-1 is True, Statement-2 is True ; Statement-2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
15. The correct statement(s) concerning the structures E, F and G is (are) (JEE Adv. 2008)

H3 C O OH H3 C CH3
H3 C
H3C CH3 H3C CH3 H3C OH
(E) (F) (G)
(A) E, F and G are resonance structures (B) E, F and E, G are tautomers
(C) F and G are geometrical isomers (D) F and G are diastereomers
16. The correct statement(s) about the compound given below is (are) :- (JEE Adv. 2008)
(A) The compound is optically active Cl H
(B) The compound possesses centre of symmetry
H 3C CH 3
(C) The compound possesses plane of symmetry
(D) The compound possesses axis of symmetry Cl H
17. The correct statement(s) about the compound H3C(HO)HC – CH = CH – CH(OH)CH3 (X) is
(are) : (JEE Adv. 2009)
(A) The total number of stereoisomers possible for X is 6
(B) The total number of diastereomers possible for X is 3
(C) If the stereochemistry about the double bond in X is trans, the number of enantiomers possible
for X is 4
(D) If the stereochemistry about the double bond in X is cis, the number of enantiomers possible for
X is 2

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 Stereochemistry
18. The bond energy (in kcal mol–1) of a C–C single bond is approximately : (JEE Adv. 2010)
(A) 1 (B) 10 (C) 100 (D) 1000
19. In the Newman projection for 2,2–dimethylbutane X (JEE Adv. 2010)
H 3C CH 3

X and Y can respectively be –

(A) H and H (B) H and C2H5
H H
(C) C2H5 and H (D) CH3 and CH3 Y
20. Amongst the given option, the compound(s) in which all the atoms are in one plane in all the possible
conformations (if any), is (are) - (JEE Adv. 2011)
H H H
C–C
(A) (B) H – C  C – C
H2C CH2 CH2
(C) H2C = C = O (D) H2C = C = CH2
21. Which of the given statement(s) about N,O,P and Q with respect to M is (are) correct?
(JEE Adv. 2012)

HO HO Cl CH3 CH3
H H
H OH H OH HO H
Cl CH3
HO H HO
H OH H
HO H HO H
CH3 Cl CH3 Cl Cl
M N O P Q

(A) M and N are non-mirror image stereoisomers (B) M and O are identical
(C) M and P are enantiomers (D) M and Q are identical

22. Newman projections P, Q, R and S are shown below: (JEE Adv. 2020)
OH
H3 C CH3
CH3 CH3 CH3
HO CH3 H H C2H5 H C2 H5 CH(CH3 )2

H3C C2 H5 H C2 H5 HO CH3 H H
CH3 CH3 C2 H5 OH
P Q R S
Which one of the following options represents identical molecules ?
(A) P and Q (B) Q and S (C) Q and R (D) R and S
23. The Fischer projection of D-erythrose is shown below:
CHO
H OH
H OH
CH2OH
D-Erythrose
D-Erythrose and its isomers are listed as P, Q, R and S in Column-I. Choose the correct relationship
of P, Q, R and S with D-erythrose from Column-II. (JEE Adv. 2020)
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 JEE
Column-I Column-II

OHC HO H

(P) H (1) Diastereomer

OH
HO

OHC
OH
(Q) HO H (2) Identical
H OH

OHC H OH

(R) H (3) Enantiomer

OH
HO

OHC
OH

(S) HO OH
H H
(A) (P)-(2), (Q)-(3), (R)-(2), (S)-(2) (B) (P)-(3), (Q)-(1), (R)-(1),(S)-(2)
(C) (P)-(2), (Q)-(1), (R)-(1), (S)-(3) (D) (P)-(2), (Q)-(3), (R)-(3),(S)-(1)

CHO
H OH
HNO3
24. Given: HO H P (JEE Adv. 2021)
H OH []D = +52.7º
H OH
CH2OH
D-Glucose

The compound(s), which on reaction with HNO3 will give the product having degree of rotation,
[ ]D  52.7º is(are)

CHO CHO CHO CHO

HO H HO H HO H H OH
HO H HO H H OH H OH
(A) (B) (C) (D)
H OH H OH HO H HO H
H OH HO H HO H H OH
CH2OH CH2OH CH2OH CH2OH

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 Stereochemistry
25. Among the following, the conformation that corresponds to the most stable conformation of meso-
butane-2,3-diol is (JEE Adv. 2021)

OH OH OH OH
H Me H OH Me OH H OH
(A) (B) (C) (D)
Me H H Me H Me Me H
OH Me OH Me

*****

EXERCISE # 4(B)(Conqueror - Variety of JEE Advanced PYQs)

1. The number of isomeric tetraenes (NOT containing sp-hybridized carbon atoms) that can be formed
from the following reaction sequence is ___. (JEE Adv. 2022)
1. Na liquid NH3
2. Br2 (excess)
3. alc. KOH

2. The total number of chiral molecules formed from one molecule of P on complete ozonolysis
(O3 , Zn/H 2 O) is___. (JEE Adv. 2022)

OH OH

HO HO OH
P

*****

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 JEE

JEE MAIN YEARLONG REVISION EXERCISE

1. Which of the following statements about optical rotation is correct?
(A) A dextro-rotatory compound can be denoted by (d) or (+) while a levo- rotatory compound can
be denoted by (1) or (-).
(B) A dextro-rotatory compound can be denoted by (d) or (-) while a levo- rotatory compound can
be denoted by (1) or (+).
(C) A dextrorotatory compound can be denoted by (1) or (+) while a levorotatory compound can be
denoted by (d) or (-).
(D) Both (A) and (B)
2. Which of the following compounds have plane of symmetry?

CH3
CH3
H Br CH3
H OH
(A) (B) H OH (C) (D) All of these
H OH
H Br CH3
CH3
CH3
3. If a molecule has two dissimilar asymmetric centres then it will be
(A) always super-imposable on its mirror image.
(B) always non-superimposable on its mirror image
(C) superimposable on its mirror image in one isomer and non-superimposable on its mirror image in
other isomers
(D) optically inactive
4. Which of the following statements is true about these molecules?

CH3 CH3
H OH HO H
H OH HO H
CH3 CH3
I II
(A) I is a mesomer (B) I and II are identical
(C) I and II are two different mesomers (D) Both (A) and (B)
5. Which of these structures represent configurationally identical molecules?

C2H5 H3C OH C2 H5
H OH C2H5 HO H
CH3 H CH3
I II III
(A) I and II (B) I and III (C) II and III (D) none of these
6. Which of the following will show geometrical isomerism?
Me Br
Me
(A) (B) (C) (D)
Br
Me
7. Increasing order of stability among theBrthree main conformation (i.e. eclipse, anti, gauche) of ethylene
glycol is :
(A) Eclipse, gauche, anti (B) Gauche, eclipse, anti
(C) Eclipse, anti, gauche (D) Anti, gauche, eclipse
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 Stereochemistry
8. Select the optically active compound among the following:

NH H3C COOH
(A) HN (B) H3C COOH

H3C CH3 HN NH
(C) HOOC COOH (D) OC CO

9. How many stereoisomers of the following molecule are possible?

HOOC.CH=C=CH.COOH
(A) two optical isomers (B) two geometrical isomers
(C) two optical and two geometrical isomers (D) None
10. Which of the following is not chiral ?
OH
Me COOH HO OH

(A) (B)
HO OH
HOOC Me
OH
Cl F
(C) H3C – CH = C = C = C= CH–CH3 (D)
F Cl
11. Which species exhibits a plane of symmetry?

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

12. Which of the following has centre of symmetry?

H
F Cl H Br
C
(A) H (B) (C) (D) PCl5
H
H F Br H Cl
13. The structures shown here are related as being:
H Br
CH3 Br

CH3 CH3 CH3

(I) (II) H

Br H Br H
(A) conformers (B) enantiomers
(C) geometrical isomers (D) diastereoisomers
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 JEE
14. The two compounds given below are

(A) enantiomers (B) identical (C) optically inactive (D) diastereomers

15. Which of the following compound has D-configuration ?

CHO CH2OH
H OH H OH
H OH H OH
(A) HO H (B) HO H
HOH2C OH H OH
H CHO

CHO H
H OH HO CH2OH
HO H H OH
(C) H OH (D) HO H
HO CH2OH H OH
H CHO
16. Number of possible stereoisomers of glucose are
(A) 10 (B) 14 (C) 16 (D) 20

17. The full name of the compound is

(A) (2R,3R)-3-chloro-2-pentanol (B) (2R,3S)-3-chloro-2-pentanol

(C) (2S,3R)-3-chloro-2-pentanol (D) (2S,3S)-3-chloro-2-pentanol
18. The R/S configuration of these compounds are respectively.
HO H
CF3 H NH2 H CH3
HS CHO
COOH
(A) R,R,R (B) R,S,R (C) R,S,S (D) S,S,S
19. Which of the following structure can show geometrical isomerism?
NO 2 NO 2

(A) (B) 2,3-Dimethyl but-2-ene

HOOC
COOH
(C) 3,4-Diethyl hex-2-ene (D) 1,4-Dichloro benzene

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 Stereochemistry
20. What is the correct IUPAC name of the following compound

(A) 2E, 4E, 6Z 4-methyl oct-2, 4, 6 triene (B) 2E, 4Z, 6Z 5-methyl oct-2, 4, 6 triene
(C) 2Z, 4Z, 6Z 5-methyl oct-2, 4, 6 triene (D) 2E, 4Z, 6E 4-methyl oct-2, 4, 6 triene
21. Molecular formula C5H10O can have :
(A) 6-Aldehyde, 4-Ketone (B) 5-Aldehyde, 3-Ketone
(C) 4-Aldehyde, 3-Ketone (D) 5-Aldehyde, 2-Ketone
22. The number of isomers of dibromoderivative of an alkene (molar mass 186 g mol–1) is
(A) 2 (B) 3 (C) 4 (D) 6
23. On chlorination of propane number of products of the formula C3H6Cl2 is
(A) 3 (B) 4 (C) 5 (D) 6
24. The correct stability order of the following species is

H H Me
H Me
Me
Me H Me
(a) Me
H H
(b) (c)
(A) c < a < b (B) c = b < a (C) c < a = b (D) a = b = c

replace Ha with D and Hb with H

(X)
CH3
25. Ha Hb
H Br
CH3 replace Hb with D and Ha with H
(Y)
Relation between (X) and (Y) is :
(A) enantiomers (B) diastereomers
(C) E and Z isomer (D) constitutional isomer
26. Which of the following cyclopentane derivative is optically inactive?

OH H OH H CH3 CH3 H CH3

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

H OH H OH H H OH H
27. Assign double bond configurations to the following:
COOH

NC
CH2OH

H2N–H2C CN
(A) E, Z (B) Z, E (C) E, E (D) Z, Z
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 JEE
28. Which of the following compounds is non-resovable (meso) compounds ?

OH Br
Br Me Br Br
Br OH
H H
(A) H (B) H (C) (D) All of these
H H
H H H
Br
29. The following molecule is fluorometholone, a steroidal anti-inflammatory agent. How many stereogenic
centers does it contain?
O CH3
CH3 OH
HO
H

F H
O
CH3
(A) 5 (B) 6 (C) 7 (D) 8
30. How many chiral carbons are there in Reserpine (an antipsychotic drug)?
O
O N O
N O
H
O O
O
O
O
(A) 9 (B) 8 (C) 7 (D) 6

31. What is the relationship between the molecules in the following pairs ?

CHO CH2OH
H OH HO H
H OH H OH
and
HO H HO H
H OH HO H
CH2OH CHO
(Fischer projections)

(A) enantiomers (B) diastereomers (C) identical (D) structural isomers

32. The absolute configurations of the two centers in the following molecule are:

1
COOH
2
H Br
3
H CN
OH
(A) 2(R), 3(S) (B) 2(R), 3(R) (C) 2(S), 3(S) (D) 2(S), 3(R)
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 Stereochemistry
33. Pure (S)-2-butanol has a specific rotation of +13.52 degrees. A sample of 2-butanol prepared in the
lab and purified by distillation has a calculated specific rotation of +6.76 degrees. What can you
conclude about the composition ?
(A) 50% (S), 50 % impurity (B) 50% (S), 50 % (R)
(C) 50% (S), 50 % racemic (D) some other mixture

CH2–OH CH2–OH CHO

H OH HO H H OH
34. HO H HO H H CH2OH
CHO CHO OH
(a) (b) (c)

(D) & (L) configuration of above carbohydrate is:

(A) L, L, D (B) L, D, L (C) L, L, L (D) L, D, D
35. In which of the following compound, possess plane of symmetry as well as centre of symmetry?

Cl Cl H3C CH3

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

Cl CH3 H3 C
36. Which of the following is correct for the given compound?
O

O O

(A) It possess centre of symmetry (B) It possess C4 axis of symmetry

(C) It possess plane of symmetry (D) Compound ís chiral
37. Which is the correct structure of D-glyceraldehyde?

CHO H CH2OH
(A) H OH (B) HO CHO (C) HO H (D) All
CH2OH CH2OH CH2OH
38. How many stereogenic centres does it contain ?

OMe

O
(A) 1 (B) 2 (C) 3 (D) 4
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 JEE
39. What is the maximum number of stereoisomers that could exist for the compound below?
Cl Cl

Cl Cl
(A) 6 (B) 8 (C) 10 (D) 16
40. Which of the following compounds may not exist as enantiomers?
(A) CH 3CH(OH)CO 2 H (B) CH 3CH 2 CH(CH 3 )CH 2 OH
(C) C6 H 5CH 2 CH 3 (D) C6 H5CHClCH 3
41. Which of the following statements is true?
(A) A mixture of enantiomers can be separated on the basis of difference in their boiling points (by
a method called fractional distillation).
(B) A mixture of enantiomers can be separated on the basis of difference in their solubility in any
solvent
(C) A mixture of enantiomers can be separated by converting them into diastereomers by reacting
them with an optically active reagent
(D) A mixture of enantiomers can be separated by passing plane polarised through their solution
42. Identify number of chiral carbons in the following compounds.
H H
(I) H3C CH CH CH2 (II) H3C H (III) H3C CH CH CH2 CH3
OH OH OH Cl H CH3 CH3
(A) 1, 2, 1 (B) 1, 1, 2 (C) 2, 0, 1 (D) 2, 1, 1
43. The correct decreasing priority of ligands  NO 2 , C  N, NH 2 and CH 2 NH 2 in absolute
configuration of an enantiomer is:
(A) NO 2  NH 2  C  N  CH 2 NH 2 (B) NO 2  C  N  NH 2  CH 2 NH 2
(C) NH 2  NO 2  C  N  CH 2 NH 2 (D) NH 2  NO 2  CH 2 NH 2  C  N
44. The compound which has maximum number of chiral centres is:
HO
OH Cl OH
Cl OH
(A) (B) (C) (D)
Cl
45. Identify number of chiral carbons in the following compounds.

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

(A) 0, 2, 2, 4 (B) 2, 2, 0, 4 (C) 1, 2, 2, 4 (D) 2, 2, 2, 4

46. Which of the following is erythro form and optically inactive?
COOH CH3 CH3 CH3
HO H H OH H Br HO H
(A) HO H (B) Br H (C) H Br (D) H Br
CH3 CH3 CH3 CH3

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 Stereochemistry
47. The structures A and B represent:

COOH COOH
H OH H3C OH
HO CH3 HO H
COOH COOH
(A) (B)
(A) enantiomers (B) diastereomers
(C) homomers (D) racemic mixture
48. The compund has:

Br F
CH3
H H CH3

F Br
(A) plane of symmetry (B) axis of symmetry
(C) center of symmetry (D) no symmetry
49. Amongst the following amino acids, the (R) enantiomer is represented by:
CH3 COOH
(A) H2N COOH (B) H NH2
H CH3

NH3 COOH
(C) H3 C H (D) H3 C NH3
COOH H
50. Which of the following is a meso compound ?

CH3 CH2–CH3 H H
H Br H OH
(A) (B) (C) (D) All of these
H Br H OH OH OH
CH3 CH2–CH3
51. Which of the following pair represent pair of diastereomers ?
CO2H CO2H
H OH HO H
(A) Meso tartaric acid and () tartaric acid (B) +
HO H HO H
CO2 – CO2 –

CH2 –CH3 O O CH2 –CH3

(C) H O C and C O H
CH3 H OH HO H CH3
CH3 CH3
(D) All of these
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 JEE

Cl

52.
Cl
How many atoms will be bisect during plane of symmetry ?
(A) 2 (B) 4 (C) 6 (D) 8
53. The pair of enantiomers among the following compound is

CH3 CH3 CH3 H

Ph H H Br Ph Br Br CH3
Br Ph H Ph
(I) (II) (III) (IV)

(A) I and IV (B) II and IV (C) II and III (D) I and II

54. Which of the following compound has one of the stereoisomers as a meso compound ?

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

55. The configurations of the carbon atoms C2 and C3 in the following compound are respectively

COOH
H OH
HO H
CHO
(A) R, R (B) S, S (C) R, S (D) S, R
56. The compound that is chiral is
(A) 3-methyl-3-hexene (B) 4-chloro-1-methycyclohexane
(C) 2-phenylpentane (D) 1,3-disopropylbenzene

*****

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 Stereochemistry

JEE ADVANCED YEARLONG REVISION EXERCISE

1. Which of the following compound has E configuration?
H Cl
CHO CH2OH CHO
(A) H (B) NH2 (C) Cl (D)
H

Br
2. Which of the following compounds are optically active?
(A) CH3.CHOH.CH2.CH3 (B) H2C=CH.CH2.CH=CH2
HOOC NO2

(C) (D)

NO2 COOH
3. Which out of the following are resolvable pair?

N + en
(A) T (B) + en
H
D
O Me
P + en
(C) Me (D) Et NH2 + en
Ph
Et
H
4. Which of the following is/are resolvable pair?

Me
O 
(A) + en (B)
N + en
Et D
H

(C) N + en (D) S + en
D Me O Et
Et Me
5. Concider the following structure and pick by the right statement:
H O
NH2 C
F OH
C C
H CH2OCH3
H CH2OCH3
CH3 OH III
I II
(A) I and II have R-configuration (B) I and III have R-configuration
(C) only III has S-configuration (D) I and III have S-configuration
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 JEE
6. Identify diastereoisomer in the following are :

H CH3 Cl
CH3

Cl CH3 H Cl
H Cl CH3 H
(A) (B) CH H CH3 H
Cl CH3 H Cl 3

Cl Cl
H CH3
CH3 CH3
H CH3
Cl CH3 Cl
H Cl H Cl H
(C) H Cl Cl H (D) H Cl
H Cl CH3
CH3 CH3
CH3
7. What is relationship between ?

HOOC Br H COOH
H Br
H COOH
H Br COOH Br
(A) Enantiomer (B) Diastereomer (C) Conformer (D) Identical
8. The structure of (2R, 3R)C2H5CH(CH3)CH(D)CH2D is

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

9. Select the correct IUPAC name of following compound:

NH2
H COOH
H CONH2
COOH
(A) 2R,3S-3- amino-2- carbamoyl butane-1,4-dioic acid
(B) 2S,3R-2-amino-3- carbamoyl butane-1,4-dioic acid
(C) 2S, 3R-3-amino-2-carbamoyl butane-1-4-dioic acid
(D) 2R, 3R-2-amino-3- carbamoyl butane-1-4-dioic acid
10. Total number of geometrical isomer of following compound.

(A) 2 (B) 4 (C) 8 (D) 16

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 Stereochemistry
11. In which of the following has minimum torsional strain and minimum Vander waal strain.

CH3 CH3
CH3 CH3 CH3
H H H CH3
CH3

CH3 H H H
H CH3 CH3 H CH3
CH3 CH3
CH3 CH3 CH3
I II III IV

(A) I (B) II (C) III (D) IV

12. Which of the following pairs can be resolved?

(A)

(B)

HOOC COOH HOOC COOH

(C)
NO2 NO2 NO2 NO2

(D)

13. Which of the following molecules is/are identical with that represented by

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

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 JEE
14. Which of the following is/are the correct Fischer projection of the following :

CH3 C2H5 Et
CH3
H OH HO H H OH H OH
(A) H OH (B) HO H (C) HO H (D) H OH
H OH HO H H OH HO H
C2H5 CH3 C2H5 CH3
15. Statement-1 : E-cyclopentadecene is having more HC (Heat of combustion) than Z isomer.
Statement-2 : E-cyclopentadecene is more stable than Z isomer.
(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 statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
16. Determine the absolute configurations of the chiral centres in the following compound.

a
O
b

Br
(A) a  R; b  S (B) a  R; b  R (C) a  S ; b  S (D) a  S ; b  R
17. Identify which of the structures below are meso structures ?

O O
O O O
O O O O
O O
O O
O O
(1) (2) (3) (4) (5)

(A) 1 and 3 (B) 1, 3 and 5 (C) 1, 3 and 4 (D) 2 and 5

Cl
18. 
2
 mixture of all isomers possible from the mono-chlorination of the structure
hv
is subjected to fractional distillation, then how many fractions will be obtained?
(A) 2 (B) 3 (C) 4 (D) 5

Br
O O
19. Number of optically active isomer is/are:

Br
(A) 0 (B) 1 (C) 2 (D) 3

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 Stereochemistry
20. Match the Column :
Column-I Column-II

COOH COOH
H OH H OH
(a) A pair of metamer (i) ;
HO H H OH
COOH COOH
(b) tautomerism (ii) CH3OC3H7 ; C2H5OC2H5
CH3 CH3
(c) A pair of geometrical isomer (iii) H OH ; HO H
COOH COOH
CH3 CH3 H3 C H
(d) A pair of distereomers (iv)
C=C ; C=C
H H H CH3

O
||
(e) A pair of optical isomer (v) CH 3CH 2CH 2CH ; CH3CH2CH=CH–OH

21. Column-I (Compound) Column-II (Total number of stereoisomer)

(A) (P) 2

(B) (Q) 4

(C) (R) 6

(D) (S) 8

22. Match the column (I) and (II)

Column-I Column-II
(A) CH 3  CH  CH  CH  N  OH (P) 2

(B) (Q) 4

(C) CH 3  CH  CH  CH  CH  CH  CH  CH 3 (R) 6
(D) CH 3  CH  CH  CH  CH  CH  CH  Ph (S) 8
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 JEE
23. Match the column-I and column-II
Column-I Column-II

H
CO2CH2CH2 OH
(A) (P) Chiral
CO2H
H
H H
CO2CH2CH2 O2C
(B) (Q) Achiral
CO2 CH2 CH2 O2C
H H
H CO2 H
OH
(C) OH (R) Meso
HO2 C H

HO2C H
H
(D) OH (S) Compound containing even number of chiral centers
HO CO2 H
24. Match the column (I) and (II)
Column-I (Molecules) Column-II (Relationship)

Cl Cl
(A) (P) Identical
and
CH3 CH3

Cl Cl
(B) (Q) Enantiomer
and
CH3 CH3

Cl CH3
(C) (R) Diastereomer
and
CH3 Cl

Cl Cl
(D) (S) Structural Isomerism
and
CH3 H3 C

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 Stereochemistry
25. Match the column-I and column-II
Column-I Column-II

CH3 H

(A) (P) Geometrical isomerism

H Et

CH3 Et

(B) (Q) Optical isomerism

H H

D
CH3 Et

(C) H (R) Compound containing plane of symmetry

H H

CH3
CH3 CH3
(D) H (S) Compound containing center of symmetry
H H

26. Match the column-I and column-II

Column-I Column-II
(Molecules) (Property)
H H
(A) C C C (P) Chiral centers containing compound
Cl Cl

H CH3
(B) (Q) Presence of stereocenter
H3C H

Cl
(C) Br F (R) Optically active compound
I

H3 C OH
(D) C N (S) Compound containing plane of symmetry
Et

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 JEE
27. Match the column-I and column-II
Column-I (Molecules) Column-II (Property)
F H
(A) C C C C (P) Polar molecule
H F
F H
(B) C C C (Q) Optically active
H F

(C) F F (R) Optically inactive

H
H F
(D) (S) Plane of symmetry
H H
H
28. With reasons, state whether each of the following compounds I to VII is chiral.

(I) (II) (III)

HO 2C CO 2H

(IV) (V) (VI) (VII) S

O Ph
Me
29. What are the relationships between the following pairs of isomers?

(a) and

Cl Cl
(b) and

Cl Cl

(c) and

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 Stereochemistry

(d) and

(e) and (f) and

(g) and (h) and

(i) and

30. Total number of streoisomers for the following molecule: (including optical)

(i) CH3 – CH – CH = CH CH = CH – CH – CH3

| |
Cl CH3

NH2
N
O N

(ii) (iii) EtO – P N N

Me
COOH OEt

OH
O

(iv) (v) (vi)

OH
O



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JEE

CONTENTS
5.0 INTRODUCTION
5.1 ALKANES
5.1.1 Methods of Preparation of Alkanes
5.1.2 Physical Properties
5.1.3 Chemical Properties
5.2 ALKENES
5.2.1 Methods of Preparation of Alkenes
5.2.2 Physical Properties
5.2.3 Chemical Properties of Alkenes
5.3 ALKYNES
5.3.1 Methods of Preparation of Alkynes
5.3.2 Physical Properties
5.3.3 Chemical Properties

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 Hydrocarbon

5.0 INTRODUCTION
Organic compounds containing only hydrogen and carbon are known as hydrocarbons. Hydrocarbons
are divided into two main classes: aliphatic and aromatic. Aliphatic hydrocarbons are further divided
into families: alkanes, alkenes, alkynes, and their cyclic analogs.
5.1 ALKANES
Alkanes or paraffins are saturated hydrocarbons with the general formula CnH2n+2. The principal
source of alkanes are petroleum and natural gas.
5.1.1 Methods of Preparation of Alkanes:
(i) Hydrogenation of alkenes and alkynes: This method involves heterogenous catalysis by
finely divided metal, usually platinum, palladium or nickel involving syn addition of hydrogen.
| | | |
— C = C — + H—H 
Pt
 —C — C —
| |
H H
(ii) Hydrolysis of Grignard reagent: Grignard reagent is obtained by treating a solution of alkyl
halide in dry ethyl ether (C2H5)2O with metallic magnesium.
R  X  Mg 
dry ether
 R  MgX (Grignard Reagent)
R  MgX  H 2 O  R  H (Alkane)  Mg(OH)X
Alkanes can similarly be obtained from alkyl lithium compounds.
R  X  2Li 
dry
ether
 R  Li  LiX

R  Li  H 2 O  R  H  LiOH
Hydrolysis of organometallic compounds to yield alkanes is displacement of a weak acid from its
salt by a stronger acid. Any compound that is more acidic than alkane can yield this reaction.

For example, RMgX + NH3 

 R–H + Mg (NH 2 )X
stronger weaker
acid acid

RMgX + CH 3OH 
 R–H +Mg(OCH3 )X
stronger weaker
acid acid

(iii) Wurtz Reaction: When alkyl halide reacts with Sodium in presence of dry ether then we get
higher alkane. Mechanism of the reaction is based on ionic and free radical both.
R – X + 2 Na + X–R dry ether
   R – R + 2 NaX
CH3Cl + 2 Na + ClCH3  CH3–CH3 + 2 NaCl
NOTE : 1. This reaction is not suitable for tertiary alkyl halides
2. This method is suitable for the preparation of even number carbon alkanes and
methane (CH4) can not be prepared from this method.
Mechanism : Two mechanism has been suggested for Wurtz reaction.
Ionic mechanism
CH CH  Br
C2 H5 Br + Na NaBr
  C2H5¯Na+ 
3 2
 NaBr
 CH3 – CH2 – CH2 – CH3

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JEE

2Na 2Na + 2e


CH3– CH 2– Br CH3– CH 2+ Br 
   
CH3CH2+ Na CH3CH2Na

  CH3– CH –2 Br
CH3CH2Na CH3 – CH2– CH 2– CH 3
– NaBr
Free radical mechanism
–2NaBr
2C2 H5 – Br + 2Na  2C2H5•  C2H5–C2H5

Na Na + e ¯

.
CH3– CH 2– Br CH3– CH +2 Br 

CH3 – CH2 + CH2 – CH3 CH3 – CH 2 – CH 2 – CH 3

(iv) Corey-House Synthesis:

R  X 
Li
Ether
 R  Li 
CuX
 R 2 CuLi

R CuLi + 2R  – X 
2  2R – R  + LiX + CuX
Lithium dialkyl (should be1°)
cuprate

This method is better than Wurtz and can be used for preparing symmetrical as well as
unsymmetrical alkanes (having an odd number of carbon atoms).
(v) Frankland’s reaction: If alkyl halide is treated with Zn dust in closed tube then higher
symmetrical alkanes will be formed.

2RX + Zn  R – R + ZnX2

This is known as Frankland’s reaction, in this reaction first Frankland’s reagent (R–Zn–R, dialkyl
Zinc) is formed. Which then react with alkyl halide to give higher alkanes. [Where R = CH3]
For Example:-
CH3 – Br + 2Zn + Br – CH3  CH3 – Zn – CH3 +ZnBr2

CH3 – Zn – CH3 + 2CH3 – Br  2 CH3 –CH3 + ZnBr2

ethane

MID LEARNING EXERCISE (MLE)-25

Q.1 In Wurtz reaction if we take CH3Cl & C2H5Cl then product will be-
(A) Propane + Ethane (B) Propane
(C) Propane + Ethane + Butane (D) Propane + Butane
Q.2 Isopropyl bromide undergoes Wurtz reaction to form-
(A) Hexane (B) Propane
(C) 2, 3-Dimethyl butane (D) Neohexame
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 Hydrocarbon
Q.3 Alkanes can be prepared from Grignard reagents by reacting with -
(A) Alcohols (B) Primary amines (C) Alkynes (D) All of them
Q.4 The order of reactivity of alkyl halides in Wurtz reaction is
(A) R  I  R  Br  R  Cl (B) R  I  R  Br  R  Cl
(C) R  Br  R  I  R  Cl (D) R  I  R  Cl  R  Br
Q.5 Which of the following compound is not suitable to obtain from Wurtz reaction?
(A) Ethane (B) Butane (C) Isopentane (D) Hexane
Q.6 If isopropyl chloride and ethyl chloride both react with Na in presence of dry ether which alkanes are
obtained
(A) n-Butane (B) 2-Methyl butane
(C) 2, 3-Dimethyl butane (D) All of them
Q.7 Which of the following does not give alkane with R – Mg – X ?
(A) Ph – OH (B) C6H6 (C) CH3COOH (D) HCl
Q.8 When ethyl chloride and n-propyl chloride undergoes Wurtz reaction which is not obtained ?
(A) n-butane (B) n-pentane (C) n-hexane (D) isobutane
Q.9 Which of the following reactions can be employed for getting unsymmetrical alkanes in good yield?
(A) Wurtz reaction (B) Corey-House reaction
(C) Both (D) None of these
Q.10 Which compound cannot be formed from Wurtz reaction?
(A) Propane (B) Butane (C) Ethane (D) Methane
Q.11 The correct order of rate or Wurtz reaction.

(I) CH 2–F 

Na
Ether
 CH 2–CH2

(II) CH 2–Cl 

Na
Ether
 CH 2–CH2

(III) CH 2–Br 

Na
Ether
 CH 2–CH2

(IV) CH 2–I 

Na
Ether
 CH 2–CH2

(A) I  II  III  IV (B) II  I  III  IV

(C) IV  III  II  I (D) In all rate of Wurtz reaction is same
Q.12 BrCH 2  CH 2  CH 2 Br reacts with Na in the presence of ether to produce -

(A) BrCH 2  CH  CH 2 (B) CH 2  C  CH 2

(C) CH 2 – CH2 (D) All of these

CH 2

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JEE
Q.13 Product of the reaction will be:

H 3C D
C=C 
H 2 /Ni

D H3C
(A) racemic mixture (B) diastereomers
(C) constitutional isomers (D) meso

Q.14 
H 2 (1 Mole)
Pt
 Product

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

Q.15 If the following compound is treated with Pd/C in excess of H2 gas, how many stereoisomers of the
product will be obtained?
(A) 1 (B) 2 (C) 3 (D) 4
Q.16 The treatment of C2H5Mgl with water produces
(A) Methane (B) Ethane (C) Ethanal (D) Ethanol
(vi) Kolbe’s Electrolysis:
(i) Sodium or potassium salt of acid on electrolysis gives higher alkane.
(ii) Reaction follows free radical mechanism.
(iii) 2R  C  ONa Electrolys
 is
 R–R + 2CO2 + NaOH + H2
||
O
2R  C  O  Na  2R  C  O ¯ + 2Na+
|| ||
O O
Anode reaction:

2R  C  O ¯  2R – C – O + 2e¯ 

–2CO 2
 2R 
||
O O
R· + R·  R – R
Cathode reaction:
2Na+ + 2e¯ + 2H2O  2NaOH + H2
Other products:
R  C  O· + R·  R  C  O  R
|| ||
O O
Ester

The best yield of alkane is obtained when electrolysis of salt of only one carboxylic acid is
carried out.
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 Hydrocarbon
(vii) Decarboxylation of sodium salt of carboxylic acids: By heating a mixture of sodium salt of
carboxylic acid with soda-lime (NaOH + CaO).
RCOO  Na   NaOH 
CaO
 R  H  Na 2 CO3
This method can be used to prepare alkanes with one carbon atom less than the corresponding
carboxylic acid.
(viii) Reduction of metal halides by metal and acid:
R  X  Zn  H   R  H  Zn 2  X 
The reaction involves electron transfer from metal to alkyl halide forming carbanion which abstracts
a proton from the solvent, forming an alkane.
(ix) Using reducing agents with alkyl halides:
4RX  LiAlH 4 
 4R  H  LiX  AlX 3

R  X  (C6 H 5 )3 SnH 
 R  H  (C6 H 5 )3 SnX
Triphenyl tin hydride

Lithium aluminium hydride can reduce primary and secondary halides. Sodium borohydride
(NaBH4) can reduce secondary and tertiary halides whereas triphenyl tin hydride can reduce all
types of alkyl halides (primary, secondary, and teritary).
(x) From aldehydes and ketones:
(a) Clemmensen Reduction: The Clemmensen reduction is most commonly used to convert
acylbenzenes to alkylbenzenes, but it also works with other ketones and aldehydes that are not
sensitive to acid. The carbonyl compound is heated with an excess of amalgamated zinc (zinc
treated with mercury) and hydrochloric acid. The actual reduction occurs by a complex mechanism
on the surface of the zinc.
O
||
Ph  C  CH 3 Zn
( Hg
)or Na ( Hg )
 Ph–CH2–CH3
HCl
(b) Wolf-Kishner Reduction: Compounds that cannot survive treatment with hot acid can be
deoxygenated using the Wolf-Kishner reduction. The ketone or aldehyde is converted to its
hydrazone, which is heated with a strong base such as KOH or potassium t-butoxide.
O NNH2
KOH, heat
N H

2 4  + N2
(diethylene glycol)

Phenyl propanone Phenyl hydrazone n-propylbenzene (82%)

(xi) From Red P + HI: It is a powerful reducing agent which will convert, aldehyde, ketone, alcohol,
carboxylic acid to alkanes with same number of carbon.
Re d P  HI
(i) R–CH3–OH   
 R –CH3
O
|| Re d P  HI
(ii) R  C  H     R –CH3
O
|| P  HI
(iii) R  C  R Re
d  R –CH2– R
P  HI
(iv) R–COOH Re d  R –CH3

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JEE

MID LEARNING EXERCISE (MLE)-26

Q.1 Kolbe's reaction is convenient for the preparation of :
(A) Methane
(B) Alkanes containing even number of carbon atoms
(C) Alkanes containing even as well as odd number of carbon atoms
(D) Alkanes containing odd number of carbon atoms
Q.2 An unknown carboxylic acid salt on Kolbe's electrolysis form cyclobutane; the carboxylic acid can
be:
(A) adipic acid (B) hexanoic acid (C) succinic acid (D) fumaric acid
Q.3 Which of the following will not produce ethane ?
(A) Reduction of CH3COOH with HI/P4
(B) Reduction of CH3COCH3 with HI/P4
(C) Decarboxylation of sodium propionate with soda lime
(D) Hydrogenation of ethene in the presence of Ni.
Q.4 Methane can be prepared by :
(A) Wurtz reactions (B) hydrogenation
(C) decarboxylation (D) dehydrohalogenation
Q.5 An aqueous solution containing sodium acetate and sodium propionate is electrolyzed. Which of the
following alkanes is expected as product ?
(A) Ethane (B) Propane (C) Butane (D) All of these
Q.6 Decarboxylation of isobutyric acid leads to -
(A) Isobutane (B) Propane (C) Butane (D) None
Q.7 On electrolysis of sodium acetate H2 gas is evolved at cathode, C2H6 is at anode. Then reaction is-
(A) Frankland (B) Kolbe (C) Clemmenson (D) Wolf-Kishner
Q.8 The compounds formed at anode in the electrolysis of an aqueous solution of potassium acetate, are
(A) C2H6 and CO2 (B) C2H4 and CO2 (C) CH4 and H2 (D) CH4 and CO
Q.9 X is heated with soda lime and gives ethane. X is :
(A) ethanoic acid (B) methanoic acid (C) propanoic acid (D) either (A) or (C)
Q.10 How many acids can be taken to obtain isobutane by decarboxylation?
(A) 4 (B) 3 (C) 2 (D) 5
Q.11 Give reactivity order for decarboxylation?
(I) CH 3  CH 2  COOH (II) CH 2  CH  COOH
(III) CH  C  COOH
(A) I > II > III (B) III > II > I
(C) III > I > II (D) None is correct
Q.12 The reagent in the Clemmensen reduction is :
(A) LiAlH4 (B) Zn-Hg/HCl (C) Zn/HCl (D) Na/EtOH

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 Hydrocarbon

Q.13 O can be converted to by

(A) Red P + HI (B) Wolf Kishner reduction

(C) Clemmensen reaction (D) All
Q.14 The pH of solution in Kolbe's electrolysis:
(A) Increase with time (B) Decrease with time
(C) Remains constant (D) Nothing can be said
Q.15 During the preparation of ethane by Kolbe’s electrolytic method using inert electrodes the pH of
the electrolyte –
(A) Increases progressively as the reaction proceeds
(B) Decreases progressively as the reaction proceeds
(C) Remains constant throughout the reaction
(D) May decrease of the concentration of the electrolyte is not very high

Q.16 on electrolysis gives:

(A) (B)

(C) (D)
Q.17 In which reaction major product is hydrocarbon?
(A) RCOOK Electrolys
 is
 2 /
(B) RCOOAg I
CH 3
Cl / hv
| C 2 H 5OH
(C) CH3–CH3 2 
 (D) CH 3  C  Cl  
|
CH 3

5.1.2 Physical Properties:

1. The first four alkanes (from methane to butane) are colourless and odourless gases. The next
thirteen (from pentane to heptadecane) are colourless and odourless liquids. And, the rest of
higher alkanes (having 18 carbon atoms or more) are colourless solids at ordinary temperature.
2. Alkanes being non-polar molecules, are soluble in non-polar solvents like benzene, ether, and
chloroform. However, they are insoluble in polar solvents like water. Their solubility decreases
with increase in their molecular weight.
3. Intermolecular forces in alkanes are weak van der Waal’s forces; the greater the surface area
the stronger the intermolecular forces. Thus, the boiling point of alkanes increases by 20°C to
30°C for each carbon atom that is added to the chain.
Among isomeric alkanes, straight chain isomers have a higher boiling point than the branched
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JEE
chain isomers. With an increase in branching, the shape of the molecule approaches that of a
sphere and there is a reduction in the surface area. This renders the intermolecular forces weak
and the same can be overcome at a relatively lower temperature.
4. The density of alkanes increases with the size of the molecule and approaches a constant specific
gravity of 0.8 for n-hexadecane, that is, all alkanes are lighter than water.
5. The melting point of alkanes increase with an increase in the number of carbon atoms. However,
the rise is not uniform. The rise in melting point is more as one moves to higher alkanes having an
odd number of carbon atoms as compared to those having an even number of carbon atoms.
This is because the melting point depends not only on the size of molecules but also on how well
they can fit into crystal lattice, that is, how symmetrical is a molecule. Alkanes with an even
number of carbon atoms are more symmetrical and thus have a higher melting point.
5.1.3 Chemical Properties:
(i) Halogenation: Alkanes react with bromine or chlorine in the presence of sunlight or UV light or
in dark at high temperatures (250°C– 400°C) forming a mixture of substituted products.
For example, CH 4 
Cl2
hν
CH 3Cl 
Cl2
hν
CH 2 Cl2 
Cl2
hν
CHCl3 
Cl2
hν
CCl4
The yield of monohalogenated product can be increased by using substrate (alkane) in excess.
The reactivity of halogens follows the order: F2  Cl 2  Br2  I 2 .
Direct fluorination is explosive and can be achieved by the action of inorganic fluorides on bromo or
iodo derivatives.
2C 2 H5 Br  HgF2 
 2C 2 H5 F  HgBr2
Bromination is slower than chlorination and is carried out at higher temperatures.
Iodination is reversible and can be carried out sufficiently in the presence of strong oxidising agents
like iodic acid (HIO3) or nitric acid (HNO3) that destroys hydroiodic acid (HI) and shifts the equilibrium
towards the right.
CH 4  I 2  CH 3 I  HI
5HI  HIO 3  3I 2  3H 2 O
Alkyl iodides can be prepared conveniently by Contant-Finkelstein reaction which involves treating
chloro or bromoderivative with NaI in acetone.
RCl  NaI 
acetone
 RI  NaCl 
Alkyl chlorides or bromides cannot be prepared by this method of halide exchange because NaCl
and NaBr are insoluble in acetone.
 Mechanism of Halogenation: The mechanism involves the following steps:
(a) Chain-initiation step:

250  400 C
X 2 
or UV light
2X 
(b) Chain-propagation step:
X   R  H 
 H  X  R

R   X 2 
 R  X  X
(c) Chain-termination step:
X   X  
 X2

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 Hydrocarbon

R   X  
 RX

R   R  
 RR
Radical inhibitors stop chain propagation by reacting with free radical intermediates.
•• •• •• ••
Ex. R • + •O — O  
 R – O — O
•• •• •• ••
Peroxy radical

 Orientation of Halogenation: In complex alkanes, isomeric products are possible on halogenation.

For example, chlorination of isobutane at 25°C gives a mixture of two isomeric monochlorides

CH3 CH3 CH 3
| | |
CH 3 — CH — CH 3 
Cl2
hv
CH 3 — CH — CH 2 Cl  CH 3 — CH — CH 3
(64%) |
iso-Butyl chloride
Cl
(36%)
tert-Butylchloride

Given below are the factors that determine relative yields of isomeric products.
Probability Factor
This is based on the number of each kind of hydrogen atoms in the alkane molecule. In the above
example, there are nine 1° hydrogens and only one 3° hydrogen. Thus, probability factor favours the
abstraction of 1° H by a factor of 9 : 1.
Reactivity of H
The order of reactivity of hydrogen atoms is 3° > 2° > 1°.
Reactivity of X•
If the attacking species is more reactive, it will be less selective and the product composition will be
determined by probability as well as reactivity of hydrogen atoms but if the attacking species is less
reactive it will be more selective and the product composition will be determined by the reactivity of
hydrogen atoms to a large extent.
At room temperature, the relative rates of chlorination are 5.0 : 3.8 : 1.0 respectively for 3°, 2°, and
1° hydrogen atoms, whereas at 127°C the relative rates of bromination are 1600 : 82 : 1. In the latter
case, the differences in reactivity are so marked as vastly to outweigh probability factors. Thus, less
reactive bromine is more selective than chlorine.
Illustration 1. Find out the percentage composition of products from mono-chlorination of n-butane at
25°C.
Solution: Monochlorination of n-butane can form two isomers: sec-butyl chloride by abstraction of 2°
H and n-butyl chloride by abstraction of 1°H.

CH 3
|
CH 3CH 2 CH 2 CH 3 
Cl2
hv
CH 3 CH 2 CH  Cl  CH 3 CH 2 CH 2 CH 2 Cl

Relative ratio of products can be determined as

n-butyl chloride number of 1°H reactivity of 1°H 6 1.0 6
    
sec-butyl chloride number of 2°H reactivity of 2°H 4 3.8 15.2

6
% of n-butyl chloride   100  28.3%
6  15.2

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JEE

15.2
% of sec-butyl chloride   100  71.7%
6  15.2
(ii) Isomerization: Lower alkanes are not isomerised but butane or higher number of alkanes if
heated with aluminium chloride at high temperature then they convert into stable isomers by the
rearrangement reaction. Isomerisation is also held by heating alkane with- (AlX3 + HX; X = Cl, Br,
I or Al2(SO4)3 + H2SO4) at 200ºC.

AlCl
3
 CH3  CH  CH3
400 º C |
CH3
n - butane iso butane
If we take n- heptane then it converts into most stable form Triptane (trivial name).

CH3-(CH2)5 –CH3 

n- heptane 2, 2, 3- trimethyl butane

If we take n - octane, iso-octane is formed.

CH3(CH2)6 CH3 

n- octane iso-octane
(iii) Combustion: Combustion is a rapid oxidation that takes place at high temperatures, converting
alkanes to carbon dioxide and water. Little control over the reaction is possible, except for moderating
the temperature and controlling the fuel / air ratio to achieve efficient burning.
CnH(2n+2) + excess O2 heat
 nCO2 + (n+1) H2O
Example: CH3CH2CH3 + 5 O2 heat

 3 CO2 + 4 H2O
 y y
CxHy +  x   O2  xCO2 + HO
 4 2 2
(iv) Aromatization: For converting aliphatic to aromatic.
CH3
Cr O  Al O Cr O  Al O
(i) n-Hexane   (ii) n-Heptane  
2 3 2 3 2 3 2 3

CH3 C2H5
CH3
(iii) n-Octane Cr 3  Al 2 O3
2O  +


o–Xylene Ethyl benzene

(v) Nitration: Under certain conditions, alkanes react with nitric acid, a hydrogen atom being replaced
by a nitro-group, NO2. This process is known as nitration. Nitration of the alkanes may be carried out
in the vapour phase between 150°C and 475 °C, whereupon a complex mixture of mononitroalkanes
is obtained.

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 Hydrocarbon

NO 2
HNO3
|
CH3CH2CH3 400
 CH CH CH NO + CH 3CHCH 3 + C H NO + CH NO
C 3 2 2 2 2 5 2 3 2
Nitration of alkanes follow the free-radical mechanism.

MID LEARNING EXERCISE (MLE)-27

Q.1 The compound with the highest boiling point is:
(A) n-hexane (B) n-pentane
(C) 2,2-dimethyl propane (D) propane
Q.2 When n-heptane is reacted in the presence of Cr2O3 and Al2O3 at high temperature and pressure,
then major product will be ?
(A) Benzene (B) Toluene (C) Ethylbenzene (D) Phenol
Q.3 Arrange the following in correct order of reactivity towards halogenation
CH3
|
(A) CH 4 (B) CH 3CH 3 (C) CH 3CH 2CH 3 (D) CH3  C H  CH3
(A) A > B > C > D (B) D > C > B > A (C) B > C > A > D (D) C > B > D > A
Q.4 Which halogen, the reaction of alkane are expolosive-
(A) F 2 (B) Cl2 (C) I 2 (D) Br 2
Q.5 The chain propagating step is fastest in the reaction of an alkane with
(A) Fluorine free radical (B) Chlorine free radical
(C) Iodine free radical (D) Bromine free radical
Q.6 Halogenation of alkanes gives a mixture of monohalo products. The ease of substitution follows the
order
(A) (A) Tertiary H > primary H > secondary H (B) Primary H < Secondary H < Tertiary H
(C) Primary H > Secondary H > Tertiary H (D) Secondary H > Tertiary H < Primary H
Q.7 Which gives maximum yield of C2H5Cl ?
(A) C 2 H 6  Cl2 
hv
Light
 C 2 H 5 Cl  HCl (B) C2 H 6  Cl 2 
hv
Light
 C2 H 5Cl  HCl
Excess Excess

(C) C 2 H 6  Cl 2 
hv
Light
 C 2 H 5 Cl (D) C 2 H 6  Cl2 
Dark
 C 2 H5 Cl + HCl
Q.8 Bromination of an alkane as compared to chlorination proceeds
(A) At a slower rate (B) At a faster rate
(C) With equal rates
(D) With equal or different rate depends upon the temperature
Q.9 The pyrolysis of higher hydrocarbon into lower hydrocarbon, the process is called:
(A) Aromatisation (B) Cracking (C) Isomerisation (D) None
Q.10 2-Methylbutane on reacting with bromide in the presence of sunlight gives mainly:
(A) 1-Bromo-3-methylbutane (B) 2-Bromo-2-methylbutane
(C) 2-Bromo-3-methylbutane (D) 1-Bromo-2-methylbutane
Q.11 Pyrolysis of alkanes is a:
(A) Nucleophilic addition reaction (B) Electrophilic addition reaction
(C) Free radical substitution reaction (D) Free radical elimination reaction

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JEE
Q.12 The most volatile alkane is :
(A) n-pentane (B) isopentane (C) neopentane (D) n-hexane
Q.13 How many moles of O2 required for complete combustion of one mole of propane ?
(A) 7 (B) 5 (C) 16 (D) 10
Q.14 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.
Q.15 When n-butane is heated in the presence of AlCl3/HCl it will be converted into –
(A) Ethane (B) Propane (C) Butene (D) Isobutane
5.2 ALKENES
Alkenes or olefins are unsaturated hydrocarbons having general formula CnH2n that contain the
structural unit C = C . In alkenes, each doubly bonded carbon undergoes sp2 hybridisation and the
three sp2 orbitals lie in the plane of carbon nucleus and are directed towards the corners of an
equilateral triangle. The two doubly bonded carbon atoms lie in the same plane and there is a 
electron cloud formed by lateral overlap of pz-pz orbitals lying above and below the plane of double
bonded carbon atoms.
The  bond prevents free rotation about the carbon-carbon double bond and thus an alkene having
two different substituents on each doubly bonded carbon has geometric isomers. For example, there
are two stereoisomers of 2-pentene.
CH3 CH H CH
C=C 2 5 C=C 2 5
H H CH 3 H
cis-2-pentene trans-2-pentene
(bulky groups on same side) (bulky groups on opposite sides)

H CH3
However, propylene C=C does not exhibit geometrical isomerism as one of the doubly
H H
bonded carbon atom has identical groups (H atoms) on it.
5.2.1 Methods of Preparation of Alkenes:
(i) Reduction of Alkynes:

H2 R R
Lindlar catalyst C=C (Syn addition)
R—C C—R H H
R H
Na or Li/liq. NH3 C=C (Anti addition)
(Birch reduction) H R

Metallic palladium deposited on calcium carbonate and conditioned with lead acetate and quinoline is
Lindlar’s catalyst. It reduces alkynes to cis alkenes whereas trans alkenes are obtained predominantly
by reduction with sodium or lithium in liquid ammonia.
(ii) Dehydrohalogenation of Alkyl Halides:
X
| | | |
— C — C — + KOH  alcohol
 — C = C —  KX + H 2 O
| |
H
Dehydrohalogenation belongs to a general class of reactions called 1, 2-elimination reactions or -
elemination.
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 Hydrocarbon
Such elimination reactions are characterised by the following:
(a) The substrate should contain a leaving group (an atom or group that leaves the molecule, taking
its electron pair with it).
(b) The substrate should have an atom or a group in a position beta to leaving group (nearly always
hydrogen) that can be extracted by a base, leaving its electron pair behind.
(c) The reaction is brought about by a base. It can be a basic anion like hydroxide or an alkoxide
derived from alcohol like ethoxide ( C2 H5 O – ) and tert-butoxide [ (CH3 )3 CO – ].
Mechanism of Dehydrohalogenation (E2 Mechanism)
The reaction simultaneously involves:
(i) pulling of a proton away from the carbon by the base
(ii) removal of a halide ion
(iii) formation of a double bond

–
X X
---

b
—C – C  — C -—
-- C —  : X – + C=C + B:H
f b
–
H H - -f - B–
:B –
Transition State
Dehydrohalogenation proceeds by second-order kinetics where the rate-determining step involves
both alkyl halide and base molecules. The mechanism was proposed by Hughes and Ingold and was
named E2 (bimolecular elimination) mechanism.
Rate of E2 reaction = k[RX] [:B–]
Orientation and Reactivity of Dehydrohalogenation
Dehydrohalogenation often yields a mixture of isomeric alkenes.
Example: CH3CH2 CHBr CH3 
KOH (alc)
 CH3CH = CHCH3 + CH3CH2CH = CH2
81% 19%
The orientation of elimination is determined by “Saytzeff rule” which states that in dehydrohalogenation
the preferred product is the more substituted alkene (alkene that has the greater number of alkyl
groups attached to doubly bonded carbon atoms).
Ease of Formation of Alkenes
R2C = CR2 > R2C = CHR > R2C = CH2, RCH = CHR > RCH = CH2 > CH2 = CH2
The order of reactivity of alkyl halides in E2 dehydrohalogenation is 3° > 2° > 1° and
R—I > R—Br > R—Cl > R—F.
 Exceptions to Saytzeff’s Rule:
When dehydrohalogenation is carried out with a strong and bulky base such as potassium tert-
butoxide, it may lead to the formation of a less substituted alkene in higher amount (Hoffman’s
product). Another case where Hoffman’s product is predominant is when the leaving group is poor
like a fluoride ion.

CH3
CH3 CH2
(CH3)3C—O– + CH3—CH2—C—Br CH3—CH = C + CH3CH2 C
(bulky base) CH3 CH3
CH3 (Saytzeff's product) (Hoffman's product)
(minor) (major)

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JEE

MID LEARNING EXERCISE (MLE)-28

Q.1 Which of the following must be an alkene?
(A) C2H4 (B) C3H6 (C) C4H8 (D) All of these
Q.2 The compound 1, 2-butadiene has
(A) only sp hybridised carbon atoms (B) both sp and sp2 hybridised carbon atoms
(C) only sp hybridised carbon atoms
2
(D) sp, sp2 and sp3 hybridised carbon atoms
Q.3 When a haloalkane with Beta-hydrogen is heated with alcoholic solution of KOH the product and the
type of mechanism is ?
(A) Alcohol, SN1 (B) Alkene, alpha-elimination
(C) Alcohol, SN2 (D) Alkene, Beta-elimination

Q.4 + H 2 
Ni/Δ
BaSO 4
 ?
(1eq.)

H H H

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

Na  Liq·NH3
Q.5 CH3  CH 2  C  C  CH3  H 2   ?
CH 3 – H2C H
(A) CH 3  CH 2  CH 2  CH 2  CH 3 (B) C=C
H CH3

CH 3 – H2C CH3
(C) C=C (D) CH 3  CH 2  CH  CH  CH 3
H H
Q.6 CH 3  CH  CH  CH 3 
Alc. KOH

?
| |
CH3 Cl

(A) CH3  C H  CH  CH 2 (B) CH3  C H  C H  CH3

| | |
CH 3 CH 3 OH

(C) CH 3  C| H  CH  CH3 (D) CH 2  C  CH 2  CH 3

|
CH 3 CH 3
Q.7 For the reaction :
Br
+ CH 3CH 2 ONa 
C 2 HO5 H


the major product is formed by:

(A) SN1 reaction (B) SN2 reaction (C) an E1 reaction (D) an E2 reaction

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 Hydrocarbon

Br
CH 3
Q.8 CH 3 
alc.KOH
 Product

The product can be:

CH 3
CH 3 CH 3 CH 3 CH 3
(A) CH 3 (B) CH 3 (C) (D)
CH 3
Q.9 Which is most easily dehydrohalogenate?

Cl Cl Cl

(I) (II) (III)

(A) I (B) II
(C) III (D) All with same reactivity
Q.10 In dehydrohalogenations the base (alcoholic KOH) abstracts:
(A) The halide ion
(B) The proton present on the carbon next to the carbon to which the halogen is attached.
(C) The proton present on the carbon to which the halogen is attached.
(D) The proton on the  -carbon.
Q.11 In the elimination of reactions, that is, in the formation of alkenes, the reactivity of halogens in alkyl
halides is in the order :
(A) I > Br > Cl (B) Cl > Br > I (C) Br > Cl > I (D) None
Br

t-BuOK
Q.12  product

Major product is:

Br

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

Q.13 CH 3  CH  CO 2 K 
electrolys
 is
 (A) (Major)
|
CH 3  CH  CO 2 K 
Major product (A) of above reaction
(A) (B)

(C) (D)

(104)
JEE
Q.14 In the reaction

C H O

2 5

C2 H5OH
Br
The major product obtained is:
OC2H5
(A) (B) (C) (D)

Q.15 Which of the following alkyl halide gives only one product (excluding stereoisomer) when undergo E2
reaction ? (E2 = elimination bi-molecular)

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

CH3
Ph H alc.KOH
Q.16  Major product of the reaction is:
Ph Br (E 2 reaction)

CH3

Ph CH3 Ph Ph
(A) C C (B) C C
Ph CH3 H3C CH3

H3C Ph
(C) C C (D) Ph CH CH Ph
Ph CH3
CH3 OH

(iii) Dehydration of Alcohols:

Alcohols form alkenes on dehydration by
(a) Reaction with conc. H2SO4 at 100°C
(b) Reaction with phosphoric acid (H3PO3) at 200°C
(c) Passing alcohol vapour over alumina (Al2O3), P2O5 or anhydrous ZnCl2 at 350°–400°C

| | | |
— C — C — 
acid
Δ
 — C = C —  H2O
| |
H OH
 Mechanism of Dehydration (E1 Mechanism):
Dehydration of alcohols is also an elimination reaction and occurs through the following steps:

(i) —C—C— + H – B —C—C— + : B–

H OH H OH2


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 Hydrocarbon

(ii) —C—C— —C—C— + H2O: (rds)


H OH2 H


(iii) —C—C— C=C +H:B


H
:B–
Step (1) is a fast acid-base reaction giving protonated alcohol (oxonium ion) and the conjugate base.
The protonated alcohol undergoes heterolysis to form carbocation and water in step (2) which is the
RDS step of reaction. In step (3), the carbocation loses a proton to the base to yield an alkene.
Note: The carbo-cation intermediate may undergo rearrangement (if possible) before forming an
alkene.
Reactivity of Alcohols in Dehydration 3° alcohol > 2° alcohol > 1° alcohol
Experimental conditions like temperature and acid concentration are harshest for primary alcohols
and extremely mild for tertiary alcohols.
 Orientation of Dehydration:
When alcohols can yield more than one alkene on dehydration, the product composition is determined
by Saytzeff rule but only when the generated carbocation does not undergo rearrangement. For
example,

H+
CH3 CH2 CH CH3   CH3 CH = CH CH3 + CH3 CH2 CH = CH2
Δ (major) (minor)
OH (more substituted
(less substituted
alkene)
alkene)
But when a carbocation rearrangement is possible, for example

CH3 CH3 CH3 CH3 CH3

+
H
CH3—C—CH—CH3 
 CH3—C = C—CH3 + CH3—CH—C = CH2
Δ (major) (minor)
CH3 OH

Here, none of the products is predicted by Saytzeff Rule. The steps involved are

CH3 CH3 CH3

H+ –H2O
CH3—C—CH—CH3 CH3—C—CH—CH3 CH3—C—CH—CH3

CH3 OH CH3 OH2 CH3

The carbocation formed here is 2° and can rearrange to a 3° carbocation through methanide shift

CH3 CH3
–CH 3 
CH3—C—CH—CH3   CH3—C—CH—CH3
 (methanide shift)
CH3 CH3

(106)
JEE
And now Saytzeff rule is applicable to the rearranged carbocation:

CH3 CH3

CH3—C—CH—CH3 CH3—C = C —CH3 + CH2 = C—CH—CH3
CH3 CH3 CH3 CH3
(major) (minor)

Rearrangement of carbocation can also lead to change in ring size forming a more stable ring.
For example,

OH 
 Rearrangement 
1. H +,  (ring expansion) 1, 2 Hydride shift –H +
2.–(H 2O)
1-Methyl cyclopentene

(iv) Dehalogenation of Vicinal Dihalides:

X
| | | |
Alconol
 C  C   Zn    C  C   ZnX 2
| | or acetic acid
X
Vicinal dihalides are compounds having two halide atoms on adjacent carbon atoms. Compounds
having two halide atoms on same carbon atom are called geminal (or gem) dihalides.
(v) Hoffmann’s Elimination of Quaternary Ammonium Hydroxides:
A compound having the structure R4N+ OH– is called a quaternary ammonium hydroxide (the
four alkyl groups attached to nitrogen may be same or different). When a quaternary ammonium
hydroxide is heated strongly (to 125°C or higher), it decomposes to yield water, a tertiary amine,
and an alkene. For example,

CH3 CH3
+   heat + CH2 = CH CH3 + H2O
CH3—N—CH2CH 2CH3 OH– CH3—N
CH3 CH3
Trimethyl-n-propylammonium hydroxide

The product formation is governed by Hoffmann’s Rule (i.e, less substituted alkene is major
product) For example,

OH
CH3 CH2 CH2 CH CH3 
CH3 CH2 CH2 CH = CH2 (96%) + CH3 CH2 CH = CH CH3
 N(CH ) Hoffman's product
3 3
2-pentyltrimethyl ammonium ion

Note: When two or more alkyl groups have -hydrogen atoms, elimination occurs from the alkyl
group that contains greater number of -hydrogens.

(107)
 Hydrocarbon

MID LEARNING EXERCISE (MLE)-29

Q.1 n-Butyl alcohol on dehydration forms -butylene as the chief product. This happens because of the
rearrangement-
 
(A) CH 3  CH 2  CH 2  C H 2 to CH 3  C H  CH 2  CH 3

 
(B) CH 3  CH 2  CH 2  C H 2 to  CH 3  2 CH  C H 2

 
(C) CH 3  C H  CH 2  CH 3 to  CH3 3 C

 
(D)  CH 3 3 C to CH 3  CH 2  CH 2  C H 2

OH

Q.2 
Conc.H 3 PO 4
Δ
 Major Product:

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

Q.3 CH 2  OH 
Conc. 3HPO 4

 Major Product :

(A) CH2 (B) CH3 (C) (D)

Q.4 Arrange the following alkanols 1, 2 and 3 in order of their reactivity towards acid catalyzed dehydration:

OH OH
| |
(1) CH 3  C H  CH 2  C H 2 (2) CH 3  C  CH 2  CH3 (3)  CH 3 2 CH  C CH 3
| | |
CH 3 OH CH 3

(A) 1 > 2 > 3 (B) 2 > 1 > 3 (C) 2 > 3 > 1 (D) 3 > 2 > 1
Q.5 The dehydration of neo-pentanol gives
CH3 CH 3
| |
(A) CH3  C H  CH  CH 2 (B) CH 2  C  CH 2  CH 3

(C) CH 3 –CH 2 –CH=CH–CH 3 (D) None of these

Q.6 Formation of 2-butene as major product by dehydration of 2-butanol is according to-
(A) Markonikoff rule (B) Saytzeff rule
(C) Peroxide effect (D) Anti markonikoff rule
Q.7 H2SO4 reacts with 3, 3-dimethyl-2 Butanol to form the compound :
(A) 3, 3-dimethyl-2-butanol (B) 2, 3-dimethyl butene-1
(C) 2, 3-dimethyl butene-2 (D) None of these

(108)
JEE
Q.8 How many 1,2-Shifts are involved during the course of following reaction ?
OH


Conc. H 2SO4



(A) 1 (B) 2 (C) 3 (D) 4

CH 3
Q.9 CH 3 
H +
 (X).
Δ
OH
Product (X) is :
CH 3
(A) (B) (C) (D)
CH 3
Q.10 Rate of dehydration when given compounds are treated with conc. H2SO4.

(P) (Q) (R) (S)

(A) P > Q > R > S (B) Q > P > R > S (C) R > Q > P > S (D) R > Q > S > P

Q.11 H


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

Q.12 Which carbocation is least likely to form as an intermediate?

 
(A) (C6 H 5 )3 C (B) (C) (D)

conc.H SO
Q.13 CH3  CH  CH 2  CH3 
2 4
Product (I) + Product (II)
|
OH
What is not true regarding the products?
(A) Product-I and II are position isomers
(B) Product-I and II contains the same number of sp3 and sp2 carbon atoms
(C) The yield of the product I and II is same
(D) Reaction obeys Saytzeff rule

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 Hydrocarbon

KOH (alc.)
Q.14 CH2—CH—CH3
Cl
The major product is

(A) CH = CH—CH3 (B) CH2—CH = CH2

(C) CH2—CH—CH3 (D) CH2—CH2—CH2—OH

OH

CH3
CH3 CH CH CH3 Me3CO K (C)
– + NBS
Q.15 (A)
(major product)
Br Br2
(D)

(D) is
(A) 1,2,3-tribromo-3-methyl butane (B) 1,2,3-tribromo-2-methyl butane
(C) 1,1,3-tribromopentane (D) 1,3,3-tribromo-3-methyl butane
Q.16 2, 3 dibromobutane on heating with Zn dust forms
(A) 2-butyne (B) 2-butene
(C) 1-butene (D) 1-butyne
Q.17 Some compounds are given below. Which one will have a higher rate of dehydrohalogenation?

Cl
(A) CH3 — CH2 — CH2 — CH2—Cl (B) CH3– CH2 — CH—CH3

Cl Cl
(C) CH3— CH—CH— CH3 (D) CH3— CH—C— CH3

CH3 CH3 CH3

Q.18 1-phenyl - 2 - chloropropane when treated with alcoholic potash gives mainly
(A) 1-phenyl propene (B) 3-phenyl propene
(C) 1 phenyl - 2 - propane (D) 1-phenyl - 3 - propanol
5.2.2 Physical Properties:
(i) The first three members are gases, the next 14 are liquids, and the higher ones are solids. They
are colourless and odourless. Ethylene, an exception, has a faint sweet smell.
(ii) Being non-polar, alkenes are soluble in non-polar solvents but insoluble in polar solvents like
water.
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JEE
(iii) Their melting and boiling points increase with an increase in the number of carbon atoms. As in
alkanes, branching decreases the boiling point for a given number of carbon atoms.
(iv) Alkenes have a very low or zero dipole moment. Generally, cis isomer has a stronger dipole
moment than the trans form.
5.2.3 Chemical Properties of Alkenes:
Alkenes contain a double bond comprising of a strong  bond and a weak  bond. In the structure of
a double bond, there is a cloud of  electrons above and below the plane of atoms and the double
bond serves as a source of electrons. Thus, the typical reactions of alkenes are Electrophilic
Addition Reactions.
(i) Catalytic Hydrogenation:

Pt, Pd or Ni
—C = C— + H2 —C—C—
Alkene
H H
Alkane

The reaction involves heterogenous catalysis by finely divided metals and occurs exothermically and
reversibly. Hydrogenation proceeds stereoselectively in syn fashion. For example,

Me Me
H2/Ni H Me
Me
H
cis –1, 2–Dimethyl cyclohexane

(ii) Addition of Bromine and Chlorine:

X
—C = C— + X2  —C—C—
Alkene (X2 = Br2, Cl2)
X
vicinal dihalide
Alkenes react rapidly with bromine in CCl4 at room temperature. The red-brown colour of bromine
disappears instantly forming colourless vicinal dibromide.
Mechanism
The mechanism is believed to be electrophilic addition and occurs in two steps. The mechanism
involves a halonium ion intermediate.
Br 
R + – + –
(a) C=C Br—Br Br + R—C—C— (Bromonium ion)

Br  Br
Anti-attack
(b) R—C—C— Br R—C—C— (vicinal dibromide)
Br
As  electrons of an alkene approaches the bromine molecules, the electrons of the bromine-bromine
bond drift in the direction of the bromine atom more distant from the approaching alkene causing the
bromine molecule to break heterolytically into bromonium ion Br  and bromide ion Br Θ . Br  adds
to a double bond forming a cyclic bromonium ion. The cyclic bromonium ion is attacked by Br Θ from
below as the top-side is blocked and the three membered ring opens in trans manner. Thus, the
(111)
 Hydrocarbon
overall addition of Br2 to alkenes follows trans stereoselectivity. For example, addition of Br2 to
cyclopentene gives a pair of trans-1, 2-dibromocyclopentane enantiomers.

Br2
Br H + H Br
CCl 4

H Br Br H
racemic mixture
(iii) Halohydrin Formation:
Halogenation of alkene in CCl4 produces vicinal dihalide. But, the halogenation carried out in aqueous
solution produces halohydrin as the major product which contains halogen and hydroxyl group on
adjacent carbon atoms. The reaction occurs in two steps:

R
(a) C=C + X2 R—C—C— + X
(X2 = Br2, Cl2) 
X
Cyclic halonium ion


(b) R—C—C— + H2O R—C—C— –H R—C—C— (Halohydrin)

X  OH2 X OH X

Since the reaction proceeds via cyclic halonium ion intermediate, the addition of X and –OH occurs
in trans manner. In case of unsymmetrical alkenes, the halogen adds to carbon atom with a greater
number of hydrogen atoms and hydroxyl groups add to carbon atom with a lesser number of hydrogen
atoms. For example,

CH3 CH3
Br2, H2O
CH3—CH—CH = CH2 CH3—CH—CH—CH2—Br
or HOBr
OH
Similar reaction for Cl2 + H2O or HOCl, NOCl
MID LEARNING EXERCISE (MLE)-30
Q.1 Which is expected to react most readily with bromine ?
(A) CH3CH2CH3 (B) CH2 = CH2 (C) CH  CH (D) CH 3  CH  CH 2

Q.2 + Br2 
 A, A will have configuration

Br Br
(A) (B) (C) both are (D) none is true
Br Br
Q.3 Ethylene reacts with Br2 to give 1, 2-dibromoethane. The anti-addition takes place due to the formation
of which intermediate?
(A) CH 2  Br  C (B) CH2 – CH2 (C) BrC  HC (D) CH2 – CHBr

Br Br

(112)
JEE

Ph
Q.4 C = CH2 
Cl +H O
2
 Major Product
2

H3C
Ph OH Ph Cl
(A) C (B) C
H3C CH 2Cl H3C CH 2–OH

Ph CH2–Cl Ph CH2–OH
(C) C (D) C
H 3C Cl H 3C H
Q.5 A reagent used to test unsaturation in alkene is :
(A) Ammonical Cu2Cl2 (B) Ammonical AgNO3
(C) Solution of Br2 in CCl4 (D) Conc. H2SO4
Q.6 The addition of bromine to 3-Methyl Cyclohexene in 1, 2-dichloroethane produces _____ dibromo
derivatives:
(A) 2 (B) 3 (C) 4 (D) 6
Q.7 The addition of Br2 to trans-2-butene produces
(A) (+) 2, 3-dibromobutane (B) (–) 2, 3-dibromobutane
(C) rac-2, 3-dibromobutane (D) meso-2, 3-dibromobutane

Q.8 
Cl2
CCl4
 Products

CH 3
Stereochemistry of the product are:
(A) diastereomers (B) meso (C) racemic mixture (D) pure enantiomers
CH 3
Q.9 
Cl2
CH 3OH

CH 3 CH 3 CH 3 CH 3
Cl OCH3 Cl OCH3
(A) OCH 3 (B) Cl (C) H (D) H
H H OCH 3 Cl

H3C D
H /Ni
Q.10 C C 
2

 Product of above reaction will be :
D CH3
(A) racemic mixture (B) diastereomers
(C) meso (D) constitutional isomers
H3C CH3
H /Ni
Q.11 C C 
2

 Product of above reaction will be :
D D
(A) racemic mixture (B) diastereomers
(C) meso (D) constitutional isomers
(113)
 Hydrocarbon

Li/ NH ( )
Q.12 C C C C 
3
 Product:

(A) (B)

(C) Both (A) and (B) (D)

Q.13 Which of the following alkenes is most reactive towards electrophilic addition reaction?
H3 C
(A) H 2 C = CH 2 (B) CH 3 – CH = CH 2 (C) C CH2 (D) H 2 C = CH – Cl
H3 C

H3 C Ph
C C Cl ,CCl
Q.14 
2 4

H H

Ph Ph Ph
H Cl H Cl H Cl
(A) (B) (C) Ph  C  C  CH 3 (D)
Cl H H Cl H CCl3
CH3 CH3 CH3
Q.15 Give the major product of the following reaction

BrCN
 Major product

Br Br Br CN
(A) Br (B) H (C) CN (D) H
H CN H Br
Q.16 Propene is more reactive than ethene towards HBr because
(A) propene can more readily undergo a free radical chain reaction
(B) propene gives rise to a more stable carbonium ion
(C) the double bond in case of propene is unstable
(D) the methyl group attached to double bond withdraws the electrons and facilitates the attack

(iv) Addition of Hydrogen Halides:

The mechanism for addition involves the following steps:

R R
•• ••
(a) —C = C— + H — X •• slow —C—C— + ••X ••
••  ••
H
(Carbocation)
(114)
JEE

R R
•• —C—C—
(b) —C—C— + ••X••
 •• fast
H X H

The first step is the slower step of the two and is thus the rate determining step.
Addition of an unsymmetrical reagent to a double bond is determined by Markovnikov’s Rule
which states that the negative part of the unsymmetrical reagent goes to the carbon atom which
bears lesser number of hydrogen atoms.
For example, CH3 CH2 CH = CH2 + HI CH3 CH2 CH CH3 (Markovnikov’s Product)
I
1-Butene 2-Iodobutane
(major)

But Markovnikov’s rule cannot always predict the orientation. The exceptions are the cases where
the intermediate carbocation formed is capable of rearrangement. For example,

CH3 CH3 CH3

CH2 = CH—CH—CH3 HI CH3 CH CH CH3 + CH3 CH2 C CH3
I (minor) (major) I
2-Iodo-3-methyl butane 2-Iodo-2-methyl butane

The first product is as predicted by Markovnikov’s rule. However, the second product (major) is the
result of carbocation rearrangement as given below.
CH3 CH3
CH = CH—CH—CH H +
CH —CH—CH—CH (2°)
2 3 3 3
 Hydride shift
CH3 CH3
I
CH3—CH2—C — CH3 CH3 —CH2 —C—CH3 (3°)

I
When the intermediate carbocation formed has three different alkyl groups attached to the positively
charged carbon atom, a racemic mixture of optically active addition products is obtained.
For example,
H 
CH3 CH2 CH = CH2 CH3 CH2 CH CH3
CH3 CH3

CH3 CH2 CH CH3 + X H X X H
C2H5 C2H5
equimolar mixture of
enantiomers

 Markovnikov Effect: The addition of an asymmetrical reagent to an unsymmetrical alkene is

governed by Markovnikov’s rule.

(115)
 Hydrocarbon

OSO3H
CH3—CH2—C = CH—CH3 + H + – OSO3H CH3—CH2—C—CH2—CH3
Sulphuric Acid
CH3 CH3
Sulphonic Acid

The sulphonic acid formed can be converted back to an alcohol and sulphuric acid by hydrolysis.
OSO3H OH
H2O
CH3—CH2—C—CH2—CH3 boil CH3 CH2 C—CH2—CH3 + H2SO4
CH3 CH3

However, there can be exceptions to Markovnikov’s rule even in the absence of radicals. For example,
HCl
CF3 CH = CH2 CF3 CH2 CH2 Cl
(major product)

This is an exception to Markovnikov’s rule because the carbocation, CF3 CH CH3 , generated

according to the rule is unstable due to a strongly electron-withdrawing group attached to the positive
carbon. CF3 CH2 CH2 is more stable due to lesser electron-withdrawing effect on the positive

carbon and yields the product.
(v) Addition of Hydrogen Bromide: Peroxide Effect:
Addition of hydrogen bromide to isobutylene under polar conditions yields tert-butyl bromide, but in
the presence of peroxides the same reaction yields isobutyl bromide.

CH3
CH3 no peroxides
CH3—C—CH3 Markovnikov
addition
CH3—C = CH2 HBr
Br
CH3
peroxides
CH3—C—CH2 Br Anti-Markovnikov
addition

The difference of orientation in the two additions is that in the first case reaction is initiated by a
proton and the intermediate involved is a carbocation, whereas in the latter case (in the presence of
peroxides) the reaction is initiated by a bromine atom and the intermediate involved is an alkyl radical
as shown below:
(a) Chain Initiation
R—O—O—R  2 RO•
(peroxides)
R O• + H — Br  RO — H + Br•
(b) Chain Propagation
CH3 CH3 Br CH3
CH3—C = CH2 + Br•  CH3 — C — CH2 + CH3 C CH2
• •
(3° radical) Br
more stable (1° radical)

(116)
JEE

CH3
CH3 — C — CH2 Br + HBr  CH3 — CH — CH2 Br + Br•
•
CH3
Thus, addition of HBr to alkenes in the presence of peroxides follows anti-Markovnikov’s rule and
this effect is known as peroxide effect or kharasch peroxide effect. This effect does not apply to
additions involving hydrogen chloride, hydrogen iodide, or hydrogen fluoride. The reason is that homolytic
bond dissociation energy follow the order: HF > HCl > HBr > HI. Thus, HF and HCl are too stable
to be broken into free radicals and though HI breaks easily it has a greater tendency to recombine to
form iodine molecule rather than add to a double bond.
(vi) Addition of Water:
This can be achieved in three ways:
(a) Acid-catalysed hydration: It involves Markovnikov’s addition of water to a double bond and
can be used for preparation of a low molecular weight alcohol. For example,
H O/H +
CH3CH = CH2   CH3—CH—CH3
2
or
dil.H 2SO 4
OH
2-propanol
The drawbacks of using this method for alcohol preparation are
(i) Primary alcohols other than ethanol cannot be prepared.
(ii) Carbocation rearrangements limit the utility of this method for alcohol preparation.
(b) Oxymercuration-Demercuration: Alkenes react with mercuric acetate in the presence of
water to give hydroxy-mercurial compounds which on reduction by NaBH4 yield alcohols.

R H H H
C=C + H2O + Hg(OAc)2 Oxymercuration
R—C—C—H
H H Mercuric
Alkene
Acetate OH HgOAc
Demercuration NaBH4
[–OAc = CH3 COO–] H H
R—C—C—H
OH H

The reaction is free from rearrangement, involves syn addition, and follows Markovnikov’s rule.
For example,
Hg(OAc) 2 NaBH 4
CH3(CH2)2CH = CH2 CH3(CH2)2 CH CH3
H2O
OH
CH3 CH3
Hg(OAc) 2 NaBH 4
OH
H2O

(c) Hydroboration-Oxidation: Hydroboration involves addition of BH3 (borane), mono-substituted

(RBH2) or dibsubstituted borane (R2BH) to a double bond with hydrogen being attached to one
doubly bonded carbon and boron to the other. The alkyl borane can then undergo oxidation with
alkaline H2O2 in which boron is replaced by –OH.
(117)
 Hydrocarbon
R
R Hydroboration H2O2,OH–
C=C + H—B —C—C— —C—C—
oxidation
H B H OH

H—B = H—BH2, H—BHR, H—BR2

The reaction is free from carbocation rearrangement.

In the overall reaction, H2O is added to a double bond following anti-Markovnikov’s rule involving
syn addition. For example,
(BH3)2 H2O2, OH–
CH3 CH = CH2 CH3CH2–CH2 OH
CH3 CH3
(BH3)2 H2O2, OH–
CH3—CH = C—CH3 CH3—CH—CH—CH3
OH

MID LEARNING EXERCISE (MLE)-31

Q.1 The reaction, CH 2  CHCH 3  HBr  CH 3 CHBrCH 3 is a type of :
(A) Nucleophilic addition reaction (B) Free radical addition reaction
(C) Electrophilic addition reaction (D) Electrophilic substitution reaction
Q.2 Alkene not showing addition of HBr according to Anti-Markownikov's rule is:
(A) 1-Pentene (B) 2-Butene (C) 1-Butene (D) Propene
Q.3 Which alkene gives same product with both Markownikoff's and anti Markownikoff's method ?
(A) -Butylene (B) Propylene (C) Isobutylene (D) -Butylene
Q.4 Action of bromine in CCl4 on ethene gives-
(A) 1, 2-Dibromo ethane (B) 4-Bromo, 2-chloro ethane
(C) Both the above (D) 1,1,1-tribromoethane
Q.5 Addition of HI on double bond of propene yields isopropyl iodide & not n-propyl iodide as the major
product because addition proceeds through.
(A) A more stable carbonium ion (B) A more stable carbanion
(C) A more stable free radical (D) None of these
Q.6 Arrange the following reactions in decreasing order of electrophilic addition reaction:
CH 3 CH3 CH3
C = CH2  
HCl
 C = CH 2  
HCl
 C = CH 2  
HCl

CH 3 CH 3–O:
:
:

CH 3–NH
(P) (Q) (R)
(A) P > Q > R (B) Q > R > P (C) R > Q > P (D) P = Q = R
Q.7 For the ionic reaction of hydrochloric acid with the following alkenes, predict the correct sequence of
reactivity as measured by reaction rates:
(I) ClCH = CH 2 (II) (CH 3 ) 2 ·C = CH 2
(III) OHC.CH=CH 2 (IV) (NC) 2 C = C(CN) 2
(A) IV  I  III  II (B) I  IV  II  III (C) III  II  IV  I (D) II  I  III  IV
(118)
JEE

Q.8 
HBr (1Mole)
Major Product:

Br Br
(A) (B) (C) (D) None of these
Br
Q.9 Reaction of HBr with propene in the presence of peroxide gives -
(A) Isopropyl bromide (B) 3-bromo propane (C) Allyl bromide (D) n-propyl bromide
Q.10 "The negative part of the added molecule goes to that carbon atom of unsymmetrical unsaturated
hydrocarbon which contain least number of H-atom" this statment is related to-
(A) Saytzeff's Rule (B) Peroxide effect
(C) Markownikoff's Rule (D) None
Q.11 Products of the reaction,

CH 3
+
H3C CH 2 
D O/D

2

CH 3

CH 3 CH 3 CH3

(A) H3C CH 2D (B) H3C CH 2D

CH 3 OD OD

CH 3 H CH 3

(C) H3C CH 3 (D) H3C CH2

OD D CH 3 D OD
D
Q.12 Which of the following is used for the conversion of 1-methylcyclo-pentene to
CH3
(A) BD3/THF followed by CH3COOH (B) BH3/THF followed by CH3COOD
(C) BD3/THF followed by CH3COOD (D) BH3/THF followed by CD3COOH

BD /THF
Q.13 
3
 Product ‘A’, A is-
H 2O2 /OH

CH3
(A) OH (B) D
OH
CH3
OH
(C) OH (D)
D D
(119)
 Hydrocarbon

BD
Q.14 CH3  CH  CH 2  3
 Product ‘X’, X is-
H O /OH  2 2

(A) CH3  CH  CH 2 D (B) CH3  CH  CH 2OH

| |
OH D
(C) CH3  CH  CH3 (D) none is correct
|
OD
CH3
(1) Hg 2 OAc 2 /H 2 O/THF
Q.15  A
(2) NaBH 4 / NaOH/H 2 O

A is
CH3
CH3 OH
CH3 CH3
(A) (B) (C) (D)
OH
OH

(vii) Hydroxylation: Formation of 1, 2 -diols:

The two hydroxyl groups can be added from the same side (syn hydroxylation) using KMnO4 or
OsO4(osmium tetroxide) or from opposite sides (anti hydroxylation) using peroxyacids (RCOOOH).
(a) Syn Hydroxylation: It is carried out by reaction with cold alkaline or neutral aqueous potassium
permagnate solution. (Cold dilute alkaline KMnO4 is known as Baeyer’s reagent)
3CH2 = CH2 + 2KMnO4 + 4H2O  3 CH2—CH2 + 2MnO2 + 2 KOH
OH OH
1,2 -Ethanediol
Syn hydroxylation can also be achieved with osmium tetroxide (OsO4) and both cases (with
KMnO4 and OsO4) involve formation of cyclic intermediates followed by cleavage at the oxygen-
metal bond producing the glycol (1, 2 -diol) and MnO2 or Os metal.

OH —C—C—
C=C —C — C— + MnO2
H2O
O O OH OH
Mn
O O–

O
O
Os
O CH3
OsO4 O H H2O H OH
CH3—CH = CH—CH3 CH3 H OH
cis
CH3 H CH3
meso-Butan -3, 4-diol

(120)
JEE

Baeyer's Reagent H H

OH OH
cis-1, 2-cyclopentanediol
(syn addition)
(b) Anti Hydroxylation: Peroxyacids (RCOOOH) hydroxylate alkenes in anti manner to yield 1,
2-diol. Ex. CF3COOOH
OH H
CH3 CH3
RCO 3 H
C=C CH3—C—C—CH3
H+, H 2O
H H H OH
trans -2, 3-Butanediol

RCO3H
H OH
H +, H 2O
OH H
trans-1, 2-cyclopentanediol
(anti addition)
(viii) Oxidative Cleavage by KMnO4:
Alkenes are oxidatively cleaved by hot alkaline potassium permagnate solution. The terminal CH2
group of 1-alkene is oxidised to CO2 and H2O. A disubstituted carbon atom of double bond
R
(=CRR1) is oxidised to ketonic group C = O . A mono-substituted carbon atom (CHR) is oxidised
R1
to aldehydic group which on further oxidation yields carboxylic acid group. For example,
O
KMnO4, OH– H+
CH3 CH = CH CH3 2 CH3 C 2 CH3 COOH

O–
CH3 CH3
CH3 CH2 C = CH CH3 KMnO4, OH
–
H+ CH3 CH2 C = O + CH3 COOH


CH2 = CH2 KMnO4+, OH

–

H
CO2 + H2O
CH3
KMnO4, OH– H+
CH3 C(CH2)4 COOH
O
(ix) Ozonolysis: Locating Position of Double Bond:
Ozonolysis involves cleavage of a double bond by ozone, and it is carried out in two stages.
(a) Formation of ozonide:
O
O3
—C = C— —C—C— —C C—
O O O—O
O
Molozonide Ozonide
Ozone gas is passed into a solution of alkene in some inert solvent (CCl4) to yield an unstable,
explosive compound called ozonide.
(121)
 Hydrocarbon
(b) Reduction of ozonide to yield cleavage products: Reduction can be either oxidative or
reductive.
In oxidative ozonolysis, the products are carboxylic acids and/or ketones. Here, H2O2 present in
solution oxidises any aldehydes formed to carboxylic acids. For example,
O3
(CH3)2 C = CH—CH3 H2O
(CH3)2 C = O + CH3 COOH
(oxidative)

O
CH3 CH2 CH = CH CH2 CH3 O3 CH3 CH2HC CH CH2 CH3
O—O Zn, H2O

2 CH3 CH2 CHO

CH3
O3 Zn, H2O
CH3 CH2 CH = C—CH3 CH3 CH2 CHO + CH3 C CH3
O
Illustration 2. An organic compound on ozonolysis gives the following compounds. Determine the organic
compound.
(a) two moles of CH3CHO
CH3
(b) (CH3)2C = O + CH3CH2 C = O
(c) HCHO + CHO—CHO + (CH3)2C = O
(d) O = CH CH2 C = O

CH3
Solution: (a) Formation of a single carbonyl compound suggests a symmetrical alkene.
O3
CH3 – C = O + O = C—CH3 CH3 CH = CH CH3
2-Butene
H H
(b) Two different ozonolysis products indicates an unsymmetrical alkene.
O3
CH3—C = O + O = C CH2 CH3 CH3—C = C CH2 CH3
CH3 CH3 CH3 CH3
2,3-Dimethyl pent-2-ene
(c) Four carbonyl groups indicate a diene.
O
H 2C  O  O  CH  CH  O  O  C  CH3 3 CH 2  CH  CH  C  CH3
| |
CH3 CH3
4-Methyl pent-1,3-diene
(d) Two carbonyl groups in the same compound suggest a cycloalkene.
O3 CH3
O = CH CH2 C = O
CH3
(x) Free Radical Halogenation: Substitution verses Addition:

(122)
JEE
Propylene reacts with chlorine in two different reaction conditions to yield two different products.
low temperature,
CCl4 solution
CH3 CH—CH2 Heterolytic
addition
Cl2 (high conc. of Cl2) Cl Cl
CH3—CH = CH2
500-600°C or light, Free radical
gas phase
Cl—CH2 CH = CH2 substitution
+ HCl
The second reaction is a free radical halogenation at allylic position (carbon atom next to a double
bond). The ease of abstraction of hydrogen atoms homolytically to produce radicals is
allylic > 3° > 2° > 1° > CH4 > vinylic
Allylic bromination can be carried out by using N-bromosuccinimide (NBS).
NBS functions by providing a constant, low concentration of bromine as

O O
H2 C—C H2 C—C
HBr + N—Br Br2 + N—H
H2 C—C H2 C—C
O O
N-Bromosuccinimide Succinimide

NBS
CH3 — CH = CH2 light CH2—CH = CH2
Br
Allyl bromide
There are two reactions, substitution and addition, competing in this case. The kinetics can be shifted
in favour of substitution by using radical-generating conditions like high temperature or light.
A low concentration of halogen can also favour substitution because a low bromine concentration
has more pronounced effect on slowing the rate of addition thereby increasing the tendency towards
substitution.
MID LEARNING EXERCISE (MLE)-32
Q.1 Propene can be converted into 1-propanol by oxidation. Which set of the reagents is used to effect
the conversion?
(A) OsO 4  CHCl3 (B) O3 /Zn  H 2 O
(C) Alkaline and cold KMnO4 (D) B2H6 and alc. H2O2
Q.2 Ozonolysis of CH 3  CH  C  CH 2 will give
(A) Only CH3CHO (B) Only HCHO
(C) Only CO2 (D) Mixture of CH3CHO, HCHO & CO2
Q.3 Ozonolysis of buta-1, 3-diene gives.
(A) HCHO and glyoxal (B) CH3CHO and glyoxal
(C) CO2 and glyoxal (D) HCHO, glyoxal and CH3CHO
Q.4 On the ozonlysis of 2, 4-dimethylpent-2-ene products are-
(A) two molecules of aldehydes
(B) two molecules of ketone
(C) one molecule of aldehyde and one molecule of ketone
(D) neither aldehyde nor ketone
(123)
 Hydrocarbon
Q.5 Ozonolysis of m-xylene gives -
(A) Glyoxal (B) Glyoxal + Methyl glyoxal
(C) Glyoxal + methyl glyoxal + dimethyl glyoxal (D) Methyl glyoxal + dimethyl glyoxal
Q.6 Ethylene reacts with osmium tetroxide to form an osmic ester which on hydrolysis gives:
(A) ethyl alcohol (B) glyoxal (C) ethylene glycol (D) glycollic acid
Q.7 The compound formed when 2-butene is treated with hot alkaline KMnO4 is:
(A) Acetaldehyde (B) Acetic acid (C) CH 2OHCH 2O (D) CH 3CHCO 2H
Q.8 Which of the following compound on oxidative ozonolysis give malonic acid as only product ?
(A) CH 2  CH  CH 2  CH  CH 2 (B) CH 2  CH  CH  CH 2

(C) (D)

Q.9 Alkene A 

O3 / H 2 O 2
 CH3COOH  CH3  C  COOH
||
O
A can be:
CHCH 3 CH 3 C(CH3 ) 2
|| ||
(A) CH 3  C CH  C (B) CH 3  C CH  HC  CH3
CH 3
(C) Both correct (D) None is correct
Q.10 Which of the compounds with molecular formula C5H10 yields acetone on ozonolysis ?
(A) 3-Methyl-1-butene (B) Cyclopentane (C) 2-Methyl-1-butene (D) 2-Methyl-2-butene
Q.11 Product formed by simplest alkene with Baeyer's reagent is -

C H 2  OH
C H 2  OH |
|
|
(A) CH3OH (B) CH3CH2OH (C) | (D) C H 2  OH
CH 2  OH |
|
CH 2  OH
re age nt R 2 re age nt R 1
     
Q.12
HO OH HO OH
R1 and R2 are -
(A) Cold alkaline KMnO4, OsO4/H2O2 (B) Cold alkaline KMnO4, HCO3H
(C) Cold alkaline KMnO4, hot alkaline KMnO4 (D) C6 H 5 CO3 H, HCO3 H
Q.13 Which of the following is true about this reaction?
H CH3
cold alkaline

KMnO4
H3 C H
(A) A is meso-2, 3-butanediol formed by syn addition
(B) A is meso-2, 3-butanediol formed by anti addition
(C) A is a racemic mixture of d and l-2, 3-butanediol formed by anti addition
(D) A is a racemix mixture of d and l-2, 3-butanediol formed by sysn addition
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JEE
Q.14 Propene can be converted into 1-propanol by oxidation. Which set of the reagents is used to effect
the conversion?
(A) OsO 4  CHCl3 (B) O3 /Zn  H 2 O
(C) Alkaline and cold KMnO4 (D) B2H6 and alc. H2O2
Q.15 The major product formed in the reaction
CH2
NBS

CCl4 , 
 is

Br
CH3 CH2Br CH3 CH2Br
(A) (B) (C) (D)
Br
5.3 ALKYNES
Alkyne family has a carbon-carbon triple bond as the functional group having the general
formula Cn H2n–2 .
In alkynes, the triply bonded carbon atoms use sp hybridised orbitals. For example, in acetylene
(HC  CH), the carbon atoms use two sp hybridised orbitals to form two sigma bonds—sp-
sp between carbon atoms and sp-s between carbon and hydrogen. The angle between the
two orbitals is 180° giving a linear shape to the acetylene molecule. Each carbon has two p-
orbitals containing 1 electron each. The lateral overlap of p-orbitals produces two -bonds
which together make a single cylindrical sheath about the line joining the nuclei.

s-sp sp-sp sp-s

H C C H

5.3.1 Methods of Preparation of Alkynes:

(i) Dehydrohalogenation of Alkyl Dihalides:
H H H
alc. KOH NaNH2
—C—C— –HX
—C = C— —C  C—
–HX
X X X
vic-dihalide vinyl-halide alkyne
(very unreactive)
The elimination of one molecule of hydrogen halide yields vinyl halide which is very unreactive.
Under mild conditions, the dehydrohalogenation stops at vinylic halide stage but more vigorous
conditions— like the use of a stronger base like amide ion (NH2–)—are required for alkyne formation.
(ii) From Tetrahaloalkanes (Dehalogenation):
X X X X
| | | |
 
R  C  C  H  Zn (dust)   R  C  C  H  R  C  C  H
| | 300º Zn (dust)
X X
In the above reaction it is necessary that the four halogen atoms must be attached at vicinal
carbons. If they are attached at the two ends then the product cyclo alkene is obtained.

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 Hydrocarbon
(iii) From Kolbe's Synthesis:
O O
|| + | | .–.
H– C – C – O K H– C – C – O
+
|| +  || .–. + 2K
H– C – C – O K H– C – C – O
|| ||
O O

Potassium Malaete
At Anode:
O O
|| .–. ||

H– C – C – O H– C – C – O H–C
|| .–.  || + 2e¯ 
 ||| + 2CO2
H– C – C – O H – C – C – O H–C
|| ||
O O
At Cathode:
2K+ + 2e–  2K•
2K• + 2H2O  2KOH + H2
(iv) Laboratory method of preparation of Acetylene :
(a) In laboratory acetylene is prepared by hydrolysis of calcium carbide.
–
2+ C CH
Ca ||| + 2H2 O  ||| + Ca(OH)2
C– CH
(b) It can also be prepared from CHCl3 with Ag dust.
2CHCl3 + 6Ag 
 H–C  C–H + 6 AgCl
(v) Alkyl Substitution in Primary Alkynes: Preparation of Higher Alkynes:

—C  C••– Li +
Li NH2
—C  C—H + RX —C  C—R + LiX
Terminal alkyne or NaNH 2
(must be 1° alkyl halide)
Acetylene can be alkylated either once to make a terminal alkyne or twice to make an internal
alkyne. For example,
–
HC  CH + NaNH2 HC  C Na+ n–C4H9Br CH3(CH2)3 C  CH
1-Hexyne
– – n–C3 H7Br
HC  CH + 2NaNH2 + Na C  C Na + CH3CH2 CH2 C  C CH2CH2 CH3
(2 eq.) 4-octyne
Terminal alkynes (1-alkynes) have acidic hydrogens that are easily removed by an amide base or an
electropositive metal forming acetylide ions. These ions are highly basic and attack a primary alkyl
halide molecule forming higher alkynes through SN2 mechanism.
RC  C•• + R—X R —C  C—R  + X
(1°)
If the alkyl halide used is secondary or tertiary, then a strongly basic acetylide ion causes elimination
rather than substitution forming an alkene and an alkyne.
Br
RC  C•• + —CH 2—CHR CH2 = CHR + Br + RC  CH

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JEE
5.3.2 Physical Properties:
The physical properties of alkynes are the same as that of alkenes. Alkynes are soluble in organic
solvents of a low polarity but insoluble in polar solvents like water. They are less dense than water.
Their boiling point show a usual increase with an increasing carbon number and the usual effects of
chain branching are observed. For the same number of carbon atoms, the boiling point of alkenes and
alkynes are nearly the same.
MID LEARNING EXERCISE (MLE)-33
Q.1 Kolbe's electrolysis of sodium maleate at anode gives.
(A) Only acetylene (B) Only CO2 (C) Acetylene + CO2 (D) CO2 + H2
Q.2 R – CH2 – CCl2 – R   R – C  C – R . The reagent is-
Reagent

(A) Na (B) HCl in H2O (C) NaNH 2 (D) Zn in alcohol

Q.3 1, 1, 2, 2 tetra bromo ethane on heating with Zn dust gives
(A) Ethyl bromide (B) Ethane (C) Ethene (D) Ethyne
Q.4 Chloroform is heated with Ag powder in laboratory what will be the product -
(A) Acetylene (B) Ag2O (C) CH2Cl 2 (D) CH 4
Q.5 Acetylene can be prepared from -
(A) Potassium fumarate (B) Calcium carbide (C) Ethylene bromide (D) All
Q.6 Acetylene may be prepared using Kolbe's electrolytic method employing -
(A) Pot. acetate (B) Pot. succinate (C) Pot. fumarate (D) None of these
Q.7 To prepare But-2-yne from 2, 2, 3, 3-Tetrachlorobutane, reagent used is :
(A) Zinc/ (B) Sodamide (C) Alc. KOH (D) aq. KOH
Q.8 Which of the following method is not applicable to the preparation of acetylene ?
(A) Dehydro chlorination of a vicinal dihalide with two carbon atoms
(B) Debromination of tetrabromoethane
(C) Dehydration of glycol
(D) Heating of vinyl chloride with sodamide
Q.9 The homologue of ethyne is -
(A) C2H2 (B) C2H6 (C) C3H8 (D) C3H4
Q.10 Carbide, which react with water to give propyne is -
(A) CaC2 (B) SiC (C) Mg2C3 (D) Al4C3
Red hot
Q.11 3CH3  C  CH 
Cu tube

CH3

(A) (B)

CH3 CH3
CH3
(C) (D)
H3C CH3

Br (i) alc. KOH

Q.12 2
   (A); Producrt (A) is-
CCl (ii) NaNH
4 2
major

(A) H 2 C  CH  CH  CH 2 (B) CH 3  C  C  CH 3
(C) CH 3  CH 2  C  CH (D) CH 3  CH  C  CH 2

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 Hydrocarbon

CH2–CH2–CH3

Q.13 ; This conversion can be acheived by:

(A) NaNH 2 ,CH 3CHO (B) NaNH 2 ,CH 3  CH 2  CH 2  Br

(C) KOH,CH 3  CH 2  Br (D) KOH,CH 2  CH 2

| |
Br Br

Cl
|
3NaNH 2
Q.14 Ph  C  CH3   (A) ; Product (A) is-
| Product
Cl


(A) Ph  CH  CH 2 (B) Ph  C  CH (C) Ph  CH 2  CH 3 (D) Ph  C  C Na
(i) NaNH ,NH H
Q.15 C  CH 
3 3
(A) 
2
(B) ; Product (B) is
(ii) CH3Br Lindlar catalyst

C  C – CH3 H CH3
C=C
(A) (B) H

H H H H
C =C C =C
(C) CH3 (D) H

5.3.3 Chemical Properties:

The chemical behaviour of alkynes is similar to that of alkenes. Alkynes form addition products with
two or four univalent atoms or groups. They are generally less reactive than alkenes towards
electrophilic addition reactions even though  electron density is higher in alkynes. This is because
on moving from alkene to alkyne, the C—H bond has more of s character (33% in alkenes as
compared to 50% in alkynes). Therefore, the -electrons are more firmly held by carbon nuclei in
alkynes and are thus less reactive to an electrophile.
(i) Hydrogenation:
Alkynes can be hydrogenated to alkanes in the presence of finely divided Pt, Pd, or Ni.

H H
2H2
—C  C— Pt/Pd/Ni —C—C—
H H

Alkynes can also be partially hydrogenated to alkenes using Lindlar’s catalyst (Pd poisoned with
BaSO4) or P—2 catalyst (nickel boride) or Na or Li in liquid NH3.
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JEE

Na or Li H
C=C (Anti)
Liq. NH3
(Birch reduction) H
—C  C—
H2 (Syn)
C=C
Lindlar or P–2 catalyst H H
Ex.

Na or Li CH3 H
C=C trans-2-Butene
liq. NH3
H CH3
CH3—C  C—CH3
H2 H H
C=C cis-2-Butene
Lindlar catalyst
CH3 CH3

(ii) Addition of Water:

Addition of water to alkynes is carried out in the presence of acid and mercuric sulphate.

H2 O H H
HC  CH HgSO 4, H 2SO 4
H—C = C—H Tautomerizes
H—C—C = O
H O—H
vinyl alcohol H
(enolic form-less stable) Acetaldehyde

H2 O
CH3—CH2—C  CH CH3—CH2—C = CH2 CH3CH2—C—CH3
HgSO4, H2SO4
O—H O
(enol) (ketone)

C  CH HO—C = CH2 O = C—CH3

H 2O
HgSO4, H2SO4
Acetophenone

(iii) Addition of Halogens (Br2, Cl2):

Br Br Br
Br2 Br2
—C  C— —C = C—
CCl4
—C—C—
CCl4
Br Br Br
Alkynes add two molecules of Br2 in CCl4 and decoloration of bromine water is used to detect the
presence of a double or triple bond.
(iv) Addition of Hydrogen Halides:
Alkynes add one molecule of hydrogen halide to yield vinyl halide which adds another molecule of
hydrogen halide forming a gem-dihalide.

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 Hydrocarbon

X
HX HX
R—C  C—H R—C = CH2 R—C—CH3
X X
(vinyl halide) (gem-dihalide)

The orientation of addition is predicted by Markovnikov’s rule.

(v) Addition of Boron Hydride:
(i) With mono-alkyl acetylene, R2BH gives an intermediate which on hydrolysis gives alkene but on
alkaline oxidation yields aldehyde.

R H CH3COOH
R—C  C—H + R2BH  C=C RCH = CH2
hydrolysis
Dialkyl H BR2
borane oxidation H2O2, NaOH

RCH2CHO

(ii) With dialkyl acetylenes, the product of hydrolysis is cis-alkene and that of oxidation is a ketone.
R R
R—C  C—R + BH3  C =C B
H
3
Dialkyl acetylene vinyl borane
H 2O2 , CH3COOH
NaOH oxidation hydrolysis
R R R R
R–CH 2 –C–R  C=C C=C
H OH H H
O keto-ene cis-alkene
ketone
(vi) Ozonolysis:
The ozonolysis of alkynes yields a mixture of carboxylic acids.
O
H2O H2O2
R—C  C—R + O3  R—C—C—R R—C—C—R RCOOH + R COOH
Hydrolysis oxidation
O—O O O

(vii) Oxidation with KMnO4:

Alkynes are oxidised to carboxylic acids with the hydrolysis of triple bond.
CH3 CH3
KMnO4
CH3 CH C  C CH2 CH2 CH3 alkaline
CH3 CH—COOH + CH3(CH2)2COOH

(viii) Formation of Metal Acetylides:


CH3CH—C C—H + LiNH2 ether CH3—CH—C C: Li + NH3
CH3 CH3
Lithium iso-propylacetylide

HC  CH + C2H5 MgBr HC  C MgBr + C2 H6

Ethynyl magnesium bromide

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JEE
These reactions are attributed to the acidity of hydrogen in terminal alkynes. Alkynes being stronger
acids than ammonia and ethane displace them from their respective salts. Alkynes are more acidic
than alkenes or alkanes because in alkynes hydrogen is bonded to an sp hybridised carbon whereas
as in alkenes to an sp2 hybridised carbon and an sp3 hybridised carbon in alkanes. Now, electronegativity
of an orbital increases with an increase in s-character. Thus,
Electronegativity: sp > sp2 > sp3
50% 33.3% 25%
s character s character s character
In alkynes, hydrogen bonded to an sp hybridised carbon is thus more acidic.
Acetylene has pKa of about 25. It is a far weaker acid than water (pKa = 15.7) or alcohols
(pKa = 16–19) but is more acidic than ammonia.
Relative acidities: H2O > ROH > HC  CH > NH3 > RH
Relative basicities: OH– < OR– < HC  C– < NH2– < R–
Terminal alkynes give insoluble salts with heavy metals. For example,
 
CH3—C C—H + [Ag(NH3)2] CH3—C C—Ag + NH4 + NH3
silver methyl acetylide
(white ppt.)
This reaction is used for identification of terminal alkynes as the salt formed is a white precipitate.
1
CH3—C  C—H + Na  CH3—C  C—Na + H2
2
CH3—C  C—H + [Cu(NH3)2]+  CH3—C  C—Cu + NH4+ + NH3
(red ppt.)

MID LEARNING EXERCISE (MLE)-34

Q.1 In which of the following hydrocarbons, hydrogen is most acidic ?
(A) C 6 H 6 (B) CH 2  CH 2 (C) CH  CH (D) CH 3  CH 3
Q.2 CH3CH2Br reacts with sodium acetylide to form-
(A) 1-Butyne (B) 1-Butene (C) 2-Butene (D) 2-Butyne
Q.3 Which hydrocarbon reacts with sodium and liquid NH3 -
(A) CH 3  CH 2  CH 2  CH 3 (B) CH 3  C  C  CH 3
(C) CH 3  CH  CH  CH 3 (D) CH 3  CH 2  CH  CH 2
Q.4 B 
Lindlar
 R – C  C – R 
Na/NH3
A
A and B are geometrical isomers (R – CH = CH – R) –
(A) A is trans, B is cis (B) A and B both are cis
(C) A and B both are trans (D) A is cis, B is trans
Q.5 Which reagent will be used for the given conversion?
– –
O O

C C 


(A) Na / Liq· NH 3 (B) H 2 , Pd – BaSO 4 (C) LiAlH4 (D) H2, Pt


Q.6 CH 3  C  CH  H 2 O 
H
Hg 2
 'A' , Here A is:
(A) Aldehyde (B) Ketone (C) Alkane (D) Alcohol
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 Hydrocarbon
Q.7 The ozonolysis of a triple bond produces
(A) a mixture of aldehyde/ketone and carboxylic acid
(B) a mixture of aldehydes/ketones
(C) a mixture of carboxylic acids
(D) CO2 and H2O
Q.8 Addition of 2 mol of HCl to 1-butyne would yield :
(A) CH 3 CH 2 CH 2 CHCl2 (B) CH 3CH 2 CCl2 CH 3
(C) CH 3CH 2 CHClCH 2 Cl 2 (D) CH 3 CH 2 CH  CHCl
Q.9 Which of the following alkyne will form 2-butanone on hydration ?
(i) CH 3 CH 2 C  CH (ii) CH 3C  C  CH 3
(A) (i) (B) (ii) (C) Both (i) & (ii) (D) None of these
Q.10 Which of the following statements is correct?
(A) Alkynes are more reactive than alkenes towards halogen additions
(B) Alkynes are less reactive than alkenes towards halogen additions
(C) Both alkynes and alkenes are equally reactive towards halogen additions
(D) Primary vinyliccations (RCH = CH+) is more reactive than secondary vinyliccation (RC+ = CH)
Q.11 The end product of the following sequence is:
CaO  C 
heat
 A 
H2O
 B 
H 2SO4
HgSO4
C
(A) ethanol (B) ethyl hydrogen sulphate
(C) acetaldehyde (D) ethylene glycol
Q.12 Identify the compounds A and B in the following reaction sequence.
CaC2 ( s )  H2 O(l ) 
 A( g ) 
H 2SO4
HgSO4
 B(l )
(A) A is ethylene, B is acetaldehyde (B) A is acetylene, B is propionaldehyde
(C) A is ethane, B is ethanol (D) A is acetylene, B is acetaldehyde
Q.13 1-butyne can be distinguished from 2-butyne by using
(A) bromine water (Br2 in CCl4)
(B) cold alk. KMnO4 (Baeyer’s Reagent)
(C) ammoniacal solution of silver (Tollen’s Reagent)
(D) diethyl ether
Q.14 A mixture of CH4, C2H4 and C2H2 gaseous are passed through a Wolf bottle containing ammonical
cuprous chloride. The gas coming out is
(A) Methane (B) Acetylene
(C) Mixture of methane and ethylene (D) original mixture
BH THF
Q.15 B  
3
 CH3–CCH HgSO

/ H SO
 4 24  A
H 2O 2 , OH

A and B are –
O O
|| ||
(A) CH 3CH 2CHO, CH 3  C  CH 3 (B) CH 3  C  CH 3 CH 3CH 2CHO

(C) CH3CH2CHO (both) (D) CH 3  C  CH 3 (both)

||
O
*****
(132)
JEE

QUICK RECAP
 The most important source of alkanes is natural gas and crude oil.
 Alkanes are separated in an oil refinery by fractional distillationand processed into many different
products.
 Methane and ethane are the main components of natural gas; they are normally stored as gases
under pressure. It is, however, easier to transport them as liquids: This requires both compression
and cooling of the gas.
 Presence of electron attracting group (-I) in the hydrocarbon part of the fatty acid increases the
decarboxylation. If -I is more effective group then weak base may be taken.
like

(i) R – CH – CH 2 COOH 

NaHCO3
Δ
 R – CH – CH 2 – H
| |
OH OH

(ii) R – CH – CH 2 COOH 

NaHCO
Δ
 R – CH – CH 2 – H
3

| |
NO 2 NO 2

(iii) -Keto acids are decarboxylated readily simply on heating (soda lime is not required)
 They are also known as olefins since ethene, the first member of the homologous series forms oily
liquid substance when treated with halogens.
 Saytzeff Rule : When two possible alkense are obtained by the elimination reaction than that alkene
will be in good yield, containing maximum number of alkyl group on double bonded C-atoms.
 Hoffmann's Rule: During elimination of quaternary ammonium salt is presence of base moist
Ag2O, less stable alkene is major product.
 Polyethylene is a thermoplastic polymer consisting of long hydrocarbon chains.
 Ziegler-Natta catalysts are used to polymerize terminal 1-alkenes like ethylene and alkenes with the
vinyl double bond nCH 2  CHR   CH 2  CHR  n
 Due to stability of vinyl halide by resonance there is partial double bond in which elimination does not
take place by alc. KOH so stronger base NaNH2 is used.
 In presence of Lindlar's catalyst [ Pd/CaCO3 + quinoline or Nickle boride] alkynes give cis - alkene
 In presence of Na/NH3 alkynes give trans-alkene. (Birch Redcuction)
 Polyacetylene is an organic polymer with the repeating unit (C2H2)n. The high electrical conductivity
discovered for these polymers led to intense interest in the use of organic compounds in
microelectronics (organic semiconductors).
 Alkynes undergo diverse cyclo-addition reactions. Most notable is the Diels-Alder reaction with 1,3-
dienes to give 1,4-cyclohexadienes.

*****

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 Hydrocarbon

SOLVED EXAMPLES
Example 1. When isobutane is monochlorinated in the presence of ultraviolet light, the product obtained in
higher yield is
(A) n-butyl chloride
(B) iso butyl chloride
(C) sec-butyl chloride
(D) tert-butyl chloride
Answer: (B)

Cl
Cl2
Solution: CH3—CH—CH3 
hv
 CH3—C—CH3 + CH3—C—CH2Cl
CH3 CH3 CH3
tert-Butyl chloride Isobutyl chloride

% of isobutyl chloride no. of primary H reactivity of 1° H 9 1 9

= × =  
% of tertbutyl chloride no. of tertiary H reactivity of 3° H 1 5 5

9
% of isobutyl chloride =  100  74.3%
95
9
% of tertbutyl chloride = 100  25.7%
14
Example 2. The product of reaction CH3CH2CH2 MgBr + HC  CCH3 
is
(A) CH3CH2CH3 (B) CH3CH2CH2C  CCH3
(C) CH3CH2CH2OH (D) CH3CH2CHO
Answer: (A)
Solution: Grignard reagent reacts with any compound having active hydrogen producing an alkane.
n—C3H7 MgBr + HC  CCH3  n—C3H8 + CH3C  CMgBr
Example 3. CH3—CH—CH = CH2 + HCl  (A)
CH3

The major product (A) in above given reaction is:

(A) CH3—CH—CH— CH3 (B) CH3—CH—CH2—CH2 Cl
CH3 Cl CH3

Cl
(C) CH3—C—CH2—CH3 (D) CH2—CH—CH2—CH3
CH3 Cl CH3

Answer: (C)
Solution: The reaction proceeds as follows:

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JEE

H+  Hydride shift 
CH3 CH CH = CH2 CH3 CH CH—CH3 CH3 C CH2 CH3
CH3 CH3 CH3
(3°)
Cl– (2°) Cl–
Cl
CH3 CH—CH—CH3 CH3—C CH2 CH3
CH3 Cl CH3
(minor product) (major product)

Markovnikov’s rule is not applicable because of carbocation rearrangement.

Example 4. The ozonolysis of an alkene gives propanone and ethanal. The alkene is
(A) 2-methyl butene-2 (B) but-2-ene
(C) propene (D) 2,2-dimethyl but-2-ene
Answer: (A)
CH3 O3 CH3
Solution: C=CO= O + O=
+ CH—CH
O = CH—CH
3 C = CH—CH3
CH3 CH3
2-methyl but-2-ene
Example 5. One of isomers (A) of 2-butene gives a racemic mixture on addition of Br2 whereas another
isomer (B) gives a meso compound on addition of Br2. (A) and (B) are respectively:
(A) cis and trans-2-butene (B) trans and cis-2-butene
(C) both are cis (D) none of the above
Answer: (A)
Solution: Cis isomer on anti-addition gives a racemic mixture and a meso compound on syn-addition but a
trans isomer gives a meso compound on anti-addition and a racemic mixture on syn addition. Br2
also adds in anti manner.
Example 6. An alkene with the lowest heat of hydrogenation is
(A) CH3 CH = CH CH3 (B) CH3 C = C—CH3
CH3 CH3

(C) CH3—C = CH2 (D) CH3—C = CH—CH3

CH3 CH3
Answer: (B)
Solution: The more substituted an alkene the more stable it is and lower its heat of hydrogenation.
Example 7. Predict the order of base strength of anions from the reactions given below.
HC  CH + LiNH2 HC  C– Li+ + NH3
HC  C Li + H2O HC  CH + LiOH
(A) OH < HC  C < NH2–
– – (B) HC  C– < OH– < NH2–
(C) OH– < NH2– < HC  C– (D) NH2– < OH– < HC  C–
Answer: (A)
Solution: A stronger acid replaces a weaker acid from its salt.
Hence, HC  CH > NH3 (acidic strength) and H2O > HC  CH.

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 Hydrocarbon
 H2O > HC  CH > NH3 (acidic strength order)
Hence, for conjugate bases: OH– < HC  C– < NH2– (basic strength order)
Example 8. Which of the following halides does not form precipitate with alcoholic silver nitrate?
(A) ethyl chloride (B) 3-chloropropene
(C) chlorobenzene (D) isobutyl chloride
Answer: (C)
Solution: Only aryl and vinyl halides are incapable of forming silver halide precipitates with alc. AgNO3.

KOH (alc.)
Example 9. CH2—CH—CH3
Cl
The major product is

(A) CH = CH—CH3 (B) CH2—CH = CH2

(C) CH2—CH—CH3 (D) CH2—CH2—CH2—OH

OH
Answer: (A)
Solution: The conjugation of double bond with an aromatic ring yields a highly stable system.

C = C— Unusually stable

Hence, (a) being highly stable is the major product.

Example 10. CH3—CH—CH2—X gives CH3—CH—CH2—OH as the major product on hydrolysis.

CH3 CH3
The yield of the product will be maximum when
(A) water is solvent and X = I
(B) dimethyl sulfoxide is solvent and X = I
(C) water is solvent and X = Br
(D) water is solvent and X = Cl.
Answer: (B)
Solution: The mechanism of reaction must be SN2, because if it was SN1 the carbo-cation rearrangement
would yield (CH3)3C—OH as the major product. SN2 reaction is assisted by an aprotic solvent-
like dimethyl sulfoxide and a good leaving group like iodide.
Example 11. Hydrolysis by SN2 mechanism will be shown by
(A) C6H5CH2Br (B) CH3Br
(C) CH2 = CH CH2Br (D) (CH3)3 C Br
Solution: (a), (c), and (d) can form highly stable carbo-cations and thus show SN1 mechanism. CH3Br is a
(1°) halide and has a greater tendency towards SN2 reaction.
The answer is (b)
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JEE

CH3
NBS, h
Br 2
Example 12. CH3 CH CH CH 3 Me3CO– K+ (A) (C) (D)
(major product)
Br
(D) is
(A) 1,2,3-tribromo-3-methyl butane (B) 1,2,3-tribromo-2-methyl butane
(C) 1,1,3-tribromopentane (D) 1,3,3-tribromo-3-methyl butane
Answer: (A)

CH3
Me3CO– K+
Solution: CH3 CH CH CH3 CH2 = CH—CH(CH3)2
(bulky base) (Hoffman's product)
Br
NBS

CH2 = CH—C—(CH3)2
Br
Br2
CH2Br CH Br—CBr (CH3)2
1,2,3-Tribromo-3-methyl
butane

Example 13. What is the order of reactivity of the following compounds towards aq. NaOH?
Cl NO2
CH2Cl

NH2 Cl Cl
(I) (II) (III) (IV)
(A) IV > II > III > I (B) III > II > I > IV (C) I > II > III > IV (D) IV > I > III > II
Answer: (A)
Solution: (IV) is an alkyl halide and undergoes substitution fastest through SN2 mechanism.
(I), (II), and (III) are aryl halides and undergo substitution through bimolecular displacement
reaction where reactivity is increased by electron-withdrawing groups ortho/para to halogen and
decreased by electron-releasing groups.
Example 14. How many isomers will be produced by monochlorination of 2-chlorobutane? How many of
these isomers will be optically active?
Solution: CH3—CH—CH2—CH3 monochlorination CH2Cl—CH—CH2—CH3 +
Cl Cl
(I)

Cl
CH3—C—CH2—CH3 + CH3 CH—CH CH3 + CH3 CH CH2 CH2
Cl Cl Cl Cl Cl
(II) (III) (IV)

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 Hydrocarbon
(I), (III), and (IV) will be optically active. (I) and (IV) with one chiral carbon atom exist in two
enantiomeric forms. (III) with two chiral carbons being a symmetric molecule will exist in two
enantiomeric forms and a meso form. Therefore, the total number of isomers is equal to 8, and
the total number of optically active isomers is 6.
Example 15. A hydrocarbon (A) (molecular formula C6H12) decolorises Br2 in CCl4 and is oxidised by hot
acidified KMnO4 to a resolvable carboxylic acid, C4H9COOH.
Determine (A).
Solution: Since the carboxylic acid, C4H9COOH is resolvable (optically active) it must have a chiral centre
and only structure of the acid that is optically acive is
*
CH3—CH2—CH—COOH
CH3
And, the alkene which on oxidation with hot acidified KMnO4 gives the acid is
CH3—CH2—CH—CH = CH2 KMnO4/H+
CH3 CH2 CH COOH + CO2

CH3 CH3
Hence, (A) is 3-methyl pentene
Example 16. (a)Outline synthesis of propyne from isopropyl bromide.
(b) One mole of a hydrocarbon (A) reacts with one mole of bromine giving a dibromo compound
C5H10Br2. (A) on treatment with cold alkaline KMnO4 forms compound of molecular formula
C5H12O2. On ozonolysis, (A) gives equimolar quantities of propanone and ethanal. Deduce the
structural formula of (A).
Solution: (a) CH3 CH CH3 alc. KOH Br2
CH3 CH = CH2 CH3 CH CH2
–HBr CCl4
Br Br Br
NaNH 2
CH3 CH CH2   CH3 C  CH
–2HBr
Propyne
Br Br
(b) Hydrocarbon (A) must be an alkene because
(i) it shows addition reaction
(ii) undergoes ozonolysis reaction giving propanone and ethanal
Hence, (A) should be
CH3 CH3
O3
CH3—C = O + O = CH CH3 CH3C = CH CH3
2-Methylbut-2-ene
(A)

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JEE

CH3 CH3 Br
Br2
CH3—C = CH CH3 CH3—C—CH—CH3 (C5 H10 Br2)
Baeyer's Reagent Br

CH3
CH3—C—CH CH3 (C5 H12 O2)
OH OH
Example 17. An alkane (A), C5 H12 on chlorination at 300°C gives a mixture of four different monochlorinated
derivatives (B), (C), (D), and (E). Two of these derivatives give the same stable alkene (F) on
dehydrohalogenation. On oxidation with hot alkaline KMnO4 followed by acidification, (F) gives
two products (G) and (H). Give structures of (A) to (H).
Solution: The only alkane of molecular formula C5H12 that gives four monochlorinated isomers is

Cl2
CH3 CH2CH CH3 CH2 CH2CH CH3 + CH3 CH CH CH3
300°C
CH3 Cl CH3 Cl CH3
(B) (C)
Cl
+ CH3 CH2 C CH3 + CH3 CH2 CH CH2 Cl
CH3 CH3
(D) (E)

Out of these, (C) and (D) give the same alkene on dehydrohalogenation.

(C) CH3 CH CH CH3

Cl CH3 –HCl
CH3 CH = C CH3 2-Methyl but-2-ene
Cl
CH3
(D) CH3 CH2 C CH3
(F)
CH3

On oxidation with hot alkaline, KMnO4 (F) gives

CH3 CH = C CH3 alk. KMnO4

CH3 COO– K+ + CH3 C CH3

CH3 H+ O
(F)
CH3 COOH + CH3 C CH3
O
(G) (H)

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 Hydrocarbon

EXERCISE # 1(A) (Level 1 – Beginner)

1. 
HI
 P (Major Product)

‘P’ is
I
(A) I (B) (C) (D)
I I
2. Anti-Markownikoff's addition of HBr is not observed in-
(A) Propene (B) But-2-ene (C) Butene (D) Pent-2-ene
3. For the ionic reaction of hydrochloric acid with the following alkenes, predict the correct sequence of
reactivity as measured by reaction rates:
(I) ClCH  CH 2 (II) (CH 3 ) 2 ·C  CH 2

(III) OHC.CH = CH 2 (IV) (NC) 2 C  C(CN) 2

(A) IV  I  III  II (B) I  IV  II  III (C) III  II  IV  I (D) II  I  III  IV
4. 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 (D) 2-Butene
5. Which of the following reagents cannot be used to locate the position of triple bond in
CH 3  C  C  CH 3

(A) Br2 /H 2 O (B) O 3 (C) Cu 2 Cl 2 (D) H  /KMnO 4 ,Δ

6 Which will dehydrate at fastest rate by H3PO4 ?
(A) 2-methyl butane-2-ol (B) 3-methyl butane-2-ol
(C) Butane-1-ol (D) 2-methyl butane-1-ol
7. Rate of dehydration when given compounds are treated with conc. H2SO4.

OH OH OH
CH 2OH CH 3 CH 3 CH 3
(P) (Q) (R) (D)

(A) P > Q > R > S (B) Q > P > R > S (C) R > Q > P > S (D) R > Q > S > P
8. Which one of the following carbocation would you except to rearrange ?

CH 3 CH 3 CH 3 CH 3


(A) (B) (C) (D)
 

9. On heating CH3COONa with soda lime the gas evolved will be

(A) C 2 H 2 (B) CH 4 (C) C 2 H 6 (D) C 2 H 4
10. Which of the following will have least hindered rotation about carbon-carbon bond ?
(A) Ethane (B) Ethylene (C) Acetylene (D) hexachloro ethane
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JEE

11. A sample of 17.9 mg of a compound of molar mass 90 g mol–1 when treated with CH3MgI releases
1.34 ml of a gas at STP. The number of active hydrogen in the molecule is :
(A) 1 (B) 2 (C) 3 (D) 4
12. The addition of Br2 to trans-2-butene produces
(A) (+) 2,3-dibromobutane (B) (–) 2,3-dibromobutane
(C) rac –2, 3-dibromobutane (D) meso-2, 3-dibromobutane
13. The treatment of CH 3 C(CH 3 )  CHCH 3 with NaIO4 or boiling KMnO4 produces

(A) CH 3COCH 3  CH 2 O (B) CH 3CHO  CH 3CHO

(C) CH 3 COCH 3  CH 3COOH (D) CH 3COCH 3  HCOOH

14. Which of the following alkene will react fastest with H2 under catalytic hydrogenation condition?

H H R H R R R R
(A) (B) (C) (D)
H H H H R H R R
15. Identiry the species X in the reaction :
–
Propene  [O] 
(O3 /H 2 O 2 , OH )
 X  Formic acid
(A) Acetone (B) Acetaldehyde (C) Isopropanol (D) Acetic acid
16. Most stable intermediate of the hydration of isopentene

CH 3 CH 3
 | |
(A) CH 3 CH CH CH 3 (B) CH 3 C CH 2 CH 3 (C) Both (A) and (B) (D) None of these


17. When acetylene reacts with HCl in the presence of HgCl2 the product is
(A) Methyl chloride (B) Dichlorethane
(C) Vinyl chloride (D) Ethylidine chloride
18. Propionic acid is subjected to reduction with hydroiodic acid in the presence of a little P, the product
formed is:
(A) Ethane (B) Propane (C) Butane (D) None of these
Cl

Mg/ether D ONa/ether
19.   
2
   (A)

Br
A is :

(A) Cl Cl (B) D D

(C) Cl D (D) D D

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 Hydrocarbon
20. The product obtained when methyl magnesium bromide reacts with methyl alcohol is
(A) Acetone (B) Alcohol (C) Methane (D) Ethane
21. When HCl gas is passed through propene in the presence of benzoyl peroxide, it gives
(A) n-propyl chloride (B) 2-chloropropane (C) Allyl chloride (D) No reaction
22. Methane reacts with conc. HNO3 at high temperature to yield
(A) CO2 and H2O (B) HCHO (C) HCOOH (D) CH3NO2
23. A mixture of CH4 and steam on passing over Nickel suspension on Alumina at 800°C gives
(A) CO only (B) H2 Only (C) CO and H2 (C) None of these
24. Cyclopentene on treatment with alkaline KMnO4 gives:
(A) Cyclopentanol
(B) Trans-1, 2-cyclopentanediol
(C) Cis-1, 2-cyclopentanediol
(D) 1 : 1 mixture of cis-and trans-1, 2-cyclopentanediol

25. CH  CH 
NH 4 Cl
Cu 2 Cl2
 Product

Product is
(A) CuC  CCu (B) CH 2  CHC  CH

(C) CH  CCu (D) CuC  CNH 4

26. Rank the transition states that occur during the following reaction steps in order of increasing stability
(least  most stable):
+
(1) H 3C  O H 2  CH 3+  H 2 O
+
(2)  CH3 3 C  O H 2   CH3 2 C+  H 2 O
+
(3)  CH3  2 CH  O H 2   CH 3 2 CH  H 2 O
+

(A) 1 < 2 < 3 (B) 2 < 3 < 1 (C) 1 < 3 < 2 (D) 2 < 1 < 3
27. Which of the following will decolourise alkaline KMnO4 solution?
(A) C3H8 (B) CH4 (C) CCl4 (D) C2H4

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JEE

EXERCISE # 1(B) (Level 2 – Learner)

1. End product of the following sequence is :
2
CaO  C 
Heat
(A) 
H2O
(C) 
Hg
H 2SO 4
(C)

(A) Ethanol (B) Ethyl hydrogen sulphate

(C) Ethanal (D) Ethylene glycol
2. Hydrogenation of the compound
Me Me
H

H
Me
H
In the presence of piosoned palladium catalyst gives :
(A) An optically active compound (B) An optically inactive compound
(C) A racemic mixture (D) A diastereomeric mixture
H2C
3.  A (predominant), A is:
CH2  HBr 
CH 3
Br
H2C H2 C Br
(A) CH3 (B)
CH 3
CH 3

Br

H3C C CH2CH 3
(C) (D) None of these
CH 3

Br
4. When isobutane is brominated, the percentage of H3 C CH3 would be
CH 3
(A) 0% (B) 83% (C) 10% (D) 100%
5. Which of the following is used for aromatization of n-hexane?
(A) AlCl3 (B) Na in liquid NH3
(C) Cr2O3/Al2O3 with heat (D) Wilkinson's catalyst
6. Propene can be converted into 1-propanol by oxidation. Which set of the reagents is used to effect
the conversion?
(A) Hg(OAc) 2 , H 2 O & NaBH 4 (B) O3 / Zn  H 2 O
(C) Alkaline and cold KMnO4 (D) B2H6 and alk. H2O2
7. In the following sequence of reactions, identify the product (D).
CH  CH 
HBr
(A) 
HBr
(B) 
alk. KOH
(C) 
NaNH 2
(D)
(A) Ethanol (B) Ethyne (C) Ethanal (D) Ethene
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 Hydrocarbon

8. 
Zn/Hg
HCl
 
NBS
 
alk. KOH
  
HCl
 Final product is :

Cl Cl OH
Cl OH Cl
(A) (B) (C) (D)

9. CH 3  C H  CH 2  CH 3 
|
Cl2
hv  x   Number of monochloro product including stereoisomers.
CH 3
(A) 4 (B) 5 (C) 6 (D) 7

10. H  H 2 
Pd

CH 2
CH3
Product of the above reaction will be
(A) Racemic mixture (B) Diastereomers
(C) Meso (D) Constitutional isomers
COOK
11. 
Electrolysis Major product of reaction :
COOK
COO
(A) (B) (C) (D)
COO

CH 3  CH CH 3

12. CC 

H 2 /Pt


D D
Product of the above reaction will be :
(A) Racemic mixture (B) Diastereomers
(C) Meso (D) Constitutional isomers
–
O HO
13. Br P (major)

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

14. Mixture of one mole each of ethene and propyne on reaction with Na will form H2 gas at S.T.P. -
(A) 22.4 L (B) 11.2 L (C) 33.6 L (D) 44.8 L

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JEE

D
15. 
2
Product will be:
Pt
H3 C H

D H CH3 H D D
(A) (B) (C) (D) Both (B) and (C)
CH3 D D D CH3 H
16. Which of the following reagent not gives syn addition when react with alkene.
(A) H2 + Pd (CaCO3 + Quinoline) (B) P – 2 catalyst
(C) Raney Nickel (D) Li/ liq. NH3

17. CH3  C  C  CH3 H2

Pd-BaSO4
 (A) 
cold KMnO 4
(B) . Compound (B) is :
(A) Meso (B) Racemic mixture (C) Diastereomers (D) All
18. CH 3  C  C  CH3 Na
liq. NH3
(A) 
cold. KMnO4
 (B) Compound (B) is
(A) Meso (B) Racemic mixture (C) Diastereomers (D) All
19. CH3  C  C  CH3 ( A) 
(B) Compound (B) is
H2
Pd  BaSO 4
Br2
CCl4

(A) Meso (B) Racemic mixture (C) Diastereomers (D) All

20. CH3  C  C  CH3 
 (A) 
(B) Compound (B) is
Na
liq. NH3
Br2
CCl4

(A) Meso (B) Racemic mixture (C) Diastereomers (D) All

21. 
alc.KOH
Δ
 (A)
Br
Total number of possible products
(A) 2 (B) 3 (C) 4 (D) 5

22. 
HCl
Peroxide
 (x) (major product)

Structure of (x) will be

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

23. conc
 .H 2SO 4
 J (Major)


OH
J is

(A) (B) (C) (D) None of these

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 Hydrocarbon

OH
 (i) O
24. H
 A   3  Product(s). Product is/are?
 (ii) Zn / H2O

CHO
(A) + HCHO

(B) || CH = O
O
O
(C) + CH3CHO

CHO
(D)
OHC
H3C H
C alkaline KMnO
25.    4  A, which is true about this reaction?
C
H3C H
(A) A is meso 2, 3–butan–di–ol formed by syn addition
(B) A is meso 2, 3–butan–di–ol formed by anti addition
(C) A is a racemic mixture of d and l, 2, 3–butan–di–ol formed by anti addition
(D) A is a racemic mixture of d and l 2,3–butan–di–ol formed by syn addition

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JEE

EXERCISE # 2(A) (Adept – JEE Main PYQs)

1. What will be the major product of following sequence of reactions? (JEE Main 2022)
(i) n  BuLi,
n  C5 H11Cl
n  Bu  
(ii) Lindlar cat, H 2
n-Bu n-Bu C5 H11
C5 H11 n-Bu
(A) (B) (C) (D)
H11 C 5 n-Bu C5 H11 n-Bu
2. Choose the correct option for the following reactions. (JEE Main 2022)
CH3
|
B 
(BH 3 )2
H 2 O2 /OH
 H 3C – C – CH  CH 2 
Hg(OAc)2 H 2 O
NaBH 4
A
|
CH3
(A) ‘A’ and ‘B’ are both Markovnikov addition products.
(B) ‘A’ is Markovnikov product and ‘B’ is anti-Markovnikov product.
(C) ‘A’ and ‘B’ are both anti-Markovnikov products.
(D) ‘B’ is Markovnikov and ‘A’ is anti-Markovnikov product.
3. Major product ‘B’ of the following reaction sequence is: (JEE Main 2022)
CH3  C  CH  CH3  A  B (major product)
Br2
CH3 OH
HI

|
CH3

HO Br I Br
| | | |
(A) CH 3  C  C H  CH3 (B) CH 3  C  CH  CH 3
| |
CH 3 CH 3

Br OH Br I
| | | |
(C) CH 3  C  C H  CH 3 (D) CH 3  C  CH  CH 3
| |
CH 3 CH 3
4. A compound ‘A’ on reaction with ‘X’ and ‘Y’ produces the same major product but different byproduct
‘a’ and ‘b’. Oxidation of ‘a’ gives a substance produced by ants. (JEE Main 2022)
CH 3 CH 3
X
a + O = C – CH2 – C – CH3
CH 3 CH 3
CH3
H2C = C – CH 2 – C – CH3
CH 3 CH 3
CH 3 Y
b + O = C – CH2 – C – CH3
Compound ‘A’
CH 3
‘X’ and ‘Y’ respectively are
(A) KMnO4/H+ and dil. KMnO4, 273 K (B) KMnO4(dilute), 273 K and KMnO4/H+
(C) KMnO4/H+ and O3, H2O/Zn (D) O3, H2O/Zn and KMnO4/H+
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 Hydrocarbon
5. Two isomers ‘A’ and ‘B’ with molecular formula C4H8 give different products on oxidation with
KMnO4 in acidic medium products on oxidation with KMnO4 in acidic medium. Isomer ‘A’ on
reaction with KMnO4/H+ results in effervescence of a gas and gives ketone. The compound ‘A’ is
(A) But-1-ene (B) cis-But-2-ene (JEE Main 2022)
(C) trans-But-2ene (D) 2-methyl propene
6. ‘A’ and ‘B’ respectively are:
A 
(1) O3
(2) Zn  H 2 O
Ethane  1, 2  dicarbaldehyde  Glyoxal / Oxaldehyde

B 
(1) O3
(2) Zn  H 2 O
5  oxohexanal (JEE Main 2022)
(A) 1-methylcyclohex-1,3-diene & cyclopentene
(B) Cyclohex-1,3-diene & cyclopentene
(C) 1-methylcyclohex-1,4-diene & 1-methylcyclopent-1-ene
(D) Cyclohex-1,3-diene & 1-methylcyclopent-1-ene
7. In the following reaction ‘X’ is (JEE Main 2023)
CH3 (CH 2 ) 4 CH3 
Anhy.AlCl3
HCl.
 'X '
Major product

(A) CH3(CH2)4CH2Cl (B) Cl – CH2 – (CH2)4 – CH2 – Cl

(C) CH 3 CH  (CH 2 ) 2 CH3 (D)

|
CH3
8. When a hydrocarbon A undergoes complete combustion it requires 11 equivalents of oxygen and
produces 4 equivalents of water. What is the molecular formula of A? (JEE Main 2023)
(A) C 9H 8 (B) C 11 H 4
(C) C 5H 8 (D) C 11 H 8
9. When a hydrocarbon A undergoes combustion in the presence of air, it requires 9.5 equivalents of
oxygen and produces 3 equivalents of water. What is the molecular formula of A?
(JEE Main 2023)
(A) C 8H 6 (B) C 9H 9
(C) C 6H 6 (D) C 9H 6
10. The product formed in the following multistep reaction is: (JEE Main 2023)
(i) B2 H 6
(ii) H 2 O 2 , NaOH
CH 3  CH  CH 2 

(iii) PCC
(iv) CH 3 MgBr

OH
|
(A) CH3  CH 2  CH  CH 3 (B) CH 3  CH 2  CH 2  CH 2  OH

O OH
|| |
(C) CH 3  CH 2  C  OCH 3 (D) CH 3  C  CH 3
|
CH 3

2-hexene 
(i) O3
11. (ii) H 2 O Products (JEE Main 2023)
The two products formed in above reaction are -
(A) Butanoic acid and acetic acid (B) Butanal and acetic acid
(C) Butanal and acetaldehyde (D) Butanoic acid and acetaldehyde

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JEE

12. Choose the correct set of reagents for the following conversion
trans (Ph - CH = CH – CH3)  cis (Ph - CH = CH – CH3) (JEE Main 2023)
(A) Br2, alc KOH, NaNH2, Na(Liq NH3)
(B) Br2, alc KOH, NaNH2, H2 Lindlar Catalyst
(C) Br2, aq KOH, NaNH2, H2 Lindlar Catalyst
(D) Br2, aq KOH, NaNH2, Na(Liq NH3)
13. A hydrocarbon ‘X’ with formula C6H8 uses two moles of H2 on catalytic hydrogenation of its one
mole. On ozonolysis, ‘X’ yields two moles of methane dicarbaldehyde. The hydrocarbon ‘X’ is :
(JEE Main 2023)
(A) hexa-1, 3, 5-triene (B) 1-methylcyclopenta-1, 4-diene
(C) cyclohexa-1, 3-diene (D) cyclohexa-1, 4-diene
14. In the following given reaction ‘A’ is (JEE Main 2023)
CH3
|
C=CH 2 + HBr 
 'A'
major product

CH 3 CH 3
Br
Br
(A) (B)

Br CH 3 CH 3 CH 3
CH 3 Br
(C) (D)

15. But-2-yne is reacted separately with one mole of Hydrogen as shown below. (JEE Main 2023)

B Na
liq NH3
CH 3  C  C  CH 3 
Pd /C

A
H2
(i) A is more soluble than B.
(ii) The boiling point & melting point of A are higher and lower than B respectively.
(iii) A is more polar than B because dipolemoment of A is zero.
(iv) Br2, adds easily to B than A.
Identify the incorrect statements from the options given below:
(A) i and ii only (B) ii, iii & iv only
(C) i, iii & iv only (D) ii and iii only
16. Cold KMnO 4
A   Meso butane 2, 3-diol
(A) Cis-2-butene (B) Trans 2-butene (C) 1-butene (D) Iso-butene
17. Consider the given chemical reaction: (JEE Main 2024)
KMnO –H SO

4 2 4
 Product ‘A’’
Heat

Product ‘A’ is :
(A) picric acid (B) acetic acid
(C) adipic acid (D) oxalic acid
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 Hydrocarbon
18. Identify the product A and product B in the following set of reactions. (JEE Main 2024)
H2O, H+
Major Product A
CH3–CH=CH2
(BH3)2
Major Product B
H2O, H2 O2 , OH
(A) A : CH 3CH 2 CH 2  OH B : CH3 CH  CH3
|
OH
(B) A : CH3CH 2 CH 3 B : CH3CH 2 CH 3
(C) A : CH 3CH 2 CH 2  OH B : CH 3CH 2 CH 2  OH
(D) A : CH3 CH  CH3 B : CH 3CH 2 CH 2  OH
|
OH
19. In the given reactions identify A and B. (JEE Main 2024)
H3C C2H5
Pd/C
H 2  A  C C
H H
Na/ Liquid NH3
CH3  C  C  CH3  H 2   ‘B’
(A) A : 2-Pentyne; B : trans - 2 - butene (B) A : n-Pentane; B : trans - 2 - butene
(C) A : 2 - Pentyne; B : Cis -2 - butene (D) A : n-Pentane; B : Cis -2 - butene
20. The final product , formed in the following reaction sequence is: (JEE Main 2024)
(i) BH3
Θ
(ii) H 2O 2 ,OH
Ph – CH = CH 2  A
(iii) HBr
+
(iv) Mg, ether, then HCHO/H3O

(A) Ph  CH 2  CH 2  CH 3 (B) Ph  CH– CH3

|
CH3
(C) Ph  CH – CH 3 (D) Ph  CH 2  CH 2  CH 2  OH
|
CH 2 OH
21. Identify product A and product B : (JEE Main 2024)
hv
Product A
+ Cl2
CCl4
Product B
Cl Cl Cl
Cl
(A) A : B: (B) A : B:
Cl
Cl Cl Cl
Cl
Cl Cl Cl
(C) A : B: (D) A : B:
Cl Cl Cl
Cl

(150)
JEE
22. Compound A formed in the following reaction reacts with B gives the product C. Find out A and B.
B
CH3  C  CH  Na  A  CH3  C  C CH 2  CH 2  NaBr
(C) | (JEE Main 2024)
CH3

(A) A  CH 3  C  CNa, B  CH3  CH 2  CH 2  Br

(B) A  CH 3  CH  CH 2 , B  CH 3  CH 2  CH 2  Br
(C) A  CH 3  CH 2  CH 3 , B  CH 3  C  CH

(D) A  CH3  C  C a, B  CH3  CH 2  CH3
23. Product A and B formed in the following set of reactions are: (JEE Main 2024)
CH3
BH
B
2 6
 H + /H O

2
A
H 2O2 , NaOH(aq.)

CH2OH CH2OH CH3 CH3

(A) A = ,B= (B) A = OH , B =
OH OH
CH2OH CH3 CH3 CH3
(C) A = ,B= (D) A = ,B= OH
OH OH

24. The product (C) in the below mentioned reaction is: (JEE Main 2024)
KOH HBr 
CH 3  CH 2  CH 2  Br 
( dik )
A 
 B 
C
 KOH[ a ]

(A) Propan-1-ol (B) Propene (C) Propyne (D) Propan-2-ol

25. Major product of the following reaction is- (JEE Main 2024)

D–Cl
?

CH3

Cl D H D D CH3
(A) (B) (C) (D) None of these
H CH3 Cl CH3 H Cl

*****

(151)
 Hydrocarbon

EXERCISE # 2(B) (Scholar – JEE Main PYQs)

H3C H
CCl 4
1. + Br 2 Product ‘P’ (JEE Main 2021)
H3C H
Consider the above chemical reaction. The total number of stereoisomers possible for product ‘P’
is-
2. The number of sigma bonds in (JEE Main 2021)

H 3C  C  CH  C  C  H is _______ .
|
H
3. Consider the following chemical reaction, find the number of sp2 carbon in the product.
CH  CH 
(1) Red hot Fe tube, 873K
(2) CO, HCI, AlCl3
 Pr oduct (JEE Main 2021)
4. The total number of monobromo derivatives formed by the alkanes with molecular formula C5H12 is
(excluding stereoisomers) ________. (JEE Main 2022)
5. A hydrocarbon ‘X’ is found to have mojar mass of 80. A 10.0 mg of compound ‘X’ on hydrogenation
consumed 8.40 mL of H2 gas (measured at STP). Ozonolysis compound ‘X’ yields only formaldehyde
and dialdehyde. The total number of fragments/molecules produced from the ozonolysis of compound
‘X’ is ____. (JEE Main 2022)
6. The major product ‘A’ of the following given reaction has ___sp2 hybridized carbon atoms.
H
2, 7-Dimethyl-2, 6- octadiene  A (JEE Main 2022)
Major Pr oduct

7. Number of bromo derivatives obtained on treating ethane with excess of Br2, in diffused sunlight is
_____. (JEE Main 2023)
8. Maximum number of isomeric monochloro derivates which can be obtained from 2,2,5,5-
tetramethylhexane by chlorination is __________. (JEE Main 2023)
9. 17 mg of hydrocarbon (M.F.C10H16) takes up 8.40 mL of the H2 gas measured at 0°C and 760 mm
of Hg. Ozonolysis of the same hydrocarbon yields
CH3 – C – CH3 , H – C – H, H – C – CH2 – CH2 – C – C – H
O O O O O
The number of double bond/s present in the hydrocarbon is _________. (JEE Main 2023)
10. The number of possible isomeric products formed when 3-chloro-l-butene reacts with HCl through
carbocation formation is _______. (JEE Main 2023)
11. Molar mass of the hydrocarbon (X) which on ozonolysis consumes one mole of O3 per mole of (X)
and gives one mole each of ethanal and propanone is ______ g mol–1
(Molar mass of C : 12 g mol–1 , H : 1 g mol–1) (JEE Main 2023)
12. Total number of isomeric compounds (including stereoisomers) formed by monochlorination of 2-
methylbutane is _______. (JEE Main 2024)

13. 3-Methylhex-2-ene on reaction with HBr in presence of peroxide forms an addition product (A). The
number of possible stereoisomers for 'A' is (JEE Main 2024)
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JEE

H3C H
(i) O
14. C C 
3
(P)
(ii) Zn/H 2O
H CH3
Consider the given reaction. The total number of oxygen atoms present per molecule of the product
(P) is ______. (JEE Main 2024)

15. Number of alkanes obtained on electrolysis of a mixture of CH 3COONa and C2 H5COONa is ___.
(JEE Main 2024)

16. Number of isomeric products formed by monochlorination of 2-methylbutane in presence of sunlight

is___. (JEE Main 2024)

*****

(153)
 Hydrocarbon

EXERCISE # 3(A)(Proficient – JEE Advanced Level Questions)

1. The addition of bromine to (3S)-3-Methyl Cyclohexene in 1,2-dichloroethane (solvent) produces___
dibromo derivatives:
(A) 2 (B) 3 (C) 4 (D) 6
2. Which compound will yield 2-methyl-6-oxoheptanal upon treatment with ozone followed by Zn/H2O.

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

X  major 
2+ +
3. H 3C  C  C  OCH 3 
Hg / H3O

X is :
(A) H 3C  C CH 2  O  CH 3 (B) H 3C  CH 2  C OCH 3
|| ||
O O

(C) H 3C  CH 2  C H (D) H3C  CH 2  C||  C||  H

||
O O O
4. The reaction of cyclooctyne with HgSO4 in the presence of aq. H2SO4 gives
OH OH O
(A) (B) (C) (D)
OH OH
5. Get the product P1 and P2 in the following reaction :
CH3
(i) BH3  THF

(ii) H 2 O 2 / NaOH
 P1
D
CH3

dil H2SO4
 P2
D

OH H H OH
CH3 CH 3 CH3 CH 3
(A)
and (B)
and
D D D D
H OH OH H

OH OH H H
CH3 CH 3 H D
and and
(C) D H (D) H OH
H D CH 3 H
6. How many products will be formed excluding stereo when cis-1,3,5-trimethyl cyclohexene reacts
with NBS?
(A) 3 (B) 4 (C) 5 (D) 6

(154)
JEE

7. X 
Electrolysis
 2, 3-dimethyl butane
Which of the following anion will be migrates towards anode to prepare 2, 3-dimethyl butane in the
given reaction.

O
O O O
(A)  (B)  (C)  (D) O
O O O

O
8. 
NH 2 NH 2 +OH¯/Δ
 Most stable conformer of product will be (across C2 – C3 bond) :
(A) gauche (B) Anti (C) Eclipsed (D) Partially eclipsed
O
9. 
Zn – Hg + HCl

 most stable conformer of product will be :

H H H H
H H H H H H

(A) (B) Et (C) (D) Me

H H H H H H
H H H H
Et Me

H H CH 3
H H H H H H

10.
CH3 CH 3 H H CH 3 CH 3
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

O
||
ONa+
11.
+

Electrolysis
 major product will be
ONa
||
O

(A) 1-butyne (B) n-butane (C) 2-butene (D) 2-butyne

12. In kolbe's electrolytic synthesis the pOH of solution will be
(A) decreases (B) Increases (C) Constant (D) None of these
13. Which of the following is produced as an intermediate when 2-Butyne react with lithium in presence
of liquid ammonia ?

•
(A) (B) (C) (D) 
..
 • • • • ..
(155)
 Hydrocarbon
14. 1-Penten-4-yne reacts with bromine at – 80°C to produce:
(A) 4, 4, 5, 5-Tetrabromopentene (B) 1, 2-Dibromo-1, 4-pentadiene
(C) 1, 1, 2, 2, 4, 5-hexabromopentane (D) 4, 5-dibromopentyne
15. Select incorrect statement :
(A) Methane cannot be prepared by catalytic hydrogenation of alkene
(B) Al isomers of the formula C6H14 can be prepared by catalytic hydrogenation of alkene
(C) All isomers of the formula C5H12 can be prepared by catalytic hydrogenation of alkene
D
H2
(D) 
Ni
product obtained show no optical rotation
D

NaNH 2 CH3–I H2
16. CH3 – C C – H (A) Pd–CaCO 3
(B)

H2
Li/Liq. NH3
(C)

Relation between (B) and (C) is :

(A) Enantiomer (B) Diastereomer
(C) Geometrical isomer (D) Meso

17. (X) 

NaOH
 
C aO

(X) will be
COONa
(A) (B) (C) (D) COONa
COONa COONa

18. Ph  C  CH 3 
A

 Ph  CH 2  CH 3
||
O
A could be:
(A) NH2NH2, glycol/OH– (B) (Zn-Hg)/conc. HCl

(C) Red P/HI (D) CH 2 – CH 2 ; Raney Ni – H2 (mozingo)

| |
SH SH
19. Which of the following is not produced as an Intermediate during the reaction :
Br Na
Dry ether

Br


(A) CH2 (B) • (C) (D)

(156)
JEE
20. Possible product during the reaction will be :

2EtBr  
Na
Dry ether

(A) (B) (C) CH3 – CH3 (D)

21. (A)C 4 H 6 

H 2 /Pt
(B)C 4 H 8 
O3 / H 2 O
 CH3 COOH
Hence A and B are
(A) CH 3C  CCH3 , CH 3CH  CHCH 3 (B) CH 2 =CHCH  CH 2 , CH 3CH  CHCH 3

(C) , CH 3CH  CHCH 3 (D) None

22. Which of the following acid salt does not give alkene as an major product when it is electrolysed.
(A) Maleic acid (B) Oxalic acid (C) Succinic acid (D) Adipic acid
23. Bromination can take place at

NBS
 / hv

CCl4

(A) 1 (B) 2 (C) 3 (D) 4

24. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with:
(A) SO2Cl2 (B) SOCl2 (C) Cl2/h (D) NaOCl
25.  (i) OSO4
(ii) NaHCO3 /H 2 O
 (x)

Stereochemistry of product will be

(A) Optically active (B) Optically inactive (C) Recemic mixture (D) Meso
26. An alkene on ozonolysis yields only ethanal. There are an structural isomers of this which on ozonolysis
yields:
(A) propanone (B) ethanal (C) methanal (D) only propanal
NBS
27. CH2 = CHCH2CH = CH2 
 possible products can be-
(A) CH 2  CH CH CH  CH 2 (B) CH2=CHCH=CH–CH2Br
|
Br

(C) CH2 = CH CH2 CH = CHBr (D) CH 2 =CHCH 2 C = CH 2

|
Br
*****

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 Hydrocarbon

EXERCISE # 3(B)(Amateur - Variety of JEE Advanced Level Questions)

Comprehension Based Questions:
Paragraph # 1 for (Ques. 1 to 3)

 A  
Al O
2
250°C
  B  
3 HI
(ii) AgOH
  C  
Al O
2
150°C
3
  B   (i) B H
2
(ii) H O , OH
2 2
A
6


In the above reaction sequence (A) and (C) are isomers. Molecular formula of B is C5H10, which
can also be obtained from the product of the reaction with CH3CH2MgBr and (CH3)2CO and followed
by acidification.
1. Identify the structure of A

(A) CH 3  CH 2  CH 2  C H  CH3 (B) (CH 3 ) 2 CHCHOHCH 3

|
OH

(C) (CH 3 ) 2 C  CH 2  OH (D) CH 3  CH 2  C H  C 2  CH3

|
OH
2. Identify the structure of B

CH 3
|
(A) (CH 3 ) 2  CH  CH  CH 2 (B) CH 3  C C  CH 2
|
CH 3

(C) (CH 3 ) 2 CH  CHCH 3 (D) CH 3  CH  C H  CH3

|
CH 3
3. Identify the structure of C

CH3
|
(A) CH 3  CH 2  CH 2  C H  CH3 (B) CH 3  CH 2  C  CH 3
| |
OH OH

(C) (CH 3 ) 2 C  CH 2  OH (D) CH 3  CH 2  C H  CH 2  CH 3

|
OH
Paragraph # 2 for (Ques. 4 to 6)
The halogens, Br2 and Cl2, add to alkanes. When the -electrons of the alkene approach a molecule
of Br2 or Cl2, one of the halogen atoms accepts them and releases the shared electrons to the other
halogen atom. Therefore, in an electrophilic addtion reaction, Br2 behaves as if it were Br+ and Br–
and Cl2 behaves as if it were Cl+ and Cl–.
+
:Br:
.. .. .. .. ..
H 2C = CH2 + :..Br – ..Br: H2 C – C2 H + :..Br:– :BrCH
.. 2 CH2Br
.. :
1,2-dibromoethane
a bromonium ion a vicinal dibromide

4. cis-2-butene 
Br2
CCl4

How many products will obtained in this reaction
(A) 1 (B) 2 (C) 3 (D) 4
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JEE

I
|
5. CH 3  CH  CH 2 
(X)
(A)  (Y)
CH 3  C H  CH 2
(intermediate) |
Br
Reagent (X) and (Y) in above reaction.
(A) X = I2 , Y = NaBr (B) X = Br2 , Y = NaI (C) X = NaBr, Y = I2 (D) X = I2, Y = Br2
6. Decreasing order of rate of reaction toward halogenation of alkene.
Me Me Me Me
(P) H2C = CH – CO2H (Q) Et – CH = CH2 (R) C=C (S) C=C
H Et Me Me
(A) P > Q > R > S (B) S > R > Q > P
(C) R > S > Q > P (D) P > R > S > Q

Paragraph # 3 for (Ques. 7 to 9)

Addition of mercuric acetate in the presence of water is called as oxymercuration. The adduct
obtained gives alcohol on reduction with NaBH4 in alkaline medium. This is known as demercuration.
Oxymercuration-demercuration allows Markownikoff's addition of H, OH without rearrangement.
The net result is the addition of H2O. Answer the following question:
CH 3
|
 HI Conc.
7. CH 3  C CH  CH 2 
(i) Hg(OAc)2 .THF
(ii) CH 3 OH, NaBH 4 NaOH
 A   B , Product B is :
|
CH 3

(A) (CH3 )3 CC H  CH3 (B) CH 3 I

|
OH

(C) CH 3CH 2 I (D)  CH3 3 CC H  CH 3

|
I
O
1) Hg(OAc)2 , THF 

8. CH3CH = CH2 + N–Br 

 A 
2) H 2 O
3) NaBH 4 , NaOH
 B 
OH
C

O
The product 'C formation from B occurs through
(A) enol formation (B) SN1 mechanism
(C) Neighbouring group particitation (D) SNAr mechanism
OH

9. 
1) Hg(OAc)2 ,THF
2) NaBH 4 ,NaOH
 A , Product 'A' is :

OH OH
(A) HO (B) (C) (D)
OH OH
HO OH

(159)
 Hydrocarbon
Matrix Match Type Questions :
10. Column-I Column-II
O
||
C – CH 3 CH 2 – CH3
(A) (P) Birch reduction
Cl Cl
O
||
C – CH 3 CH 2 – CH3
(B) (Q) Oxidation number of carbon
HO HO
changes from +2 to –2

(C)  (R) Wolf-Kishner reduction

O
(D)  (S) Clemmensen reduction
11. Match the column
Column-I Column-II
(A) RCOONa electrolysis
R R (P) Correy-House reaction
(B) R  CH 2  COOH 
NaOH,CaO

 R  CH 3 (Q) Kolbe electrolysis

(C) RCOOH   R  Cl

(i) AgNO3
(ii) Cl2 /  (R) Oakwood degradation/Soda lime process
(D) R   X  R 2 CuLi 
 R  R (S) Hunsdiecker reaction

12. Column-I Column-II

(A) CH 3  C  C  CH 3 
 cis-2-butene (P) Na / NH 3 (l )
(B) CH 3  C  C  CH 3 
 trans-2-butene (Q) H 2 / Pd / BaSO 4
(C) CH3C  C  CH 3 
1-Butene (R) alc.KOH,
(D) CH 3  CH3  C  CH 
 2-Butyne (S) NaNH 2 , 
13. Column-I Column-II
CH 3
|
(A) Ph  C = CH 2 
Hg(OAC)2 ,H 2 O
(P) Cis
NaBH ,OH 4

(B) 
(i) M-CPBA
(ii) H + /H O (Q) Trans
2

(C) 
(i) B2 H 6 –THF
(ii) H O /OH –
 (R) Optically active
2 2

(D) 
Bayers
Reagent (S) Optically inactive

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JEE
14. Match List-I with List-II and select the correct answer using the codes given below the lists:
Column-I (Reaction) Column-II (Reagents)
(A) CH 3  CH  CH 2  CH 3  CHBr  CH 3 (P) HBr

(B) CH 3  CH  CH 2  CH 3  CH  CH 2 Br (Q) Br 2

(C) CH 3  CH  CH 2  BrCH 2  CH  CH 2 (R) HBr/peroxide

(D) CH 3  CH  CH 2  CH 3  CHBr  CH 2 Br (S) NBS

15. Column-I Column-II

(A) CH 3 – C = CH 2  
(i) BH3 /THF
Θ (P) CH 3  CH 2  CH  CH 2
| (ii) H 2 O 2 / O H

CH 3

(B) CH 3 – C = CH 2  
(i) Hg(OAc)2 /HOH
(ii) NaBH4 (Q) CH 3  CH  CH – CH 3
|
CH 3

Cl
|
CH3 ONa / 
(C) CH 3  CH 2  CH  CH3   (R) CH 3  CH – CH 2 OH
|
CH 3

Cl OH
| |
(D) CH 3  CH 2  CH  CH 3 
(CH 3 )3CONa

 (S) CH 3  C – CH 3
|
CH 3

16. Column-I Column-II

(A) 
HOBr/H

+
(P) Racemix Mix.

CH 3

(B) 
(i) Peracid
(ii) H + /H O
 (Q) Meso
2

CH 3

(C) 
Br2 /CCl4
 (R) Diastereomer

CH 3

CH 3 H
(D) C=C 
Br2 /CCl4
 (S) Enantiomer
H CH 3

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 Hydrocarbon
17. Match the column
Column-I (Reaction) Column-II (Major Product)
OD
(A) D /D2 O (P)
D 
 D

D
D 
1. BH3 THF
(B) 2.D2 O2 /OH (Q) D
OD
OD
(C) D 

1.Hg(OCOCH 3 )2 ×D 2 O
(R) D
2.NaBH 4 /OH

Integer Type Questions :

 
 2CH 4    X  
2  
Y
CH MgBr excess CO dry ice excess +
18. H  C  C  H 
3
1  2 
H
3


H 2 /Pd/CaCO3
4   Z   5   W 
D 2 / Ni

The total number of stereoisomers formed at the end product 'W' is :

19. CH 3  C H  C  C  C H  CH 3
| |
OH (X) OH
(i) The total no. of stereoisomers of the abvoe compound.
(ii) Total no. of stereoisomers of the product when above compound (X) is reduced by lindlar’s
catalyst.
(iii) Total no. of stereoisomers of the product when (X) is reduced by Na/liq NH3 (Birch reduction)
(iv) No. of products formed when optically inactive form formed in part (B) reacts with PhCOOOH
followed by hydrolysis.

CH3 CH 3

20. CC  CH 2 N 2 

UV
m 
 Total no. of products

H H

CH3
21.  
Cold Dil
KMnO4
 
HIO4
 
NH 2 OH
 excess  Products

Total no. of isomers (including stereo) are formed in the products.

Cl
22. (A) R-2-chloropentane 
hv
2
 Optically active di-chloro products (P)

Cl
(B) 
2
 Optically active dichloro products (Q)
hv

Cl
(C) R-2-chlorobutane 
hv
2
 Optically active di-chloro products (R)

Sum P + Q + R is:

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JEE
23. How many distinct monochlorinated products, (including stereoisomers) may be obtained when the
alkane shown below is heated in the presence of Cl2 ?

24. How many distinct monochlorinated products, (including stereoisomers) may be obtained when the
alkane shown below is heated in the presence of Cl2 ?

CH3
Cl
25. H Cl 2
 (x), (x) = total number of di-chloro product
hv
CH2 CH2 CH2 CH3
S-2-chloro hexane

*****

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 Hydrocarbon

EXERCISE # 4(A)(Expert – JEE Advanced PYQs)

1. In the following reaction, the major product is : (JEE Adv. 2015)

CH3
1 equivalent HBr
CH2
H2C

CH3 CH3
CH3
(A) H2C (B) H3C
Br
Br
CH3 CH3

(C) H2C Br (D) H3C Br

Paragraph for Question nos. 2 to 3

In the following reactions : (JEE Adv. 2015)


C8 H 6 Pd BaSO4
 C8 H8 i
. B2H 6
  X
H2 ii. H 2 O 2 , NaOH , H 2O
 H 2O
 HgSO 4 , H 2SO 4
C8 H 8O i
. EtMgBr , H 2O
      Y
ii. H  , Heat

2. Compound X is
O OH
(A) CH3 (B) CH3

OH
CHO
(C) (D)

3. The major compound Y is

(A) CH3 (B) CH3

CH2 CH3
CH3
(C) (D) CH3

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JEE
4. The correct statement(s) for the following addition reactions is(are) (JEE Adv. 2017)

H 3C H H 3C CH3
Br2 / CHCl3
(i)   
 M and N (ii) Br / CHCl3
2   O and P

H CH3 H H
(A) O and P are identical molecules
(B) Bromination proceeds through trans-addition in both the reactions
(C) (M and O) and (N and P) are two pairs of enantiomers
(D) (M and O) and (N and P) are two pairs of diastereomers
5. Which of the following reactions produce(s) propane as a major product? (JEE Adv. 2019)
H3C H3C
(A)  (B)
COONa  COONa + H2O 
NaOH,CaO, electrolysis

Br
(C) H C Cl 
Zn, dil. HCl
 (D) Br 
Zn

3
H3C
6. Consider the following transformations of a compound P. (JEE Adv. 2020)
(i) NaNH 2
R P
(optically active) (ii) C 6H5COCH 3 (C 9H12)
(iii) H 3O / 
+

Pt/H2
CH 3

(i) X (reagent) Q
P (C 8H12O6)
(ii) KMnO 4 /H2SO4/ (optically active acid)
Choose the correct option(s).

(A) P is (B) X is Pd-C/quinoline/H2

(C) P is (D) R is

7. The major product formed in the following reaction is ___. (JEE Adv. 2021)
NaNH2
Na liq. NH3

(A) (B)

(C) (D)
*****
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 Hydrocarbon

EXERCISE # 4(B) (Conqueror - Variety of JEE Advanced PYQs)

1. The total number of cyclic structural as well as stereo isomers possible for a compound with the
molecular formula C5H10 is _________. (JEE Adv. 2009)
2. The number of hydroxyl group(s) in Q is (JEE Adv. 2015)
+
H aqueous dilute KMnO4(excess)
H P Q
heat 0°C
HO
H3C CH3
3. The maximum number of possible isomers (including stereoisomers) which may be formed on mono-
bromination 1-methylcyclohex-l-ene using Br2 and UV light is __________. (JEE Adv. 2021)
4. The number of -CH2-(methylene) groups in the product formed from the following reaction sequence
is ____ . (JEE Adv. 2022)
1. O3 , Zn/H2 O
2. KMnO4
3. NaOH, electrolysis
4. Cr2 O3, 770K, 20 atm
5. The total number of chiral molecules formed from one molecule of P on complete ozonolysis (O3,
Zn/H2O) is ________ . (JEE Adv. 2022)
OH OH

HO HO OH
P
6. The number of isomeric tetraenes (NOT containing sp-hybridized carbon atoms) that can be formed
from the following reaction sequence is ___. (JEE Adv. 2022)
1. Na, liquid NH3
2. Br2 (excess)
3. alc. KOH

*****

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JEE

JEE MAIN YEARLONG REVISION EXERCISE

1. Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one isomer of
mono substituted alkyl halide? (JEE Main 2012)
(A) Isohexane (B) Neohexane
(C) Tertiary butyl chloride (D) Neopentane.
2. A gaseous hydrocarbon gives upon combustion 0.72 g of water and 3.08 g of CO2. The empirical
formula of the hydrocarbon is: (JEE Main 2013)
(A) C3H4 (B) C6H5 (C) C7H8 (D) C2H4
3. Which one of the following class of compounds is obtained by polymerization of acetylene?
(JEE Main 2014)
(A) Poly-yne (B) Poly-ene (C) Poly-ester (D) Poly-amine
4. Which compound would give 5 – keto – 2 – methyl hexanal upon ozonolysis ? (JEE Main 2015)

CH3 CH3
CH3 CH3
(A) (B) H3C (C) CH3 (D)
CH3 CH3
5. The product of the reaction given below is: (JEE Main 2016)

1. NBS/hv
X
2. H2O/K2CO3

CO2H OH O

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

6. The reaction of propene with HOCl (Cl2 + H2O) proceeds through the intermediate:
(JEE Main 2016)
(A) CH3–CHCl–CH2 + +
(B) CH3 –CH –CH2 –OH
+
(C) CH3– CH –CH2 –Cl (D) CH3– CH(OH) – CH2+
7. The major product obtained in the following reaction is : (JEE Main 2017)

Br
H t
BuOK
C6H5

C6H5
(+)
(A) C6H5CH = CHC6H5 (B) (+) C6H5CH (OtBu) CH2C6H5
(C) (–) C6H5CH(OtBu) CH2C6H5 (D) (±) C6H5CH(OtBu) CH2C6H5

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 Hydrocarbon
8. 3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an addition product. The
number of possible stereoisomers for the product is : (JEE Main 2017)
(A) Zero (B) Two (C) Four (D) Six
9. The trans-alkenes are formed by the reduction of alkynes with: (JEE Main 2018)
(A) Na/liq.NH3 (B) Sn-HCl
(C) H2-Pd/C, BaSO4 (D) NaBH4
10. When 2-butyne is treated with H2/Lindlar's catalyst, compound X is produced as the major product
and when treated with Na/liq. NH3 it produces Y asthe major product. Which of the following
statementsis correct? (JEE Main 2018)
(A) Y will have higher dipole moment and higher boiling point than X
(B) Y will have higher dipole moment and lower boiling point than X
(C) X will have lower dipole moment and lower boiling point than Y
(D) X will have higher dipolemoment and higher boiling point than Y
11. Consider the following reaction : (JEE Main 2019)
Ag2 O
A
NaBH 4 ZnCl2 Turbidity
Hg2+/H+ within
B C
conc. HCl 5 minutes
‘A’ is:
(A) CH  CH (B) CH 3  C  C  CH 3 (C) CH 3  C  CH (D) CH 2  CH 2
12. The major product of the following reaction is: (JEE Main 2019)

CH 3C  CH 
(i) DCl (1 equiv.)
(ii) D I

(A) CH 3CD(I)CHD(Cl) (B) CH 3CD(Cl)CHD(I)

(C) CH 3CD 2 CH(Cl)(I) (D) CH 3C(I)(Cl)CHD 2

13. But-2-ene on reaction with alkaline KMnO4 at elevated temperature followed by acidification will
give: (JEE Main 2019)
(A) CH3 – CH – CH – CH3

OH OH
(B) one molecule of CH2CHO and molecule of CH3COOH
(C) 2 molecules of CH3COOH
(D) 2 molecules of CH2CHO
14. Which one of the following alkenes when treated with HCl yields majorly and anti Markovnikov
product? (JEE Main 2019)
(A) CH3O – CH = CH2 (B) Cl – CH = CH2
(C) H2N – CH = CH2 (D) F3C – CH = CH2
15. 25 g of an unknown hydrocarbon upon burning produces 88 g of CO2 and 9 g of H2O. This unknown
hydrocarbon contains: (JEE Main 2019)
(A) 20 g of carbon and 5 g of hydrogen (B) 22 g of carbon and 3 g of hydrogen
(C) 24 g of carbon and 1 g of hydrogen (D) 18 g of carbon and 7 g of hydrogen

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JEE
16. The major product obtained from the following reaction is (JEE Main 2020)

CC
2 
O2N OCH 3 
Hg / H
H O
 2

OCH3 O OH

(A) (B)
O2N O O2N

OH O OCH3

(C) (D)
O2N O O2N
17. The major product (Y) in the following reactions is: (JEE Main 2020)
CH 3
HgSO4 , H2SO4 (i) C 2 H5 MgBr,H2O
CH3 – CH – C CH X Y
H2 O (ii) Conc. HSO
2 4/

CH 3 CH 2
(A) CH3 – CH – C = CH – CH3 (B) H3 C – C – CH – CH3
CH3 C2 H5

CH 3 CH 3
(C) CH3 – CH – C = CH2 (D) CH3 – CH – C – CH3
CH 2CH 3 CHCH 3
18. The increasing order of the boiling point of the major products A, B and C of the following reactions
will be: (JEE Main 2020)
O
(i) (C6H5CO)2
+ HBr A

(ii) + HBr B

(iii) + HBr C

(A) ii < iii < i (B) iii < i < ii (C) i < ii < iii (D) i < iii < ii
19. Which of the following optically active compounds produces an optically inactive compound on
hydrogenation?
(JEE Main 2020)

H CH 3 H CH 3
H CH3 H CH 3
(A) (B) (C) (D)

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 Hydrocarbon
20. The correct order of heat of combustion for following alkadienes is: (JEE Main 2020)

(i) (ii) (iii)

(A) (i) < (ii) < (iii) (B) (i) < (iii) < (ii) (C) (iii) < (ii) < (i) (D) (ii) < (iii) < (i)
21. An unsaturated, hydrocarbon X on ozonolysis gives A. Compound A when warmed with ammmical
silver nitrate forms a bright silver minor along the sides of the test tube. The unsaturated hydrocarbon
X is: (JEE Main 2021)
CH3 CH3 – C = C – CH3
(A) (B)
CH3 – C = CH 3 CH 3

(C) HC  C  CH 2  CH3 (D) HC3  C  C  CH 3

22. The major product formed in the following reaction is:


HBr
 Major product (JEE Main 2021)
(excess)

Br

(A) (B)
Br
Br
Br
(C) (D) Br
Br
23. Choose the correct statement regarding the formation of carbocation A and B given
+
CH 3 - CH2 - CH 2 - CH2 + Br –
“A”
CH 3 - CH 2 - CH = CH 2 + HBr
+ (JEE Main 2021)
CH 3 - CH2 - CH - CH 3 + Br –
“B”
(A) Carbocation A is more stable and formed relatively at slow rate.
(B) Carbocation A is more stable and formed relatively at faster rate
(C) Carbocation B is more stable and formed relatively at slow rate
(D) Carbocation B is more stable and formed relatively at faster rate

Cl

24. 
A
 Identify the reagent(s) ‘A’ and condition(s) for the reqaction

Cl
(JEE Main 2021)
(A) A = HCl ; Anhydrous AlCl3 (B) A = Cl2 ; UV light
(C) A = Cl2 ; dark, Anhydrous AlCl3 (D) A = HCl, ZnCl2

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JEE

CH 3
|
conc.H PO (i ) O
25. CH 3 — C— CH = CH 2 dil

.H 2SO 4
  34  3 
|  ( ii ) Zn / H 2O
CH 3

Final product is / are

O O
|| ||
(A) CH  C  CH (B) HCHO + CH 3  C  CH  CH 3
3 3 |
CH 3

(C) CH3CHO + (D) CH3CHO + HCHO

26. For the reaction

(
i ) CF3CO3H
  Final product is

( ii ) H3O

O OH OH
(A) O (B) (C) (D)
OH OH

27. CH3–CH2–CCH CH3CC–CH3

A and B are –
(A) alcoholic KOH and NaNH2 (B) NaNH2 and alcoholic KOH
(C) NaNH2 and Lindlar (D) Lindlar and NaNH2
28. A hydrocarbon C8H14 consumes only one mole of H2 on catalytic hydrogenation. The hydrocarbon
when heated with hot and concentrated alkaline KMnO4 gives cyclohexanone and acetic àcid (after
acidification). The hydrocarbon is :
(A) 1-ethylcyclohexene (B) 1, 2-dimethylcyclohexene
(C) ethylidenecyclohexane (D) cyclohexylethene
29. The major product of the following reaction is:

Na/ Ether Br , hv Alc. KOH

Br Cl 
 
2
 


(A) (B)

(C) (D)

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 Hydrocarbon

30. Which of the following reactions is expected to give a fairly good yield of (CH 3 )3 C  CH  CH 2 ?

CH3 OH CH3 Br
(A) H2SO4 (B) CH Zn, acetone
CH3 C CH CH3  3 C CH CH3 

CH3 CH3

CH3
H3 C CH2 CH2
CH3 N CH3 Br
OH,  Me3 CO
(C) CH3 C CH CH3 (D) CH3 C CH CH3 
CH3 CH3
31. Which reagent is best to perform the following transformation?

(A) HBr, NaOH (B) HBr, R  O  O  R, hv; Me3CO K 

(C) BH3 .THF, NaOH  H 2 O 2 (D) Br2, NaOH

32. NaNH /NH ( ) CH CH Br Li,NH (  )

CH3CH 2C  CH 
2 3
 
3 2
 
3

(A) CH 3CH 2CH  CH  CH3 (B) CH 3CH 2 CH  CH 2

CH3CH2 H CH3CH2 CH2 CH3

(C) C C (D) C C
H CH2CH3 H H

NMe3
HO– A
33.  (Major)

Major product A is:

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

OH
H SO
34. 
2 4
 A
Δ (Major)
Major product A is:

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

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JEE
35. In which of the following reaction Saytzeff alkene is major product?

CH3
|  EtO –
HO –
(A) CH 3  CH 2  C  NMe3  (B) CH 3  CH 2  CH 2 – CH – CH3 
Δ

| Δ |
CH3 F

CH3 Br
| |
t-BuOK CH 3OK
(C) CH 3  CH 2  C  CH3  (D) CH 3  CH 2  CH 2  C  CH3  
| Δ | Δ
Br CH3

Br Br
| |
36. xNaNH 2 yCH 3I
CH3  C  C  CH3     CH 3  C  C  C  C  CH3
| |
Br Br
x and y mole consumed. Value of x + y =
(A) 5 (B) 6 (C) 7 (D) 8
37. When isobutane is monochlorinated in the presence of ultraviolet light, the product obtained in higher
yield is
(A) n-butyl chloride (B) iso butyl chloride
(C) sec-butyl chloride (D) tert-butyl chloride
38. The product of reaction CH3CH2CH2 MgBr + HC  CCH3  is
(A) CH3 CH2 CH3 (B) CH3 CH2 CH2 C  C CH3
(C) CH3 CH2 CH2 OH (D) CH3 CH2 CHO
39. CH3—CH—CH = CH2 + HCl  (A)
CH3
The major product (A) in above given reaction is:
(A) CH3—CH—CH— CH3 (B) CH3—CH—CH2—CH2 Cl
CH3 Cl CH3

Cl
(C) CH3—C—CH2—CH3 (D) CH2—CH—CH2—CH3
CH3 Cl CH3

40. 1-butyne can be distinguished from 2-butyne by using

(A) bromine water (Br2 in CCl4) (B) cold alk. KMnO4 (Baeyer’s Reagent)
(C) ammoniacal solution of silver (Tollen’s Reagent) (D) diethyl ether
41. One of isomers (A) of 2-butene gives a racemic mixture on addition of Br2 whereas another isomer
(B) gives a meso compound on addition of Br2. (A) and (B) are respectively:
(A) cis and trans-2-butene (B) trans and cis-2-butene
(C) both are cis (D) none of the above
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 Hydrocarbon
42. An alkene with the lowest heat of hydrogenation is
(A) CH3 CH = CH CH3 (B) CH3 C = C—CH3
CH3 CH3

(C) CH3—C = CH2 (D) CH3—C = CH—CH3

CH3 CH3
43. Substitution with chlorine at a high temperature is easily possible in
(A) CH3 CH = CH2 (B) CH2 = CH2 (C) CH  CH (D) none of the above
44. The reaction of HX with (CH3)2 C = CH2 is
(A) (CH3)2 C X CH3 (B) (CH3)2 CH CH2 X
(C) (CH3)2 CH — CH3 (D) (CH3)2 C X CH2 X
45. The major product formed by monobromination of methylcyclopentane is

Br Br
(A) CH2Br (B) CH2Br (C) CH2Br (D)
CH3
Br
46. Which of the following compounds do not liberate CH4 when treated with excess of methyl magnesium
iodide in dry ether?
(A) CH3 — CH2 — CH2OH (B) H3C —CH2 — C  CH
(C) H3C — CH2 — CO2 H (D) H3C —CH2 — CHO
NBS HBr Mg
47. CH3 CH = CH2   (A)  (B)  (C)
ROOR
which of the following is true about the reaction above?
(A) (A) is Br2 CH CH = CH2 (B) (A) is BrCH2 CH2 CH2 Br
(C) (C) is Br Mg CH2 CH2 CH2 Mg Br (D) (C) is cyclopropane
48. A hydrocarbon (A) having molar mass 72 gives a single monochloride and two dichlorides on photo
chlorination. The hydrocarbon (A) is
(A) CH3 CH2 CH2 CH2 CH3 (B) cyclopentane
(C) (CH3)2 CH CH2 CH3 (D) neopentane
49. 2-octyne is converted to trans-2-octene on reaction with
(A) H2.Pd / BaSO4 (B) H2 / Pt (C) Na, NH3 (D) all of the above
50. The compound C2 H4 Cl2 has two isomers. Which of the following can be used to distinguish between
them?
(A) aq. KOH (B) alco. KOH (C) bromine water (D) NaNH 2
51. Which of the following compounds has an inert halogen in it?
CH2Cl
(A) CH3 — CH2Cl (B) (CH3)3 C.Cl (C) CH2 = CHCl (D)

52. A mixture of 1-chlorobutane and 2-chlorobutane when treated with alcoholic KOH gives
(A) 1-butene (B) 2-butene
(C) Isobutylene (D) mixture of 1 butene + 2 butene

*****
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JEE

JEE ADVANCED YEARLONG REVISION EXERCISE

1. Point out (A) in the given reaction sequence:

(A) 
O3 / H 2 O
(B)   2CH3COOH  CO 2

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

2. The product of reaction between one mole of acetylene and two mole of HCHO in the presence of
Cu2Cl2 -
(A) HOCH 2  C  C  CH 2 OH (B) H 2 C  CH  C  C  CH 2 OH
(C) HC  C  CH 2 OH (D) None of these
+
Y  
(i) BH3 ,THF
3. (ii) H 2 O 2 , OH –

H 3O
 (X).

(i) Hg(OAC)2, H2O

(ii) NaBH4

(Z)
(X), (Y) and (Z) will be respectively (X, Y and Z are major products)

(A) , , OH
OH OH

(B) , ,
OH OH
OH

(C) , ,
OH OH
OH

(D) , OH,
OH OH
CH 3
4. 
HBr
Peroxide
 Major product will be :

Br
CH3 CH3 CH3
H Br
(A) (B) (C) (D)
Br H Br
O

5. 
H2
Ni


Me
Product of above reaction is
(A) Meso (B) Racemic
(C) Diastereomers (D) Optically active products.
(175)
 Hydrocarbon

6. 
D2
Pt


Product of above reaction is

(A) racemic (B) Diastereomers (C) Enantiomer (D) None

7. 
H2
Pt


Product of above reaction is

(A) Racemic (B) Diastereomers (C) Enantiomer (D) Meso
O
8. ||
CH3  C  C  CH 2  CH  CH  CH 2  C  Cl
(a) (b) (c)
Reactivity toward catalytic hydrogenation
(A) a > b > c (B) b > a > c (C) a > c > b (D) c > a > b
H SO
9. 4  P (Major) NBS
2   Q (Major). The structure of Q is


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

18

10. 
(i)CH3 COO O H
(ii) H3 O
 X.

The probable structure of ‘X’ is

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

11. Ozonolysis of CH3–CH=C=CH2 will give

(A) Only CH3CHO (B) Only HCHO
(C) Only CO2 (D) Mixture of CH3CHO, HCHO & CO2
12. O-xylene on ozonolysis will give
O CH 3  C  O O
CHO || ||
(A) | & CH 3  C  CHO (B) | & CH 3  C  CHO
CHO CH 3  C  O

CH 3  C  O O
CH 3  C  O CHO || CHO
(C) | & | (D) | , CH 3  C  CHO & |
CH 3  C  O CHO CH 3  C  O CHO

(176)
JEE

13. 
OSO4 (1eq)
H 2 O/Acetone
 X.

Identify ‘X’.

(A) (B)

(C) (D) Reaction will not occur

H Br
14. Conc
 . H 2SO 4
    
Na / ether Product (Major)
H 2O 2

(A) (B)

(C) (D)

15. Which reagent is the most useful for distinguishing compound I from the rest of the compounds
(I) CH3CH2CCH (II) CH3CCCH3
(III) CH3CH2CH2CH3 IV CH3CH=CH2
(A) alk. KMnO4 (B) Br2/CCl4
(C) Br2/CH3COOH (D) Ammonical AgNO3
HgSO
16. C6H5–CC–CH3  
4  A [IIT ‘2003]
H 2SO 4

(A) (B)

(C) C6 H 5  C  CHCH 3 (D) C 6 H 5  CH  C  CH 3

| |
OH OH
17. CH3–CH=CH2 + NOCl  P
Identify the adduct.
(A) CH  CH  CH (B) CH 3  CH  CH 2
3 2
| | | |
Cl NO NO Cl

NO
|
(C) CH 3  CH 2  CH (D) CH 2  CH 2  CH 2
| | |
Cl NO Cl

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 Hydrocarbon
18. The number of optically active products obtained from the complete ozonolysis of the given compound
is
CH3 H

CH3–CH=CH–C–CH=CH–C–CH=CH–CH3

H CH3

(A) 0 (B) 1 (C) 2 (D) 4

19. How many 1,2-Shifts are involved during the course of following reaction:



(A) 1 (B) 2 (C) 3 (D) 4

20. An organic compound of molecular formula C4H6, (A), forms precipitates with ammoniacal silver
nitrate and ammoniacal cuprous chloride. ‘A’ has an isomer ‘B’, one mol of which reacts with one
mol of Br2 to form 1, 4-dibromo-2-butene. Another isomer of A is ‘C’, one mole of C reacts with only
1 mol. of Br2 to give vicinal dibromide. A, B & C are

(A) CH3–CH2–CCH and CH2=CH–CH=CH2 ;

(B) CH3–CC–CH3 and CH3–CH=C=CH2 ; CH3–CC–CH3

CH 2  CH
(C) C=CH2 and | || ; CH2 = CH–CH=CH2
CH 2  CH

(D) CH3–CC–CH3 and ; CH2 = CH–CH = CH2

(i ) O
C4H8  CH3 – CHO
3
21.
( ii ) H 2O / Zn

Baeyer
reagent Meso compound
C4H8 is
(A) But-1-ene (B) Trans-but-2-ene (C) Cis-but-2-ene (D) Isobutylene
22. Which of the following will give same product with HBr in presence or absence of peroxide.
(A) Cyclohexene (B) 1-methylcyclohexene
(C) 1, 2-dimethylcyclohexene (D) 1-butene
23. In which of following reaction racemic mixture will form.
CH3 H
(A) CH3 – CH2 – CH = CH2 
HBr
 (B) C=C 
HBr

CCl4 CCl4
H CH3
CH3 CH3
C=C
(C) H H 
HBr
CCl4
 (D) None
(cis)
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JEE

Ph
H H
alc.KOH
24. H Cl   Product(s), Possible products are
CH3

Ph
Ph CH3
(A) (B)

(C) Ph–CH2–CH = CH2 (D) Ph –HC = C = CH2

25. Which of the following can be produced by Wurtz reaction in good yield.

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

26. Choose all alkane that give only one monochloro derivative upon reaction with chlorine in sun light.

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

27. Aqueous solution of potassium propanoate is electrolysed. Possible organic products are:
(A) n-Butane (B) C2H5COOC2H5 (C) CH3–CH3 (D) CH2=CH2
28. Which is / are true statements/ reactions?
(A) Al4C3 + H2O  CH4 (B) CaC2 + H2O  C2H2

(C) Mg2C3 + H2O  CH3C CH (D) Me3C–H + KMnO4 H
 Me3C–OH
H / Ni Conc. H PO
Mg2C3 D2O
 2     (S)
1. BH3 .THf 3 4
29.     
2. H 2 O / O H 

Product (s) are :

(A) H C  CH  CD 3 (B) H 2 C  CH  CD 2 (C) H2C = CH–CD3 (D) H 2 C  C CH 3

| | |
D D D

—
30. OH

The above compound undergoes elimination on heating to yield which of the following products?

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

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 Hydrocarbon
31. Which of the following reaction is/are not showing the correct major product ?

Na
(A) Br Cl Ether Cl Cl

Na
(B) CH3 – CH– Br Ether
CH3– CH2 – CH3 + CH3 –CH=CH2
CH3

Ag
(C) 


Cu
(D) 


32. Select true statement(s):

(A) I2 does not react with ethane at room temperature even though I2 is more easily cleaved
homolytically than the other halogens.
(B) HC  CH is more reactive than H2C = CH2 toward electrophilic addition reaction
(C) The rate of bromination of methane is decreased if HBr is added to the reaction mixture.
(D) Allylic chloride adds halogens faster than the corresponding vinylic chloride.
dil. H2SO4 (i) O3
33. P1 (ii) Zn/H2O
P3
(Hydroboration
oxidation)

P2
The realtionship among P1, P2 & P3 are:
(A) P1 and P2 are functional isomers
(B) P2 and P3 have one common functional group.
(C) P2 can also be obtained by reductive ozonolysis of 2-hexyne.
(D) P1 can also be obtained by ozonolysis of 2,3-dimethyl butene.



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JEE

CONTENTS
6.0 INTRODUCTION
6.1 UNIMOLECULAR NUCLEOPHILIC SUBSTITUTION REACTION SN1
6.1.1 Characteristics of SN1 reactions
6.1.2 Factor's affecting the rates of SN1
6.2 SN2 REACTION OF ALKYL HALIDE
6.2.1 Characteristic of SN2 Reactions
6.2.2 Factor's affecting the rate of SN2 reaction
6.2.3 Some SN2 Reactions of Alkyl Halide
6.3 COMPARISION BETWEEN SN1 / SN2 REACTION
6.4 SUBSTITUTION REACTION OF ALKYL HALIDE
6.5 SN1 REACTION OF ALCOHOLS
6.5.1 Reaction with hydrogen halides
6.6 SN2 REACTION OF ALCOHOL
6.6.1 By the action of phosphorus halides
6.6.2 By reaction with thionyl chloride in presence of pyridine
6.7 SNi REACTION OF ALCOHOL
6.8 NUCLEOPHILIC SUBSTITUTION REACTION OF ETHERS
6.8.1 Reaction with HX
6.9 BIMOLECULAR NUCLEOPHILIC SUBSTITUTION IN AROMATIC
COMPOUND (SN2 Ar) REACTION
6.10 NEIGHBOURING GROUP PARTICIPATION (NGP) & ANCHIMERIC
ASSISTANCE
6.11 METHODS OF PREPARATION
6.11.1 General Methods of Preparation of Aryl Halides
6.11.2 Physical Properties of Alkyl Halides
6.12 GRIGNARD REAGENT
6.12.1 Introduction of Organometallic compounds
6.12.2 Preparation
6.12.3 Reactivity of Grignard Reagent
6.12.4 Reaction with acidic Hydrogen (H)
6.13 FREONS
6.13.1 Preparation of freons
6.13.2 Properties & uses of freons

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 Alkyl Halide & Aryl Halide

6.0 INTRODUCTION
The replacement of hydrogen atom(s) in a hydrocarbon, aliphatic or aromatic, by halogen atom(s)
results in the formation of alkyl halide (haloalkane) and aryl halide (haloarene), respectively.
Haloalkanes contain halogen atom(s) attached to the sp3 hybridised carbon atom of an alkyl group
whereas haloarenes contain halogen atom(s) attached to sp2 hybridised carbon atom(s) of an aryl
group. Many halogen containing organic compounds occur in nature and some of these are clinically
useful. These classes of compounds find wide applications in industry as well as in day-to-day life.
They are used as solvents for relatively non-polar compounds and as starting materials for the
synthesis of wide range of organic compound.
6.1 UNIMOLECULAR NUCLEOPHILIC SUBSTITUTION REACTION (SN1)
Nucleophilic substitution which involves two step process
(a) First step: Slow step involves ionisation to form carbocation
It is the RDS (Rate determining step) of reaction.
R  g  R   g 
(b) Second step: Fast attack of nucleophile on carbocation to result into product.
R   Nu   R  Nu
 SN1 Reaction of alkyl halide:

R 
R R R
Ionisation of alkyl halide C Nu 
R' C     C + C
Slow step (rds)
X R R fast step
Nu R''
R'' Carbocation intermediate Nu R'
R'' R'
6.1.1 Characteristics of SN1 reactions: (d + l mixture)
(i) It is unimolecular, two step process.
(ii) Carbocation intermediate is formed so rearrangement is possible in SN1 reaction.
(iii) It is first order reaction
(iv) Kinetics of the reaction Rate  [Alkyl halide]
Rate = k [(CH3)3C – X]
Rate of SN1 reaction is independent of concentration and reactivity of nucleophile.
(v) Energy profile daigram of the SN1 reaction.

T.S1 T.S2


Ea2
E Ea1

R Nu–
R–X + Nu–

R–Nu + X
Reaction coordination 
6.1.2 Factor's affecting the rates of SN1
(a) The structure of the substrate: The Rds of the SN1 reaction is ionization step, in this step
form a carbocation. This ionisation is strongly endothermic process, rate of SN1 reaction de-
pends strongly on carbocation stability because carbocation is the intermediate of SN1 reaction
which determines the energy of activation of the reaction.
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JEE

Reactivityof SN 1  Stability of Carbocation

 SN1 reactivity: 3° > 2° > 1° > CH3 – X

(b) Concentration and reactivity of the nucleophile: The rate of SN1 reactions are unaffected
by the concentration and nature of the nucleophile
(c) Nature of nucleophile:
 Weak, neutral, mostly solvents (protic) itself functions as nucleophiles in SN1 reaction.
# In SN1 reaction, mostly the solvent functions as nucleophile. So SN1 reaction are termed as
solvolysis reaction.
Water  hydrolysis
C2H5OH  ethanolysis
CH3COOH  acetolysis
NH3  ammonolysis
SN reaction is disfavoured by strong, anionic nucleophiles which attacks faster before ionisation
1

takes place leading to SN2 mechanism.

For SN1 reactions, weak neutral nucleophiles are suitable and mostly solvent molecules function
as nucleophiles with oxygen and nitrogen as donor atoms.

OH2 –H
R – X + H2O  R R O H  R – OH + HX
H
(d) Effect of the solvent: The ionizing ability of the solvent :
Because to solvate cations and anions so effectively the use of a polar protic solvent will greatly
increase the rate of ionization of an alkyl halide in any SN1 reaction. It does this because solva-
tion stabilizes the transition state leading to the intermediate carbocation and halide ion more
than it does the reactant, thus the energy of activation is lower.

R – X  R + X (Solvolysis)
–d
+d +d
O
H –d H H H
O +d
H H +d +d
H X H H
–d O R O –d –d
O +d O
+d H
O
H
H H H –d
H
–d H+d O
–d
Solvated ions
Dielectric constants () and ionisation rates of t-Butylchloride in few common solvents

Solvent  Relative Rate

H2 O 80 8000
CH3OH 33 1000
C2H5OH 24 200
(CH3)2CO 21 1

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 Alkyl Halide & Aryl Halide
(e) The nature of the leaving group: In the SN1 reaction the leaving group begins to acquire a
negative charge as the transition state is reached stabilisation of this developing negative charge
at the leaving group stabilizes the transition state and ; this lowers the free energy of activation
and thereby increases the rate of reaction.
   
Leaving ability of halogen is I  Br  Cl  F
(f) Stereochemistry of SN1 Reactions: In the SN1 mechanism, the carbocation intermediate is
sp2 hybridized and planar, A nucleophile can attack on the carbocation from either face, if
reactant is chiral than after attack of nucleophile from both faces gives both enantiomers of the
product, which is called racemization.
Concentration of Inverted product is slightly greater than retention product.
 Mechanism of racemization (SN1
Nu
 Retention of
Nu ck R3 C configuration
R2 p atta R1
Br To R2
C R1 Bo
R3 C 
  R tto
m R2
R1 solvolysis 3

att
a ck R3 R1 Inversion of
R2
Nu C configuration

Nu
 Reagents for alkyl halide are : H2O , RCOOH , ROH & RSH

CH3 CH3
H 2O  Acetone
e.g. CH3 C Br 
 CH3 C OH + HBr
CH3 CH3

(3° alkyl halide hence no SN2 reaction)

CH3 CH3
CH 3OH /Ag 
e.g. CH3 C CH2 Br  CH3 C CH3 (Carbocation Rearrangement)
H OCH3

CH3 CH3 CH3

H 2O
e.g. H Cl 
AgNO3
 H OH + HO H (Racemic product)
C2H5 C2H5 C2H5

6.2 SN2 REACTION OF ALKYL HALIDE

 Mechanism:

R R R
d– d–
Nu C X  Nu C X  Nu C + XsLeaving group
H H D H D
D
Transition state

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 JEE
6.2.1 Characteristic of SN2 Reactions:
(i) It is bimolecular, one step process
(ii) It is second order reaction because in the RDS two species are involved
(iii) Kinetics of the reaction rate  [alkyl halide] [nucleophile]
rate = k[alkyl halide] [nucleophile]
If the concentration of alkyl halide in the reaction mixture is doubled, the rate of the nucleophilic
substitution reaction is double. If the concentration of nucleophile is doubled the rate of reaction is
also double. If the concentration of both are doubled then the rate of the reaction quadriples.
(iv) Energy diagrams for SN2 reaction:
d– d–
Nu – R – X [T.S]

 Ea
E
–
R–X + Nu

R–Nu + X
Reaction coordinate 
(v) No intermediates are formed in the SN2 reaction, so rearrangement is not possible.
(vi) The stereochemistry of SN2 reactions  As we seen earlier, in an SN2 mechanism the nucleo-
phile attacks from the back side, that is from the side directly opposite to the leaving group. This
mode of attack causes an inversion of configuration at the carbon atom that is the target of
nucleophilic attack. This inversion is also known as walden inversion.

T Nu
+d –d Inversion
Nu C X 
 C T+X
H
H D D
6.2.2 Factor 's affecting the r ate of SN2 reaction
Number of factors affect the relative rate of SN2 reaction, the most important factors are
(a) Effect of the structure of the substrate
Order of reactivity in SN2 reaction : – CH3 > 1° > 2° >> 3° (unreactive), the important factor
behind this order of reactivity is a steric effect. Very large and bulky groups can often hinder the
formation of the required transition state and crowding raises the energy of the transition state
and slows down reaction.
 In SN2 reaction carbon has pentavalent transition state which has anion like character so elec-
tron withdrawing group favours SN2 reaction.
Relative rate of reactions of alkyl halide in SN2 reaction
Substituent Compound Relative Rate
Methyl CH3X 30
1° CH3CH2X 1
2° (CH3)2CHX 0.02
Neopentyl (CH3)3CCH2X 0.00001
3° (CH3)3CX ~0

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 Alkyl Halide & Aryl Halide
(b) Concentration and reactivity of the nucleophile
As nucleophilicity of nucleophile increases rate of SN2 increases.
Anionic nucleophiles mostly give SN2 reaction
A stronger nucleophile attacks upon -carbon with faster rate than the rate of departing of
leaving group.
R– > NH2– > OH– > F–
RO– > ROH
NaOH > H2O
NH3 > H2O
(c) The effect of the solvent: Polar aprotic solvent have crowded positive centre, so they do not
solvate the anion appreciably therefore the rate of SN2 reactions increased when they are
carried out in polar aprotic solvent.
Example: DMF, DMSO, Acetone etc.
(d) The nature of the leaving group  Weaker bases are good leaving groups. A good leaving
group always stabilize the transition state and lowers its free energy of activation and thereby
increases the rate of the reaction. Order of leaving ability of halide ion F¯ < Cl¯ < Br¯ < I¯
 Order of leaving groups:

CH3 SO3– > I > Br > Cl > F > OAc > NR3 > OR > NR2
Reagents for alkyl halide are : OH–, SH–, I– , CN–, NH3... (strong anionic nucleophile)
KOH
e.g. (CH3)2CHCH2CH2 – Br 
H2O
 (CH3)2CHCH2CH2 – OH

H Br HO H
C KOH
C
e.g. 2  CH2 CH3
CH3 CH2 CH3 SN CH3
(S)-2-Bromobutane (R)-2-Butanol
100% inverted configuration

6.2.3 Some SN2 Reactions of Alkyl Halide: Nuc:   R  X  Nuc  R  X 

Nucleophilc Product Class of Product

R – X + I:  R – I:

– –
alkyl halide
 
–  
R – X + :OH 
 R – OH alcohol
 
 
R – X + –:OR   
 R – OR ether
 
–  
R – X + :SH 
 R – :SH thiol(mercaptan)
 
– 
R – X + :SR   R – 
 SR  thioether (sulfide)
 
R – X + :NH 3  R – NH3 X –
 amine
 = N = N:
 –  = N = N:
 –
+ +
R –X+ –
:N 
 R–N azide
R –X+ –
:C  C – R   R – C  C – R
 alkyne
R –X+ –
:C  N: 
 R – C  N: nitrile
 –
R – X + R  – COO:  R  – COO – R
 ester

R – X + :P(Ph)3 
 [R – PPh 3 ] + –
X phosphoniumsalt

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 JEE
D
NaOH
Ex. 1 H CH3
SN2
OH
D
NaN3
H CH3
Br SN2
N3
H CH3
D
D NaSH
SN2 H CH3
SH
D
EtONa
H CH3
SN2
OEt
6.3 COMPARISION BETWEEN SN1 / SN2 REACTION
Conditions / Characteristics:
S
No.
Characteristics SN2 SN1

1TS 2TS
1. Energetic

2. Kinetics r = k[RX] [NU–] r = k[RX]

3. Stereochemistry Inversion Racemisation
4. Rearrangement Not possible Possible
Me – X > R– CH2 –X > R3CX > R2CHX >
5. Nature of R – X
R2 – CH – X > R3–CX RCH2X > CH3X
6. Nucleophile Strong/Anionic Weak/Neutral
Illustration 1. Write the structure of the nucleophilic substitution products in each of the following:
CH3
PhS 
H2C  
Cl
H3 C

S CH3
Solution: Ph
CH3
Here due to steric crowding, the nucleophile attack from * electron density and this reac-
tion is called SN2' reaction.
Illustration 2. Predict the product of SN2 reaction below. Be sure to indicate the stereochemistry of each
product where appropriate:
H3C Br
Cl– + 
CH3
H
(187)
 Alkyl Halide & Aryl Halide

CH2CH3
Solution: Cl + Br–
CH3
H
Illustration 3. Why is PhO– a weaker nucleophile than RO– ?
Solution: The nucleophilic pairs of electrons on oxygen are involved in resonance in the case of PhO–
. This resonance interaction decreases their availability to participate in nucleophilic pro-
cesses.

O O O … and so on

No such resonance is possible in the case of the alkoxide ion. It is also this resonance
interaction that makes phenoxide less basic than alkoxide, as well as making phenols more
acidic than alcohols.

MID LEARNING EXERCISE (MLE)-35

Q.1 Arrange the following in decreasing order of reactivity towards SN1 reaction:
I II III IV
(i) CH3Cl CH3CH2Cl CH3CH2–CH2–Cl CH3CHClCH3

Br Br CH3 Br
CH3 |
(ii) CH  CH  CH 3 C6 H5  CH  C6 H5
CH3 |
Br
CH3
CH2 Br CH2 CH2 Br Br
H3C CH3 H3 C C Br
(iii)

CH2 Br CH2 Br
CH2 Br CH2 Br

(iv)

OH NO2
CH3
CH3 Br CH3 O
(v) C6H5 C Br CH3 C CH Br (CH3)2CHBr

CH 3 CH3

Cl

(vi) (C6H5)2CHCl CH2= CHCH2Cl C6H5CH 2Cl

(188)
JEE
Q.2 Arrange the followings in decreasing order of reactivity towards SN2 reaction :
I II III IV
(i) CH3Cl CH3CH2Cl CH3CH2–CH2–Cl CH3CHClCH3

CH3 CH3 CH3

(ii) CH3CH2 CH CH2Cl CH3 CH CH2CH2Cl CH3CH2CH2CH2Cl CH3CH2CH2 CHCl
CH 3 CH3 CH3
(iii) CH3 C CH 2 Cl CH3 C Cl CH3 C Cl CH3 – CH2 – Cl

CH3 CH3 H

CH2 Cl CH2 Cl CH2 Cl

CH3 H3C CH3
(iv)

(v) N  C – CH2 – Br CH3 CH CH3 CH3 – CH2 – Br

Br
(vi) CH2 = CH – CH2Cl CH3CH2CH2Cl CH2 = CHCl
CH2 Br CH2 Br CH2 Br CH2 Br

(vii)

NH2 CH3 NO2

Q.3 Which of the following can not give SN1 reaction easily?
Br Br
Br Br

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

Q.4 Which will give white ppt. with AgNO3?

(A) Cl (B) Cl (C) CH2Cl (D) Both A & C

Q.5 Rate of SN2 depends on :

(A) Conc of Nucleophile (B) Conc of substrate
(C) Nature of leaving group (D) All of the above
Q.6 SN2 reaction will be favourable in
Br Br Br Br

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

Q.7 SN1 and SN2 is not favourable in

(A) H 2C = CH – CH – CH3 (B) Ph – CH2 – Cl
|
I
(C) Ph – Cl (D) H2C = CH – CH2 – Cl
(189)
 Alkyl Halide & Aryl Halide
Q.8 In which of the following replacement of Cl– is most difficult ?

Cl Cl
(A) (B) (C) (D)
Cl Cl
Br CH3 – S 2
Q.9 + OH 
 A ; A is:
N

H H

HO CH3 H CH3
(A) (B) (C) Both (D) None
H H OH H
Q.10 Which one of the following statement is correct about SN1 reaction
(A) Perfect racemisation is observed (B) Only Walden inversion is observed
(C) Total retention of configuartion is observed (D) Polar protic solvent is preferred
Q.11 The SN2 reactivity order for halides:
(A) R – F > R – Cl > R – Br > R – I (B) R – I > R – Br > R – Cl > R – F
(C) R – Br > R – I > R – Cl > R – F (D) R – Cl > R – Br > R – F > R – I
Q.12 In SN1 reaction, the first step involves the formation of:
(A) Free radical (B) Carbanion (C) Carbocation (D) Final product
Q.13 The rate law for the reaction, RCl + NaOH (aq.)
ROH + NaCl is given by, rate = K1[RCl]. The rate of the reaction will be:
(A) Doubled on doubling the concentration of sodium hydroxide
(B) Halved on reducing the concentration of alkyl halide to half
(C) Decreased on increasing the temperature of the reaction
(D) Unaffected by increasing the temperature of the reaction
Q.14 Chlorobenzene is:
(A) More reactive than ethyl bromide (B) More reactive than isopropyl chloride
(C) As reactive as methyl chloride (D) Less reactive than benzyl chloride
Q.15 Vinylic halides are unreactive towards nucleophilic substitution because of the following except:
(A) C - halogen bond is strong
(B) The halogen is bonded to sp2 carbon
(C) A double bond character is developed in the carbon-halogen bond by resonance
(D) Halide ions are not good leaving groups
Q.16 Tertiary butyl halide on boiling with water gives tertiary butyl alcohol. The reaction follows -
(A) E2 mechanism (B) SN1 mechanism (C) SN2 mechanism (D) E1 mechanism
Q.17 Which of the following does not give white precipitate when boiled with alcoholic silver nitrate -
(A) Allyl chloride (B) t-butyl chloride (C) Chlorobenzene (D) Benzyl chloride
6.4 SUBSTITUTION REACTION OF ALKYL HALIDE
(i) Reaction with KCN and AgCN (Ambident Nucleophile)
δ+ δ– + –
R — X + K — CN
Alc.

Δ  R – C  N + KX
Ionic bond Cyanide
(190)
JEE

d+ d– Alc.
R X + Ag CN 

 R – N  C + Ag – X
Covalent bond Isocyanide

(ii) Reaction with KNO2 and AgNO2: (Ambident Nucleophile)

δ+ δ– +
R — X + K – O – N = O 
Alc.
Δ  R – O – N = O + KX

Ionic bond (Alkyl nitrites)

d+ d– O
Alc.
R X + Ag O N O  R N + Ag – X

Covalent bond O
Nitroalkane

Sodium and Potamium salts are ionic in nature. Thus carbon has a negative charge due to which it
acts a better nucleophile, R – CN (cyanide) is the major product, but silver salts have more covalent
in nature. So carbon is bonded to silver atom and lone pair of nitrogen is free. Nitrogen atom having
unbonded lone pair act as a better nucelophile, thus R – NC (Iso cyanide) will be the major product.
(iii) Halogen Exchange:
(a) Finkelstein reaction:
Acetone
R – Cl or R – Br + KI 
SN 2
 R – I + KCl or KBr

Best method for the preparation of Iodo alkenes

(b) Swartz reaction:
DMSO
2CH3Cl + HgF2 
SN 2 2CH3 – F + HgCl2

(c) Borodine Hundiecker Reaction:

CCl
R – COOAg + Br2 
4
 R – Br + CO 2 (  ) + AgBr(  )
Silver salt of carboxylic acid is heated with Br2 by which formation of alkyl bromide take
place. It follows free radical mechanism.
Reactivity order: 1º (R – X) > 2º (R – X) > 3º (R – X)
(iv) Williamson's synthesis:
R – X + Na – O – R  R – O – R + NaX [SN2 Reaction]
Note: 3º R–X favours the elimination reaction.
Mechanism : [SN2 Reaction]

C2H5 O Na  C2 H5 O + Na

H H H H
C2H5O
Slow
C I 
Fast
 C2H5 O C I   C2H5 – O – CH3 + I
H H

Na   I  NaI
(191)
 Alkyl Halide & Aryl Halide
Ex. (i) CH3—CH2—Cl + NaOCH3  CH3—CH2—O—CH3
(ii) CH3 CH CH3 + NaOCH3  CH3 CH CH3
Cl O CH3 (or elimination product)

CH3
(iii) CH3 C CH3 + NaOCH3  CH3 C CH2 + NaCl + CH3OH
Cl CH3
(3º R – X) (Major Product)
(v) Reaction with Dry Ag2O:

2RX + Ag2O   R – O – R + 2AgX

Ex. 2CH3 – CH2 – Cl + Ag2O   CH3CH2OCH2CH3 + 2AgCl
(vi) Reaction with NH3:
Δ
Ex. (a) R – X + NH 3   R – NH 2 + H – X

R
Δ
(b) R – X + NH 3 
 R N R X
(excess)
R
Δ R—X R—X
(c) R – X + NH3 
 R – NH 2   R– NH – R   R N R
R
R X

R
R N R X
R

(d) CH3 – CH2 – Cl + NH3  CH3 – CH2 – NH2 + HCl

(e) CH3 CH CH3 + NH3  CH3 CH CH3 + HCl
Cl NH2 (or elimination product)

CH3 CH2
(f)  CH3 C Cl + NH3  CH3 C + NH4Cl
CH3 CH3
(more reactive) (Elimination is more)

6.5 SN1 REACTION OF ALCOHOLS

6.5.1 Reaction with hydrogen halides:
H–X
Eg. R – CH2 – OH 
ZnCl2
 RCH2 – X

H+  –
X
Mechanism : R CH2 OH (H – X) R CH2 O H 
 H 2O
 R  CH 2  R – CH2– X
H
(Unstable) (Product)
(192)
 JEE
SN1 in case of 2° and 3° alcohol, SN2 in case of 1° alcohol.
Reactivity order for alcohol: Reactivity  stability of carbocation ,
So reactivity order : Tertiary Alcohol > Secondary Alcohol > Primary Alcohol
Reactivity order of H – X is : HI > HBr > HCl
HI is maximum reactive so it reacts readily with 1°, 2° and 3° alcohols.
R – OH + HI  R – I + H2O
HCl and also 1° alcohol are less reactive so ZnCl2 or some amount of H2SO4 is needed to increase
the reactivity.
ZnCl2
Ex. CH3 – CH2 – OH + HCl   CH3 – CH2 – Cl
At normal condition :
CH3 – CH2 – OH + HCl  (no reaction)
Note: HCl + ZnCl2 is called as Lucas reagent, alcohol gives turbidity with lucas reagent.
 Reactivity towards lucas reagent (difference in 1°, 2° and 3° alcohol).

Degreeof Alcohol Time to give turbidity

1º alcohol 30min .
2º alcohol 5-7 min.
3º alcohol Instant

6.6 SN2 REACTION OF ALCOHOL

6.6.1 By the action of phosphorus halides:
R—OH + PCl5 R—Cl + POCl3 + HCl
3R—OH + PCl3  3RCl + H3PO3
PBr3 and PI3 are less stable, thus for bromides and Iodides, (P + Br2) Or (P + I2) mixture is used.
H3 C H H3C Cl
PCl5
 
H OH H H
6.6.2 By reaction with thionyl chloride in presence of pyridine:
R  OH  SOCl 2 
Pyridie
(1 mole)
 R  Cl  SO 2  HCl
One mole One mole

In presence of base such as pyridine the reaction proceeds by SN2 mechanism and involve inversion
of configuration at the substrate center.

H O H O
C2 H5 N
CH3 C OH + Cl S Cl  CH3 C O S Cl
C2 H5 C2 H5 H

H O
CH3 C O S Cl
C2H5
+
+ C5 H5 NHCl

(193)
 Alkyl Halide & Aryl Halide

H O H
CH 3 C O S Cl 
 Cl C CH3 SN 2
Cl inversion

C2H 5 C2 H5

CH3 CH3
Ex. H OH  Cl
SOCl2
Py
H
C2H5 C2H5

6.7 SNi REACTION OF ALCOHOL

(Darzen's procedure):
R  OH  SOCl2 
 R  Cl  SO 2  HCl
One mole One mole

Mechanism: This is the best method to convert an alcohol into R-Cl.

(i) In the absence of a base: The reaction proceed by SNi Mechanism (internal nucleophilic
substitution) and involves retention of configuration at substrate centre.
 It is the best method to prepare chloroalkane as side product SO2 & HCl are gases. So there is
no need to purify the product.

H O H O
CH3 C OH + Cl S Cl 
 CH3 C O S Cl + Cl–
C2H5 C2H5 H

H H
CH3 C Cl + SO2  
 CH3 C O
S O
C2 H5 C2H5
Cl
H OH H Cl
SOCl2
C O C
Ex. CH3(CH2)4CH2 CH3 CH3(CH2)4CH2 CH3
O

CH3 CH3
Ex. H OH 
SOCl2
H Cl
C2H5 C2H5

6.8 NUCLEOPHILIC SUBSTITUTION REACTION OF ETHERS

6.8.1 Reaction with HX:
 Ethers are unreactive towards most bases, but they can react under acidic conditions.
 A protonated ether can undergo substitution or elimination with the expulsion of an alcohol.
 Ethers react with conc. HBr and HI because these reagents are sufficiently acidic to
protonate the ether, while bromide iodide are good nucleophiles for the substitution.
 Reactivity of HX HI > HBr > HCl
Ethers forms oxonium salt with cold and conc. HCl (less reactive)
Cold conc. HI and HBr (more reactive) break C–O bond.
(194)
JEE

  
 If oxonium ion gives more stable carbocation [ PhCH 2 , CH2= CH – CH 2 , (CH 3 )3C ] then SN1
reaction occurs.

 If oxonium ion gives less stable carbocation [ CH 3CH 2 ] then SN2 reaction occurs, and X 
attacks at less hindered carbon.
 If excess of HI is used then two moles of alkyl halides are formed.
HI
CH3CH2 – O – CH2Ph   CH3CH2OH + PhCH2I 
HI
 S 1
CH3CH 2 – I + PhCH 2 – I
N

Mechanism:


 –
 R'   R' – X
H X
R – O – R'  R O R' 
 ROH

Ex. HCl
(CH3)3COC(CH3)3   (CH3)3COC(CH3)3
SN 1
H

(CH3)3C – O – C(CH3)3  
 (CH3 )3 C + (CH3)3COH
H

(CH3)3C + Cl 
 (CH3)3CCl

H H
OH
HBr
Ex. O  
SN 2
H
H Br
1,2-Epoxycyclohexane trans-2-bromo cyclohexanol

H3C CH3 OCH3

CH3OH
Ex. C C 
 CH3 CH C CH3
H 2SO4
H O CH3 SN 2 HO CH3
2,2,3-trimethyl oxirane 3-methoxy-3-methyl-2-butanol
MID LEARNING EXERCISE (MLE)-36
Br DMF
Q.1 + KF   ? Product is

F
F
(A) (B)

(C) (D) No reaction will occur

F
(195)
 Alkyl Halide & Aryl Halide
OH
SOCl2
Q.2   Product of above reaction is

Cl Cl

(A) (B) (C) (D) None of these

OH
SOCl 2
Q.3 
Pyridine
 ; Product of above reaction is

Cl Cl

(A) (B) (C) (D) None of these

Br
Q.4 CH3 – COOAg 2
CCl4
 ; Product of above reaction is

(A) CH3CH2Br (B) CH3Br (C) CH3COOBr (D) CH 3COOH

Q.5 Which of the following can not give alkyl halide on reaction with ethanol ?
(A) PCl 3 (B) PCl 5 (C) SOCl2 (D) NaCl
Q.6 Propane  2-Iodopropane; Best reagent for above conversion is :
(A) I 2 / h (B) NaI / acetone
(C) F2 / h, NaI / acetone (D) Br2 / h, NaI / acetone
Q.7 Among the following correctly matched option is:
(A) MeCl + KCN  MeNC (B) MeCl + AgCN  MeCN
(Major) (Major)

(C) MeCl + Ag2O  Me–OH (D) MeCl + AgNO2  Me–O–N=O

(Dry)
Q.8 Which of the following reaction doesn't involve formation of alkyl halide :
(A) Swartz reaction (B) Grooves process / Lucas test
(C) Finkelstein's reaction (D) Williamson's synthesis
O O Et
Q.9 
xHI
How many (x) moles of HI consumed ?
O O Et
(A) 1 (B) 2 (C) 3 (D) 4
Q.10 Mark the correct increasing order of reactivity of the following compounds with HBr
CH2OH CH2OH CH2OH

NO2 Cl
(a) (b) (c)
(A) a < b < c (B) b < a < c (C) b < c < a (D) c < b < a
Q.11 Treatment of ammonia with excess ethyl chloride will give:
(A) Diethylamine (B) Ethane
(C) Methylamine (D) Tetraethyl ammonium chloride
(196)
 JEE

Q.12 In the reaction CH3CHCl2 

aq. KOH
 X. X is:
(A) CH3CH2OH (B) (CH3)2CO (C) CH2 CH2 (D) CH3CHO
OH OH
Q.13 Organic product is not obtained in reaction -
Br ONa

(A) + CH3ONa 
 (B) + CH3–Br 


NO2

(C) O CH3 + HI 
 (D) O–CH2 + HI 

18
Q.14 Which of the following cannot be prepared by using Williamson’s synthesis ?
(A) Methoxybenzene (B) Benzyl-p-nitro phenyl ether
(C) Methyl tert. butyl ether (D) di-tert. butyl ether
Δ
Q.15 The reaction products of : C6 H5OCH 3 + HI   is :
(A) C6H5OH + CH3I (B) C6H5I + CH3OH (C) C6H5CH3 + HOI (D) C6H6 + CH3OI
Q.16 Reactivity towards KCN :
(I) Benzyl chloride (II) Chlorobenzene (III) Ethyl chloride
(A) I > II > III (B) III > II > I (C) I > III > II (D) III > I > II
Q.17 In Finkelstein Reaction, which reactants are used:
(A) NaI + C2H5OH (B) NaCl + acetone
(C) NaBr + CH3COCH3 (D) NaI + CH3COCH3

Q.18 C2H5Cl + AgF   C2H5F + AgCl

The above reaction is called:
(A) Hunsdiecker (B) Swartz (C) Strecker (D) Wurtz
Q.19 Action of sodium ethoxide on an alkyliodide is
(A) A nucleophillic addition (B) An electrophillic addition
(C) A nucleophillic substitution (D) An electrophillic subsititution
6.9 BIMOLECULAR NUCLEOPHILIC SUBSTITUTION IN AROMATIC COMPOUND
(SN2 Ar) REACTION
 C–X bond in aryl halide is stable due to delocalisation of electrons by resonance. Also (C–X)
bond possesses a double bond character like vinyl chloride and is stronger than C–X bond in
alkyl halide.

(197)
 Alkyl Halide & Aryl Halide
Hence, SN reaction is not possible in benzene nucleus under ordinary conditions. However, under
high temperature and pressure, SN reaction is made possible.

X Nu
X Nu
G + Nu 
G G
(Formation of carbanion as an Intermediate)
G withdraws electrons : stabilizes carbanion, activates

(– N (CH3)3, –NO2, –CN, –SO3H, –COOH, –CHO, –COR, –X)
(ii) A group that releases electrons tends to intensify the negative charge, destabilizes the carbanion,
and thus slows down reaction.
X

G G releases electrons : destabilizes carbanion, deactivates

(–NH2, –OH, –OR, –R)

 Orientiation in nucleophilic aromatic substitution:
(i) At para position:

Nu X Nu X Nu X

NO2 NO2 NO2

I II III
(Especially stable:) charge on carbon bearing substituent)

(ii) At meta position:

Nu X Nu X Nu X

NO2 NO2 NO2

I II III

(iii) At ortho position:

Nu X Nu X Nu X
NO2 NO2 NO2

I II III
(Especially stable: charge on carbon bearing substituent)

Note: If electron withdrawing group in present at ortho and para position it especially activates the
aromatic nucleophilic substitution reaction.
(198)
JEE

MID LEARNING EXERCISE (MLE)-37

Q.1 Give correct order of reactivity towards nucleophilic aromatic substitution.
F Cl Br I
NO2 NO2 NO2 NO2
(1) (2) (3) (4)

(A) 4 > 3 > 2 > 1 (B) 1 > 2 > 3 > 4 (C) 2 > 3 > 1 > 4 (D) 1 > 4 > 3 > 2

Cl
Cl
NaOH
Q.2   Product of above reaction is:

NO2

OH Cl Cl OH
Cl OH Cl Cl
(A) (B) (C) (D)

NO2 NO2 OH OH
Q.3 Which of the following is most reactive towards nucleophilic aromatic substitution.

Cl Cl Cl Cl
NO 2 NO2
(A) (B) (C) (D)
NO2
NO 2 NO2
Q.4 Replacement of Cl of chlorobenzene to give phenol requires drastic conditions but chlorine of 2, 4-
dinitrochlorobenzene is readily replaced because :
(A) NO2 makes the electron rich ring at ortho and para positions.
(B) NO2 withdraws electrons at meta position
(C) NO2 donate electrons at m–position.
(D) NO2 withdraws electrons at ortho and para positions.
Q.5 Aryl halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halides
due to:
(A) The formation of less stable carbonium ion
(B) Resonance stabilization
(C) Longer carbon–halogen bond
(D) The inductive effect
Q.6 Identify the principal organic product of the following reaction.
F
+ NaSCH3  Product
O2N Br

F SCH3 CH3S F F
(A) (B) (C) (D)
CH3S Br O2N Br O2 N Br O2 N SCH3

(199)
 Alkyl Halide & Aryl Halide
Q.7 Rank the following in order of decreasing rate of reaction with alkoxide ion (CH3CH2O–) in a
nucleophilic aromatic substitution reaction :

Br Br Br Br
NO2 NO2

NO2
NO2
NO2 NO2
1 2 3 4

(A) 3 > 4 > 1 > 2 (B) 3 > 4 > 2 > l (C) 2 > l > 4 > 3 (D) 4 > 3 > 2 > l
Q.8 The major product of the following reaction is-

Me Br

F  
Ph S Na
dimethylformamide


NO2

Me SPh Me Br Me SPh
Me SPh
F SPh SPh
F
(A) (B) (C) (D)

NO2 NO2 NO2

NO2
X OCH3

Q.9 
CH3O Na –

NO2 NO2
Above reaction is an example of Nucleophilic aromatic substitution. Which of the following halide
(–X) is most readily replaced.
(A) –F (B) –CI (C) –Br (D) –I
Me

Q.10 
NaSH
 A; Product (A) of the reaction is:

Cl

SH CH2 SH SH

(A) (B) No reaction (C) (D)

CH3 Cl Cl

(200)
 JEE
Q.11 In which case SN2Ar reaction is fastest ?

Cl Cl Br Cl
NO2 NO2
(A) (B) (C) (D)

NO2 NO2 NO2

NO2

EtONa
Q.12 
 The product is:
(1 mol),Δ
Cl
Cl

NO2 NO2 NO2 NO2

Cl
(A) (B) (C) (D)
Cl EtO Cl OEt
OEt OEt Cl Cl
Q.13 Among the following which one will undergo the fastest ArSN reaction ?

Cl Cl Cl Cl

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

Me Me NO2
NO2 NO2 NH2

CN

(CH ) NH
Q.14 
3 2
 The product is:
Cu 2O, Δ

NMe2 CN CN NMe2
NMe2
(A) (B) (C) (D)

NMe2 NMe2 F F

(201)
 Alkyl Halide & Aryl Halide

Q.15 The product of the reaction is ROK 




H3C
NO2
OR F F F
OR
(A) (B) (C) (D)
CH3 OR CH3 H3 C
NO2 NO2 OR NO2
Q.16 The final product of the following reaction is:
NO2

O2 N X+ H N 



NO2

O2N N

(A) N (B) O2N X

NO2

NO2 NO2

(C) (D) O2N N X

N X
H

I

Q.17 I– + CH3ONa  
O2N

I
OCH3
I
(A) + (B) O–CH3
O2N
O2N

(202)
 JEE

OCH3
I
(C) I (D)
O2N OCH3
O2N

Q.18 Find the major product of the following reaction:

CH2 —Br
KSH

Br

CH2 —Br CH2 —SH CH2 —SH

(A) (B) S (C) (D)
SH SH Br

6.10 NEIGHBOURING GROUP PARTICIPATION (NGP) & ANCHIMERIC ASSISTANCE

Substitution with Retention of Configuration (Outlines of Neighbouring Group Participation) and
Anchimeric Assistance
The neighboring group effect involves essentially two SN2 substitutions, each causing inversion, the
net result being retention of configuration. In the first step the neighboring group Z acting as a
nucleophile pushes out the leaving group but still retains attachment to the molecule. In the subsequent
step the external nucleophile pushes out the neighboring group.

R R R R
Z R Step 1 + R –; + R
 Z +L Z 
Step 2
Z R
R L R R Nu R Nu
R R R R
Often when the neighbouring group effect is operative, one may not get the substitution product but
a rearrangement.

CH3
CH3 CH3
Z CH
+
Z
CH Nu –  H C Nu
H3C C L 
 
C CH3 Z C CH3
CH3
CH3 CH3

Et
+ OH 
Et2N CHEt Cl   Cl
 Et2 N CHEt 
 Et2 N
slow
OH
(I) (II)
(III)
In such cases both substitution and rearrangement occur
It is also possible that the intermediate formed after neighbouring group participation may stabilize in
some other way Examples are formation of an epoxide and a -lactone.
(203)
 Alkyl Halide & Aryl Halide

H
OH O+ O Br O H3C
C C 
 C C 
 C C +H + 

H 2O

CH3 O–  Br 
O
O
X

In some cases (usually in solvolysis reactions), a neighbouring group may not actually migrate, but
plays a part in the expulsion of the leaving group in the rate-determining step. The departing group is
then said to have received anchimeric assistance from the neighbouring group.

R S R R S R S
CH 2 CH 2  Cl

 S+ 
 H 2O CH2 CH2  H

 CH2 CH2
slow fast fast
Cl H2C CH2 OH2 OH
-chloro-sulphide
Consider the reaction of 2-bromopropanoic acid, with a concentrated solution of a strong nucleophile
like hydroxide ions. The anion of this acid reacts by a normal SN2 with inversion of configuration .
Significantly when a weak nculeophile like silver oxide is used 2-bromopropionic acid, on the other
hand, is hydrolysed with retention of configuration.
O O
OH OH
H3C 
 H3 C
Br OH
2-bromopropanoic acid Lactic acid
(i) Strong Nucleophile taken viz. OH–

CO2– CO2– CO2–

– –
d d
H C Br
HO– + S 2

N
 HO C Br 
 HO C
H
CH3 H CH3 CH3
(S)-2-bromopropanoate ion
(R)-lactate ion
Inversion of configuration
(ii) Weak Nucleophile taken viz. silver oxide:

O
– O
C O
d– C O
C O C
H Br 
NGPS
 
 O + AgBr
+ C d– C
CH3 Ag H Br
A CH3 Ag+ H H3C
Optically active a-Lactone (cannot be isolated)
...(i)

(204)
JEE

O O CO2
C – C
O OH2 O
C C

 d+  H
C OH
OH2 CH3
H H3C H CH
3 B
Optically active lactate anion 100% retention ...(ii)
The deamination of optically active alanine with nitrous acid yielded optically active lactic acid with
retention of configuration. This is due to neighbouring group participation of the -carboxylate anion.

CO2 O O H

H NH2 
HNO2
O
H O

2
H OH
CH3 CH3
CH3
D(-)alanine D(-)lactic acid

(iii) NGP of lone pair:

SR R SR
S
CH3 N3 CH 3 CH3 H
H NaN 3/DMF CH 3 H H SR
CH3 CH3
H CH3 H
N3
Br H N3 CH3 H
(d + )
If intermediate contains Racemic mixture
POS it will enantiomers
SR R
SR
S
 H
H H
CH3 CH 3 NaN 3/DMF N3 CH 3
CH3 CH 3
H CH3 H
Br H
N3
If intermediate contains axis of (Single product)
symmetry if will give single product

(iv) NGP of Phenyl ring:

CH 3 CH 3 CH 3
NaN 3/DMSO
+
OTs N3 N3
CH 3 CH 3 (d + ) CH3
Racemic mixture (Enantiomer)

N3


H 3C CH 3
(Intermediate stable by Resonance)
(Intermediate contains plane of symmetry)

(205)
 Alkyl Halide & Aryl Halide

CH 3 NaN3 /DMSO CH3

OTs N3 (Single product)

CH 3 CH 3


N3


H3 C CH3

(Intermediate contains axis of symmetry)

(v) Effect of Neighboring Groups Containing Oxygen Atom (Hydroxyl or Alkoxyl Groups):
H H
O Cl O
 Cl
O+ H 
  
fast

slow
I (II)

Me
Me Me
O OBs
 Cl
O+ AcOH
O OAc
  
fast

slow
(III)
Illustration 4. Identify A and B in the following reactions:

base
(a)  A
OH Br

(b) Br 
CH3CH2 OH
 B (SN1 product)

Solution: (a)
O
O CH3
(b)

Illustration 5. A student prepared a pure sample of 1-chloro-2-(dimethylamino) propane. After standing

for several weeks in a sealed container he opened it and found it was mostly 2-chloro-1-
(dimethylamino) propane. Resolve the students' dilemma and explain what has happened.
Cl CH3
Cl–
Solution: CH3 CH CH2 Cl 
 Cl
 CH3 CH CH2 CH3 CH CH2 N
+ CH3
N N
H3C CH3 H3 C CH3

(206)
JEE

MID LEARNING EXERCISE (MLE)-38

O Conc. NaOH
(P)
Q.1 SN2
OH
NaOH/AgNO3
Br (Q)
SNGP

O O O O

OH OH OH OH
(A) , (B) ,
OH OH OH OH
(P) (Q) (P) (Q)
O O O O

OH OH OH OH
, ,
(C) OH OH (D)
OH OH
(P) (Q) (P) (Q)

H SR
Q.2 Aq.NaOH


Br H

OH SR H SR SR H
(A) ; (single product) (B) + ; (Enantiomers)
H H OH H H OH

H SR OH SR SR OH
(C) ; (single product) (D) + ; (Enantiomers)
OH H H H H H
Q.3 The relative rate of solvolysis of following iodides are:
I I I
O

(x) (y) (z)

(A) (x) > (y) > (z) (B) (y) > (x) > (z) (C) (x) > (z) > (y) (D) (z) > (x) > (y)
Q.4 Compare the rate of hydrolysis:

TsO H TsO H

(a) (b)
(A) a > b (B) a < b (C) a = b (D) Can't determined
(207)
 Alkyl Halide & Aryl Halide

CH3
Q.5 H2N H 
NaI/Acetone
 Product :
H Cl

CH3

CH3 CH3
H2N H CH3 NH 2 CH3 CH3
HN H C C C
(A) 2 (B) C
H I I H (C) H (D)
H NH2
CH3
CH3 CH3

14
Q.6 For the reaction: H2C CH CH2 Cl + CH3O– 
CH3OH
 (A) major product (A) is:
O

14 14
(A) H2C CHCH2 OCH3 (B) CH3 O CH2 CH CH2
O O
OCH3
14
(C) CH3O CH2CH CH2Cl (D) HO CH2CH·CH 2 OCH3
OH
Q.7 Major products of the following reaction in its most stable form is:
OTs
ACOH
 P
OAc

OAc OAc OAc

(A) (B) (C) (D) All of the above
OAc OAc OAc
(d+l)
O S
Br B
Q. 8
CH3
OH
O
Br
(A) S (B) S
CH3 CH3
O

(C) S (D) None of the above

CH3
(208)
 JEE
Q.9 In the given reaction:
 * HOH
CH 3  CH 2  S  CH 2  CH 2  Br  [X]
[X] will be:
* *
(A) CH 3  CH 2  S  CH 2  CH 2  OH (B) CH 3  CH 2  S  CH 2  CH 2  OH
(C) 1 : 1 mixture of (A) and (B) (D) 2 : 1 mixture of (A) and (B)
Br2
Q.10 CH2=CH–CH2–CH2–CH2–CH2–SH 
CCl4
?

Major product of this reaction is:

(A) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
Br

(B) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
CCl 3

(C) Br2  CH 2  CH  CH 2  CH 2  CH 2  CH 2  SH
|
Cl

(D)
Q.11 Find the final product of the reaction:
OTs CH COOH
1. 14 
3
CH COONa

3

2. Cl H2O
S  
D D
3. Cl 
2 H O

H
OH 
4. Me COONa 
H O

2

Br

COONa
NaNO 2
5. 
HCl

NH2

OH
83
6. HBr

Br

(209)
 Alkyl Halide & Aryl Halide
 Elimination versus substitution:
The table below summarizes the general pattern of reactivity expected from various structural
classes of alkyl halides (or tosylates, mesylates) in reaction with a representative range of nucleophiles
(which may behave as bases).
Strongly basic Strongly basic,
Weakly basic
Poor nucleophile unhindered hindered
nucleophile
(e.g., H2O, ROH) nucleophile nucleophile
(e.g., I–, RS–)
(e.g., I–, RS–) (e.g. DBU, t-BuO–)

Methyl H3C – X no reaction SN2 SN2 SN2

primary X no reaction
SN2 E2 E2
(hindered)

primary X no reaction
SN2 E2 E2
(hindered)

Secondary X SN1, E1 SN2 E2 E2

(slow)

X SN1 E1 or SN1 E2 E2
Tertiary
O X
 E1cB E1cB E1cB
 to anion  E1cB
stabilizing group

MID LEARNING EXERCISE (MLE)-39

Q.1 Select option in which correct major product is shown
H D
D

(A) 
conc. H 3 PO 4

 (B) 

 + AcOH
OH
OAc H
Me
H Br
(C) Ph  CH 2 CH  CH3 
OH –
 Ph  CH  CH  Me (D) 
Br2
CCl4
 H Br

| Me

NEt 3
Q.2 Base / + 1-butene is obtained as a major product when.
G 1-butene 2-butene
+
(A) G is –F (B) G is –NR3
CH3
(C) When base is CH3 – C – OK (D) All of the above
CH 3

(210)
JEE

CH3

Q.3 + OH —   Olefinic product., Identify major product
NMe3

Et Et

(A) (B) (C) (D) None of these

Q.4 Select INCORRECT statement-

(A) 2-Chlorobutane give more saytzeff product on reaction with Alc. KOH
(B) 2-Flourobutane give more Hoffmann product on reaction with Alc. KOH
(C) 2-Chlorobutane give more Hoffmann product on reaction with tBuOK
(D) Alc. KOH preferably gives substitution reaction with 2-bromobutane.

Me SOCl2
P1
Q.5 Select the correct product from the following H OH
PCl3
P2
P1 and P2 are respectively: D

Me Me Me Me
(A) H Cl & H Cl (B) Cl H & Cl H

D D D D

Me Me Me Me
(C) H Cl & Cl H (D) Cl H&H Cl
D D D D
Q.6 Match the column-I and column-II and select the correct answer:
Column-I Column-II
Cl
aq. KOH
(i) (P) E1

Cl
alc. KOH
(ii) (Q) SN1

Cl
H2O
(iii) (R) SN2

OH

H /
(iv) (S) E2

(A) i-S, ii-R, iii-P, iv-Q (B) i-R, ii-S, iii-Q, iv-P
(C) i-R, ii-P, iii-Q, iv-S (D) i-Q, ii-S, iii-R, iv-P
(211)
 Alkyl Halide & Aryl Halide
Q.7 Give the correct order of initials T or F for following statements. Use T if statement is true and F if
it is false.
(a) SOCl2, PCl3 and HCl/ZnCl2 all converts an alcohol into alkyl halide.
(b) Mechanism of all the three reagent are identical
(c) Mechanism for SOCl2 and PCl3 are identical but different mechanism is followed in case of HCl
(A) TTT (B) TTF (C) TFT (D) TFF
Q.8 Select reaction with incorrect major product:
(A) Me  Br 
AgCN
 MeCN
(B) Me  Br 
AgNO2
 Me  NO2

(C) CH 3CH 2  Cl 

alc. KOH
 CH 2  CH 2

(D) CH 3CH 2 CH  CH 3   CH3CH 2 CH  CH 2
|

NMe3O 

C H OH
Q.9 Predict the major product expected in given reaction 2-Bromo-1, 1-dimethylcycopentane 
2 5


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

Q.10 R1 R2 
alc. KOH
 Alkene The Alkene formed is mainly

H R3
R4

R1 R R1 R R1 R R1 R2
(A) C C R2 (B) C C R3 (C) C C R4 (D) C C
R4
R4 3 R2 4
R2 3 R3
Q.11 Which compound should gives white turbidity immediately on reaction with Luca's reagent?
OH

(A) (B)
OH

OH CH 3
|
(C) CH (D) H 3C  C  CH 2  CH 2  OH
|
CH 3
Q.12 When ethyl bromide is treated with dry Ag2O, main product is:
(A) Ethyl methyl ether (B) Ethanol
(C) Ethoxy ethane (D) All of the above

(212)
JEE

CH3

Q.13 C NaI
 / acetone
 P, P is
H
F
D

CH3 CH3 CH3

C C
(A) I (B) (C) No reaction (D) C + en
H H I I
D D H
D

Q.14 Find the product of the following reaction:

Br
CH OH

3


OCH3
(A) (B) (C) (D)
OCH3
Q.15 Find the major product of the following reaction:

HO

2

Δ
I

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

OH
Q.16 Find the major product of the following reaction:

Br
C H OH

2 5


OC2 H5 OC2H5

(A) (B) (C) OC2H5 (D)

OC2H5
Q.17 The product of the reaction

CH2CH2Br   P
Alc.KOH

P is:

(A) OH (B) CH2–CH2OH

O
(C) (D) CH=CH2

(213)
 Alkyl Halide & Aryl Halide

6.11 METHODS OF PREPARATION

X2 / h
R–H
HX
Alkene
HBr/Peroxide
Alkene
Cl – N = O
R – NH2 (Tilden reagent)
R–X
Darzen reaction
R – OH SOCl2 / Pyridine
PCl 3 or PCl5
R – OH
HI or HBr or
R – OH NaBr + H 2 SO4
HCl + ZnCl 2
R – OH (Lucas reagent)
Br 2 / CCl 4
R – C – OAg Hunsdiecker reaction
O

6.11.1 General Methods of Preparation Aryl halides:

Fe
C6 H 6  Cl 2   C6 H5Cl  HCl
Fe
C6 H 6 Cl  Cl 2   C6 H5Cl2  HCl
Chlorobenzene o-and p-Dichlorobenzene

CH3 CH3 CH3

Cl
Fe
+ Cl2   +

Cl
Mixture of o- and p-chlorotoluene

(214)
 JEE
Cl
CuCl/HCl
Heat (Sandmeyer reaction)
Chlorobenzene

Br
CuBr/HBr
N2+ Cl– Heat (Sandmeyer reaction)
Bromobenzene
I
Benzene
diazonium KI
chloride Heat (Sandmeyer reaction)
Iodobenzene
F
NaBF4
Heat (Balz-schiemann reaction)
Fluorobenzene
Cl
Cu, HCl (Gattermann reaction)

Chlorobenzene
Br
Cu, HBr (Gattermann reaction)

Bromobenzene
O
Br
O–Ag+ + Br2  + AgBr + CO2 (Borodine Hundiecker Reaction)

BrC6 H5 COONa  NaOH 

 C6 H 5 Br  Na 2 CO3
6.11.2 Physical Properties of Alkyl Halides:
(i) Alkyl halides are colourless with sweet smell or pleasant smell oily liquid, whereas CH3F, CH3Cl,
CH3Br, CH3CH2F, CH3CH2Cl are gaseous in nature.
(ii) Although carbon-halogen bond is polar in nature therefore alkyl halides are partial soluble in
H 2 O.
(iii) These are completely soluble in organic solvents.
molecular weight
(iv) Boiling point  No. of Branches

 Order of boiling point:

(a) CH3I > CH3Br > CH3Cl > CH3F
(b) CH3CH2CH2Cl > CH3CH2Cl > CH3Cl
(215)
 Alkyl Halide & Aryl Halide

CH3
(c) CH3CH2CH2CH2 – Cl > CH3 CH CH2 CH3 > CH3 C CH3
Cl Cl
Cl
(d) CH2 CH2 CH CH3 > CH3 CH CH2 > CH3 C CH3
Cl Cl Cl Cl Cl
 Very Important Order:
Cl
Cl Cl
Cl

Cl Cl
b.p./K 453 446 448
m.p./K 256 249 323
(a) Chloroform is colourless and pleasant smelling liquid while iodoform is yellow crystaline solid.
(b) Chloroform is used as an anaesthatic agent
(c) Iodoform is more reactive than chloroform due to large size of iodine atom.
CHI3 + AgNO3  AgI (Yellow ppt)
CHCl3 + AgNO3  No white ppt of AgCl
(d) Carbon tetrachloride is colourless liquid and used as FIRE EXTINGUISHER under the trade
name PYRENE.
(e) Chloroform is kept in dark coloured bottles to avoid following oxidation.
CHCl3  [O]
air and light
 COCl2 (Phosgene) + HCl
(Poisonous)

 Test of chloroform (Before Anaesthatic Use):

S. No. Test Pure CHCl3 [COCl2 + HCl]

(i) Litmus paper Blue  Blue Blue  Red

(ii) AgNO3 No ppt. White ppt. (AgCl)

(iii) H2SO4 No Colouration Yellow colour

 Fluorides and Chlorides are lighter than water whereas bromides and iodides are heavier than
H2O due to more density of bromine than oxygen. CH2I2 is heavier liquid after Hg.
 All haloalkanes burn on copper wire with green flame (BELESTEIN TEST for halogens)
MID LEARNING EXERCISE (MLE)-40
Q.1 Finkelstein reaction is:

(A) 2CH3CH2Cl+ Ag2O (dry) 

 CH3CH2OCH2CH3+ 2AgCl
Acetone
(B) CH3CH2Br + NaI   CH3CH2I+ NaBr

(C) CH3CH2Br + Ag2O (moist) 

 CH3CH2OH + AgBr

(D) CH3CH2Cl + NaOCH3 

 CH3CH2OCH3 + NaCl
(216)
JEE

ZnX
Q.2 In reaction C2H5OH + HX 
2  C H X + H O the order of reactivity of HX is
2 5 2

(A) HBr > HI > HCl (B) HI > HCl > HBr
(C) HCl > HBr > HI (D) HI > HBr > HCl
Q.3 Which of the following leads to the formation of an alkyl halide:
Red P  Br SOCl
(A) C2H5OH 
2
 (B) C2H5OH 
2

KBr  Conc. H2SO4

(C) C2H5OH   (D) All
Q.4 The reaction of silver carboxylates with bromine dissolved in carbon tetrachloride is called -
(A) Hofmann reaction (B) Borodine reaction
(C) Borodine-Hunsdiecker reaction (D) Hypobromide reaction
Q.5 Silver benzoate reacts with bromine in acetone to form:

Br COBr COOAg

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

Br

Q.6 Which of the following statement is correct:

(A) Decreasing order of density of alkyl halides is RI > RBr > RCI > RF
(B) The stability order of alkyl halides is RF > RCl > RBr >RI
(C) Among isomeric alkyl halides the decrease in boiling point 1º > 2º > 3º
(D) All are correct
Q.7 An alkyl halide is insoluble in water because-
(A) Alkyl halide is non polar & H2O is polar
(B) Both are polar
(C) Alkyl halide does not form hydrogen bond with water
(D) Alkyl halide has halogen atom in it.
Q.8 Addition of bromine on propene in the presence of brine yields a mixture of:
(A) CH3CHClCH2Br and CH3CHBrCH2Cl
(B) CH3CHClCH2Br and CH3CHBrCH2Br
(C) CH3CHClCH2Cl and CH3CHBrCH2Br
(D) CH3CHClCH2Cl and CH3CHBrCH2Cl
Q.9 Which of the following will give the Belestein Test
(A) C 2H 5OH (B) C2H5Cl (C) C 2H 6 (D) All
Q.10 Which statement is not true?
(A) Chloroform is colourless and pleasant smelling liquid while iodoform is yellow crystaline solid.
(B) Carbon tetrachloride is colourless liquid and used as Fire Extinguisher under the trade name
Pyrene
(C) Chloroform is kept in dark coloured bottles to avoid the formation of Phosgene gas
(D) Pure Chloroform can give white ppt with AgNO3 solution

(217)
 Alkyl Halide & Aryl Halide

CH3
H OH HBr
Q.11
H Br 
 Product(s)
CH3
Product(s) formed in above reaction is / are
CH3 CH3 CH3
H Br H Br Br H
(A) (B) &
H Br H Br H Br
CH3 CH3 CH3

CH3 CH3 CH3 CH3

H Br H Br Br H H Br
+ en + +
(C) Br H (D) H Br H Br Br H
CH3 CH3 CH3 CH3
Q.12 Consider the reaction.

CH 3
|
CH 2  CH  CH 2  CH  CH  CH 3 Alc  Product Major..
.KOH

|
Cl
The major product is
CH 3 CH 3
| |
(A) CH 2  CH  CH  CH  CH  CH 3 (B) CH 2  CH  CH  CH 2  CH  CH 3

CH 3 CH 2
| ||
(C) CH 2  CH  CH 2  CH  CH  CH 3 (D) CH 2  CH  CH 2  CH 2  C  CH 3

Q.13 R1 Zn
dust



R2 Zn
dust


Compound R1 & R2 respectively.
Me Me Me Me
Br H Br H Br H Br H
(A) , (B) ,
H Br Br H Br H H Br
Me Me Me Me
Me Me Br
Br Br
(C) H Br , Br H (D) ,
Br
Et Et

(218)
 JEE

Br

/
Q.14 EtOH
  

Which statement is correct.

(A) Major product is formed by E2 reaction.
(B) Minor product is formed by E1 reaction.
(C) Major product is formed by dehydrohalogenation by E1 mechanism
(D) Major product is formed by E1CB
Br
Ph H
Q.15 H Br NaI
 / acetone
 P,,
Ph
P is :
Ph Ph Ph Br Ph H Ph H
(A) (B) (C) C=C (D)
H Br H H Ph H H Ph

6.12 GRIGNARD REAGENT

6.12.1 Introduction of Organometallic compounds:
Organometallic compounds are the organic compounds in which a metal atom is directly attached to
carbon atom through covalent bond or ionic bond. For example
 
C  M or C M e.g. R  MgX, R 2 CuLi, R 2 Zn
(Where C is a carbon atom of an organic molecule and M is a metal atom)
If the metal atom is attached to oxygen, nitrogen. sulphur, etc., then such an organic compound is not
regarded as an organometallic compound. The following structural formula do not belong to the
family of organometallic compounds.
RONa (Sodium alkoxide). CH3COONa (Sodium acetate), CH3COOAg (Silver acetate), RSK (Po-
tassium mercaptide) RNHK (N-Alkylpotassamide), (CH3COO)4Pb (Lead tetraacetate), etc.
 Note : It should be noted that (CH3)4Si (Tetramethylsilane, TMS) is also not an organometallic
compound because silicon is a nonmetal.
Most important examples of organometallic compounds are Grignard's reagents. In Grignard's re-
agent, the carbon and magnesium atoms are bonded with each other through polar covalent bond
and magnesium atom is attached to halogen by ionic bond.
 
C  Mg X (Functional part of a Grignard's reagent molecule)
In organometallic compounds, the metal atom can be bonded to carbon atom of a hydrocarbon
radical (Saturated, unsaturated, aliphatic, alicyclic or aromatic) or carbon atom of a heterocyclic
radical. Some examples are given below.
(i) Saturated Aliphatic Grignard's reagent:

(219)
 Alkyl Halide & Aryl Halide
R – MgX (Alkylmagnesium halide)
CH3 – MgI (Methylmagnesium iodide)
(ii) Unsaturated Aliphatic Grignard's reagent
(a) Alkenyl Grignard's reagent
CH2 = CH – CH2 – MgX (Allylmagnesium halide)
(b) Alkynyl Grignard's reagent
CH  C – CH2 – MgX (Propargylmagnesium halide)
(iii) Alicyclic Grignard's reagent:

MgX (Cyclohexylmagnesium halide)

(iv) Aromatic Grignard's reagent:

MgX (Phenylmagnesium halide)

C6H5CH2MgCl (Benzylmagnesium halide)

6.12.2 Preparation:
RX  Mg 
Dry and pure
Ether
 RMgX
Ether is used as a solvent because it is a Lewis base that donates its lone pair of electrons to
electron-deficient magnesium atom, therefore providing stability to the Grignard's reagent by com-
pleting the octet on magnesium atom.

Et Et
R R
Et O Et O
+ Mg  Mg
Et O X Et O X
Et Et
Alkylmagnesium halide
dietherate

 Process : To an etherial solution of alkyl halide Mg metal is added at very low temp. (0 – 5°C).
A vigorous reaction takes place , and a solution of G.R. is obtained. It cannot be evaporated to get it
in solid state. The reaction will be explosive. It is stable only in solution state.
 Reactivity order with respect to X (For preparation of RMgX):
R – X:

R – I > R – Br > R – Cl > R – F

Most
commonly
used

Iodides forms organometallic compounds at the fastest rate.

 Structural stability of G.R:
If the alkyl part has more stable negative charge, then RMgX is more stable. It will be less reactive
e.g. CH3 – CH2 – MgX ; CH2 = CH – MgX ; CH3C  C – MgX
Reactivity order : 1 > 2 > 3
Stability order : 1 < 2 < 3
(220)
 JEE
6.12.3 Reactivity of Grignard Reagent:
It has been found out by estimation that there is 52% ionic character in carbon-magnesium bond of
Grignard's reagent. Therefore, there is a tendency of forming carbanion by heterolysis of this polar
coordinate bond as follows.
  
R M g X 
R :  Mg X
The carbanion (a nucleophile) formed as shown above, attacks the positively, charged electrophilic
centre of other compound. Therefore. It can be said that if a Grignard reagent is regarded as the
substrate, then electrophilic displaces MgX, i.e. electrophilic substitution (SE) reaction takes place.
 

R  MgX 
 R : 
E
 R  E (SE Product)
If Grignard reagent is regarded as the attacking reagent, then the nucleophilic carbanion of Grignard's
reagent will attack the other compound taken as substrate.

R + C = O  R C O

Except X (halogen) all other functional groups must be absent in the alkyl group otherwise. G.R. will
be destroyed by internal reactions. [– NO2, – CN must also be absent]
6.12.4 Reaction with acidic Hydrogen (H):
Compounds having reactive hydrogen or halogen atom give substitution products on reacting with
Grignard's reagent.
Z – H + R – MgX  R – H + Z – MgX
(where Z is an atom or group having high electron attracting capacity)
Z – X + R – MgX  Z – R + MgXX
(Where X and X are halogen atoms)
Both the above are examples of nucleophilic substitution reaction of Z – H and Z – X (not of the
Grignard's reagents).

R–Mg–X + H–OH 
 R–H + Mg(OH)X

R–Mg–X + R–OH 
 R–H + Mg(OR)X

R–MgX + R –COOH 
 R–H + Mg(OOCR )X

R–Mg–X + R  – C  CH 
 R–H + Mg (C  CR )X
In the above reactions Grignard reagent act as a strong base.
 Reactions involving addition on polar  Bond:
Grignard's reagents form adducts by addition on the following types of pi bonds.

C = O, C =S, C = N and C  N , – N = O, S=O

R – MgX + C = O  R C OMgX

Adduct

(221)
 Alkyl Halide & Aryl Halide

 With R C X (Acid halide)

O

R'
R'MgX
R C X 
 R C R'  R'MgX +
 
H 3O
 R C R'
O O OH

 With R C OR'
O

R''
R''MgX +
H3O
R C OR'  R''MgX
 R C R''     R C R'' + R'OMgX
O O OH
+ R'OMgX
 With Epoxides:

R + CH2 CH2  R HOH

CH2 CH2   R CH2 CH2
MgX O Oxirane OMgX OH
1° Alcohol
having two more C
 With Oxygen:
R – MgX + O = O  R – O – O – MgX
R – O – O – MgX + R – MgX  2R – O – MgX
R – O – MgX + HOH  R – O – H + Mg(OH)X
Primary, secondary and tertiary alcohols can be obtained by above reaction.
Phenol is obtained on hydrolysis of the product obtained by reaction of arylmagnesium bromide with
oxygen.
C6H5MgBr + O = O  C6H5O – OMgBr
C6H5O – OMgBr + C6H5MgBr  2C6H5 – OMgBr
C6H5 – OMgBr + H2O  C6H5 – OH + Mg(OH)Br
Other phenols can be prepared by taking any aryl (Ar) group in place of phenyl group.
O=O Ar– MgBr
Ar – MgBr   Ar – O – OMgBr   2Ar – O – MgBr
HOH
Ar – OMgBr  ArOH
 With CO2 (Synthesis of carboxylic acids):
A carboxylic acid is formed on hydrolysis of the adduct formed by passing carbon dioxide in the
ethereal solution of a Grignard's reagent.
HOH
R MgX + O C O  R C OMgX  R C OH
–Mg(OH)X
O O

(222)
JEE
With R – C  N :

R
d– d+ (1) rds H 2O 
R MgX + R C  R' C NMgX 
N 

NH3 +

 Applications:
G.R. is used to prepare alcohols from those alkyl halides / aryl halides which do not give normal SN
reactions
 Di-Grignard Reagent :

Mg/Ether
(i) C – C – C – C – C 
or Na/ether C–C–C–C=C
| |
X X
(1, 2)
Mg/Ether
C
(ii) C – C – C – C – C  C – C – C |
or Na/ether
| | C
X X
(1, 3) CH3
Mg/ Ether No reagent
(iii) C  C  C  C  C  
 C  C  C  C  C 
(long time)

| or Na/ether
| | |
X X (1 eq.) X Mg X

Mg/Ether
(iv) C – C – C – C – C 
or Na/ether
| |
X X
(1, 5)

MID LEARNING EXERCISE (MLE)-41

Q.1 The reaction of 1 mole each of p-hydroxy Toulene and methyl magnesium iodide will give :

CH 3 CH 3 OH CH 3
MgI
(A) CH4 + (B) (C) (D)

OMgI OCH3 CH2MgI OCH3

r
Q.2 (i) + Ph Mg Br 
1
Ph CH2 CH2 OH
O

r2
(ii) + Ph Mg Br  Ph CH2 CH2 CH2 OH
O
(A) r2 > r1 (B) r1 > r2 (C) r1 = r2 (D) r1 = 2r2

(223)
 Alkyl Halide & Aryl Halide
Q.3 How many moles of Grignard reagent will be required by one mole of given compound?
O
SH
HO C – OEt

C – Cl
CH2–CH2 O
Cl

(A) 7 (B) 6 (C) 8 (D) 5

Q.4 The best yield of given product can be obtained by using which set of reactants X and Y respectively:

CH3
Ether
|
X + Y   CH2 – C – CH3
|
CH3
(A) PhLi + Neopentyl chloride
(B) PhMgBr + Neopentyl bromide
(C) t-Bu – MgBr + Benzyl bromide
(D) Benzylchloride + t-Butyl chloride  Na

Q.5 The order of reactivity of alkyl halide in the reaction R – X + Mg  RMgX is :
(A) RI > RBr > RCl (B) RCl > RBr > RI
(C) RBr > RCl > RI (D) RBr > RI > RCl
Q.6 On conversion into Grignard followed by treatment with ethanol, how many alkyl halides (excluding
stereoisomers) would yield 2-methyl butane.
(A) 2 (B) 3 (C) 4 (D) 5
Q.7 How many litres of methane would be produced when 0.595 g of CH3MgBr is treated with excess
of C4H9NH2
(A) 0.8 litre (B) 0.08 litre (C) 0.112 litre (D) 1.12 litre
MgBr OH

Q.8 +  A

O – Ph

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

1 equivalent Mg
Q.9   X 
D2 O
 Y; Y is
ether

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

(224)
 JEE
Q.10 Compounds are shown with the no. of RMgX required for complete reaction, select the incorrect
option:
(A) CH3COOC2H5 1 (B) CH3COCl 2

(C) HOCH2COOC2H5 3 (D) 4

Q.11 What will be the order of reactivity of the following carbonyl compounds with Grignard's reagent?
H H CH3 Me3C
(I) C=O (II) C=O (III) C=O (IV) C=O
H CH3 CH3 Me3C
(A) I > II > III > IV (B) IV > III > II > I
(C) II > I > IV > III (D) III > II > I > IV
Q.12 Consider the following reaction,
OCH2CH3
CH 3CH 2 OH  CH 3CH 2 MgBr  CH3CH 2 H  Mg which of the following
Br
statements is (are) correct?
(A) CH3CH 2 OH  CH3CH 2 H comes from the Grignard reagent.

(B) H in CH 3CH 2 H comes from the Grignard reagent.

(C) H in CH 3CH 2 H comes from ethanol.

(D) H in CH 3CH 2 H comes from the alkyl group of alcohol.

Q.13 Find the product of the following reaction CH 3CH 2 MgBr  HgCl2  ( X );( X ) will be :
(A) (CH 3CH 2 ) 2 Hg (B) CH 3CH3 (C) CH 3CH 2 Cl (D) CH 3CH 2 HgCl

MgCl Cl

Q.14 + (P)

Compound (P) is-

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

Br Mg, THF
Q.15
(2 Mole)
Find the major product:
(A) (B) (C) (D)

(225)
 Alkyl Halide & Aryl Halide
 Chemical reactions of alkyl halides:
(Wurtz reaction) Na/dryether
R – R
(Frank land reaction) Zn/dryether
R – R
Corey-House reaction

(i) Li (ii) CuX (iii) R' – X
R – R'

Reduction
R – H
LiAlH4 or NaBH4 or Ph 3SnH

R – MgX or RLi or RNa or R Zn


2
R–R
or R2CuLi (Organo metallic reagents)

R – CH = CH – MgX
R – CH = CH – R

R – C  C – Na or R – C  C – MgX
R – C  C – R
(Finkelstein reaction) NaI/acetone
R – I
(Swart reaction) AgF/DMSO
R – F
(Williamson reaction) RONa
R – O – R
(Streker reaction) Na SO

2 3
R – SO3 – Na
: :

ROH or dry Ag O
R
: : : :

2
–O–H
: :

H O or aq. NaOH or moist Ag O

R–X R
2 2
– OH
RCOONa or RCOOAg
R – COOR
:

NH
R
:

3
– NH2
:

R – NH
R
:

2
– NH – R
:

R – NH – R R–X  –
R3N  R4N X
:

KCN/(Ionic)
R – C  N

AgCN (covalent)
R – N = C

KO – N = O (Ionic)
R – O – N = O

Ag – O – N = O (covalent)
O
R – N
O
(226)
JEE
 Chemical Properties and preparation methods of Dihalides:

(227)
 Alkyl Halide & Aryl Halide
 Chemical Properties and Preparation methods of Chloroforms:
O
aq. NaOH ||
H – C – ONa (salt)
(excess)
O
|| OH
CH3 – C – CH 3 |
Lab. Method CH3 – C – CH3 Chloretone
(Hypnotic)
CH3 – CH – CH3 |
| (CaOCl2 + H 2O)/
CCl3
OH
Cl
HO – NO 2/D
Ind. Method O2N – C — Cl + H 2O Chloropicrin or
CH3 – CH – H
aq. NaCl/electrolysis Cl (–H2O)
Cl Nitro chloroform
|
(Tear Gas)
OH H – C — Cl
(i) alc. KOH
Cl R – N = C (Ho ffmann's Isocyanide Test)

:
(ii) R – NH2
NaOH
H – C – CCl3
|| Chloroform
O air & light COCl2 + HCl
(Chloral) (Oxidation) Phosgene (Poisonous)
Zn + HCl
3Cl2/h CH 2Cl2
(–HCl)
CH4 Reduction
Zn+H 2O
CH 4
(–3 HCl)
Ag/
HC  CH

 Chemical Properties and preparation methods of Carbontetrachloride:

Cl 2/h aq. NaOH

CHCl3
(–HCl) (excess)

3Cl 2/AlCl 3 2HF/SbCl5

CS2 Cl Cl CF2Cl 2 + 2HCl
(–S2Cl 2) (Freon-012)
C

Cl Cl
Refridgerent
4Cl2/h Carbon tetra Oxidation
CH4 chloride COCl 2 + 2HCl
(–4HCl) H2O [Steam] Phosgene (Poisonous)

9Cl2/500°C Reduction
CH3 – CH2 – CH3 CHCl 3
(–C2Cl 6) Fe/H2O
(–8HCl)

6.13 FREONS
These are poly chlorofluoro derivative of alkane
6.13.1 Preparation of freons:
SbCl
CCl4 + HF 
5
CCl3F + HCl
SbCl
C2Cl6 + 2HF 
5  C F Cl + 2HCl
2 2 4

(228)
 JEE
6.13.2 Properties & uses of freons :
(i) Freons are colourless, odourless, unreactive & non-combustible liquids.
(ii) Having very low boiling points (e.g CF2Cl2 = –29.8ºC). They easily converted from gaseous
state to liquid state, therefore they are used as a coolant in A.C. & Refrigerator.
(iii) Used as a aerosol propellant in aeroplane & rockets.
(iv) Also used as a solvent.
Note: Main cause of Ozone layer decay (CFC–chlorofluoro carbon)
(Follow the free radical mechanism)
 Chemical Reactions of Aryl Halide:
CH3 CH2 – Cl/2Na/Ether
 CH 2CH3
Wurtz-Fitting Reaction

Cl/2Na/Ether

Fitting Reaction

OH
NaOH/300°C
 (carbanion intermediate)
Aromatic N.S.R.

NH2
NaNH2/NH3 (liq.)
 (Benzyne intermediate)
Elimination + Addition

Cl Cl
Cl2 /AlCl 3 Cl
 +
Halogenation (E.S.R.)
Cl Cl

Cl Cl
Aryl CH3Cl/AlCl 3 CH3
Chloride  +
Friedel-Craft Reaction
(E.S.R.)
CH3

O Cl Cl O
|| ||
CH3 – C – Cl/AlCl 3 C CH
 + 3
Friedel-Craft Reaction
(E.S.R.)
C
O CH3

Cl Cl
CH3Cl/AlCl 3 CH3
 +
Friedel-Craft Reaction
(E.S.R.)
CH3

Cl Cl
H2SO 4/  SO3H
 +
Sulphonation
(E.S.R.)
SO3 H
(229)
 Alkyl Halide & Aryl Halide

QUICK RECAP
 The replacement of hydrogen atom(s) in a hydrocarbon, aliphatic or aromatic, by halogen atom(s) results in the
formation of alkyl halide (haloalkane) and aryl halide (haloarene), respectively.
 Comparison between SN2 and SN1:
S
No.
Characteristics SN2 SN1

1TS 2TS
1. Energetic

2. Kinetics r = k[RX] [NU:] r = k[RX]

3. Stereochemistry Inversion Racemisation

4. Rearrangement Not possible Possible

Me – X > R– CH2 –X > R3CX > R2CHX >
5. Nature of R – X
R2 – CH – X > R3–CX RCH2X > CH3X
6. Nucleophile Strong/Anionic Weak/Neutral

 Reactions of alkyl halides:

R–X R–X
R – O – H

: : :
(Wurtz reaction) Na/dryether
R – R
: :

H O or aq. NaOH or moist Ag O

R
2 2
– OH
(Frank land reaction) Zn/dryether
R – R RCOONa or RCOOAg
R – COOR
Corey-House reaction
 R – R'
:

(i) Li (ii) CuX (iii) R' – X NH

R
:

3
– NH2
Reduction
R – H
:

R – NH
R
:

LiAlH4 or NaBH4 or Ph 3SnH 2

– NH – R
:

R – MgX or RLi or RNa or R2Zn R – NH – R R–X RN  –

 R–R R3N 
:

or R 2CuLi (Organo metallic reagents) 4 X

R – CH = CH – MgX KCN/(Ionic)
 R – CH = CH – R R – C  N
R – C  C – Na or R – C  C – MgX AgCN (covalent)
 R–CC–R R – N = C
(Finkelstein reaction) NaI/acetone
 R–I KO – N = O (Ionic)
R – O – N = O
(Swart reaction) AgF/DMSO
R – F
Ag – O – N = O (covalent)
O
(Williamson reaction) RONa
R – O – R R – N
O
(Streker reaction) Na2SO3
R – SO3 – Na
: :

ROH or dry Ag O
R
: :

2
–O–H

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 JEE

SOLVED EXAMPLES
Example 1. Which one of the following compounds most readily undergoes substitution by SN2 mechanism?
CH 3
(A) H3 C —– (B) H3 C —–
Cl
Cl
Cl CH3
H3 C
(C) H3C —– (D)
Cl
C3H7 H 3C
Answer: (B)
Solution: Less hindered carbon follows SN2 mechanism.
Example 2. Which of the following derivatives of benzene would undergo hydrolysis most readily with aq.
KOH ?
Cl
Cl Cl Cl
O2 N NO2 NO2
(A) (B) (C) (D)

N
Answer: (B) NO2 NO 2 NO2 H3C CH3
Solution: –NO2 group increases SNAR because of – R and –I effect.
KCN
Example 3. CH3Br 
A
I.U.P.A.C. name of A is
(A) Methyl cyanide (B) Methyl isonitrile (C) Acetonitrile (D) Ethane nitrile
Answer: (D)

Solution: CH3Br   CH3CN

CH3CN Ethane nitrile
Example 4. In two separate experiments equal quantities of an alkyl halide, C4H9Cl were treated at the
same temperature with equal volume of 0.1 molar and 0.2 molar solutions of NaOH respec-
tively. In the two experiments, the times taken for the reaction of exactly 50% of the alkyl halide
were the same. The most likely structure of halide is:
(A) CH3CH2CH2CH2Cl (B) CH3CH(Cl)CH2CH3
(C) (CH3)2 CHCH2Cl (D) (CH3)3 CCl
Answer: (D)
CH 3

Solution: (CH ) CCl H3C — C+

3 3
(After rearrangement)
CH 3

CH
3

CH –
Cl
3

H3C — C +  H3C Cl

CH 3

CH
3

As we already mentioned that Hydrolysis of 3º alkyl halide is independent of nucleophilic

concentration.
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 Alkyl Halide & Aryl Halide
Example 5. Which of the following method cannot be considered suitable for the preparation of alkyl halide:
(A) Halogenation of alkane (B) ROH and PX3
(C) ROH and HX (D) Alkene and HX
Answer: (A)
high temperature 400°
Solution: (A) R  H  X 2  UV light
 R  X  HX
This is most drastic method as it required high temperature or catalyst CuCl2, FeCl3, FeBr3 etc.
(B) ROH + PX3 
 3RX + H3PO3
(C) ROH + HX 
 R – X + H2O
R H R H
(D) + HX  X H
H H H H
(B), (C) & (D) are very feasible process.
Example 6. The heterolytic bond dissociation energy of C – Cl bond in vinyl chloride is 207 kcal/mol as
compared to 191 kcal/mol in the case of C – Cl bond in ethyl chloride. One explanation for this
observation is
(A) That in ethyl chloride the bond energy is decreased through resonance involving lone pair of
electrons on chlorine.
(B) The hyper conjugation stabilization in ethyl chloride
(C) That in vinyl chloride the C – Cl bond gets partial double bond character through resonance.
(D) That in vinyl chloride the chlorine atom is attached to sp hybridised carbon whereas in ethyl
chloride it is attached to sp3 hybridised carbon.
Answer: (C)

Solution: H2C
Cl
Vinyl chloride
–
H2C H2 C
+
Cl : Cl :

As we can see that C = Cl bond is formed in vinyl chloride so its bond dissociation energy
207kcal/mol as compared 191 kcal/mol for C - Cl bond.
Example 7. When tert-butyl chloride is made to react with sodium methoxide, the major product is
(A) Dimethyl ether (B) Di-tert butyl ether
(C) Tert-Butyl methyl ether (D) Isobutylene
Answer: (D)
Solution: Tertiary halides on treatment with base, such as sodium methoxide, readily undergo elimination
resulting in the formation of alkenes.
Example 8. Which of the following compounds would be hydrolysed most easily ?
(A) C2H5Br (B) CH3Br
(C) CH2 = CH – Br (D) CH2 = CH – CH2Br
Answer: (D)
Solution: Allylic halides undergo substitution very easily.

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 JEE
Example 9. An alkyl halide on reaction with sodium in the presence of ether gives 2, 2, 5, 5-tetramethyl
hexane. The alkyl halide possibly is
(A) 1-Chloropentane (B) 1-Chloro-2, 2-dimethyl propane
(C) 3-Chloro-2, 2-dimethyl butane (D) 2-Chloro-2-methyl butane.
Answer: (B)
Solution: CH3 CH3
| |
CH3– C – CH2 –––– CH2 – C – CH3
| |
CH3 CH3

Wurtz reaction

CH3 CH3
| |
CH3– C – CH2 Cl + ClCH2 – C – CH 3
| |
CH3 CH3

Example 10. An alkyl chloride produces a single alkene on reaction with sodium ethoxide and ethanol. The
alkene further undergoes hydrogenation to yield-2-methylbutane. Identify the alkyl chloride from
amongst the following.
(A) ClCH2 C(CH3)2CH3 (B) ClCH2CH2CH2CH2CH3
(C) ClCH2CH(CH3)CH2CH3 (D) CH3C(Cl)(CH3)CH2CH3
Answer: (C)
Solution: Formation of 2-methylbutane indicates that the carbon chain skeleton in the chloride is
C C C C
C
Hence, choice (A) and (B) are ruled out. Out of (C) and (D), compound (D) can yield two
products on dehydrohalogenation.
Cl –
ONa+
NO2 NO2
Example 11. Dil. NaOH


NO2 NO2
The above transformation proceeds through
(A) Electrophilic-addition substitution (B) benzyne intermediate
(C) Nucleophilic addition substitution (D) Free radical mechanism
Answer: (C)
Solution: –NO2 groups activate the molecule towards nucleophilic substitution by stabilizing the intermediate
carbanion.
Example 12. A hydrocarbon (A) of molecular weight 54 reacts with excess of Br2 in CCl4 to give a compound
(B) whose molecular weight is 593% more than that of (A). However on catalytic hydrogenation
with excess of hydrogen (A) forms (C) whose molecular weight is only 7.4% more than that of
(A). (A) reacts with CH3CH2Br in the presence of NaNH2 to give another hydrocarbon (D)
which on ozonolysis yields diketone (E). (E) on oxidation gives propanoic acid. Give structures
of (A) to (E) with reasons.

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 Alkyl Halide & Aryl Halide
Solution: Compound (A) Compound (B)
Molecular weight 54 Molecular weight
(593% more than A)
CH3CH 2Br
in NaNH 2 Catalytic

Hydrogenation
(C)
(D) Molecular weight 7.4% of (A)

O3

Diketone (E)

100 gm of (A) add Br2 and the new weight is 593 gm

593  54
 54 gm of (A) add Br2 and the new weight is = 320.2 gm
100
Weight 360.2
 No. of moles of Br2 =  = 2 mole
Molecular weight 160
(i) As two moles of Br2 adds hence compound has two  bonds hence general formula should
(CnH2n-2)
CnH2n–2 = 54
12n + 2n – 2 = 54
n = 4 molecular formula = C4H6
(ii) (A) reacts with CH3CH2Br in presence of NaNH2  Compound (A) should be terminal
alkyne. i.e., 1-butyne
Br
Br2
CH  CCl4 H 3 C Br
(A) Br
Br
CH3CH 2Br
in NaNH2 Catalytic CH 3

Hydrogenation
H 3C
(C)
C2H5
(D)
H3C
O3
O
||
H3C || C2H5
O
(O)

2CH3CH2COOH
Example 13. A hydrocarbon C8H10 (A) on ozonolysis gives compound C4H6O2(B) only. The compound (B)
can also be obtained from the alkyl bromide C3H5Br (C) upon treatment with magnesium in dry
ether followed by CO2 and acidification. Identify (A), (B) and (C) and also give equations for
the reactions.
Solution: (i) (C) is an alkyl bromide C – C  bond is absent in it.

(ii) Molecular formula (C3H5Br) (C) shows (C) would be a cyclic compound Br

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 JEE
(iii) CO2 and on acidification would give carboxylic acid compound (A) would be symmetrical
alkyne (B) is obtained by ozonolysis of (A) C8H10.

Br Mg
  (i) CO 2
MgBr 
ether
(ii) H O
 C – OH
3
Cyclopropyl
||
bromide (C) O
Cyclopropane
carboxylic acid
(B)

ozonolysis
C – OH  CC
|| Dicyclopropyl
O acetyline (A)
Example 14. How would you synthesize CH3CHCyclopropane
2C  CH from(B)
CH3CH2I ?
carboxylic acid
Solution: (A) What are the connectivities of the two compounds? How many carbon atom does each
contain? Are there any rings? What are the position of branches and functional groups on
the carbon skeletons? The starting material has a two-carbon chain, an ethyl group, with an
iodine atom bonded to one carbon. The product has a four-carbon chain in which the two
carbons that have been added to the ethyl group are bonded to each other by a triple bond.
(B) How do the functional groups change in going from starting material to product? Does the
starting material have a good leaving group?
The iodine atom in the starting material is a leaving group and has been replaced in the
product by an alkyne functional group.
(C) Is it possible to dissect the structures of the starting material and product to see which bonds
must be broken and which formed?

CH3 CH 3–I CH3

CH
Bond to be broken new bond to be formed
CH3 CH 2 C CH

the pieces that have to be brought together

(D) New bonds are created when an electrophile reacts with a nucleophile. Do we recognize
any part of the product molecule as coming from a good nucleophile or an electrophilic
addition?
The ethyl group is attached to a leaving group in the starting material and so must serve as the
electrophilic center. A check reminds us that the – C  CH group is related to the nuclophile HC
 C:–, the conjugate base of an alkyne.
(e) What type of compound would be a good precursor to the product?
A displacement of the iodine atom by the nucleophile will give us the product we want.

CH
d+ CH2
CH3 CH2 I H3C
+
+
C CH I
(f) After this last step, do we see how to get from starting material to product? If not we need
to analyze the structure obtained in step 5 by applying questions 4 and 5 to it. These steps
are a restatement of the way of thinking about problems. It will be helpful to you to ask
yourself these questions in a systematic way for each problems you work, on until this way
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 Alkyl Halide & Aryl Halide
of thinking becomes familiar and easy.
Example 15. Predict the product(s) of the reaction.

Br + S– Na+ 
H3C
(A) To what functional group classes do the reactants belong?
(B) Does either reactant have a leaving group?
(C) Are any of the reactants acids, bases, nucleophiles, or electrophiles?
(D) What is the most likely first step for the reaction? Most common reactions classified as
either protonation – deprotonation reactions or reactions of a nucleophile with an electrophile.
(E) What are the properties of the species present in the reaction mixture after this first step? Is
any further reaction likely to occur?
Solution: (A) One reactant is an alkyl halide, the other is a sulphur anion (remember that sodium ions are
usually spectator ions, they are to balance charge but not to participate in the reaction).
(B) Yes, the bromine atom in 1-brompropane is a leaving group.
(C) The sulfur anion is a nucleophile. The alkyl halide contains an electrophilic carbon atom.
(D) No strong acids (pKa < 1) or bases (pKa of conjugate acid > ~13) are present this reaction
mixture so a protonation-deprotonation reaction is not probable. Reaction of the nucleophilic
sulfur atom with the electrophilic carbon atoms is most likely.
Br: S
d+
:

CH3
+

: :
Br– :
: :

:S
(E) All species formed are stable. No further reaction will occur. The complete equation is:
S
Br + S– Na+  H3C
H3 C + Na+ Br–

CH2
Example 16. (i)  (ii) H C  H3C NH2
3
CH 3 CH2
CH2
(iii) H C 
3

Br
Br2 alc. KOH
 
Solution: (i) hv
CH3 CH 3 CH2
CH2 
HBr
 H3C NH3
(ii) H C H 2O2 Br   H3C NH2
3

CH2 (i) Br2 /h

(iii) H C 
(ii) alc. KOH

3

CH3
CH3MgBr
Example 17. Identify A to E in the following: A   Ph CH3
H 3O 
OH
O
Solution: A=
CH3
*****
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 JEE

EXERCISE # 1(A)(Level 1 – Beginner)

1. Which one of the following compounds will be most reactive for SN1 reactions:

I Cl Br Cl

O O O
(A) (B) (C) (D)
O
2. Arrange the following compounds in order of decreasing rate of hydrolysis for SN1 reaction:

(I) CH2 Br (II) H3C CH2 Br

H3 C
(III) CH3 CH2 CH2 Br (IV) CH CH2 Br
H3C
(A) II > III > IV > I (B) IV > III > II > I (C) III > IV > II > I (D) I > II > III > I
3. Among the bromides I–III given below, the order of reactivity in SN1 reaction is:

(I) (II) (III)

Br Br
Br
(A) III > I > II (B) III > II > I (C) II > III > I (D) II > I > III
4. Which of the following is not expected to be intermediate of the following reaction ?
OH
I

H 2O


OH2

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

5. Which one of the following compounds will give (d) and () form in SN1 reaction (as major product):

CH3 H C2H5 H
(A) CH3 C Br (B) CH3 C Br (C) CH3 C Br (D) CH3 CH C Br
CH3 C2 H5 C2H5 CH3 CH3

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 Alkyl Halide & Aryl Halide

Me
Br
Aq.
6. 
AgNO
 (B); Which statement is correct about the above reaction?
3

(A)
Me

OH
(A) Product (B) is (I) by SN1 mechanism.

OH
(B) Product (B) is (II) by SN2 mechanism.
Me
Me

OH
(C) Product (B) is (I) by SN2 mechanism.

OH
(D) Product (B) is (II) by SN1 mechanism.
Me
7. The given compound CH3–O–CH2–Br gives which one of the following reactions:
(A) Only SN1 (B) Only SN2 (C) SN1 as well as SN2 (D) E1

8. When the concentration of alkyl halide is tripled and the concentration of OH ion is reduced to half,
the rate of SN2 reaction increases by:
(A) 3 times (B) 2 times (C) 1.5 times (D) 6 times
9. In the following reaction the most probable product will be:
Br
H CH3 OH

SN 2
H3C H
C2H5
OH CH 3 C2H5 CH 3
H CH3 H OH H CH3 HO H
(A) (B) (C) (D)
H3C H H3C H H3C H H3C H
C2H5 C2H5 OH C2H5
H
SOCl2 Product, Identify the product:
10.
C2 H5
C  
OH
CH3
H H H H
(A) Cl C (B) Cl C (C) HS C (D) H C C
CH3 C H C H 5 2 SH
C2H5 CH 3 2 5 CH 3 2 5 CH3
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 JEE

11. 
 rearranged carbocation is:
OH

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

OH OH HO
OH
12. In the reaction involving C – OH bond hetrolytic cleavage, the order of reactivity is:
(A) 1º > 2º > 3º (B) 3º > 2º > 1º (C) 2º > 3º > 1º (D) None of these
13. HBr reacts fastest with:
(A) 2-Methyl propan-2-ol (B) Propan-1-ol
(C) Propan-2-ol (D) 2-Methyl propan-1-ol
14. The name of the compound B in the following sequence is:
PCl alc
CH3CHOHCH3 
5
 A  B
KOH
(A) Propene (B) Propane (C) Propyne (D) Propanol
15. When 3,3-dimethyl-2-butanol is heated with conc. H2SO4, the main product formed is:
(A) 3,3-Dimethyl-1-butene (B) 2, 3-Dimethyl-2-butene
(C) 2, 3-Dimethyl-1-butene (D) Cis and Trans isomers of 2-butene are obtained
16. Which of the following is least reactive towards ZnCl2 and Conc. HCl mixture:
(A) 2-Butanol (B) 1-Butanol
(C) 2-Methyl-2-butanol (D) 3-Methyl-1-butanol
17. The relative rate of acid catalysed dehydration of following alcohols would be,
CH3 CH 3
CH CH CH3 CH CH2 CH2 OH
OH

I II

CH3 CH3
C CH2 CH3 C CH2 OH
OH CH3

III IV
(A) III > I > II > IV (B) III >IV > I > II (C) I > III > IV > II (D) III > IV > I > II
18. For making (CH3)3C–O–C2H5 the ideal combination is:
(A) (CH3)3CONa and C2H5Br (B) (CH3)3CBr and C2H5ONa
(C) Both the above (D) None
19. Diethyl ether acts as a:
(A) Lewis acid (B) Lewis base (C) Reducing agent (D) Oxidising agent
20. 1–chlorobutane on reduction with alcoholic KOH gives:
(A) 1-butene (B) 1-butanol (C) 2-butene (D) 2-butanol

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 Alkyl Halide & Aryl Halide
21. The product obtained by reduction of Benzyl bromide with LiAIH4 is:

Br
Br CH 3 CH 3

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

Cl H 3C
22. The reaction H3C KOH (aq) OH + Cl– is an example of:
CH 3 H 3C
(A) Reduction (B) Oxidation
(C) Neutralisation (D) Nucleophilic substitution
23. In the given pair in which pair the first compound is more reactive than second for SN1 reaction.

Cl
(A) Cl CH2Cl (B)
Cl

Cl Cl

(C) (D)
Cl Cl
24. Consider the following groups:
(I) —OAc (II) —OMe
(III) —O—SO2—Me (IV) —O—SO2—CF3
The order of leaving group nature is:
(A) I > II > III > IV (B) IV > III > I > II (C) III > II > I > IV (D) II > III > IV > I
25. For CH3Br + OH–  CH3OH + Br–
the rate of reaction is given by the expression:
(A) rate = k [CH3Br] (B) rate = k[OH–]
(C) rate = k [CH3Br][OH ] – (D) rate = k[CH3Br]° [OH–]°
26. Arrange these compounds in order of increasing SN2 reaction rate:

(A) III < I < II < IV (B) III < II < I < IV (C) IV < III < I < II (D) III <IV < I < II
27. The given reaction is an example of C2 H5 Br  KCN(aq.)  C 2 H5CN  KBr
(A) elimination (B) nucleophilic substitution
(C) electrophilic substitution (D) redox change

*****

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 JEE

EXERCISE # 1(B)(Level 2 – Learner)

1. A chloro derivative 'X' on treatment with Zn and HCl gave a hydrocarbon with five carbon atoms in
the molecule when X is dissolved in ether and treated with Na, 2, 2, 5, 5-tetra methyl hexane is
obtained. The compound X is:
(A) 3-chloro 2,2,-dimethyl propane (B) 1-chloropropane
(C) 1-chloro 2,2,dimethyl propane (D) 2-chloro-2-methyl butane
2. An alkyl halide of formula C6H13Cl on treatment with potassium t-butoxide gives two isomeric alkenes
(C6H12). Both alkenes on hydrogenation give 2, 3-dimethyl butane. Isomeric alkenes are:

H3 C H 3C
CH 3 CH 3
(A) H C and H 3C
2

CH 3 CH 3

H3C
CH 3 H3C
(B) H2C and
CH3
CH 3

CH 3 H 3C CH 3
(C) H3C and
H 3C CH 3

H3 C CH 3
CH 3
(D) H2 C and H 2C
CH 3 CH 3

Br

(i) alc.KOH NaNH 2

3. A B. A and B:
(ii) NaNH 2 CH 3CH2Cl
Br

CH 2
(A) A B

CH
(B) A B

CH CH
(C) A B

(D) None of these

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 Alkyl Halide & Aryl Halide

Cl

4. On treatment with aqueous KOH gives:

HC
3 CH 3

OH OH OH
CH 3 CH 3 CH 3

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

CH 3
H3C CH3 H3C CH 3 H3C OH
CH 3
PCl
KCN Hydrolysis
5. CH3OH 
3
A  B   C. The compound C is:
(A) CH3OH (B) HCOOH (C) CH3CHO (D) CH3COOH
6. For a given alkyl group, the densities/b.pt./m.pt. are in the order:
(A) RI < RBr < RCl (B) RI < RCI < RBr (C) RBr < RI < RCl (D) RCl < RBr < RI
7. 3-methyl – 2-pentene on reaction with HOCl gives:
(A) 3-chloro-3-methyl pentanol-2 (B) 2,3-dichloro-3-methyl pentane
(C) 2-chloro-3-methyl pentanol-3 (D) 2,3-dimethyl butanol-2
8. The reaction,
Alcohol + HCl  Alkyl halide + H2O
is reversible. For the completion of the forward reaction _____ is used:
(A) Anhydrous zinc chloride (B) Concentrated H2SO4
(C) Excess of water (D) Calcium chloride
9. The correct order of melting and boiling points of the primary (1°), secondary (2°) and tertiary (3°)
alkyl halides is:
(A) P > S > T (B) T > S > P (C) S > T > P (D) T > P > S
10. Pick up the correct statement about alkyl halides:
(A) They show H-bonding (B) They are soluble in water
(C) They are soluble in organic solvent (D) They do not contain any polar bond
11. Reduction of alkyl halide by LiAlH4 is the type of reaction:
(A) Nueleophilic substitution reaction (B) Electrophilic substitution reaction
(C) Electrophilic Addition reaction (D) None of these
12. Which of the following statements is invalid:
(A) The more stable the carbocation the faster it is formed
(B) Propyl cation changes to more stable isopropyl carbocation by 1,2 shift of a hydrogen
(C) Isopropyl chloride reacts with sodium ethoxide to form 1-ethoxypropane
(D) Propyl halides reacts with sodium ethoxide to form 1-ethoxypropane

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 JEE
13. Which is incorrect about Hunsdiecker reaction?
(A) Only Cl2 can give alkyl halide (B) I2 will give ester when treated with RCOOAg
(C) The reaction proceeds through free radical (D) F2 cannot give alkyl halide
14. Arrange the following in the increasing order of reactivity towards SN1 reaction:
CH3–O–CH2–Cl (P) ; CH3–NH–CH2–Cl (Q);

Ph–CH2–Cl (R); Cl (S)

(A) P > Q > R > S (B) R > Q > P > S (C) Q > P > R > S (D) Q > P > S > R
15. Non-occurence of the following reaction
Br– + CH3OH  BrCH3 + OH–, is due to
(A) Attacking nucleophile is stronger one (B) Leaving group is a strong base
(C) Alcohols are not good substrate (D) Hydroxide ions are weak bases
16. Which of the following nucleophile will show minimum reactivity towards SN2 reaction:
(A) Me3CO (B) MeO (C) Et  O (D) Me 2 CHO 
OH
17. Br / CCl 4
2  
Which compound will be major product for the above reaction?

OH Br
(A) (B)
Br O

(C) O (D) O
Br Br
Br
18. Select the incorrect statement about the product mixture in the following reaction :

Br
2  Products
CCl4
(A) it is optically active (B) it is racemic mixture
(C) it is a resolvable mixture (D) it is a mixture of erythro compounds
Θ
OEt/EtOH
19.   A (Major product),
Δ
Br
A is :

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

OEt OEt
20. Arrange the following nucleophiles in the order of their nucleophilic strength:
   
(A) OH   CH 3COO   OCH 3  C6 H5 O  (B) CH 3COO  C6 H 5O  OCH 3  OH

(C) C6 H 5O   CH 3COO   CH 3O   OH  (D) CH 3COO   C6 H 5O   OH   CH3O

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 Alkyl Halide & Aryl Halide
21. Correct order of leaving group tendency is:
(A) I   Br   Cl  F (B) F  Cl  Br   I
(C) Cl  F  Br   I (D) I   Cl  Br   F
22. Which of the following leads to the formation of an alkyl halide?
Red P  Br SOCl
(A) C2 H5OH 
2
 (B) C2 H5OH 
2

KBr  Conc. H SO
(C) C2 H5OH  2 4
 (D) All of these
23. What is the principal product of the following reaction ?

CH3
H Br
H H + NaN3  Product
H Cl
CH3

CH3 CH3 CH3 CH3

H N3 N3 H N3 H H N3
(A) H H (B) H H (C) H H (D) H H
H Cl Cl H H Cl Cl H
CH3 CH3 CH3 CH3

H CMgBr
24. In the given reaction; 
3
  Product
H /H 2O
O
Find the product of reaction:
OH
(A) (B) (C) (D)
OH
OH
25. Among the following pairs, in which pair (II) is more reactive than (I) for SN1 reaction :

(A) , (B) O ,
Br Cl Cl
Br

(C) , (D) ,
Br Br I Br
26. In the following compound, arrange the reactivity of different bromine atoms toward NaSH in
decreasing order:
Br (R)
Br Br (Q)
(S)
Br (P)
O
O
(A) P > Q > R > S (B) S > Q > P > R (C) Q > S > P > R (D) P > S > Q > R
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 JEE

* OTs
NaCN
27. 
 Product

* CN CN
(A) (B) *

(C) Both (A) and (B) (D) None of these

CH3
NBS KCN
28.  A  B ; Product B is-
(2 Mole) (1Mole)

CH2CH3

Br CN Br Br

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

Br Br CN
29. Find the major product of the following reaction:

Cl
HO

2


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

30. Which of the following reactions is not feasible?

CH3OH C2H5OH
(A) (B) Br 

Cl
CH3 CH3
C 2H5OH I
(C)  (D) H3 C C Cl C
Br H3C CH2
CH3
*****

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 Alkyl Halide & Aryl Halide

EXERCISE # 2(A)(Adept – JEE Main PYQs)

1. Which of the following compounds will show retention in confuguration on nuclephic substitution by
OH– ion? (JEE Main 2020)
(A) CH3 CH Br (B) CH3 CH Br
C6 H5 CH3
Br
(C) CH3 CH CH2Br (D) CH3 C H
C2H5 C6H13
2. Consider the reaction sequence given below: (JEE Main 2020)

Br 
OH
H2O
 OH  Br 

rate = k[t-BuBr] …(1)

CH3

OH–
+ HOH + Br –
C 2H5OH H2C CH3 …(2)
rate = k[t-BuBr][ OH– ]
Which of the following statements is TRUE ?
(A) Changing the concentration of base will have no effect on reaction (2)
(B) Changing the concentration of base will have no effect on reaction (1)
(C) Changing the base from OH to °OR will have no effect on reaction (2)
(D) Doubling the concentration of base will double the rate of both reactions
3. The major product obtained from E2-elimination of 3-bromo-2-fluoropentane is: (JEE Main 2020)
Br F
(A) CH3 CH2 CH CH = CH2 (B) CH3 CH = CH CH CH3
Br
(C) CH3 CH2CH = C F (D) CH3 CH 2 C = CH CH3
CH 3
4. The mechanism of SN1 reaction is given as (JEE Main 2020)
+ – + – Y– –
R X R X R || X R Y+X
Ion pair Solvent
separated ion
pair
A student writes general characteristics based on the given mechanism as:
(i) The rection is favoured by weak nucleophiles.
(ii) Rwould be easily formed if the substituents are bulky
(iii) The rection is accompanied by recemization.
(iv) The reaction is favoured by non-polar solvents.
Which observations are correct?
(A) (ii) and (iv) (B) (i) and (iii) (C) (i) and (ii) (D) (i), (ii) and (iii)
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 JEE
5. The major product in the reation: (JEE Main 2021)

CH3 CH3
+ –
CH3 – C – Cl + K O – C – CH 3 ? is:
CH3 CH3
(A) t-Butyl ethyl ether (B) 2, 2-Dimethyl butane
(C) 2-Methyl pent-1-ene (D) 2-Methyl prop-1-ene

OH

6. In the given reaction 2A 

(i) 2Mg,THF
 C 'A' can be:
(ii) Methylbenzoate

(iii) H 2O/H

(A) Benzyl bromide (B) Bromobenzene

(C) Cyclohexyl bromide (D) Methyl bromide
(i)Cl ,
7. A 
2
 4-Bromophenyl acetic acid In the above reaction 'A' is: (JEE Main 2021)
(ii)CN
(iii) H 2O/H 

Br
Br

(A) (B)

CH2CH3

CH3 CH = CH2
(C) (D)
Br Br
8. Compound 'A' undergoes following sequence of reactions to give compound 'B'. The correct structure
and chirality of compound 'B' is: (JEE Main 2021)
[where Et is – C2H5]

(i) Mg,Et O

2 B
(ii) D 2O
Br
Compound 'A'

(A) , Achiral (B) , Chiral

D OD

(C) , Chiral (D) OD , Achiral

D

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 Alkyl Halide & Aryl Halide
9. The product formed in the first step of the reaction of

Br
CH3 CH 2 CH CH2 CH CH3 with excess Mg/Et2O (Et = C2H5) is: (JEE Main 2021)

Br
(A) CH3 CH 2 CH CH2 CH CH 3 (B) CH3 CH 2 CH CH2 CH CH 3

CH 3 CH CH2 CH CH2 CH3 CH3 CH 2 CH CH2 CH CH3

MgBr
CH 2
(C) CH3 CH2 CH CH 2 CH CH3 (D) CH3 CH
CH CH3
MgBr

AgCN NaCN
10. 'A '  Cl   'B' .
(Major Pr oduct) C 2H5OH  H 2O C2 H5OH  H 2O Major Product

Considering the above reacions, the compound 'A' and compound 'B' respectively are:
(JEE Main 2022)
– + + –
(A) N  C, NC (B) C  N, C N
+ – + –
(C) N  C, C N (D) C  N, NC
11. Assertion-A: Hydrolysis of an alkyl chloride is a slow reaction but in the pressure of NaI, the rate
of the hydrolysis increases.
Reason-R: I– is a good nucleophile as well as a good leaving group. In the light of the above
statements, choose the correct answer from the options given below: (JEE Main 2022)
(A) A is false but R is true
(B) A is true but R is false
(C) Both A and R are true and R is the correct explanation of A
(D) Both A and R are true but R is NOT the correct explanation of A
12. Decreasing order toward SN1 reaction for the following compounds is:

Cl Cl Cl Cl

NO2 OMe Cl
(i) (ii) (iii) (iv)

(A) (i) > (iii) > (iv) > (ii)

(B) (i) > (ii) > (iii) > (iv)
(C) (ii) > (iv) > (iii) > (i)
(D) (iv) > (ii) > (iii) > (i)

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 JEE
13. The correct orderof melting point of dichlorobenzenes is: (JEE Main 2022)

Cl Cl Cl Cl Cl Cl
Cl Cl
(A) > > (B) > >
Cl Cl
Cl Cl
Cl Cl Cl Cl Cl Cl
Cl Cl
(C) > > (D) > >
Cl Cl
Cl Cl
14. Identify the incorrect option from the following: (JEE Main 2022)
Br OH +
(A) + KOH (aq) 
KBr
Br
(B) + KOH (alc) 
+
KBr OH
Cl Cl O
O
(C) anhyd AlCl3
+ H3C – C – Cl   CH3 + HCl

Cl OH
(i) NaOH, 623 K,
(D) 
(ii) HCl

15. The correct orderof reactivity of following haloarenes towards nucleophilic substitution with aqueous
NaOH is:
NO2
Cl Cl Cl
NO2 Cl
OMe
(i) (ii) (iii) (iv)
O2N NO2
Choose the correct answer from the options given below: (JEE Main 2023)
(A) (i) > (ii) > (iv) > (iii) (B) (iii) > (i) > (iv) > (ii)
(C) (iv) > (iii) > (ii) > (i) (D) (iv) > (ii) > (i) > (iii)
16. Identify the correct order of rectivity for the following pairs towards the respective mechanism:
Br
Br > Br Br >
(i) SN2 (ii) SN1

Br
Cl Cl
Br
>
(iii) EAS > (iv) EAS

NO 2
NO 2
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 Alkyl Halide & Aryl Halide
Choose the correction answer from the options given below: (JEE Main 2023)
(A) (ii), (iii) and (iv) only (B) (i), (ii), (iii) and (iv)
(C) (i), (ii) and (iv) only (D) (i), (iii) and (iv) only
17. The major product 'P' formed in the given reaction is:

CH3O Cl
anhy.

AlCl
 'P ' (JEE Main 2023)
3 (major)
O2N

CH3 CH 3
CH3O CH3O NO2
(A) (B)
O2N O2N OCH3
CH3 CH3 CH 3

CH3
CH3O
(C) CH3O (D)
O2N CH 3
O2N
18. 2-Methyl propyl bromide reacts with C2H5O– and gives 'A' whereas on reaction with C2H5OH it
gives 'B'. The mechanism followed in these reactions and the products 'A' and 'B' respectively are:
(A) SN2, A = iso-butyl ethyl ether; SN1, B = tert-butyl ethyl ether (JEE Main 2023)
(B) SN1, A = tert-butyl ethyl ether; SN1, B = 2–butyl ethyl ether
(C) SN2, A = 2–butyl ethyl ether; SN2, B = iso-butyl ethyl ether
(D) SN1, A = tert-butyl ethyl ether; SN2, B = iso-butyl ehtyl ether
19. Match List-I with List-II.
1-Bromopropane is reacted with reagents in List-I to give product in List-II
List-I (Reagent) List-II (Product)
(a) KOH (alc) (i) Nitrile
(b) KCN (alc) (ii) Ester
(c) AgNO2 (iii) Alkene
(d) H3CCOOAg (iv) Nitroalkane
Choose the correct answer from the options given below: (JEE Main 2023)
(A) (a)-(iii), (b)-(i), (c)-(iv), (d)-(ii) (B) (a)-(i), (b)-(ii), (c)-(iii), (d)-(iv)
(C) (a)-(i), (b)-(iii), (c)-(iv), (d)-(ii) (D) (a)-(iv), (b)-(iii), (c)-(ii), (d)-(i)
20. The major product formed in the Friedel-Craft acylation of chlorobenzene is: (JEE Main 2023)

Cl Cl
COCH3
(A) CH3 (B)
COCH3
O
O CH 3

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 JEE

Cl Cl

(C) CH 3 (D)

O O CH 3
21. Identify the correct set of reagents or reaction conditions ‘X’ and ‘Y’ in the following set of
transformation. (JEE Main 2024)
X Y
CH3  CH 2  CH 2  Br  Product  CH3  CH  CH3
|
Br
(A) X = dil. aq. NaOH, 20ºC, Y = Br2/CHCl3
(B) X = conc. alc. NaOH, 80ºC, Y = Br2/CHCl3
(C) X = dil. aq. NaOH, 20ºC, Y = HBr/acetic acid
(D) X = conc. alc. NaOH, 80ºC, Y = HBr/acetic acid
22. In the abvoe reaction product ‘P’ is- (JEE Main 2024)

Br
KCN (alc)

 Major Product ‘P’

OCH3

CN OCH3 CN
CN CN
(A)
OCH3 (B) (C)
OCH3
(D)
OCH3
alc. KOH Br 2 KCN
23. C2H5Br A CCl4 B Excess C (JEE Main 2024)
H 3O +
Excess

D
Acid D formed in above reaction is:
(A) Gluconic acid (B) Succinic acid (C) Oxalic acid (D) Malonic acid
24. The final product A, formed in the following multistep reaction sequence is:
Br (i) Mg, ether then CO,H 
(ii) NH 3 , 
 A (JEE Main 2024)
(iii) Br2 ,NaOH

O O O
NH2
(A) NH2 (B) (C) Br (D) OH

25. The correct statement regarding nucleophilic substitution reaction in a chiral alkyl halide is;
(A) Retention occurs in SN1 reaction and inversion occurs in SN2 reaction. (JEE Main 2024)
(B) Racemisation occurs in SN1 reaction and retention occurs in SN2 reaction.
(C) Racemisation occurs in both SN1 and SN2 reactions.
(D) Racemisation occurs in SN1 reaction and inversion occurs in SN2 reaction.
*****
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 Alkyl Halide & Aryl Halide

EXERCISE # 2(B)(Scholar – JEE Main PYQs)

1. A chloro compound ‘A’.
(i) forms aldehydes on ozonolysis followed by the hydrolysis.
(ii) when vaporized completely 1.53 g of A, gives 448 mL of vapour at STP.
The number of carbon atoms in a molecules of compound A is____. (JEE Main 2021)
2. Observe structures of the following compounds (JEE Main 2022)
NH2
Cl OH OH
H2N
OH
O O
The total number of structures/compounds which possess asymmetric carbon atoms is ____.
3. Optical activity of an enantiomeric mixture is +12.6° and the specific rotation of (+) isomer is
+30°. The optical purity is ____%. (JEE Main 2022)
Cl

4. NaOH
P
H 2O (Major Product)
Consider the abvoe reaction. The number of -electrons present in the product ‘P’ is ____.
(JEE Main 2022)
5. Number of moles of AgCl formed in the following reaction is ______.
Cl
Cl Cl
AgNO

3
 (A) + X AgCl  (JEE Main 2023)
H
Cl
6. Maximum number of isomeric monochloro derivatives which can be obtained from 2, 2, 5, 5 –
tetramethylhexane by chlorination is ______. (JEE Main 2023)
7. 2-chlorobutane + Cl2  C4H8Cl2 (isomers)
Total number of optically active isomers shown by C4H8Cl2, obtained in the above reaction is ___.
(JEE Main 2024)
C2H5OH
Product (A)
8. CH3CH2Br + NaOH (JEE Main 2024)
H2O
Product (B)
The total number of hydrogen atoms in product A and product B is ____.
9. The number of halobenzenes from the following that can be prepared by Sandmeyer's reaction
F Cl Br I At

(JEE Main 2024)

(I) (II) (III) (IV) (V)
10. The major products from the following reaction sequence are product A and product B.
(i) Br 2 (i) Br 2
B (ii) alc. KOH (3eq.) A (JEE Main 2024)
(ii)  O–Na+ (1.0 eq.)
The total sum of -electrons in product A and product B are _____. (nearest integer)
*****
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 JEE

EXERCISE # 3(A)(Proficient – JEE Advanced Level Questions)

CH3
OH – OH 
1.   + HO H
II I
Et
Steps I and II are
(A) Both SN1 (B) Both SN2 (C) I-SN1, II-SN2 (D) I-SN2, II-SN1

2. What are A & B in the following reaction ?  

Mg/THF
(1) eq.
 A 
(i) CH3CHO
 B
(ii) aq.NH 4 Cl

(A) & (B) &

(C) & (D) None of these

H O
3. Ester A (C4H8O2) + CH3MgBr  3
 C4H10O
(2 pair) (alcohol)
(B)
Alcohol B reacts fastest with Lucas reagent. Hence A and B are
O O
|| ||
(A) CH 3  C  O  C 2 H 5 , (CH 3 )3 COH (B) H  C  O  C3H 7 , (CH 3 ) 2 CHOH

O O
|| ||
(C) CH 3  C  O  C 2 H 5 , (CH 3 ) 2 CHOH (D) H  C  O  C3H 7 , (CH 3 )3 COH
4. The product formed when glycerol reacts with PCl5 is:
(A) 1,2,3–trichloropropane (B) Glycero monochlorohydrin
(C) Glycero dichlorohydrin (D) All of these
5. On heating glycerol with excess amount to HI, the product formed is:
(A) Allyl iodide (B) Isopropyl iodide
(C) Propylene (D) 1,2,3–tri–iodopropane
6. What will be the reduction product of following reactions:

(A) CH2Cl2, CH3Cl, CH4 (B) CH4, CH3Cl, CH2Cl2

(C) CH3Cl, CH2Cl2, CH4 (D) CH3Cl, CH4, CH2Cl
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 Alkyl Halide & Aryl Halide
7. In the given reaction:

Br2
 [X]; X is:


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

Br , hv
8. 2  Major(s)

CH 3 CH 3
| |
(A) CH 3  CH  CH 2 Br (B) CH 3  CBr  CH 3

Br
|
(C) CH3CH2CH2Br (D) CH 3  CH  CH 3

Me
Br
9. Me 
MeO ,  Θ
 Correct statement regarding product.
Me
(A) Only one alkene is produced (B) Non resolvable major product
(C) Major product shows geometrial isomerism (D) Major product can show optical isomerism

10. CH3—CH—CH2 CH

3MgCl

H 2O
O

(A) CH3  CH  CH 2OH (B) CH3  CH  CH 2  CH 3

| |
CH 3 OH

(C) CH3  CH  CH 3 (D) HO – CH2 – CH2 – CH2 – CH2 – OH

|
CH 3
11. Consider the following statements?
(A) CH3–CH2–CH2–I will react more readily than (CH3)2 CHI for SN2 reactions.
(B) CH3–CH2–CH2–Cl will react more readily than CH3–CH2–CH2–Br for SN2 reaction.
(C) CH3–CH2–CH2–CH2–Br will react more readily than (CH3)3C–CH2–Br for SN2 reactions
(D) CH3–O–C6H5–Br will react more readily than NO2–C6H5–CH2Br for SN2 reaction

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 JEE
12. A solution of (R)-2-iodobutane, [] = –15.9° in acetone is treated with radioactive iodide, until 1.0%
of iodobutane contain radioactive iodine, the specific rotation of recovered iodobutane is found to be
15.58°, which statement is correct about above information.
(A) It has optical purity 96% (B) % of R in solution is 99%
(C) Racemic mixture is 2% (D) Final solution is dextrorotatory
13. Which are possible products in following:

moist Ag O


2


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

14. In which product formation takes place according to Hoffmann's rule:

 
t-Bu O K CH3CH 2 O K
(A) CH 3CH 2  CH  CH 3  (B) CH 3CH 2  CH  CH 3 

Δ Δ
| |
Br Br

 
OH OH
(C) 
 (D) CH 3CH 2CH  CH 3 

 Δ
|

S(CH 3 ) 2
( i ) Et O H CrO
15. A + B  

2
 Alcohol 2 
4  Ketone
 Acetone
( ii ) H 3 O

Ketone is if A is grignard reagent, then

(A) A is isobutyl magnesium bromide (B) B is CH 3  CH  CH  O

|
CH 3

CH 3
|
(C) B is CH 3  CHCOCl (D) A is isopropyl magnesium iodide

16. Which of the following will react with AcOAg

(A) R–NH2 (B) R–OTs (C) R–N3 (D) R–Br

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 Alkyl Halide & Aryl Halide
17. Consider the given reaction:

CH3
NaCN
H OTs  CH 3CH 2 CH  CN
Et |
CH 3
Which of following statements are correct for above reaction ?
(A) Product formation takes place due to the breaking of O–Ts
(B) The reaction is S
N2

(C) The reaction is S

N1
(D) Configuration of product is (R)
18. Benzoyl chloride is less reactive than acetyl chloride for nucleophilic acyl substitution reaction
because:

O
||
(A) – C – group of benzoyl chloride is in conjugation with benzene ring. This makes benzoyl
chloride more stable than acylchloride.
(B) CH3– group of acetyl chloride make C–Cl bond stronger due to the +I effect.
(C) C6H5– group of benzoyl chloride make C–Cl bond weaker due to +R effect.
(D) Carbonyl carbon in benzoyl chloride is less electron deficient than acetyl chloride
19. Bromination can take place at:

NBS
 / hv

CCl 4

(A) 1 (B) 5 (C) 3 (D) 4

20. Which of following will give syn-elimination:
(A) CH 3 CH 2 CH 2  OCOCH 3

(B) CH 3CH 2 CH –CH3

|
Cl

(C) CH 3CH 2 CH 2 –O– C –S–CH 3

||
O

CH 3
|
(D) CH 3CH 2 CH 2 N  –O
|
CH 3

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 JEE
21. Which of following are correct for given reaction:




(A) Major product of reaction is

(B) Major product is

(C) The reaction is thermal elimination reaction

(D) The reaction is cyclic E2 reaction
22. 3-Phenyl-3-pentanol can be prepared from grignard reagent & other component which can be:
(A) 3-pentanone (B) Ethylbenzoate
(C) Ethyl phenyl ketone (D) Propanoyl chloride
23. In which of following reaction inverted product will obtained:
(A) SN1 (B) SN2
(C) S (D) SNi
N NGP

24. Rate of SN2 will be negligible in:

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

CH 3 CH3 CH 3
| | |
25. CH 3  C  Cl CH3  C  Br CH 3  C  I
| | |
H H H

From left to right correct statements are :

(A) Rate of SN1 mechanism increases in polar protic solvent
(B) Rate of SN2 mechanism increases in DMSO
(C) Rate of E2 mechanism increases
(D) Rate of E1 mechanism increases

*****

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 Alkyl Halide & Aryl Halide

EXERCISE # 3(B)(Amateur - Variety of JEE Advanced Level Questions)

Comprehension Based Questions:
Paragraph # 1 for (Ques. 1 to 3)
Preparation of Grignard reagent.
δΘ δ
R–X + Mg Et
 O
 R – Mg – X (Organomagnesium halide)
2
Grignard reagent may be made from primary, secondary and tertiary alkyl halide as well as from
vinyl halide and aryl halides. Grignard reagent is strong nucleophile and strong bases.

O
||
1. PhMgBr + CH  C  Et    (P)
3 ( ii ) H 

Major product (P).

OH Et OH
| | |
(A) Ph  C  Et (B) Ph  C  CH 3 (C) Ph  C  Ph (D) None
| | |
CH 3 CH 3 Ph
2. In which of following reaction tertiary alcohol will be obtained as a product.
O
(A) C—CH3 + Et MgBr ( 
ii ) H 

O
||
(B) Ph  C  Cl + excess PhMgBr   
( ii ) H 

O
||
(C) Cl  C  O  Et + excess PhMgBr   
( ii ) H 

(D) All

3. Ph  CH  OEt CH
3  (P) + PhMgBr (
MgBr
 (Q)
ii ) H 
|
OH
End product (Q) is
O
||
(A) Ph  CH  CH 3 (B) Ph  C  Ph
|
OH
O
||
(C) Ph  C  H (D) Ph  CH  Ph
|
OH

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 JEE
Paragraph # 2 for (Ques. 4 to 5)

Cl

2 Mono chloro derivatives
h

4. How many dextrorotatory monochloro derivatives will form in above reaction?

(A) 4 (B) 6 (C) 3 (D) 2

5. How many fractions will be obtained by fractional distillation of mixture of products?

(A) 4 (B) 6 (C) 8 (D) 5

Matrix Match Type Qusetions:

6. Match the List I (reaction) with List II (reaction intermediate) and select the correct answer using
the codes given below the Lists:
List-I List-II
(A) CF3–CHCl2  CF2 = CCl2
alc.KOH/Δ
(P) Only one Transition state

CH 3
|
H
(B) CH — C — OH  (Q) Carbocation
3 CH 3 – C = CH 2
| |
CH 3 CH 3

(C) CH3–CH2–Br 

alc.KOH

 CH2=CH2 (R) Carbanion

Br
|
(D) CH – C – CH 
aq.KOH/Δ
 CH3 – C = CH 2 (S) Free radical
3 3
| |
CH 3 CH 3
7. Match List I with List II and select the correct answer from the codes given below:
List-I List-II

(A) CH3–O–SO2CH3 + C2 H5O (P) CH3–CH2–PH2
(B) CH3–CH2–I + PH3 (Q) CH3–O–C2H5

(C) HC  C Na + CH3–CH2–Br (R) CH3–O–CH3

(D) CH3–Cl + CH3– O (S) CHC–CH2–CH3
8. Match List-I with List-II for given S reaction & select the correct answer from the codes given
N2

below: Z  CH 2 Br  CH3 O 
 Z  CH 2  OCH 3  Br 
List-I (Z) List-II (Relative rate of SO2)
(A) H– (P) 0.1
(B) CH3– (Q) 3
(C) C2H5– (R) 1
CH 3
(D) CH— (S) 100
CH 3

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 Alkyl Halide & Aryl Halide
9. Match List-I & List-II and select correct answer:
List-I List-II

H O
(A) R–MgX + HCHO  Adduct 
3
 (P) Ketone
n-carbon


H O
(B) R–MgX + (CH2)2O  Adduct 
3
 (Q) 1° Alcohol (n + 1) carbon
n-carbon


H O
(C) R–MgX + CO2  Adduct 
3
 (R) Acid (n + 1) carbon
n-carbon


H O
(D) R–MgX + Ph–CN  Adduct 
3
 (S) 1° Alcohol (n + 2) carbon
n-Carbon

10. Match the following:

List-I List-II


CH CH O
(A) 
3 2  (P) E1
Δ


CH CH O
(B) 
3 2 
(Q) E2
CH3CH 2OD

Ag O
(C) 
2
 (R) E1cb
moist

(D) alc
. KOH
 (S) Ei

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 JEE
11. Ethers on acidic hydrolysis (H+/H2O) give alcohols / mixture of alcohols.
Ethers Mechanism followed

(A) O (P) SN1

(B) O (Q) SN2

(C) CH2–O–CH3 (R) No reaction

(D) CH3 – CH – CH2

O

12. Column-I Column-II

AlCl
(A)  Ph  CH2  Cl 
3
 (P) Nucleophilic substitution

O
AlCl
(B) + Ph Cl 
3
(Q) Electrophilic substitution

Br
KOH (aq.)
(C) 
 (R) Cation intermediate

CH3
(D) H3C C Br2 , hv (S) Free radical substitution
CH3  
CH3

13. Column-I Column-II

Ph
HO
(A) H3C 
2
 (P) Inversion
Et Br

OH
(B) H3 C CH Cl 
 (Q) Racemisation
D

CH2 CH2 CH3

CH OH
(C) Cl 
3
 (R) 1st order
H3 C Et
Θ
SH
(D) H2 C CH CH Cl 
Acetone
 (S) 2nd order
CH3

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 Alkyl Halide & Aryl Halide
14. Match the Column-I and Column-II
Column-I (Reaction) Column-II (Type of reaction)
KSH
(A) R-2-chlorobutane 
acetone
 (P) SN1



EtO Na
(B) R-2-chlorobutane   (Q) SN2
EtOH

HO
(C) 2-bromo-2-methyl propane 
2
 (R) E1
H SO
(D) 2-butanol 
2

4
 (S) E2

Integer Type Questions:

14
15. Cl  CH 2  CH 2  S  CH 2  CH 3 NH
3  Number of amines produced

16. alc.KOH
Br    Number of alkene produced.

Me

OH HI
17. Et 
Ph
How many iodides are produced in more than 5% yield.
18. On conversion into grignard followed by treatment with ethanol. How many monochloro alkane
would yield 2-methyl butane.
19. (a) Among various alkyl halide which one is the most reactive towards SN1 reaction.
(Write 1 for 1° RX, 2 for 2° RX, 3 for 3° RX.)

Me
Re d P
(b) D OH  ?
HI
Et
(Number of organic product formed)

OH

HI
(c) 

Number of chiral carbon formed in the major product.

Write answer of part (a), (b) & (c) in the order X Y Z and present the three digit number as
answer. For example : Answer of (a) is 1 , (b) is 2 and (c) is 3 you will fill 123 in OMR sheet.

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 JEE
20. The alcohol among following which show dehydration reaction faster than 2-methyl propan-2-ol
OH
( ).
OH
(i) OH (ii) Ph (iii) OH (iv)
OH
OH
OH OH OH
(v) (vi) (vii) (viii)

OH OH
(ix) (x)

21. Identify number of substrate those can give SN1 and SN2 reaction both.

C2H5 CH3 Br
H3 C
CH3 Br , H3C Cl , , ,
H3 C Br Ph
CH3
Br OTf

O Cl , , ,
H3C H3C CH2 Cl ,
O
Cl Br

, , Cl

22. How many products (including stereoisomers) would you expect to obtain upon mono-chlorination of
the indicated substrate under the conditions shown?
Cl
h
+ Cl2 

O
||
PCl5 x NaNH 2 CH3I
23. Reaction-1 : Ph  C  CH3       Ph  C  C  CH3

y NaNH
Reaction-2 : 
2
 CH3  C  C  CH3

z NaNH Et–I
Reaction-3 : Ph – CH – CH 2   
 Ph  C  C  Et
2

| |
Cl Cl
x, y, z are moles used. Sum of [x + y + z = ]

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 Alkyl Halide & Aryl Halide
24. Sum of -hydrogen in major product of the reaction.
OH
H+
Reaction-1: 
 (A)
Δ

OH
H+
Reaction-2: 
 (B)
Δ

OH
H+
Reaction-3: 
 (C)
Δ

OH
H+
Reaction-4: 
 (D)
Δ

Sum of -hydrogen is A + B + C + D =

CH3 CH3
H+
25. Reaction-1: CH3 C CH CH3 
Δ

 (A)
OH

CH3
H+
Reaction-2: CH3 CH CH2 CH2 OH 
Δ
 (B)

CH3
H3C H+
Reaction-3: CH CH CH2 OH 
Δ
 (C)
H3C
Sum of -hydrogen is A + B + C =

CH3
H+
26. CH3 CH CH CH3 
Δ

 ( x) (SN 1+ E1 ) products. (including stereoisomer)
consider all product
Br
Total number of products are-

*****

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 JEE

EXERCISE # 4(A)(Expert – JEE Advanced PYQs)

1. The compound that will react most readily with NaOH to form methanol is (JEE Adv. 2001)
(A) (CH3)4N+ I– (B) CH 3OCH 3 (C) (CH3)3S+ I– (D) (CH3)3 Cl
2. 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 (JEE Adv. 2001)
(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 statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
3. An SN2 reaction at an asymmetric carbon of a compound always gives. (JEE Adv. 2001)
(A) an enantiomer of the substance (B) a product with opposite optical rotation
(C) a mixture of diastereomers (D) a single stereoisomer
4. Consider the following reaction. (JEE Adv. 2002)

H 3C – CH – CH – CH3 + Br  ‘X’ + HBr
D CH3
Identify the structure of the major product X.
 
(A) H 3C – CH – CH – CH2 (B) H 3C – CH – C – CH 3
D CH 3 D CH 3
 
(C) H 3C – C — CH – CH 3 (D) H 3C – CH – CH – CH3
D CH 3 CH 3
5. The produce of following reaction is: (JEE Adv. 2003)
OH


+ C2H5I 
C 2 H5 O (excess)
anhy.C 2 H 5 OH

(A) C 6H 5OC 2H 5 (B) C 2H 5OC 2H 5 (C) C 6H 5OC 6H 5 (D) C 6 H 5 I

6. The following compound on hydrolysis in aqueous acetone will give: (JEE Adv. 2005)
CH 3 H CH 3

MeO NO 2

H Cl CH 3

CH 3 H CH 3 CH 3 H CH 3

(K) MeO NO 2 (L) MeO NO 2

H OH CH 3 OH H CH 3

CH 3 H CH 3

(M) MeO NO 2

H CH 3 OH
It mainly gives
(A) K and L (B) Only K (C) L and M (D) Only M

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 Alkyl Halide & Aryl Halide

CH 3

Cl2 , h
7. H 3C 
monochlorination
 (isomeric products) N 
Fractional
distillation
 M (isomeric products).
CH3

What are N and M ? (JEE Adv. 2006)

(A) 6, 6 (B) 6, 4 (C) 4, 4 (D) 3, 3
8. The reagent(s) fot the following conversion: (JEE Adv. 2007)
Br 
?
 H ——
—
Br — H
is / are :
(A) alcoholic KOH (B) alcoholic KOH followed by NaNH2
(C) aqueous KOH followed by NaNH2 (D) Zn/CH3OH
9. The major product of the following reaction is: (JEE Adv. 2008)

H 3C Br
F
 PhSNa
dimethyl formamide


NO 2

H 3C SPh H 3C SPh H 3C Br H 3C SPh

F F SPh SPh
(A) (B) (C) (D)

NO 2 NO 2 NO 2 NO 2

10. KI in acetone, undergoes SN2 reaction with each of P, Q, R and S. The rates of the reaction vary as
(JEE Adv. 2010)

O
Cl
H 3C – Cl Cl Cl
P Q R S

(A) P > Q > R > S (B) S > P > R > Q (C) P > R > Q > S (D) R > P > S > Q

OCH3   the products are:

HBr
11. In the reaction (JEE Adv. 2010)

(A) Br OCH 3 and H 2 (B) Br and CH 3Br

(C) Br and CH 3 OH (D) OH and CH3 Br

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 JEE
12. After completion of the reaction (I and II), the organic compound(s) in the reaction mixtures is(are):
(JEE Adv. 2013)
O

CH 3  
Br2 (1.0 mol)
Reaction I: H 3C aqueous NaOH
(1.0 mol)

CH 3 
Br2 (1.0 mol)
Reaction II: H 3C CH3COOH
(1.0 mol)

O
O O

H3 C CH2Br H 3C CBr3 Br3 C CBr3

P Q R
O O

BrH2 C CH2Br H 3C ONa CHBr3

S T U
(A) Reaction I : P and Reaction II : P
(B) Reaction I : U, acetone and Reaction II : Q, acetone
(C) Reaction I : T, U, acetone and Reaction II : P
(D) Reactin I : R, acetone and Reaction II : S, acetone
13. Match the chemical conversions in List-I with the appropriate reagents in List-II and select the
correct answer using the code given below the lists: (JEE Adv. 2013)
List-I List-II

P. Cl  1. (i) Hg(OAc)2; (ii) NaBH4

Q. ONa  OEt 2. NaOEt

OH
R.  3. Et – Br


S. 4. (i) BH3; (ii) H2O/NaOH
OH
Codes:
(A) P  2; Q  3; R  4; S  4
(B) P  3; Q  2; R  1; S  4
(C) P  2; Q  3; R  4; S  1
(D) P  3; Q  2; R  4; S  1

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 Alkyl Halide & Aryl Halide
14. The major product in the following reaction is: (JEE Adv. 2014)
O
Cl 
1.CH3 MgBr, dry ether, 0°C
2.aq/ acid

CH 3
OH
O
(A) H 3C (B) H 2C CH 3
CH 3 CH 3

(C) (D) CH 3
CH 2 O CH 3
O
15. The major product of the reaction is: (JEE Adv. 2015)
H 3C CO 2H

 
NaNO 2 , aqueous HCl
0 C

CH 3 NH 2

H 3C NH 2 H 3C CO 2H
(A) (B)
CH 3 OH CH 3 OH
H 3C CO 2H H 3C NH 2
(C) (D)
CH 3 OH CH 3 OH
16. For the following compounds, the correct statement(s) with respect to nucleophilic substitution
reactions is (are) (JEE Adv. 2017)
CH 3
CH 3
Br Br | Br
(i) (ii) (iii) C3 H – C – Br (iv)
|
CH 3
(A) (i) and (iii) follow SN1 mechanism
(B) Compound (iv) undergoes inversion of configuration
(C) (i) and (ii) follows SN2 mechanicsm
(D) The order of reactivity for (i), (iii) and (iv) is : (iv) > (i) > (iii)
17. In the following reaction sequence, the correct structure(s) of (X) is (are) : (JEE Adv. 2018)
Me N3
X 

(1) PBr3 , Et 2 O
(2) NaI, Me2 CO
(3) NaN3 , NCONMe2
Enantiomerically pure

Me OH Me OH
(A) (B)

(C) (D)
Me OH Me OH

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 JEE
18. List-I contains reactions and List-II contains major products: (JEE Adv. 2018)
List-I List-II

P. +  1.
ONa Br OH

Q. + HBr  2.
OMe Br

R. + NaOMe  3.
Br OMe

S. + MeBr  4.
ONa
O
5.
Match each reaction in LIST-I with one or more products in LIST-II and choose the correct option.
(A) P  1, 5; Q  2; R  3; S  4 (B) P  1, 4; Q  2; R  4; S  3
(C) P  1, 4; Q  1, 2; R  3, 4; S  4 (D) P  4, 5; Q  4; R  4; S  3, 4
19. Match the reaction in List-I with the features of their products in List-II and choose the correct
option. (JEE Adv. 2023)
List-I List-II
aq.NaOH
(P) (–)-1-Bromo-2-ethylpentene   (1) Inversion of configuration
S 2 reaction N
(single enantiomer)

aq. NaOH
(Q) (–)-2-Bromopentane 
SN 2 reaction
 (2) Retention of configuration
(single enantiomer)

aq. NaOH
(R) (–)-3-Bromo-3-methylhexane 
S 1reaction
 (3) Mixture of enantiomers
(single enantiomer) N

aq. NaOH
(S) 
S 1reaction
 (4) Mixture of structural isomers
N
Me
H Me Br
(single enantiomer)

(5) Mixture of diastereomers

(A) (P)-1; (Q)-2; (R)-5; (S)-3 (B) (P)-2; (Q)-1; (R)-3; (S)-5
(C) (P)-1; (Q)-2; (R)-5; (S)-4 (D) (P)-2; (Q)-4; (R)-3; (S)-5
20. In the following reactions, P, Q, R, and S are the major products-
(i) Mg, dry ether
(ii) CO2dry ether
(i) Mg, dry ether
 P 
+ Q
(ii) H O (iii) H3O
2
Cl Cl (iv) NaOH

(i) ethanolic NaCN

(i) Mg, dry ether (ii) H 2 , / Ni
(ii) CH3 , CHO, then H 2O
 R 
(iii) CHCl3 / KOH, Δ
S
(iii) CrO3
Cl Cl (iv) LiAlH 4 , then H 2O

The correct statement about P, Q, R and S is: (JEE Adv. 2023)

(A) P is a primary alcohol with four carbons.
(B) Q undergoes Kolbe’s electrolysis to give an eight-carbon product.
(C) R has six carbons and it undergoes Cannizzaro reaction.
(D) S is a primary amine with six carbons.
*****

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 Alkyl Halide & Aryl Halide

EXERCISE # 4(B)(Conqueror - Variety of JEE Advanced PYQs)

1. How many chiral compounds are possible on monochlorination of 2-methl butane? (JEE Adv. 2004)

2. Match the following: (JEE Adv. 2006)

Column-I Column-II
(A) CH3 – CHBr – CD3 on treatment with alc. (P) E1 reaction
KOH gives CH2 = CH – CD3 as a major product.
(B) Ph – CHBr – CH3 reacts faster than Ph-CHBr-CD3 (Q) E2 reaction
(C) Ph-CD2 – CH2Br on treatment with C2H5OD/C2H5O –

gives Ph-CD = CH2 as the major product. (R) E1 cb reaction

(D) PhCH2CH2Br and PhCD2CH2Br react with same rate (S) First order reaction

3. The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentyhexane using

alcoholic KOH is. (JEE Adv. 2011)

4. In the following monobromination reaction, the number of possible chiral products:

CH 2CH 2CH 3

H Br 
Br2 (1.0 mole)

300°C (JEE Adv. 2016)
CH 3
(1.0 mole)
(enantiomerically pure)

5. The weight percentage of hydrogen in Q, formed in the following reaction sequence, is ___.

Cl

1. NaOH, 623K, 300 atm

Q (major product) (JEE Adv. 2022)
2. conc. H2SO4 and then conc. HNO3
[Given Atomic mass of H = 1, C = 12, N = 14, O = 16, S = 32, Cl = 35]

*****

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 JEE

JEE MAIN YEARLONG REVISION EXERCISE

OCH3
(i) NaCN
(ii) OH –
1.  A
(iii) Cyclohexanone Major Product
(iv) H 2 Ni

Br
The major product of the above reaction is: (JEE Main 2021)

OCH3 OCH3

(A) NH2 (B) HO NH 2

OCH3 OCH3

O HO
(C) (D)
C – NH2 NH2

2. The major product of the following reaction is: (JEE Main 2021)

F
 
Ph S Na

DMF

NO2

SPh I SPh SPh

F SPh SPh SPh
(A) (B) (C) (D)

NO2 NO2 NO2 NO2

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 Alkyl Halide & Aryl Halide
3. The major product (P) in the reaction: `
Ph Br 
HBr
 ? (P) [Ph is – C6H5] is (JEE Main 2021)

Br
Br
Ph Br
(A) (B) Ph
Br
Br
Ph Br Ph Br
(C) (D)
Br Br

Anhydrous,AlCl
4. + CH3CH2CH2Cl 
3 'A '
Major Product

The stable carbocation formed in the above reaction is: (JEE Main 2021)
 
(A) CH3CH 2CH 2 (B) CH3CH 2
+
CHCH2CH3


(C) CH3  CH  CH3 (D)

5. Two isomers (A) and (B) with Molar mass 184 g/mol and elemental composition C, 52.2%; H, 4.9%
and Br 42.9% gave benzonic acid and p-bromobenzoic acid, respectively on oxidation with KMnO4.
Isomer 'A' is optically active and gives a pale yellow precipitate when warmed with alcoholic AgNO3.
Isomer 'A' and 'B' are, respectively: (JEE Main 2021)

CH2Br CH2Br CH2CH3

CH3 CH3
(A) H3C – CHBr – C6H5 and (B) and

Br
CH2CH3 CH 2CH3

(C) H3C – CHBr – C6H5 and (D) and H3C – CHBr – C6H5

Br Br
H3C OH H3C Cl

20% H PO (CH ) CO K 

6. 3 4
 "A" , 
3 3
 "B" ,
358 K (Major Pr oduct) (Major Pr oduct)

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 JEE
The product "A" and "B" formed in above reactions are: (JEE Main 2021)
CH2 CH2 CH 3 CH 3

(A) A – B– (B) A– B–

CH 3 CH2 CH2 CH 3

(C) A– B– (D) A– B–

7. Ammonolysis of Alkyl halides followed by the treatment with NaOH solution can be used to prepare
primary, secondary and tertiary amines. The purpose of NaOH in the reaction is: (JEE Main 2021)
(A) To remove basic impurities
(B) To activate NH3 used in the reaction
(C) To remove acidic impurities
(D) To increase the reactivity of alkyl halide
Cl –
O Na
+

8. + NaOH  (JEE Main 2021)

The above reaction requires which of the following reaction conditions?

(A) 573 K, Cu, 300 atm (B) 623 K, Cu, 300 atm
(C) 573 K, 300 atm (D) 623 K, 300 atm
9. For the reaction RCH2 Br + I–  Acetone
 RCH2I +Br
– (JEE Main 2023)
The correct statement is:
(A) Br– can act as competing nucleophile.
(B) The reaction can occur in acetic acid also.
(C) The transition state formed in the above reactions is less polar then the localised anion.
(D) The solvent used in the reaction solvates the ions formed in rate determining step
10. Choose the halogen which is most reactive SN1 reaction in the given compound (i, ii, iii and iv):
Br(a)

(i) (ii) I I(b)

(a)
Br (b)

Br(b)
(iii) (iv)
Br (a) Br(b) Br(a)
Me
(A) (i) – Br(b); (ii) – I(a); (iii) – Br(a); (iv)–Br(a)
(B) (i) – Br(b); (ii) – I(b); (iii) – Br(b); (iv) – Br(b)
(C) (i) – Br(a); (ii) – I(a); (iii) – Br(b); (iv)–Br(a)
(D) (i) – Br(a); (ii) – I(a); (iii) – Br(a); (iv) – Br(a)
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 Alkyl Halide & Aryl Halide
11. Identify the major product in the following reaction. (JEE Main 2024)
Br

CH3

CH2 CH3 CH3 Br

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

12. The correct arrangement for decreasing order of electrophilic substitution for above compounds is:
CH3 OCH3 CF3

(JEE Main 2024)

(I) (II) (III) (IV)
(A) (III) > (I) > (II) > (IV) (B) (IV) > (I) > (II) > (III)
(C) (III) > (IV) > (II) > (I) (D) (II) > (IV) > (III) > (I)
13. Which among the following compounds will undergo fastest SN2 reaction. (JEE Main 2024)

Br Br Br
(A) (B) (C) Br (D)
14. Given below are two statements : (JEE Main 2024)
Statement (I): SN2 reactions are 'stereospecific', indicating that they result in the formation of only
one stereoisomer as the product.
Statement (II): SN1 reactions generally result in formation of product as racemic mixtures.
In the light of the above statements, choose the correct answer from the options given below:
(A) Both Statement I and Statement II are false
(B) Statement I is false but Statement II is true
(C) Statement I is true but Statement II is false
(D) Both Statement I and Statement II are true
15. Given below are two statements: one is labelled as Assertion (A) and the other is labelled as Reason
(R). (JEE Main 2024)
Assertion (A): SN2 reaction of C6 H 5CH 2 Br occurs more readily than the SN2 reaction of
CH 3CH 2 Br .
Reason (R): The partially bonded unhybridized p-orbital that develops in the trigonal bipyramidal
transition state is stabilized by conjugation with the phenyl ring.
In the light of the above statements, choose the most appropriate answer from the options given
below :
(A) (A) is correct but (R) is not correct
(B) (A) is not correct but (R) is correct
(C) Both (A) and (R) are correct but (R) is not the correct explanation of (A)
(D) Both (A) and (R) are correct and (R) is the correct explanation of (A)
16. Given below are two statements : one is labelled as Assertion (A) and the other is labelled as Reason
(R). (JEE Main 2024)
Assertion (A): Haloalkanes react with KCN to form alkyl cyanides as a main product while with
AgCN form isocyanide as the main product.
Reason (R): KCN and AgCN both are highly ionic compounds.
In the light of the above statement, choose the most appropriate answer from the options given
below:
(A) (A) is correct but (R) is not correct
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 JEE
(B) Both (A) and (R) are correct but (R) is not the correct explanation of (A)
(C) (A) is not correct but (R) is correct
(D) Both (A) and (R) are correct and (R) is the correct explanation of (A)
17. Identify A and B in the following sequence of reaction. (JEE Main 2024)
CH3
Cl /hv HO

2
 A 
2
B
373 K

COCl CHO CHCl2 CHO

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

CH2 Cl CHO
(C) (A) = (B) = (B)

CHCl2 COOH
(A) = (B) =

18. Which among the following halide/s will not show SN1 reaction: (JEE Main 2024)
(1) H2C = CH – CH2Cl (2) CH3 – CH = CH – Cl
CH2 –Cl H3C
(3) (4) CH Cl
H3C
Choose the most appropriate answer from the options given below:
(A) (1), (2) and (4) only (B) (1) and (2) only
(C) (2) and (3) only (D) (2) only
19. Identify B formed in the reaction. (JEE Main 2024)
excess NH NaOH
Cl  (CH 2 ) 4  Cl 
3
A 
 B  H 2 O  NaCl
H
N
(A) (B) H 2 N  (CH 2 ) 4  NH 2

H
  N

(C) CH3  (CH 2 )4  NH3Cl (D)

20. Given below are two statements : one is labelled as Assertion A and the other is labelled as Reason
R: (JEE Main 2024)
Assertion A: Aryl halides cannot be prepared by replacement of hydroxyl group of phenol by
halogen atom.
Reason R: Phenols react with halogen acids violently. In the light of the above statements, choose
the most appropriate from the options given below:
(A) Both A and R are true but R is NOT the correct explanation of A
(B) A is false but R is true
(C) A is true but R is false
(D) Both A and R are true and R is the correct explanation of A

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 Alkyl Halide & Aryl Halide
21. Alkyl halide is converted into alkyl isocyanide by reaction with (JEE Main 2024)
(A) NaCN (B) NH 4CN (C) KCN (D) AgCN
22. Given below are two statements:
Statement-I: High concentration of strong nucleophilic reagent with secondary alkyl halides which
do not have bulky substituents will follow SN2 mechanism.
Statement-II: A secondary alkyl halide when treated with a large excess of ethanol follows SN1
mechanism. (JEE Main 2024)
In the the light of the above statements, choose the most appropriate from the questions given below:
(A) Statement I is true but Statement II is false.
(B) Statement I is false but Statement II is true.
(C) Both statement I and Statement II are false.
(D) Both statement I and Statement II are true.
23. The correct order of reactivity in electrophilic substitution reaction of the following compounds is:
(JEE Main 2024)

CH3 Cl NO2

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

(A) II > III > I > IV (B) IV > III > II > I (C) I > II > III > IV (D) II > I > III > IV
24. In the following sequence of reaction, the major products B and C respectively are:

Na/Et2O (i) Mg/Et2O

Cl Br A (ii) D2O B
CoF2

(A) D D and F F (JEE Main 2024)

(B) and F F

(C) D D and F F

(D) D D and F F

25. Arrange the following compounds on increasing order of rate of SN1 reaction in H2O
Br Br
(I) Br (II) (III)

(A) I = II < III (B) I > II > III (C) I < II = III (D) I < II < III

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 JEE

Cl Cl
Cl
Cl Cl
Aq.KOH (excess)
26. Major product ; Major product is :
Cl Cl
Cl

HO OH HO OH
OH OH
OH OH
(A) HO (B) Cl

OH OH OH
OH OH Cl

O O
OH Cl
(C) Cl OH (D) OH
Cl

Cl OH Cl OH
Cl Cl
27. In which of the following cases SN1 reaction is not taking place
CH3 H
(A) C Br 
H 2O  C2 H 5OH
 (B) C Br 
CH3Li  ether
 
CH3 H

CH3 CH3
O
||
(C) C Br 
H 2 O CH3  C  CH 3
 (D) CH3 C CH CH3 
C 2 H 5OH

H CH3Br
28. The best reagent for converting ethanol to chloroethane is:
(A) PCl3 (B) PCl5 (C) SOCl2 (D) HCl + ZnCl2
29. The yield of alkyl bromide obtained as a result of heating the dry silver salt of carboxyic acid with
bromine what will be the order of formation w.r.t. alkyl bromide -
(A) 1º > 3º > 2º bromides (B) 1º > 2º > 3º bromides
(C) 3º > 2º > 1º bromides (D) 3º > 1º > 2º bromides
30. Consider the given organometallic compound:
(I) (CH3)2Hg (II) (CH3)2Zn (III) (CH3)2Mg (IV) CH3Li
The correct decreasing order of ionic character is :
(A) I > II > III > IV (B) II > I > III > IV
(C) I > III > II > IV (D) IV > III > II > I
(i) SH – (1 eq.)
In the given reaction CH 3  CH  CH 2  CH 2  CH  CH 3 
 (X), X will be : (ii) KOH
31.
| |
OTs OTs
OTs S SΘ SΘ
| | | |
(A) CH 3 – CH – CH 2 – CH 2 – CH – CH 3 (B) CH 3  CH  CH 2  CH 2  CH  CH 3

CH3 CH3
CH3 S CH3
(C) (D) S

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 Alkyl Halide & Aryl Halide
32. The reaction of SOCl2 on alkanols to form alkyl chlorides gives good yields because
(A) Alkyl chlorides are immscible with SOCl2
(B) The other products of the reaction are gaseous and escape out
(C) Alcohol and SOCl2 are soluble in water
(D) The reaction does not occurs via intermediate formation of an alkyl chloro sulphite
33. Which solvent is used for SN1 reaction ?
(A) Dihydrogen oxide (B) Acetone
(C) DMSO (D) Acetonitrite
34. In the given reaction:

( 
 [X]
i ) NaN 3
( ii ) NH 4 Cl ( aq )

[X] will be:

N3

(A) (B) OH

(C) Mixture of (A) and (B) (D)

35. Find out the correct order of rate of reaction towards allylic substitution.
(I) CH3–CH = CH2
(II) CH3–CH2–CH=CH2
CH 3
|
(III) CH 3  CH  CH  CH 2
(A) I > II > III (B) II > I > III (C) III > II > I (D) III > I > II
36. What is the order of reactivity with HBr.

(a) (b) (c)

(A) a > b > c (B) b > a > c (C) c > b > a (D) b > c > a
37. Addition of CCl3Br in presence of Peroxide is example of :
(A) Electrophillic Addition (B) Free Radical substitution
(C) Free Radical Addition (D) Electrophillic substitution
AgHCl ( excess )
38. CHCl3  A    B (major)

B is
Cl
(A) H 2C  CH 2 (B) H3C – CH
| | Cl
Cl Cl

(C) H 3C  C  Cl (D) H  C  CH 2  Cl
|| ||
O O

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 JEE
39. In the given pairs, which pair represent correct order of rate dehydrohalogenation reaction.
(A) < (B) <

(C) < (D) CH3–CH2–Cl < CD3 – CD2 – Cl

I Br

OH–
40. Major product.

NMe3

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

41. Which of the following compound can not decolourise bromine water-

(A) (B) (C) (D) H3C – C  C – CH3

Me
SOCl2
P
42. HO D
SOCl2
Q
H
N

P and Q are respectively

Me Me Me Me

(A)
D Cl Cl D (B)
Cl D D Cl

H H H H
Me Me Me Me

Cl D H Cl D Cl Cl H
(C) (D)
H D H D
43. Which of the following compounds is most rapidly hydrolysed by SN1 mechanism.
(A) C6H5Cl (B) Cl – CH2 – CH = CH2
(C) (C6H5)3CCl (D) C6H5CH2Cl
44. Racemic mixture is obtained due to halogenation of:
(A) n-pentane (B) Isopentane
(C) Neopentane (D) Both A & B
45. True about alkyl halides is / are:
(A) Tertiary alkyl halides undergo SN2 substitutions
(B) Alkyl iodides on exposure to sunlight gradually darken
(C) Alkyl chlorides do not give beilstein test
(D) A nucleophilic substitution is most difficult in alkyl iodides

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 Alkyl Halide & Aryl Halide

46. alcoholic
 , KOH

 A
E2

(A) (B) (C) (D) None is correct

47. To remove ‘phosgene’ from chloroform, _________ is added:

(A) Ethyl amine (B) Ethyl chloride (C) Ethyl alcohol (D) Ethane
48. Which product is obtained when bleaching powder is distilled with acetone:
(A) CCl4 (B) CHCl3 (C) CH2Cl2 (D) CH3Cl
49. SN1 & SN2 product are same in (excluding stereoisomer)

(A) (B) (C) (D) Ph  CH  CH  CH 3

| |
CH 3 Cl
50. Arrange the following compounds in decreasing order of their reactivity for hydrolysis reaction

(I) C6H5–CH2–Br (II) C6 H 5  CH  C 2 H 5 (III) (IV)

|
Br
(A) I > II > III > IV (B) IV > II > I > III (C) III > IV > II > I (D) IV > III > II > I
51. Non-occurence of the following reaction:
Br– + CH3OH  BrCH3 + OH–, is due to
(A) Attacking nucleophile is stronger one (B) Leaving group is a strong base
(C) Alcohols are not good substrate (D) Hydroxide ions are weak bases
52. When ethyl bromide is treated with moist Ag2O, main product is:
(A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above
53. When ethyl bromide is treated with dry Ag2O, main product is:
(A) Ethyl ether (B) Ethanol (C) Ethoxy ethane (D) All of the above

C H O
54.   ? Major product is:
2 5
C 2 H5OH

(A) (B)

(C) (D)

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 JEE
55. A gem dichloride is formed in the reaction except:
(A) CH3CHO and PCl5 (B) CH3COCH3 and PCl5
(C) CH2 = CH2 and Cl2 (D) CH2 = CHCl and HCl

Na / C H OH
56.  2 
5
 [A] product is :
liq. NH3

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

57. Fe/HCl reduction of ‘pyrene’(CCl4) gives:

(A) CH4 (B) CH2Cl2 (C) CH3Cl (D) CHCl3

58. is converted into by:

(A) (i) CH3 – MgI, H3O+ (ii) H2SO4, , (iii) HBr, R2O2
(B) (i) CH3– MgI, H3O+ (ii) H2SO4, , (iii) HBr
(C) (i) CH3– MgI, H3O+ (ii) HBr
(D) (i) HBr, R2O2 (ii) CH3– MgI, H3O+
59. Consider the given reaction:

H 3C  CH  CH  CH  CH 3 HBr
 [P]
| SN1
OH
In the given reaction the product [P] is :

Br
|
(A) H 3C  CH  CH  CH  CH 3 (B) CH 3  CH  CH  CH 2
|
Br
Br
|
(C) CH2=CH–CH=CH2 (D) CH 3  CH  CH 2  CH 2  OH

C = CH2
60. HBr

H D CCl4

CH3

What is stereochemistry of product?

(A) Racemic mixture (B) Optically inactive
(C) Diastereomers (D) Meso product
*****

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 Alkyl Halide & Aryl Halide

JEE ADVANCED YEARLONG REVISION EXERCISE

1. In the given reaction:

CH3
B H , THF , +
H2O2 NaOH TSCl t-BuO¯ K

2 6
      (Y)

(X)
The product ‘Y’ is:
(A) A positional isomer of X (B) Identical to X
(C) Chain isomer of X (D) An oxidation product of X

2. H /H O

2

O OCH3

(A) +CH3OH (B) +CH3OH

HO O H HO OH

(C) +CH3OH (D) +CH3OH

HO O OH O O
3. H 3C  CHBrF KOH
  Product(s)
/ DMSO

( R  Isomer ) (1.eq )

Product(s) is / are
(A) S-1-Fluoro-ethan-1-ol (B) R-1-Fluoro-ethan-1-ol
(C) R-1-Fluoro-ethan-1-ol + enantiomer (D) R-1-Bromo-ethan-1-ol
Me

4. OH + SOCl2 (
C 2 H 5 )3 N

or   Product

Et N
Product possible is / are
Me Me
 
(A) Cl (B) Cl (C) (C2 H5 )3 NH Cl (D) SO2

Et Et
5. In which of the following case configuration about chiral C) is retained:

CH Br SOCl CH ONa
(A) Na
 3 (B) 2  3

1. TsCl
(C) 
PCl3
  
CH 3ONa
(D) H 2  
.MeONa

D
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 JEE
6. Select correct statement about the product (P) of the reaction:

Br
2 /
CCl 4
 P
(A) P is optically inactive due to internal compensation
(B) P is optically inactive due to the presence of plane of symmetry in the molecule
(C) The structure of P can have three optical isomers possible.
(D) P can have four possible optical isomers.
7. In the given reaction

C7H12 (A) HBr



(A) can be

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

CH3
H Br Θ
OEt /EtOH
8.   Possible products
D H Δ

CH3

CH3 CH3 CH3 H CH3 CH3 CH3 H

(A) (B) (C) (D)
D H D CH3 H H H CH3
9. Consider the given reaction
CH 3
|
H  C  OTs NaCN
 CH 3CH 2 CH  CN
|
C 2 H 5 (S) |
CH 3
which of following statements are correct for above reaction.
(A) Product formation takes place due to the breaking of O–Ts
(B) The reaction is SN2
(C) The reaction is SN1
(D) Configuration of product is (R)
10. Which are possible products in following

/ H 2O / 
Ag
 

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

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 Alkyl Halide & Aryl Halide

11. SOCl2 Mg, O

OH Product
Pyridine Et 2O H3O
O
Product of reaction is:
O
OH CH3
(A) (B)
CH–C
O O CH3

(C) CH3 (D) OH

O CH2 C CH2 OH O CH2 CH2 C CH3
CH3 CH3

12. Br / CCl 4

2   P,, P is

Br

(A) (B) + enantiomer

Br
Br
Br
(C) (D) No reaction
Br
Br

Cl
Cl Cl
13. alc.KOH

Cl Cl
Cl

Cl Cl

(A) (B) (C) (D) No reaction

Cl Cl
Cl Cl Cl
Cl
CH3
14. Ph Cl Zn, Δ

Ph Cl
CH3

Ph Me Ph Ph Ph Me
(A) C C (B) C C (C) C C (D) No reaction
Me Ph Me Me Ph Me

(284)
 JEE

Ph
15. H3C Cl 
NaI/acetone

Δ
Cl CH3
Ph

Ph Ph Ph CH3
(A) C C (B) C C
H3 C CH3 H3 C Ph

Ph CH3
(C) C C (D) No reaction
Ph CH3
16. Pick the correct orders of reactivity:


(A) SN 1 > > Cl > Cl
Ph Cl Cl

O
(B) SN 2 
 Cl > H3CO Cl > Ph Cl > Cl
Ph

(C) E 
 Cl > Cl > Cl

O

(D) SN 1 N > > > Cl
Cl Cl Cl
17. Which of the following reactions take place by SN2 reaction?
O NaI OTs NaI
(A) Br 
 (B) 

acetone acetone
O

O CH3
NaI
(C)   (D) + H3 C C Br 

acetone
O CH2 S
O
CH3
OTs
18. Identify the compounds which may give NGP reaction:

CH3
S
O
(A) (B) H3 C Br

CH3
(C) (D) H3C CH CH2 Cl
CH2 CH2 Cl

(285)
 Alkyl Halide & Aryl Halide
19. Which one is correct for the products of the given reaction ?

Me
Me
H CN 
aqueous acetone
H H
H
Cl

OCH3

Me Me Me
Me Me Me
H
H H
H H CN OH H CN H HOH CN

H H H
H
OH H

OCH3 OCH3 OCH3

(X) (Y) (Z)

(A) only X and Z are formed (B) Z > Y (amount)

(C) X > Y (amount) (D) Y > X (amount)
20. Identify the compounds that will undergo NGP reaction:
(A) CH3CH2–S–CH2CH2Br (B) CH3–NHCH2CH2CH2Br
(C) CH 3 – CH – C= O (D) CH3–O–CH2CH2CH2Br
| |
Br O –
21. Which alkyl halide undergo E2 elimination:

(A) (B)

(C) (D)

22. NBS
 Allylic brominated products
CCl4 , 

Find out the incorrect statement.

(A) It gives total 9 allylic brominated products
(B) All allylic brominated products are optically active
(C) Substrate has 7 allylic hydrogens
(D) NBS gives Br constantly to reaction mixture.
(286)
 JEE

CH3

/ h
23. Cl
2  Monochloroderivatives

Total number of monochloroderivatives formed in above reaction are

(A) 8 (B) 12 (C) 10 (D) 6

24. HBr
 (1eq.)

40C
Which statement is incorrect about this reaction.
(A) Major product is formed by 1,2-addition.
(B) 1,4- addition product is KCP (Kinetically controlled product)
(C) TCP (Thermodynamically controlled product) is formed by 1,4-addition
(D) TCP forms as major product.
14

25. SOCl
2  Product(s)
OH
Product(s) is / are

14
Cl
14
14 Cl
(A) only (B) only (C) Both (A) and (B) (D)
Cl

conc.H2SO4 DBr
26. OH

Final major product is :
D
D Br
(A) (B)
Br
D

(C) (D)
D Br Br
CH3
Θ
18 PCl3 O –CH 3
27. H OH    R

D
R is
CH3 CH3 CH3 CH3
18 18
(A) H O–CH3 (B) H3CO D (C) H3CO H (D) H O–CH3

D H D D
(287)
 Alkyl Halide & Aryl Halide
28. For the given reaction
R1 R1
| |
R  C  X HOH
 R  C  OH
| |
R2 R2
Which substrate will give maximum racemisation?
CH 3 CH 3
| |
(A) C6 H 5  C  Br (B) CH 2  CH  C  Br
| |
C2H 5 C2H 5

Br
Br
C6H5 C NO2
C6H5 C OCH3
(C) (D)

NH3
CH3 

29.  ? Product is:

Br 2

(A) (B) (C) Both (A) & (B) (D) None of these

30. Match the column

Column-I Column-II
(A) SN1 (P) Carbocation intermediate formation is involved
(B) SN 2 (Q) Reactivity order of R–I follows
CH3
CH3 C I > CH3 CH I > CH3 CH2 I

CH 3 CH 3
CH3 CH2
(C) E 1 (R) Reactivity order follows Ph–CH–Cl > Ph–C–Cl
(D) E 2 (S) Reactivity order follows R–I > R–Br > R–Cl > R–F



(288)
JEE

CONTENTS
7.0 INTRODUCTION 7.9 EPOXIDES
7.1 PREPARATION OF ALCOHOLS 7.10 REACTIONS OF EPOXIDES
7.1.1 Grignard Synthesis 7.10.1 Acid-catalysed cleavage
7.1.2 Hydrolysis of Alkyl Halides 7.10.2 Base-catalysed cleavage
7.1.3 Hydroxylation of Alkenes 7.10.3 Reaction with Grignard reagent
7.1.4 Oxymercuration-Demercuration 7.11 PHENOLS
7.1.5 Hydroboration-Oxidation 7.12 PREPARATION OF PHENOLS
7.1.6 Reduction of Carbonyl Compounds
7.12.1 Dow Process
7.2 PHYSICAL PROPERTIES OF 7.12.2 From Cumene (Isopropyl Benzene)
ALCOHOLS 7.12.3 Hydrolysis of Diazonium Salts
7.3 CHEMICAL PROPERTIES OF 7.13 PHYSICAL PROPERTIES OF
ALCOHOLS PHENOLS
7.3.1 Reactions Involving C—OH Bond
7.14 CHEMICAL PROPERTIES OF
Cleavage
PHENOLS
7.3.2 Reactions involving O—H Bond Cleavage
7.14.1 Acidic Nature of Phenols (Salt
7.3.3 Miscellaneous Reactions
Formation)
7.4 TESTS FOR ALCOHOLS 7.14.2 Ester Formation Fries Rearrangement
7.4.1 Lucas Test 7.14.3 Ether Formation
7.4.2 Oxidation 7.14.4 Ring Substitution Reactions
7.4.3 Victor-Meyer Test 7.15 ANALYSIS OF PHENOLS
7.4.4 Iodoform test
7.4.5 Analysis of 1, 2 –Diols/Periodic Acid
Oxidation
7.5 ETHERS
7.6 PREPARATION OF ETHERS
7.6.1 Dehydration of alcohols
7.6.2 Williamson synthesis
7.7 PHYSICAL PROPERTIES OF
ETHERS
7.8 CHEMICAL PROPERTIES OF
ETHERS
7.8.1 Cleavage by acids

(289)
 Alcohol, Phenol & Ether

7.0 INTRODUCTION
Alcohols are organic compounds containing a hydroxyl group attached to a saturated carbon atom
and having the general formula R—OH, where R can be an alkyl or a substituted alkyl group.
Alcohols can be monohydric or polyhydric depending on whether they contain one or more hydroxyl
groups. Alcohols can also be classified as primary (1°), secondary (2°), or tertiary (3°) depending on
whether the hydroxyl-bearing carbon atom is attached to one, two, or three carbon atoms.

7.1 PREPARATION OF ALCOHOLS

Alcohols are starting point for organic synthesis of a number of compounds and can be obtained from
organic raw materials in nature like petroleum, natural gas, coal, and biomass. Some important methods
for preparing alcohols are-
7.1.1 Grignard Synthesis:

+ – – + –+ H2O
C = O + R — MgX — C — OMgX — C — OH + Mg(OH)X

R R

Mg(OH)X is a gelatinous material and is difficult to handle. It is converted to water-soluble magnesium

salts by mineral acids.
H+ –
Mg(OH)X Mg2+ + X + H2O

Grignard synthesis is an example of nucleophilic addition—the characteristic reaction of aldehydes

and ketones. The class of alcohol obtained in the reaction depends upon the type of carbonyl compound
used. Formaldehyde yields primary alcohols, aldehydes with more than one carbon atom yield secondary
alcohols, and ketones yield tertiary alcohols.
H
H – + H2 O
C=O + R — MgX H — C — OMgX R CH2OH
H 1° alcohol
Formaldehyde R
H
H – + H2 O
C=O + R — MgX R — C — OMgX RR CH OH
R 2° alcohol
Higher aldehydes R

R R
R – + H 2O
C=O + R — MgX R — C — OMgX R — C — OH
R
R R
Ketones 3° alcohol

(290)
JEE
A convenient synthesis of primary alcohol uses ethylene oxide, and the primary alcohol formed has
two more carbon atoms than the Grinard reagent.

H2C — CH2 + R — MgX H2C CH2R R CH2CH2OH

1°alcohol
O
OMgX
Ethylene oxide

Organolithium can also be used for the synthesis of alcohols.

+ – H2O
C=O + R — Li C — O– Li + C — OH

Aldehyde/Ketone R R
Alcohol
The synthesis of alcohols by using organolithiums is a better method than by using Grignard reagents,
because organolithium compounds are less prone to unwanted side reactions and are more reactive
than Grignard reagents. Besides, organolithiums can be used to prepare alcohols from highly crowded
carbonyl compounds.
7.1.2 Hydrolysis of Alkyl Halides:
This method involves nucleophilic substitution of a halide ion by a hydroxyl ion.
aq. NaOH
R–X R — OH
or aq. KOH
SNl or SN2

aq. NaOH
Example: CH2Cl CH2OH
7.1.3 Hydroxylation of Alkenes:
1, 2 – diols can be prepared by using this method.

Cold alk. KMnO4

C C Syn-hydroxylation
or OsO4

O H OH

C=C

OH
RCO 3H, H+
C C Anti-hydroxylation
(Peroxy acids)
OH

(291)
 Alcohol, Phenol & Ether
7.1.4 Oxymercuration-Demercuration:
It involves anti-Markovnikov’s addition of water to double bond without rearrangement.

R HgOAC R H
R Hg(OAC) 2 NaBH 4
C=C —C—C— —C—C—
H2O
Demercuration
Oxymercuration OH OH
Alkyl borane

Example:

CH3 CH 3 CH 3
Hg(OAC) 2 NaBH 4
CH 3 — C = CH2 CH 3 — C — CH2 CH3 — C — CH3
H 2O
OH HgOAC OH

7.1.5 Hydroboration-Oxidation:
It involves anti-Markovnikov’s addition of water to a double bond without rearrangement.

R R H
R C=C R H2 O2
C=C + (BH3)2 —C—C— CH–C B –
— C — C — +B(OH) 3
(2eq.) OH
Diborane 3
R OH
H BH 2
Alkyl borane

CH3 CH3
(BH3 )2 H O /OH 2 2
–

Example: CH 3 — C = CH2 CH3 — CH — CH 2 — OH

7.1.6 Reduction of Carbonyl Compounds:
Aldehydes can be reduced to primary alcohols and ketones to secondary alcohols by using chemical
reducing agents.
H2/Ni
RCHO RCH2OH 1° alcohol

R LiAlH4 R
C=O CHOH 2° alcohol
R or NaBH4 R

Carboxylic acids can be reduced to primary alcohols by using LiAlH4.

(292)
JEE

4R — COOH + 3LiAlH4 4H2 + 2LiAlO2 + (R CH2O)4AlLi

H2O

4RCH2OH
1°alcohol

Acyl chlorides can also be reduced by LiAlH4.

O
LiAlH4
R C Cl R CH2 OH
1° alcohol

In the chemical reduction of esters, the acid part is reduced to primary alcohol.
Reducing Agent
RCOOR R CH2 OH + ROH

Copper chromite, CuO.CuCr2O4, can be used for reducing esters at a high pressure and temperature.
Example:

H2, CuO.CuCr2O4
CH3CH2COOCH3 CH3CH2CH2OH + CH3OH
high T, P
H+ LiAlH4

CH3CH2CH2OH

In , unsaturated carbonyl compounds, if the double bond is to be protected while reducing the
carboxyl group to an alcohol, special catalysts can be used.

O
LiAlH4
C=C—C— C = C — CH OH (unsaturated alcohol)
or NaBH4

For reducing a double bond, hydrogenation can be carried out in the presence of Ni or Pt.

O
H2
C=C—C— — C — C — CH — (saturated alcohol)
Ni/Pt

H H OH

(293)
 Alcohol, Phenol & Ether

MID LEARNING EXERCISE (MLE)-42

Q.1 The hydroboration of 2-methyl propene yields:
(A) 1º alcohol (B) 2º alcohol (C) 3º alcohol (D) None
Q.2 LiAlH4 converts acetic acid into:
(A) Acetaldehyde (B) Methane (C) Ethyl alcohol (D) Methyl alcohol
Q.3 A tertiary alcohol is obtained when CH3MgI reacts with:
(A) CH3CHO (B) CH3CH2CHO (C) CH 3  CH  CHO (D) CH3COCH3
|
CH3
Q.4 To prepare 3-ethylpentan-3-ol, the reactants needed are:
(A) CH3CH2MgBr + CH3COCH2CH3 (B) CH3MgBr + CH3CH2CH2COCH2CH3
(C) CH3CH2MgBr + CH3CH2COCH2CH3 (D) CH3CH2CH2MgBr + CH3COCH2CH3
Q.5 Action of HNO2 on CH3NH2 gives:
(A) CH3OH (B) CH3 – O – CH3
(C) CH3 – O –N = O (D) (B) and (C) both
Identify Y in the series, CH2 = CH2   X 
HBr aq KOH
Q.6 Y
(A) C2H5I (B) C 2H 5OH
(C) CHI3 (D) CH 3CHO
2
 B   C, the product C is:
H2
Q.7 In the reaction sequence, CaC2 
H 2O
 A 
Hg
dil.H 2SO 4 Ni

(A) CH3OH (B) CH3CHO (C) C2H5OH (D) C2H4

Q.8 Action of nitrous acid on ethyl amine gives:
(A) C2H6 (B) C2H5OH (C) NH3 (D) Nitromethane
Q.9 The product of acid catalyzed hydration of 2-phenylpropene is:
(A) 3-phenyl-2-propanol (B) 1-phenyl-2-propanol
(C) 2-phenyl-2-propanol (D) 2-phenyl-1-propanol
H O+
Q.10 Ester A (C4H8O2) + CH 3 MgBr 
3
B  C4H10O 
(2 parts) (alcohol)

Alcohol B reacts fastest with Lucas reagent. Hence A and B are:

CH3 O
O H3C
H
(A) H3 C , H3C OH (B) , OH
O
O H3 C
CH3 H7C3
H5 C2

O O CH3
OH H
H3 C H3 C OH
HC O,
(C) O, 3 (D)
CH3 CH3
H5C2 H7 C2

(294)
JEE
Q.11 3-methyl-3-hexanol can be prepared by
(A) CH3MgI and 3-hexanone, followed by hydrolysis
(B) C2H5MgI and 2-pentanone, followed by hydrolysis
(C) C3H7MgI and 2-butananone, followed by hydrolysis
(D) Any of the method above
Q.12 Rate of hydration of the given compounds will be in order :
CH3
CH CH2 CH CHCH3 C CH2

(I) (II) (III)

(A) I < II < III (B) I < III < I (C) II < I < III (D) III < II < I
Q.13 Predict the product when given compound reacts with excess LiAlH4 :
O O
C C
H OCH3

O
OH O OH O
C O OCH3 C O CH3

(A) (B)

O OH
OH
O

OH C
H OH
(C) (D)

OH
OH
OCH3 OCH3

4LiAlH
Q.14 (A) Major product (A) is

CO2CH3
O OH
OH OCH3 OCH3 OCH3

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

CH2 OH OH CH2OH
OH
(295)
 Alcohol, Phenol & Ether
Q.15 3-methyl-3-hexanol can not be prepared by
(A) CH3MgI and 3-hexanone, followed by hydrolysis
(B) C2H5MgI and 2-pentanone, followed by hydrolysis
(C) C3H7MgI and 2-butananone, followed by hydrolysis
(D) C4H9MgI and propanone, followed by hydrolysis
7.2 PHYSICAL PROPERTIES OF ALCOHOLS
(i) Alcohols have a higher boiling point than hydrocarbons or alkyl halides of comparable molecular
weights. This is because alcohols are capable of hydrogen bonding to their fellow alcohol molecules.
R R

R—O H—O H—O H—O

H R
The boiling point increases with an increasing number of carbon atoms and branching for a given
number of carbon atoms reduces the boiling point.
(ii) Alcohols are highly soluble in water, because of the ability of alcohol molecules to form hydrogen
bonds with water.
H

R—O H—O

H
The solubility decreases with an increase in the number of carbon atoms.
7.3 CHEMICAL PROPERTIES OF ALCOHOLS
The chemical properties of an alcohol are characteristic of the hydroxyl group. The reactions of
alcohols can either involve breaking of a C—OH bond with the removal of an —OH group or
breaking of a O—H bond with the removal of a proton, H+.
7.3.1 Reactions Involving C—OH Bond Cleavage:
(i) Reaction with phosphorus halides or SOCl2:
3ROH + PX3 3R — X + H3PO3
(PX3 = PBr3, PI3)

ROH + PX5 R — X + POX3 + HX

(PX5 = PCl5)

ROH + SOCl2 R — Cl + SO2 + HCl

(ii) Reaction with hydrogen halides
R — OH + HX R — X + H2O
The reaction is catalysed by acids. The order of reactivity of alcohols towards HX is
allyl, benzyl > 3° > 2° > 1° < CH3
The mechanism for the reaction is SNl:
Fast 
(a) R — OH + HX R — OH 2 + X


(296)
JEE

Slow
(b) R — OH2 R+ + H2O


Fast
(c) R+ + :X– R–X
Rearrangement can occur in this mechanism since carbocation intermediates are involved.
Primary alcohols react by SN2 mechanism:
 – +
: X – + R – OH 2 [X-----R-----OH 2 ] R – X + H2O
Primary alcohols do not undergo this type of rearrangement, because no carbocation intermediates
are involved.
 Reactivity of hydrogen halides: HI > HBr > HCl > HF
Hydrogen chloride is quite unreactive and requires the presence of ZnCl2 for reaction with
primary and secondary alcohols.
Example:
dry HBr
CH3CH2CH2CH2OH CH3CH2CH2CH2Br
or
NaBr, H2SO4, 

HCl + ZnCl2
CH3CH2 CH2OH  CH3CH 2CH2Cl

CH3 CH3
conc. HCl
CH3 — C — CH3 CH3 — C — CH3
room temp.

OH Cl

(iii) Dehydration: Acid catalysed:

acid
—C—C— — C = C — + H2O

H OH

 Reactivity of ROH : 3° > 2° > 1°

Dehydration of alcohols in E1 mechanism involving carbocation intermediate has the posibility of
rearrangement.
7.3.2 Reactions involving O—H Bond Cleavage:
(i) Reactions as acids: with active metals:

1
RO — H + M RO–M+ + H
2 2
(M = Na, K, Mg, Al etc.)
 Reactivity of ROH: CH3OH > 1° > 2° > 3°
(297)
 Alcohol, Phenol & Ether
When alcohols react with active metals, hydrogen gas is released; this is because of the acidic
nature of alcohols. Alcohols are weaker acids than water as shown by the reaction where a
stronger acid (H2O) displaces a weaker acid (alcohol) from its salt.
–
RO– Na+ + H – OH Na+OH + ROH
stronger stronger weaker weaker
base acid base acid

Relative acidities: H2O > ROH > NH3 > RH

Relative basicities: OH– < OR– < NH2– < R–

1
Example: CH 3CH 2 OH 
Na
 CH3CH 2 O  Na   H2
2

CH3 CH3
Al
CH3 — C — OH CH3 — CH — O– 3Al
Aluminimum
H isopropoxide

K
(CH3)3C — OH (CH3)3CO– K+
potassium tert-butoxide
(ii) Ester formation:
O O
H+
R — OH + R — C R — C + H2O
OH OR
Alcohol Acid
O O
R — OH + R — C R — C + HCl
Cl OR
O O

R — OH + CH3 S — Cl CH3 S — OR + HCl

O O
Tosyl chloride Alkyl tosylate
(TsOR)

Ts = CH3 S — Cl

O
Reactivity of alcohols in esterfication: CH3OH > 1° > 2° > 3°
(298)
JEE

MID LEARNING EXERCISE (MLE)-43

Q.1 HBr reacts fastest with:
(A) 2-methylpropan-2-ol (B) propan-l-ol
(C) propan-2-ol (D) 2-methylpropan-l-ol
Q.2 The end product C for the following reaction is:
Na CH I
(C6H5)2CHCH2OH  X 
3
Y
(A) (C6H5)2C=CH2 (B) (C6H5) 2CHCH 2O–Na +
O
||
(C) (C 6H5) 2CHCH2O– C –S –Na + (D) (C6H5) 2CHCH 2OCH3
Q.3 Order of reactivity of HX towards ROH is:
(A) HI > HBr > HCl (B) HCl > HBr > HI
(C) HI > HBr < HCl (D) HI < HBr > HCl

CH3
CH3
HBr
Q.4 H3 C   A (predominant) A is:

CH3 OH

CH3 Br
Br CH3
(A) H3C (B) H3 C
CH3 CH3 CH3
CH3

(C) Both (D) None is correct

Q.5 The acidic character of 1°, 2°, 3° alcohols, H2O and RCCH is in the order:
(A) H2O > 1° > 2° > 3° > RCCH (B) RCCH > 3° > 2° > 1° > H2O
(C) 1° > 2° > 3° > H2O > RCCH (D) 3° > 2° > 1° > H2O > RCCH
Q.6 The dehydration of 1-butanol gives:
(A) 1-Butene as the main product (B) 2-Butene as the main product
(C) Equal amounts of 1-butene and 2-butene (D) 2-methyl propene

CH3
conc. H SO
Q.7 CH3 C CH CH3 
2 4
 A (predominant) ‘A’ is :
CH3 OH
(A) (CH3) 3C–CH=CH 2 (B) (CH3)2C=C(CH3)2
(C) CH2 C CH2 CH2 CH3 (D) None is correct
CH 3
Q.8 Which of the following reactions of an alcohol does not involve O – H bond breaking:
(A) Reaction with alkali metals (B) Reaction with an acyl chloride
(C) Reaction with sulphonyl chloride (D) Reaction with conc. sulphuric acid
(299)
 Alcohol, Phenol & Ether
Q.9 Alkyl chloride is formed when alcohol is treated with HCl in presence of anhydrous ZnCl2. The
order of reactivity with respect to alcohol is:
(A) 3º > 2º > 1º (B) 1º > 2º > 3º (C) 2º > 1º > 3º (D) 1º > 3º > 2º
Q.10 An organic compound dissolved in dry benzene, evolved hydrogen on treatment with sodium. It is:
(A) A ketone (B) An aldehyde (C) A tertiary amine (D) An alcohol
Q.11 When ethyl alcohol reacts with acetic acid, the products formed are:
(A) Sodium ethoxide + hydrogen (B) Ethyl acetate + water
(C) Ethyl acetate + soap (D) Ethyl alcohol + water
Q.12 Methyl alcohol reacts with phosphorus trichloride to form:
(A) Methane (B) Methyl chloride (C) Acetyl chloride (D) Dimethyl ether
Q.13 The –OH group of methyl alcohol cannot be replaced by chlorine by the action of:
(A) Chlorine (B) Hydrogen chloride
(C) Phosphorus trichloride (D) Phosphorus pentachloride
Q.14 R – OH + SOCl2 
Pyridine R – Cl + SO2 + HCl Pyridine in the above reaction:
(A) Catalyses the reaction (B) Used to dissolve alkyl chloride
(C) To remove excess of SOCl2 (D) None of the above
Q.15 Reaction of alcohol which does not show cleavage of R–O linkage is :
(A) ROH + PCl5 (B) ROH + SOCl2 (C) ROH + HCl (D) ROH + Na
Q.16 Replacement of –OH group in alcohol by –Cl cannot be carried out with:
(A) PCl5 (B) SO2Cl 2 (C) PCl3 (D) SOCl2
Q.17 Least soluble alcohol in water is :

(A) (B) OH
OH

(C) (D) OH
OH
Q.18 Hydrogen bonding is possible in:
(A) Ethers (B) Hydrocarbons (C) Alkanes (D) Alcohols
Q.19 The decreasing order of boiling points of 1º, 2º, 3º alcohol is:
(A) 1º > 2º > 3º (B) 3º > 2º > 1º
(C) 2º > 1º > 3º (D) None
Q.20 The solubility of lower alcohols in water is due to:
(A) Formation of hydrogen bond between alcohol and water molecules
(B) Hydrophobic nature of alcohol
(C) Increase in boiling points
(D) None of these

7.3.3 Miscellaneous Reactions:

(i) Oxidation: A primary alcohol containing two –hydrogens can either lose one of them to form
an aldehyde or both of them to form a carboxylic acid.

(300)
JEE
H
C5H5NH+CrO3Cl–
R—C=O (An aldehyde)
Pyridinium chlorochromate
R — CH2OH
(1°) KMnO4
R — COOH (A carboxylic acid)
or K2Cr2O7
– +
R — CH2OH + KMnO4 RCOO K + MnO2 + KOH
1° alcohol Purple Brown

A secondary alcohol can lose its only –hydrogen to form a ketone.

R R
K2Cr2O7
RCHOH R—C=O
or CrO3
(2°)

Prolonged oxidation or oxidation under harsh conditions oxidises secondary alcohols to carboxylic
acids involving breaking of carbon-carbon bonds.
alk. KMnO 4 alk. KMnO 4
CH3CHCH2CH3 CH3CCH 2CH3 CH3COOH + CH3COOH

OH O
A tertiary alcohol contains no -hydrogens and is not oxidised. Under harsh conditions
(e.g., acidic oxidising agent), a tertiary alcohol dehydrates to an alkene which can further be
oxidised to acids having a lesser number of carbon atoms than the parent molecule.
(ii) Reaction with Reduced Copper: Primary and secondary alcohols are dehydrogenated to
form aldehydes and ketones respectively, whereas tertiary alcohols are dehydrated to form olefins.
reduced Cu
CH 3 CH 2 OH CH 3 CHO + H 2
300°C
Primary alcohol

reduced Cu
CH 3 CH(OH)CH 3 CH 3 CCH 3 + H 2
300°C
Secondary alcohol
O
CH 3 OH CH 3
reduced Cu
C C = CH 2 + H2 O
300°C
CH 3 CH3 CH 3
Tertiary Alcohol
(iii) Action of Chlorine or Bromine: Chlorine and bromine, being mild oxidising agents, oxidise
primary and secondary alcohols to aldehydes and ketones respectively, which then undergo
halogenation on -carbon.
CH3CH 2 OH 
Cl2
CH 3CHO 
3Cl2
 CCl3 CHO
Chloral

CH 3 CH(OH)CH 3 
Br2
CH 3 COCH 3 
3Br2
 CBr3 COCH 3
1,1,1-Tribromo propanone

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 Alcohol, Phenol & Ether

7.4 TESTS FOR ALCOHOLS

Primary, secondary, and tertiary alcohols can be distinguished by the following methods:
7.4.1 Lucas Test: This test is based on different reactivities of alcohols towards Lucas reagent—a mixture
of concentrated hydrochloric acid and anhydrous zinc chloride—at room temperature.
ROH + HCl 
ZnCl2
 RCl + H 2 O
Formation of alkyl halides which are insoluble is indicated by the appearance of turbidity in the
reaction mixture. Since the reaction involves carbocation intermediate, the order of reactivity of
alcohols is benzyl, allyl > 3° > 2° > 1° > CH3OH.
Tertiary alcohols (benzyl and allyl alcohols as well) produce turbidity immediately, secondary alcohols
give turbidity within 5-10 minutes, and primary alcohols do not give turbidity at all.
7.4.2 Oxidation: Primary alcohols on oxidation give aldehydes which are further oxidised to carboxylic
acid having the same number of carbon atoms as in alcohol. Secondary alcohols are oxidised to
ketones which on prolonged oxidation or under drastic conditions give carboxylic acids containing
lesser carbon atoms than alcohol. Tertiary alcohols cannot be oxidised but under drastic conditions
dehydrate to alkenes which are oxidised to a mixture of ketones and acids containing lesser carbon
atoms.
7.4.3 Victor-Meyer Test: This test involves the following steps:
(i) Alcohol is treated with concentrated hydriodic acid or red phosphorus and iodine to form the
corresponding alkyl iodide.
(ii) Alkyl iodide is reacted with silver nitrite to form nitroalkane.
(iii) Nitroalkane formed is treated with nitrous acid (HONO).

 2NaNO 2  2HONO  Na 2SO4 

 H 2SO 4 
and then with alkali (NaOH or KOH). Different products are obtained for different alcohols.
Primary alcohols produce blood red colour, secondary alcohols produce blue colour, and
tertiary alcohols produce no colour.
Some other tests to determine definite linkages in alcohols are:
7.4.4 Iodoform test:
This test is given by methyl ketones which on treatment with iodine and sodium hydroxide (sodium
hypoiodite, NaOI) yields a yellow precipitate of iodoform (CHI3).

R – C – CH 3 +3NaOI 
 R – C – CI3 +3NaOH
|| ||
O O
R – C – CI3 +3NaOH  RCOO – Na + + CHI3
|| Iodoform
yellow precipitate
O

Alcohols of the structure R — C — CH 3 (R = H or alkyl or aryl group)

OH
also give positive iodoform test.
Hypohalites oxidise an alcohol having the above-mentiond structure to methyl ketone which gives a
positive iodoform test.
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JEE
H

R — C — CH 3 + NaOI R — C — CH 3+ NaI + H 2O

OH O
Iodoform test
gives positive
Example: CH3CHOH, CH3CHCH2CH2CH3, C6H5CHCH3 give positive iodoform test.

H OH OH
7.4.5 Analysis of 1, 2-Diols/Periodic Acid Oxidation:
Compounds containing two or more = O or –OH groups attached to adjacent carbon atoms undergo
oxidation with cleavage of carbon-carbon bonds. A C = O group is oxidised to carboxylic group,
— C — OH group is oxidised to –CHO (aldehyde) and if the carbon atom in C—OH group does

H
not have any hydrogen atom, it is oxidised to a ketonic group.
Example: R — C — CH — R + HIO4 RCOOH + RCHO

O OH

R R
HIO4
R — C — CH — R R — C = O + RCHO

OH OH

HIO4
R — CH — CH2 — CH —R no reaction

OH OH

MID LEARNING EXERCISE (MLE)-44

SOCl2 O3 /Zn
Q.1 H2C CH CH 2 CH 2 CH CH 3 
Pyridine
 (A) 
(H O) (B) 
4 NaBH
 (C)
2
C5H9ClO
OH
Compound (C) is:
OH
(A) CH3 CH CH 2 CH CH 3 (B) HOCH2 CH2 CH 2 CH 2 CH 2 CH 2 Cl
Cl
Cl
(C) HO CH 2 CH2 CH2 CH CH3 (D) HO CH 2 CH2 CH CH2 CH3
Cl
(303)
 Alcohol, Phenol & Ether

CHO
Q.2 CH OH 
2HIO4
Products obtained in the above reaction are:
CH2 OH
(A) HCHO, HCO2H (B) HCHO, 2HCO2H
(C) CO2, 2HCO2H (D) CO2, HCHO, HCO2H

CH 2 OH
CH 2OH
|
5HIO4
(ii) (CH – OH)3   Product
5HIO4
Q.3 (i) (CH OH)4  Product
|
CH2 OH CH 2 –OH

Ratio of moles of formic acid obtained in reaction (i) and reaction (ii) is
(A) 3/4 (B) 4/5 (C) 4/3 (D) 5/4
Q.4 Which are not cleaved by HIO4 ?
(I) glycerol (II) glycol
(III) 1, 3-propenediol (IV)methoxy-2-propanol
(A) I, II, III, IV (B) I, II (C) II, III (D) III, IV
Q.5 Which of the following compounds is resistant to periodic acid oxidation ?

CH2OH CH2 OH CH2 OH

CH 2OH
(A) CO (B) CH2 (C) CHOH (D)
CH2OH
CH2OH CH2OH CH2OH
Q.6 Which alcohol does not give a ketone on oxidation ?
(A) Isopropyl alcohol (B) Allyl alcohol
(C) Ethylmethylcarbinol (D) Methylphenylcarbinol

Q.7 The product of reaction CH 3CH 2 OH 
Cu /300 C

(A) C 2H 6 (B) CH3COCH3 (C) CH 3CHO (D) CH3COOH
Q.8 A compound X with molecular formula C3H8O can be oxidised to a compound Y with the molecu-
lar formula C3H6O2, X is most likely to be:
(A) Primary alcohol (B) Secondary alcohol (C) Aldehyde (D) Ketone
Q.9 Which of the following reactions does not involve reduction ?
(A) R  COOH 
 RCH 2 OH (B) RCHO 
 RCH 2 OH

(C) R  CO  R  
 R  CH 2  R  (D) R  CH  R  
 R  C  R
| ||
OH O
Q.10 A compound is soluble in concentrated H2SO4. It does not decolourise bromine in carbon tetra-
chloride but oxidised by chromic anhydride in aq. sulphuric acid within two seconds, turning orange
solution to blue green then opaque. The original compound is:
(A) A primary alcohol (B) A tertiary alcohol (C) An alkene (D) An ether
Q.11 Tertiary alcohols are resistant to oxidation because:
(A) They do not have a hydrogen atom (B) Of large +I effect of alkyl groups
(C) Of greater steric hindrance (D) All the above
(304)
JEE
Q.12 Ethanol on heating with acetic acid in the presence of a few drops of sulphuric acid gives the
smell of:
(A) Oil of wintergreen (B) Oil of mustard
(C) An ester (D) Oil of bitter almonds
Q.13 Which of the following alcohols does not give a red colour in Victor Meyer test:
(A) Isobutyl alcohol (B) Isoamyl alcohol (C) Diethyl carbinol (D) Phenylcarbinol
Q.14 Methanol and ethanol are distinguished by:
(A) Treating with Schiff’s reagent (B) Treating with Lucas reagent
(C) Heating with iodine and alkali (D) Treating with CrO3 in dil. H2SO4
Q.15 Which of the following compounds is oxidised to prepare methyl-ethyl ketone?
(A) 2-Propanol (B) ter-Butyl alcohol
(C) 2-Butanol (D) 1-Butanol
Q.16 1° alcohol can be converted to 1° aldehyde by using the reagent:
(A) Pyridiniumchlorochromate (B) Potassium dichromate
(C) Potassium permanganate (D) Hydrogenperoxide
Q.17 Methyl alcohol can be distinguished from ethyl alcohol using:
(A) Fehling solution (B) Schiff’s reagent
(C) Sodium hydroxide and iodine (D) Phthalein fusion test
Q.18 The reagent which easily reacts with ethanol and propanol is:
(A) Fehling solution (B) Grignard reagent (C) Schiff’s reagent (D) Tollen’s reagent
7.5 ETHERS
Ethers are compounds of the general formula R — O — R, Ar — O — R or Ar — O — Ar, where
Ar is an aromatic group. An ether is symmetrical if the two groups attached to the oxygen atom are
the same, and it is unsymmetrical if the groups are different.
CH3CH2CH2CHCH2CH3 CH3CH2OCH2CH2CH3
1-Ethoxypropane
OCH3
3-Methoxyhexane

7.6 PREPARATION OF ETHERS

7.6.1 Dehydration of alcohols:
H2SO4
2R — O — H R — O — R + H2O


A water molecule is lost for every pair of alcohol molecules. Dehydration is limited to the preparation
of symmetrical ethers, because a combination of two different alcohols yields a mixture of three
ethers.
Alcohols can also dehydrate to alkenes, but dehydration to ethers is controlled by the choice of
reaction conditions.
Example:
140°C
C2H5OC2H5 Diethyl ether
Conc.
CH3CH2OH H SO
2 4
180°C
CH2 = CH2 Ethene

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 Alcohol, Phenol & Ether
Ether formation by dehydration is an example of nucleophilic substitution: protonated alcohol is the
substrate and the second molecule of alcohol is the nucleophile.
The reaction is SN1 for 2° and 3° alcohols and SN2 for 1° alcohol.

R  OH  H   R  O H 2 (Protonated alcohol)
H
–H2O R OH |
R +   R– O –R  H + +R-O-R 

S N1 (3° & 2° alcohols) 
R– O H 2
 H  H
 | δ+  |
ROH R   O δ+ -- - R- -- O H   R   O  R  R   O  R  H 
S N2 (1° alcohols)  2
 
 
 
7.6.2 Williamson synthesis:
–
RO Na+
R – OR
RX
ArO–Na+
R – OAr
Yield from RX: CH3 > 1° > 2° > 3°
The reaction involves the nucleophic substitution of an alkoxide (or phenoxide) ion for a halide ion.
This method can be used for preparing symmetrical as well as asymmetrical ethers.
Na
(CH3)2 CH(OH) (CH3)2CHO–Na+ + CH3CH2CH2Br CH3(CH2)2O CH(CH3)2

aq. NaOH
OH + CH 3CH 2Br O — CH 2CH3
Ethoxybenzene
The reaction gives the best yield with 1° alkyl halides. With tertiary alkyl halides, elimination becomes
an important reaction and no ether is obtained.
CH3 CH3
aq.NaOH
CH — C — Br + C2H5OH CH3 — C = CH2

CH3

MID LEARNING EXERCISE (MLE)-45

conc. H 2SO 4
Q.1 The reaction 2C2H5OH 
140ºC
 (C2H5)2O + H2O, is an example of:

(A) an elimination reaction (E2) (B) an electrophilic substitution reaction

(C) a nucleophilic substitution (D) a nucleophilic substitution reaction
Q.2 Which of the following reactions is not expected to produce methoxybenzene?
(A) PhOH + CH3I 
NaOH
 (B) PhOH + (CH3)2SO4 
NaOH

(C) PhBr + CH3ONa  (D) PhONa + CH3OSO2CH3 
(306)
JEE
Q.3 A mixture CH3OH and C2H5OH is heated with concentrated H2SO4 at 140ºC. The product that may
be formed is:
(A) CH3CH2OCH3 (B) CH3OCH3
(C) C2H5OC2H5 (D) All of these
THF
Q.4 In the reaction, CH3CH2ONa + CH3CH2OSO2CH3 
heat
 the product formed is
(A) CH3CH2OCH3 (B) CH3CH2OCH2CH3
(C) CH2CH2OSO2OCH2CH3 (D) CH3CH2OSO2CH3
1. (CH3COO)2 Hg, CH3OH
Q.5 Consider the following reaction: CH3CH = CH2 2.NaBH
 The product formed in the
4

reaction is:
CH3 CH 3 O
(A) CH3 CH OCH3 (B) CH3CH O C CH 3
CH3CH CH2 CH3CH CH2
(C) CH3COO OCOCH3 (D) OCH3OCOCH3
Q.6 Which of the following reactions is the best choice for preparing methyl cyclohexyl ether?
ONa I
(A) + CH3I  (B) + CH3ONa 

OH I
(C) + CH3I  (D) + CH3OH 

OH
NaOH CH3CH 2 I
Q.7 In the reaction sequence   A   B. The product (B) is:

ONa CH 2CH2OH
(A) (B)

OCH=CH 2 OCH 2 CH3

(C) (D)

Q.8 For making (CH3)3C – O – C2H5 the ideal combination is:

(A) (CH3)3CONa and C2H5Br (B) (CH3)3CBr and C2H5ONa
(C) Both the above (D) None
Q.9 Which of the following should be considered as an aromatic ether?

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

(307)
 Alcohol, Phenol & Ether

OH
Na CO
Q.10 The major product formed in the reaction  CH3CH 2 I  2 3
acetone, heat

CH 2OH (1 eq.)

OCH 2CH 3 OH
(A) (B)
CH 2OH CH 2OCH 2CH 3
OCH 2CH 3 O CH 3
(C) (D)
CH 2OCH 2CH 3 O
Q.11 In which case the product is neither a cyclic ether nor open chain symmetrical ether:
C H CO H
(A) CH3 – CH = CH – CH3 
6 5 3
 (B) CH3CH2ONa + C2H5Br 
(C) KCN + (CH3)3CBr  (D) C2H5OH (Excess) + H2SO4 
Q.12 Ether is not formed in this reaction:
conc. H SO
(A) 2C2H5OH 2
140º
4
 (B) (CH3)3 C – Cl + C2H5ONa 
(C) C2H5Cl + (CH3)3 C – ONa  (D) All of these
Q.13 The major product P in the following reaction is:
H
(CH3)3COH + C2H5OH  P
(A) (CH3)3COC(CH3)3 (B) (CH3)3COC2H5
(C) C2H5OC2H5 (D) (CH3)2C=CH2
Q.14 1-Chloro-2-butene is allowed to react with a concentrate solution of The rate of reaction is found to
be dependent on the concentrations, of both the substrate and the nucleophile.
C H OH
CH 3CH = CHCH 2Cl + C 2 H 5ONa 
2 5
 The major product formed in the reaction is:
(A) CH3CH = CHCH2OC2H5 (B) CH3CH CH CH2
OC2H5
(C) CH2 = CH – CH = CH2 (D) All of these in equal amounts
S 1
Q.15 In the reaction CH3CH = CHCH2Br 
N
CH OH
 , the product formed is
3

OCH3
(A) CH3CH = CHCH2CH3 (B) CH3 CH CH CH2
(C) CH3CH = CHCH2OCH3 (D) A mixture of (B) and (C)
Br2 /CCl4 dilute KOH
Q.16 Consider the following reactions, CH2 = CHCH2CH2OH   A 25ºC

The product (B) is:
(A) BrCH2CHBrCH2CH2OH (B) HOCH2CHOHCH2CH2OH
Br
(C) CH 2Br (D)
O O

(308)
JEE

Cl
Q.17 In the reaction + CH3OH  the major product formed is
O Cl
Cl OCH 3
(A) (B)
O OCH 3 O Cl

(C) (D) CH3OCH 2CH2CH2CH CHC

OCH 3
OCH 3
Q.18 Unsymmetrical ethers are best prepared by:
(A) Swarts reaction (B) Reacting Grignard reagent with alkyl halide
(C) Treating sodium alkoxides with alkyl bromides (D) Heating an alkanol with conc. H2SO4
Q.19 In the Williamson’s synthesis for diethyl ether, which species works as a nucleophile:
(A) Halide ion (B) Ethoxide ion (C) Ethyde ion (D) Hydride ion
Q.20 Mixed ether will not be formed in the reaction:
(A) CH3OCH2Cl + C2H5MgBr (B) CH2N2 + C2H5OH
(C) C2H5ONa + CH3I (D) C2H5OH + H2SO4 (140ºC)
7.7 PHYSICAL PROPERTIES OF ETHERS
(i) The C — O — C bond angle in ethers is not 180° and the dipole moments of the two C — O
bonds do not cancel each other. Hence, ethers possess a small net dipole moment.
R
110° O
R net dipole moment

(ii) The boiling point of ethers are the same as those of alkanes of comparable molecular weights.
The boiling points of alcohols are much higher than those of ethers, as ethers are incapable of
intermolecular hydrogen bonding.
(iii) The solubility of ethers in water is comparable to that of alcohols, because ethers can form
hydrogen bonds with water molecules.
H
|
R– O --- H – O
|
R

7.8 CHEMICAL PROPERTIES OF ETHERS

Ethers are unreactive compounds. The ether linkage is quite stable towards bases, oxidising, and
reducing agents.
7.8.1 Cleavage by acids:
R — O — R + HX R — X + R

HX

R — X
Reactivity of HX: HI > HBr > HCl.

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 Alcohol, Phenol & Ether
Cleavage takes place under vigorous conditions using concentrated acids and high temperature.
A dialkyl ether initially yields an alkyl halide and an alcohol; the alcohol may further react to form
second mole of alkyl halide.
48% HBr
CH3 — CH — O — CH — CH3 2CH3CHCH3
130 – 140°C

CH3 CH3 Br

The initial reaction between an ether and an acid results in the formation of a protonated ether. The
cleavage then involves a nucleophilic attack by a halide ion on this protonated ether with the
displacement of the weakly basic alcohol molecule.
H
S 1
R — O — R+ HX R — O — R+ X– N R — X + ROH
or SN2
+ HX
Protonated ether RX

A primary alkyl group tends to undergo SN2 displacement and a tertiary alkyl group tends to undergo
SN1 displacement.

HI
CH3I + CH3CH2CH2OH
SN2
CH3 — O — CH2CH2CH3
3 – Methoxy propane
HI
excess CH3I + CH3CH2CH2I

CH3
HI
CH3 — O — C — CH3 CH3OH + (CH3)3CI
SN 1
CH3
2 – Methoxy–2–methyl propane

MID LEARNING EXERCISE (MLE)-46

Q.1 Diethyl ether acts as a:
(A) Lewis acid (B) Lewis base (C) Reducing agent (D) Oxidising agent
Q.2 Ethers like alcohols do not form strong …bonding . Hence they are more volatile:
(A) Covalent (B) Hydrogen (C) Coordinate (D) None of these
Q.3 The order of reactivity of halogen acids with ether is:
(A) HCl > HBr > HI (B) HI > HBr > HCl (C) HCl > HI >HBr (D) HI > HCl > HBr
Q.4 Which of the following is a false statement:
(A) Diethyl ether gives ethyl iodide on reacting with HI
(B) Diethyl ether and methyl isopropyl ether are chain isomers
(C) Diethyl ether is a Lewis base
(D) Diethyl ether hydrolyses to ethanol by dil.H2SO4

(310)
JEE
Q.5 Mark the correct statement:
(A) Ethers behave as Lewis base
(B) Ethers form coordination complexes with Lewis acids
(C) With cold HI diethyl ether gives ethyl alcohol & ethyl iodide
(D) All are correct
Q.6 The ordinary alkyl ethers are cleaved by:
(A) Ethanol (B) Ethyl halide (C) BF3 (D) Hydrogen iodide
Q.7 The ether in which all atoms may exist in one plane is:
(A) O (B)
O
Me O
(C) (D)
O Me Me
Q.8 Which of the ether(s) below is (are) not likely to form peroxides when exposed to air?

(A) H3 C O CH3 (B)

O

H3 C
(C) O CH3 (D) O
H3 C CH3
H3C CH3
H3 C

heat
Q.9 In the reaction (CH3 )3 C – O – CH 2CH3 + HI  The product(s) formed is (are)
(1 mole)

(A)  CH3 3 C – OH and CH3CH 2 I (B)  CH3 3 C – I and CH3CH2OH

+
(C)  CH3 3 C – I and CH3CH3 (D) (CH3)3 C – O – CH2CH3I–
H
Q.10 Which of the following compound is cleaved easily by dilute:
O
(A) (B) O (C) (D) All of these
O
O O
Q.11 In the reaction:
CH3
+ HCl 
H O
The major product formed is:
Cl OH
(A) OH (B) Cl

Cl
(C) (D) Cl
Cl

(311)
 Alcohol, Phenol & Ether

HCl (excess)
Q.12 In the reaction 
ZnCl
 the product formed is:
2
O
(A) HO  CH 2 4 Cl (B) Cl  CH 2  4 Cl (C) HO  CH 2 4 OH (D) HO  CH 2 3 CHO

O
Q.13 H O

3

O O
Product obtained in above reaction is:
(A) 3CH3CHO (B) 3HCHO (C) 3HCOOH (D) 3CH3OH

Q.14 H O

3

O OEt
Product of above reaction is:

(A) , EtOH (B) , EtOH

HO OH HO O

(C) , CH3OH (D) + EtOH

HO O O O
Q.15 The ether C6H5OCH2C6H5 on heating with concentrated HI produces:
(A) C6H5I and C6H5CH2OH (B) C6H5I and C6H5CH2I
(C) C6H5OH and C6H5CH2I (D) C6H5OH and C6H5CH2OH
Heat
Q.16 The reaction C2H5OC2H5 + 2HI   2C2H5I + H2O involves the mechanism:
(A) SN1 (B) SN2 (C) E 1 (D) E 2
Q.17 The compound obtained by the reaction of diethyl ether with chlorine in the presence of sun light, is:
(A) Perchloro diethyl ether H5C2 – OC2Cl5
(B) Perchloro diethyl ether Cl5C2 – O – C2Cl5
(C) , '- Dichloro diethyl ether ClCH2CH2 – O – CH2CH2Cl
(D) , '- Dichlorodiethylether CH3 CH O CH CH3
Cl Cl
Q.18 Ether reacts with chlorine in the dark to form:
(A) CH2Cl – CH2 – O – CH2 – CH3 (B) CH2Cl – CH2 – O – CH2 – CH2Cl
(C) CH3 – CH(Cl) – O – CH(Cl) – CH3 (D) CCl3 – CH2 – O – CH2 – CCl3
Q.19 Which of the following compounds forms an adduct with diethyl ether through coordinate bond:
(A) BF3 (B) Oxygen of air (C) HCl gas (D) All of the above
Q.20 Which of the following is a false statement:
(A) Diethyl ether gives ethyl iodide on reacting with HI
(B) Diethyl ether and methyl isopropyl ether are chain isomers
(C) Diethyl ether is a Lewis base
(D) Diethyl ether hydrolyses to ethanol by dil.H2SO4
(312)
 JEE

7.9 EPOXIDES
Epoxides are compounds containing the three-membered ring.

— C — C — (Epoxide or oxirane ring)

O
Epoxides belong to a class of compounds called cyclic ethers. The three-membered ring makes
epoxides an exceedingly important class of compounds.
CH2 — CH — CH2 — CH3 CH2 — CH2

O O
1, 2 – Epoxybutane Epoxyethane
 Preparation:
Epoxides are commonly obtained by oxidation of alkenes by peroxy acids.
O
RCO3H
C=C C — C
Peroxyacid
Alkene Epoxide
Silver oxide can also oxidise alkenes to epoxides. An internal SN2 reaction in a chlorohydrin can be
used to prepare three membered cyclic ethers.
OH – –Cl
–
Cl — CH 2 — CH — CH 3 Cl — CH 2 — CH — CH 3 CH2 — CH — CH 3

OH – O
O 1, 2 – Epoxypropane

7.10 REACTIONS OF EPOXIDES

Epoxides have highly strained three-membered rings that can undergo acid- or base-catalysed ring
cleavage.
7.10.1 Acid-catalysed cleavage:

H

O OH
O
—C—C— —C—C— —C—C—

Z: Z
z: = nucleophile
At first, the epoxide is protonated by an acid and the protonated epoxide can then undergo an attack
by nucleophilic reagents.

H+
—C—C— —C—C—
O O

(313)
 Alcohol, Phenol & Ether

H2O
—C—C— — C — C — 1, 2, - diol
–H+
OH2 OH
 OH OH
—C—C— ROH
—C—C— —C—C—
O –H+

H R O OH OR OH
H
X–
—C—C— Halohydrin

X OH

7.10.2 Base-catalysed cleavage:

Z Z
Z: + — C — C — —C—C— —C—C—
HZ
O O– OH
Under alkaline conditions, an epoxide itself undergoes nucleophilic attack.

C2H5O– Na+ + CH2 — CH2 C2H5O CH2 CH2 OH

2-Ethoxyethanol
O
NH3 + CH2 — CH2 H2N — CH2 CH2 OH
2-Aminoethanol
O

7.10.3 Reaction with Grignard reagent:

R — MgX + CH2 — CH2

– + H+
CH2 — CH2 — OMgX RCH2 CH2 OH
O Primary alcohol
R (Chain lengthened
by two carbon atoms)

MgBr + H 2 C — CH2 CH2 CH2 OMgBr

O H 2O
Phenyl magnesium Ethylene
bromide oxide
CH2 CH2 OH

2-Phenylethanol

(314)
JEE

MID LEARNING EXERCISE (MLE)-47

Q.1 Reaction of with RMgX:
O
Followed by hydrolysis will produce:
(A) RCHOHR (B) RCHOHCH3 (C) R2CHCH 2OH (D) RCH2CH2OH
Q.2 Consider the following sequence of reactions:
CH3
m  CPBA CH3ONa
C CH2 
CH Cl
 A  B
2 2CH OH 3
CH3
The major end product (B) is
CH3 OCH3 CH3
(A) C (B) C CH2OH
CH3 OCH3 CH3
OH
CH3 OCH3 CH3 OH
(C) C (D) C
CH3 CH2 OH CH3 CH2 OCH3
CH3
H3C
H O18
Q.3 
2

P, P is:
H
O

CH3 CH3

(A) H3 C (B) H 3C
OH OH
18 OH OH 18

CH3

(C) H 3 C (D) None is correct

O CH 3
OH
Q.4 Consider the following sequence of reactions:
Cl COOH
CH3
H
C CH2 A 
CH OH
B
2 2CH Cl 3
CH3
The major end product (B) is:
CH3 OCH3 CH3 OH
(A) C (B) C
CH3 CH2OH CH3 CH2OCH3

CH3 CH3 CH3 OCH3

(C) C (D) C
CH3 OCH3 CH3 OCH3

(315)
 Alcohol, Phenol & Ether
Q.5 Treatment of 2,2-diphenyl oxirane with an aqueous acid yields:
Ph


Ph 
H 3O

O
Ph Ph
(A) C CH2 (B) CH CH2 OH
Ph Ph
OH OH
Ph Ph OH
(C) CH CHO (D) C
Ph Ph OCH3
Q.6 2-Phenylethanol may be prepared by the reaction of phenylmagnesium bromide with:
(A) HCHO (B) CH 3CHO (C) CH3COCH 3 (D)
O
Q.7 Diethyl ether absorbs oxygen to form:
(A) Red coloured sweet smelling compound (B) Acetic acid
(C) Ether sub oxide (D) Ether peroxide
Q.8 Diethyl ether and air gives ether-hydroperoxide. The mechanism of the reaction is:
(A) Nucleophilic substitution (B) Free radical addition
(C) Free radical substitution (D) None of the above
Q.9 Which is mismatched:
(A) C2H5 – O – C2H5 Four primary carbon atoms
(B) CH3 – CH2 – CH(OH)CH3 Optically active
(C) CH3 – O – CH (CH3)2 Two secondary carbon atoms
(D) Diethyl ether is heated with CH3COCl in presence of AlCl3 will give CH3COOC2H5 + C2H5Cl
Q.10 The reaction of ethoxyethane and ethanoyl chloride is carried out in presence of anhydrous aluminium
chloride. The product on alkaline hydrolysis gives:
(A) CH 3CH 2OH (B) CH3CH 2OCH 2CH 3 (C) CH 3OCH 3 (D) CH2 CH2

O
Q.11 Which of the following reactions does not yield an alkyl halide?
Cl2 conc. HI
(A) CH3CH 2OCH2CH 3 
hν
 (B) CH3CH 2OCH2CH 3 
heat

PCl SOCl2
(C) CH3CH 2OCH2CH 3  5
heat
 (D) CH 3CH 2OH 
Q.12 Mark the correct statement:
(A) Ethers behave as Lewis base
(B) Ethers form coordination complexes with Lewis acids
(C) With cold HI diethyl ether gives ethyl alcohol and ethyl iodide
(D) All are correct
Ph

Q.13 H 2O18
H/  A (Major)
O
A is
18 18
Ph OH Ph OH Ph OH Ph OH
(A) (B) (C) (D)
18 18
OH OH OH OH

(316)
 JEE
Q.14 Consider the reaction of HI with the following:

I II

Which forms di-iodide on reaction with HI (excess)?

(A) I and II both (B) II only (C) I only (D) none

Q.15 RMgX
  ? Product Obtained is:
H 2O

R R'
| |
(A) R 'C  CH 2OH (B) RCH 2  C  OH
| |
R'' R' '

R R
| |
(C) R ' CH 2  C  OH (D) R ' ' CH 2  C  OH
| |
R'' R'

7.11 PHENOLS
Phenols are compounds having the general formula ArOH, where Ar is phenyl, substituted phenyl,
or some other aryl group like naphthyl group. Phenols have an —OH group attached directly to the
aromatic ring. Some of the common phenols are
OH OH
OH OH
Cl OH
CH 3 OH
o-Chlorophenol m-Cresol Catechol Resorcinol
OH
OH
OH COOH

OH
Hydroquinone 2-Napthol m-Hydroxybenzoic acid
7.12 PREPARATION OF PHENOLS
7.12.1 Dow Process:
Chlorobenzene is treated with aqueous NaOH at a temperature of 360°C under a high pressure. The
reaction involves nucleophilic substitution through elimination-addition mechanism involving benzyne
intermediate.
NaOH, 360°C HCl
Cl O– Na+ OH
4500 lb/in2
Chlorobenzene Sodium phenoxide Phenol
(317)
 Alcohol, Phenol & Ether
7.12.2 From Cumene (Isopropyl Benzene):
Cumene is converted by air oxidation into cumene hydroperoxide which is converted by aqueous
acid into phenol and acetone.

O2 H2O, H+
+ CH3 — C — CH 3

CH O
CH3 — C — O — O — H OH
CH3 CH3
Cumene CH3
Cumene hydroperoxide Phenol Acetone

The reaction involves rearrangement of hydroperoxides involving 1, 2–shift to electron-deficient

oxygen through the following steps:

H+  –H2O
CH3 — C — O — O — H CH3 — C — O — OH 2 CH3 — C = O

CH3 CH3 CH3

H2O

O OH OH2

H+ –H
CH3 — C + OH CH3 — C — O CH3 — C — O

CH3 CH3 CH3

Acid converts the peroxide I into protonated peroxide which loses a molecule of water to form an
intermediate in which oxygen bears only six electrons. A 1, 2 –shift of phenyl group from carbon to
electron-deficient oxygen yields carbocation II which reacts with water to yield hydroxy compound
III, a hemiketal, which breaks down to give phenol and acetone.
7.12.3 Hydrolysis of Diazonium Salts:
Ar — N2+ + H2O Ar — OH + H+ + N2
–
N2 + HSO4 OH
H2 O, H +
+ N2

Cl Cl
Diazonium salts can be obtained as follows:
–
NO2 NH 2 NO2 + Cl
HNO3 Reduction HONO
0°C
(NaNO2, HCl)
(318)
 JEE

7.13 PHYSICAL PROPERTIES OF PHENOLS

(i) The simplest phenols are colourless liquids or low-melting solids.
(ii) Phenols have a high boiling point because of inter-molecular hydrogen bonding.
(iii) Phenol itself is soluble in water but most other phenols are essentially insoluble in water. However,
the salts of phenols are soluble in water.
ArOH  ArO –
phenol (acid) Insoluble in water phenoxide (salt) soluble in water

7.14 CHEMICAL PROPERTIES OF PHENOLS

Phenols are highly reactive compounds and show two kinds of reactions due to
(i) —OH group:
(ii) electrophilic aromatic substitution on the ring
7.14.1 Acidic Nature of Phenols (Salt Formation):
Phenols are fairly acidic compounds. Aqueous hydroxides convert phenols into their salts and aqueous
mineral acids convert the salts back into free phenols.

 
–
OH
ArOH 
H+
 ArO
–
Phenol phenoxide ion

The acidity of various compounds vis-á-vis water and phenol is as follows:

Alcohols < Water < Phenols < Carbonic Acid < Carboxylic Acid
Both phenol and phenoxide ions are resonance stabilised but stabilisation is greater for phenoxide
ions. Thus, resonance shifts equilibrium towards ionisation, making phenol more acidic than alcohol,
which does not show resonance.
+ + + –
O—H O—H O—H O—H O—H O O

– – OH– –

H+
–

Phenol –
O O O
–

–
Phenoxide ion
Electron-withdrawing substituents like —X, or —NO2 tend to disperse the negative charge on
phenoxide ion, thereby increasing the acidity of phenols.
Electron-releasing substituents like —CH3 or —OR tend to intensify the negative charge on phenoxide
ion, thereby decreasing the acidity of phenols.
Unlike alcohols, phenols are more acidic than water and thus dissolve in aqueous hydroxides.

ArOH + NaOH(aq) 
 ArO – Na + + H 2 O
Stronger acid Weaker acid

However, being less acidic than carbonic acid, phenols are insoluble in aqueous bicarbonates or
carbonates.
ArOH  NaHCO3 (aq) 
 no reaction

(319)
 Alcohol, Phenol & Ether
7.14.2 Ester Formation Fries Rearrangement:
Phenols are converted into their esters by the action of acids, acid chlorides, or anhydrides.

RCOCl
NaOH RCO — OAr
ArO — H Ar SO2Cl
ArSO2 — OAr
pyridine
(RCO)2O
RCO — OAr

O O
NaOH Schotten Baumann
OH + C — Cl C—O Reaction
Phenyl benzoate

When esters of phenol are heated with aluminimum chloride, the acyl group migrates from the
phenolic oxygen to an ortho or para position of the ring yielding a ketone. This reaction is called the
Fries rearrangement.
Example: O
O OH
O — C — C2H 5 OH
AlCl 3 C — C2H5 +
CS2
C — C 2H 5

O
Phenyl propionate o–Hydroxy phenol p–Hydroxyphenyl
ethyl Ketone ethyl Ketone

The reaction involves self-acylation by the acylium ion, RCO  .

7.14.3 Ether Formation:
ArO   R  X 
 ArO  R  X 
(1 )

Phenols are converted into alkyl-aryl ethers by reaction with alkyl halides in an alkaline solution,
involving a nucleophilic attack by a phenoxide ion on the alkyl halide, thereby displacing the halide
ion.
aq. NaOH
CH2Br + HO CH 2 — O
Aryl-methyl ethers can be prepared using methyl sulfates, (CH3)2SO4.
aq.NaOH
OH + CH3OSO2OCH3 OCH3 + CH3OSO3– Na+
Anisole (Methoxy benzene)

(320)
JEE

MID LEARNING EXERCISE (MLE)-48

Q.1 What is the end product ‘B’ of following sequence of reaction?
HNO2 H 2O
C6H5NH2 
H 2SO4 /0ºC
 ‘A’  Δ
 ‘B’
(A) C6H5N2Cl (B) C6H6 (C) C6H5NH2·H2SO4 (D) C6H5OH
Q.2 The compound obtained by heating cumenehydroperoxide with dil. H2SO4 is:
(A) Phenol (B) Isopropyl benzene
(C) Benzene sulphonic acid (D) None of these
Q.3 Dow’s process used in the industrial preparation of phenol, is:
NaOH SiO 2
(A) C6H5Cl 
CuCl 300º
 C6H5OH + NaCl (B) C6H5Cl + H2O 
425º
 C6H5OH + HCl
2'

(C) C6H5NH2 + HNO2   C6H5OH + N2 + H2O
(D) C6H5N2Cl +H2O  C6H5OH + N2 + HCl
Q.4 Which of the following is not a phenolic compound:
(A) Salol (B) o-Cresol (C) Anisole (D) Quinol
Q.5 Unacceptable name for a compound containing one –OH group attached to benzene nucleus would be:
(A) Carbolic acid (B) Hydroxybenzene (C) Catechol (D) Phenol
Q.6 Which combination is mismatched:
OH OH
(A)
CH3 are..........homologues
OCH 3 CH2OH
(B) are ..............isomers

OH CH2OH
(C) are..........homologues

CH3 NO2
O2N NO 2
(D) O 2N NO2 are.........explosives
NO 2
Q.7 Match structures given in List I with names given in List II and then select the correct answer from
the codes given below the lists:
List-I List-II
COOH
(I) OCOCH 3 (a) Picric acid

OCOCH 3
(II) (b) Methyl salicylate
OH
NO2

O2N OH
(III) (c) Pyrogallol
NO2

OH
(IV) (d) Aspirin
HO OH
(321)
 Alcohol, Phenol & Ether
Codes:
(A) I-d, II-a, III-b, IV-c (B) I-d, II-b, III-c, IV-a
(C) I-d, II-b, III-a, IV-c (D) I-d, II-c, III-b, IV-a
Q.8 Match this List I with List II and then select the answer from the codes given below the lists:
List-I List-II

(I) HO OH (a) p-Cresol

(II) O O (b) Hydroquinone

(III) CH2 OH (c) p-Benzoquinone

OH

(IV) HO CH3 (d) Salicyl alcohol

Codes:
(A) I-b, II-c, III-d, IV-a (B) I-b, II-d, III-a, IV-c
(C) I-b, II-c, III-a, IV-d (D) I-c, II-b, III-d, IV-a
Q.9 Which of the following is not a correct statement:
(A) Phenol is a much weaker acid than benzoic acid
(B) The reaction of ferric chloride with phenol to give violet colour is characteristic of Group
(C) Phenol is a stronger acid than ethanol but weaker than benzyl alcohol
(D) Picric acid does not contain a –COOH group
Q.10 Which of the following is a correct statement:
(A) Phenol is more acidic than ethanol
(B) Phenol is less acidic than ethanol
(C) Phenol reacts with NaHCO3
(D) Phenol reacts with NH2OH and HCl to form oxime
Q.11 Phenol with Hinsberg’s reagent gives:
(A) Sulphone (B) Sulphanilic acid
(C) Sulphonic ester (D) Sulphonal
Q.12 Which of the following reaction is called ‘Schotten-Baumann’ reaction:
AlCl /CH COCl CH3COCl
(A) C6H6 
3 3
 C6H5COCH3 (B) C6H5NH2   C6H5NHCOCH3
C H COCl AlCl
(C) C6H5OH 
6 5
 C6H5OCOC6H5 (D) C6H6  3
C H COCl
 C6H5COC6H5
6 5

Q.13 A mixture of benzoic acid and phenol may be separated by treatment with:
(A) NaHCO3 (B) NaOH (C) NH3 solution (D) KOH

(322)
JEE
Q.14 Phenol does not react with NaHCO3 because:
(A) Phenol is a weaker acid than carbonic acid
(B) Phenol is a stronger acid than carbonic acid
(C) Phenol is as strong as carbonic acid
(D) Phenol is insoluble in water.
Q.15 Predict the product of reaction below:
O
OH + H3 C Pyridine
 
Cl

O
(A) O (B)
CH3 OH
O

O
(C) (D) CH3
CH3
Q.16 Phenol can be distinguished from alcohol with
(A) Tollens reagent (B) Schiff’s base
(C) Neutral FeCl3 (D) HCl

OD
D
NaOH (i) CO
Q.17   [ ] 

2 P. Here P is:
(ii) D

OH OD OD OD
D D
(A) O (B) O

OD OH
D
(C) O (D) Reaction not possible

Q.18 The product obtained in the reaction,

Phenol + KOH + chloroform  product
resembles with the product of the reaction:
(A) Phenol + CO2 (,HCl) (B) Phenol + HCN + HCl
(C) Phenol + CrO2Cl2 (D) Phenol + CH3COCl
(323)
 Alcohol, Phenol & Ether
7.14.4 Ring Substitution Reactions:
A phenolic group powerfully activates an aromatic ring towards electrophilic aromatic substitution
and therefore special precautions are needed to prevent polysubstitution or oxidation.
(i) Nitration:
OH
conc. HNO3 O 2N NO 2
OH 2, 4, 6 - Trinitrophenol

NO2
OH
OH
Phenol dilute HNO 3 NO2
+
20°C
NO2
o–Nitrophenol p-Nitrophenol
(ii) Sulfonation:
OH
OH 15-20°C SO3H
o-Phenolsulfonic acid

H2SO4 H2SO4, 100°C

OH
100°C p-Phenolsulfonic acid

SO3H
(iii) Halogenation: Treating phenols with an aqueous solution of bromine results in the displacement
of every hydrogen, ortho or para, to the —OH group and may even cause displacement of
certain other groups.
OH OH
CH 3 Br ,H O Br CH
2 2 3

4, 6-Dibromo-2-methyl phenol
Br

OH OH
Br2,H2O Br Br
2, 4, 6-Tribromo phenol
SO3 H Br
If halogenation is carried out in a solvent of low polarity like chloform or carbon disulfide, the
reaction can be limited to monohalogenation.

OH OH OH
Br2,CS2 Br
+
0°C
Br
(Major product)

(324)
JEE
(iv) Friedel-Crafts Alkylation/Acylation: Friedel-Crafts alkylation of phenols yields alkyl phenols;
however, the yield is poor. This is because AlCl3, instead of generating a carbocation, gets involved
in forming a complex with electron-rich phenol.
.. ..

OH O AlCl 3

..

..
+AlCl 3

A positively charged oxygen is electron-withdrawing, thereby decreasing the reactivity of ring

towards electrophilic substitution reactions.
Friedel-Crafts acylation of phenols also has a low reactivity and behaves the same way.
(v) Nitrosation: Phenols are one of the few compounds reactive enough to undergo attack by
nucleophilic nitrosonium ion, +NO.
Nitrous acid converts phenols into nitrosophenols.

OH OH
NaNO 2, H2SO4
7-8°C
NO
(vi) Coupling with diazonium salts:

OH N2
weakly alkaline
+ HO N=N
Phenol Diazonium salt p-Hydroxyazobenzene
(vii) Carbonation: Kolbe reaction: Treatment of salt of phenol with carbon dioxide brings about
substitution of carboxyl group for hydrogen in ring.

OH –
O Na
+
O – OH
NaOH COONa
+ C+ 125°C, 4-7 atm
Sodium salicylate
O – (major product)
H+

OH
COOH

Salicylic acid

Some p-hydroxybenzoic acid is also formed but it can be easily separated by fractional distillation.
If the reaction is carried out on potassium phenoxide, the salt of p-acid becomes the major
product.
Salicylic acid is used to produce a number of important derivatives used as medicines.

(325)
 Alcohol, Phenol & Ether
OH
CH 3OH, H+ COOCH 3 Methyl salicylate
(Oil of winter green)
(flavouring agent)
OH
COOH OH Phenyl salicylate
C6H5OH, H+ COOC 6H5 Salol
(internal antiseptic)
Salicylic acid
OCOCH 3 Acetyl salicylic acid
(CH 3CO)2O COOH (Aspirin)
(an analgesis and antipyretic)
H+
(viii) Reimer-Tiemann reaction:
– +
O Na OH
+
CHCl 3 H /H 2O
OH CHO CHO
aq. NaOH
Salicyladehyde
– +
O Na OH
+
CCl 4 H /H2O
OH COOH COOH
aq. NaOH
Salicylic acid
The reaction involves electrophilic substitution of dichloro carbene, :CCl2 on the highly reactive
phenoxide ring.
– –
CCl3 + OH :CCl3 + H2O Cl – + CCl2
H Dichlorocarbene
Chloroform

..
:O: :O: O O–
: .. H CHCl2
CCl2 CCl2
Phenoxide ion
OH
OH O–
CHO CHO
H+

The product is largely o-aldehyde with a small amout of the p-isomer. If both o-position in phenoxide
ion are substituted the reaction yields p-isomer.
(ix) Reaction with formaldehyde: Phenol reacts with formaldehyde in the presence of an acid or
alkali forming o- or p-hydroxy methyl phenol.
 Basic Catalysis:
..
:O: O OH
H CH2OH
H + – H2O
+ C=O CH2O –
H+
H

(326)
JEE
 Acidic Catalysis:
..
:OH + OH OH
H + H H2O CH2 OH
+ C = OH
CH2 OH
H
Protonated
aldehyde

7.15 ANALYSIS OF PHENOLS

Phenols react with neutral ferric chloride solution and form coloured complexes (red, blue, green,
and violet). This reaction is also shown by enols (e.g., CH2 = CHOH).
Phenols can also be identified by their unique acidic strength. They are soluble in aqueous hydroxides
but insoluble in aqueous carbonates or bicarbonates.
MID LEARNING EXERCISE (MLE)-49
Q.1 The formylating agent in ‘Gattermann Koch’ synthesis is:
(A) CO + HCl (B) CO + H2
(C) HCl + HCN (D) CHCI3 + Alc.KOH
Q.2 Which of the following is not correctly matched:
Heat
(A) Phenol + CHCl3 + NaOH   Salicylaldehyde
Heat
(B) Phenol + Phthalicanhydride 
H SO
 Phenetole
2 4

Br water
(C) Phenol 
2
 Tribromophenol
Heat, Pressure
(D) Sodium phenate + CO2  Salicylic acid
Et SO HCl, HCN
Q.3 Phenol 
2 4
NaOH
 (A) 
AlCl
(B)
3

A and B in the above reaction sequence are:

OEt OEt
OH Cl
and
(A) (B) and
CHO
OEt OEt
OH CN CHO
and
(C) (D)
and
CHO
Q.4 Which derivative of phenol gives effervescence with NaHCO3:
(A) o-Cresol (B) Catechol
(C) 2,4,6-Trinitrophenol (D) Hydroquinone

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 Alcohol, Phenol & Ether
Q.5 Phenol is converted into salicylaldehyde by:
(A) Etard reaction (B) Kolbe reaction
(C) Reimer-Tiemann reaction (D) Cannizzaro reaction
Q.6 Phenol and cyclohexanol can be distinguished by using:
(A) FeCl3 (B) Na (C) PCl5 (D) CH3COCl
Q.7 Which of the groups will increase the acidity of phenol:
(A) –NO 2 (B) –CN (C) –X (halogens) (D) All
Q.8 (I) Main product of phenol and ethyl chloride is chlorobenzene
(II) Phenol and ethanol can be distinguished by FeCl3
(III) Phenol and benzoyl chloride reaction is called Schotten-Baumann reaction
(IV) o-Cresol is the higher homologue of phenol
Of the above statements:
(A) Only I is correct (B) II, III and IV are correct
(C) I, II are correct (D) I, III and IV are correct

HNO C H OH
NaOH
Q.9 OH 
2
P 
6 5
 Q  R

Which of the following statement is correct:

(A) P is paranitrosophenol, Q is indophenol ion and Q is indophenol
(B) Colour of Q is blue and that of R is red
(C) Above reaction is Libermann test for phenol
(D) All of these
Q.10 Match List I with List II and then select the correct answer from the codes given below the lists:
List-I List-II

(I) Phenol + NaOH + C2H5I   (a) Phenolphthalein

(II) Phenol + NaOH + CHCI3   (b) Picric acid

(III) Phenol + Phthalic anhydride + conc.H2SO4   (c) Phenetole
(IV) Phenol + conc. HNO3 (d) Salicylaldehyde
(A) I-c, II-d, III-a, IV-b (B) I-b, II-c, III-a, IV-d
(C) I-c, II-d, III-b, IV-a (D) I-c, II-a, III-d, IV-b
Q.11 Ortho and para hydroxy acetophenone and anhydrous AlCl3 are related with the following reaction:
(A) Phthalein reaction (B) Fries rearrangement
(C) Schmidt reaction (D) Wurtz-Fittig reaction
NaOH CO 2 HCl soda lime
Q.12 Reaction-I: Phenol  X 
140ºC
 Y   Z 
P

CCl HCl soda lime

Reaction-II: Phenol  4
NaOH
 Y 
 X  
Q
Wrong statement about P and Q is:
(A) Both the compounds give violet colour with FeCl3
(B) Both the compounds on deoxygenation give benzene
(C) Both the compounds contain phenolic –OH group
(D) Compound P is phenol and Q is cresol
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JEE
Q.13 Ledrer-Mannase reaction dose not give the following product:
(A) o-Hydroxy benzyl alcohol (B) p-Hydroxy benzyl alcohol
(C) m-Hydroxy benzyl alcohol (D) (A) and (B) are correct
Q.14 Phenol reacts with bromine in CS2 at a low temperature, the product is:
(A) m-Bromophenol (B) p-Bromophenol
(C) o-and p-Bromophenol (D) 2, 4, 6-Tribromophenol
Q.15 Phenol reacts with conc. HNO3 in the presence of conc. H2SO4 to give:
(A) Meta nitrophenol (B) Ortho nitrophenol
(C) Ortho and para nitrophenol (D) Picric acid
Q.16 Phenol is heated with chloroform and alcoholic KOH when salicyladehyde is produced. This reac-
tion is known as:
(A) Fridel-Crafts reaction (B) Reimer-Tiemann reaction
(C) Rosenmund reaction (D) Sommelet reaction
Q.17 Phenol on heating with NaNO2 and a few drops of conc. H2SO4 gives:
(A) p-Nitrophenol (B) p-Nitrosophenol (C) o-Nitrophenol (D) m-Nitrosophenol
Q.18 Reimer Tiemann reaction involves:
(A) Carbanion intermediate (B) A carbene intermediate
(C) Carbonium ion intermediate (D) Free redical intermediate
Q.19 When phenol is reacted with CHCl3 and NaOH followed by acidification, salicyladehyde is obtained.
Which of the following species are involved in the above mentioned reaction as intermediates:

O OH
H
CHCl2
(A) CHCl2 (B)

OH
H

(C) CCl2 (D) Both (A) and (B)

OH
Q.20 Kolbe’s reaction consists in obtaining:
(A) Anisol from phenol
(B) Salicylaldehyde from phenol and CHI3
(C) Salicylic acid from sodium phenate and CO2
(D) Salicylic acid from phenol and CO2

*****

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 Alcohol, Phenol & Ether

QUICK RECAP
 Alcohols are organic compounds containing a hydroxyl group attached to a saturated carbon atom
and having the general formula R—OH, where R can be an alkyl or a substituted alkyl group.
 Alcohols can be prepared by: Grignard reagent, hydrolysis of alkyl halides, hydroxylation of alkenes,
oxymercuration-demercuration, hydroboration-oxidation, reduction of carbonyl compounds.
 Alcohols are capable of forming hydrogen bonding and thus have higher boiling point compared to
hydrocarbons having similar molecular weight.
 Higher solubility of alcohols in water is due to hydrogen bonding. The solubility decreases with an
increase in the number of carbon atoms.
 Alcohols can be distinguished by: Lucas test, oxidation, Victor-Meyer test, iodoform test, analysis of
1, 2-diols. periodic acid oxidation.
 Ethers are compounds of the general formula R — O — R, Ar — O — R or Ar — O — Ar, where
Ar is an aromatic group.
 Ethers can be prepared by: dehydration of alcohols, Williamson synthesis.
 The C — O — C bond angle in ethers is not 180° and the dipole moments of the two C — O bonds
do not cancel each other. Hence, ethers possess a small net dipole moment.
 The boiling point of ethers are the same as those of alkanes of comparable molecular weights.
 The solubility of ethers in water is comparable to that of alcohols, because ethers can form hydrogen
bonds with water molecules.
H
|
R– O --- H – O
|
R
 Ethers are unreactive compounds. The ether linkage is quite stable towards bases, oxidising, and
reducing agents.
 Epoxides are compounds containing the three-membered ring.

— C — C — (Epoxide or oxirane ring)

O
 Epoxides have highly strained three-membered rings that can undergo acid- or base-catalysed ring
cleavage.
 Phenols are compounds having the general formula ArOH, where Ar is phenyl, substituted phenyl,
or some other aryl group like naphthyl group.
 Phenols can be prepared by: dow process, from cumene (isopropyl benzene), hydrolysis of
diazonium salts.
 Phenols have a high boiling point because of inter-molecular hydrogen bonding.
 Phenol itself is soluble in water but most other phenols are essentially insoluble in water.
However, the salts of phenols are soluble in water.

ArOH  ArO –
phenol (acid) phenoxide ion (salt)
Insoluble in water soluble in water

 Phenols are highly reactive compounds and show two kinds of reactions due to
(i) —OH group (ii) electrophilic aromatic substitution on the ring

*****
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 JEE

SOLVED EXAMPLES
Example 1. Predict the product(s) of each reaction below. Be sure to specify the stereochemistry where
appropriate. (Ph, phenyl; *, isotope label)
(a) Ph—O—CH2—Ph 
excess HI

(b) (H3C) 2CH—O—C(CH3)3 
1 equiv. HBr

OCH 3
1equiv.HI
(c) 
H

O
1.PhO –
(d) 
  2.H
Ph
O
H + (catalyst)
(e) 
Ph–OH

Ph
O
+
H (catalyst)
(f) H H  
H 2O
 
H CH 2CH3

O
–
1.OH
(g) H H  
2.H +
H CH 2CH3
*
(h) O — C H 2 — CH = CH 2 
Δ

(i) CH 3 — S — CH 3  (CH 3CH 2 )3 O  BF4 



H
(j) HCl
O  

CH3

H
1.PhLi
(k) O 
2.H +

CH3
Solution: (a) Ph —OH + I—CH2—Ph SN1 cleavage at the benzyl carbon of the protonated ether
(b) (H 3C) 2 CH — OH  Br — C(CH 3 )3 SN1 cleavage at the more substituted carbon of the
protonated ether

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 Alcohol, Phenol & Ether

OH

(c) H + CH3I SN2 cleavage at the less hindered carbon of the protonated
ether

(d) Ph — CH — CH 2 — O — Ph SN2 attack at the less hindered carbon of the oxirane

OH

(e) Ph — CH — CH 2 — OH Like SN1 attack at the more substituted carbon of the protonated
OPh
oxirane

H
CH2CH 3
(f) HO—CH 2— Like SN1 attack by water on the more substituted carbon of the
OH
protonated oxirane

CH 3
(g) HO—CH 2— SN2 attack at the less hindered carbon of the oxirane, with retention
H
CH2CH 3
of configuration at the other carbon

OH 
CH2
(h) Claisen rearrangement

CH3
+
(i) H3C S BF4  (Ch 3CH 2 ) 2 O SN2 attack by the sulfide on the trialkyloxonium ion
CH2CH3

H
OH
(j) Like SN1 attack by Cl– on the more substituted carbon of the protonated
CH 3
Cl
oxirane (some Z isomer may also be formed)

Ph
(k)
H S 2 attack by “Ph–” at the less substituted carbon of the oxira
OH N
CH3

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 JEE
Example 2. Identify the reagent(s) needed for each transformation below. In some cases more than one
step may be involved.
CH3

(a) (H3C)2 C  CH 2 
 CH3CH 2 — O — C — CH 2 — Br
CH3

(b) H 2 C  CH — Br 
 H 2 C  CH — CH 2 CH 2 — OH

HO OH

(c)
H H H H

HO H

(d)
H H H OH

(e) Ph — OH 
 Ph — O — CH 2 — CH  CH 2

Solution: (a) Br2 / CH 3CH 2 OH (ethoxy bromination of the -bond)

O
(b) (1) Mg/ether (to give vinyl grignard); (2) (3)

(c) (1) OsO4; (2) NaHSO3 (cis hydroxylation)

(d) (1) mCPBA; (2) H2O/H+ (cat.) [or (2) OH–; (3) H+]
[Note how the epoxidation/ring- opening sequence gives the opposite stereoisomer from
the cis-hydroxylation in (c)]
(e) (1) NaOH (1 eq); (2) Br—CH2—CH = CH2
O
Example 3. The reaction of ethylene oxide with acidic water gives ethylene glycol, HOCH2CH2OH.

By constrast, when ethylene oxide at high concentration is treated with OH–, a polymer known
as polyethylene glycol (trade name Carbowax) is formed. Deduce the structure of polyethylene
glycol and show the mechanism by which it is formed.
Solution: This is an example of an anionic polymerization:

O O

HO – HO — CH 2 — CH 2 — O –

HO — CH 2 — CH 2 — O — CH 2 — CH 2 — O 


 
 
 HO — (CH 2 — CH 2 —) n — O — H
The properties of the resulting polymer depend on the value of n, which is determined by the
reaction conditions.

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 Alcohol, Phenol & Ether
Example 4. What significance can you attach to the following observation?
CH 3 CH 3
1 equiv. mCPBA
O
CH 3 CH 3
Solution: Even through it is more sterically hindered, the more highly substituted double bond is epoxidized
in preference to the less substituted one. this indicates that in the epoxidation reaction steric
effects are less important than the electron-donating effects of the alkyl groups, making the
tetrasubstituted double bond more nucleophilic than the disubstituted one.
Example 5. Identify the major products in the following reactions

NO 2 OH
HNO 3 CH 3
Bromine
(i) A (ii) B
O H2SO4 Water

CH 3

CH3 Br
O OH
Solution: A = O2N B=
Br CH 3
NO2
Example 6. An organic liquid with sweet smell and b.pt 78°C contains C, H and O. On heating with conc.
H2SO4 gives a gaseous product (B) of empirical formula (CH2)n. Compound (B) decolourises
bromine water and alk. KMnO4. (B) also reacts with one mole of H2 in presence of Ni. What
are (A) and (B)?
Solution: Compound (empirical formula CH2) decolourizes Br2 water, reacts with alk. KMnO4 and adds
one mole of H2 and so (B) is alkene.
Compound (B) is obtained from (A) by the action of H2SO4 and so (A) is alcohol.
A has b.pt. 78°C. So (A) is ethanol
Reactions:
Conc.H2SO4
(i) C2 H 5OH   C2 H 4
Ethanol Ethylene

(ii) C2 H 4  Br2 water  decolourises (C2H4Br2)

(B)

C 2 H 4  KMnO 4  decolourises (HCOOK) Pot. formate

(B)
(iii) C2H4+ H2  C2H6
Example 7. (a) Give SN2 and SN1 mechanisms for the cleavage of ethers with HI.
(b) Why does SN2 cleavage occurs at a faster rate with HI than with HCl?

Solution: (a) Step 1 for R  O  R   HI 

 O
+
 I-
R R'
base1 acid 2 acid 1 base2

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 JEE

H
+
O slow
Step 2 for SN 2 I–
+ R R RI + HOR (R is 1°)

Step 3 for SN1 R+ + I–  RI (R be 3°)

(b) The transfer of H+ to ROR in step 1 is greater with HI, which is a stronger acid, than with
HCl. Furthermore, in step 2, I–, being a better nucleophile than Cl–, reacts at a faster rate.
Example 8. Place the following groups of compounds in decreasing order of acidity and justify your answers.
(i) Phenol (A), o-nitrophenol (B), m-nitrophenol (C), p-nitrophenol (D);
(ii) Phenol (A), o-chlorophenol (E), m-chlorophenol (F), p-chloroophenol (G); and
(iii) (A), ocresol (H), m-cresol, (I), p-cresol (J).
Solution: (i) NO2 is electron – withdrawing and acid –strengthening by both induction and resonance. Its
resonance effect is effective from only the ortho and para positions to about an equal extent. It
predominates over the inductive effect which operates from all positions but at decreasing
effectiveness with increasing separation of NO2 and OH. Hence all the nitrophenols are more
acidic than phenol with m-nitrophenol being the weakest of the three. Since the inductive effective
from the closer o positions is the strongest, one might expect o-nitrophenol to be stronger than p-
nitrophenol. However, the intramolecular H-bond in o-nitrophenol must be broken and this requires
some energy. The decreasing order is D  B  C  A.
(ii) Although Cl is electron – donating by resonance, its electron – withdrawing inductive effect
that decreases with increasing separation of Cl and OH predominates, making all the chlorophenols
more acidic than phenol. The decreasing order is E  F  G  A.
(iii) Me is electron – donating inductive from all positions and hyperconjugatively from the ortho
and para positions. The three isomers are weaker acids than phenol. m-Cresol is the strongest
because its acidity is not weakened by hyperconjugation. The decreasing order is A  I  J  H.
Example 9. An organic compound (A) [M.F = C7H8O] is insoluble in aqueous sodium bicarbonate but dissolves
in aqueous sodium hydroxide and gives characteristic colour with aqueous ferric chloride. When
treated with bromine, (A) forms a compound (B) C7H5OBr3. Identify (A) and (B).
Solution: (A) must be a phenolic compound because
(i) it is soluble in aq. NaOH but not in aq. NaHCO3
(ii) it forms coloured compounds with FeCl3
(A) has a phenolic group and it should also have a methyl group at meta position to –OH group.
[Only then (B) is formed on bromination]

Br
Br2
(A) OH Br OH (B)
Lewis Acid
H3C H3C Br
Example 10. A compound (A) with the molecular formula C6H14O does not react with Na, but when heated
with hot HI, it converts into a mixture of two isomeric compounds of the molecular formula
C3H7I. Identify A.
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 Alcohol, Phenol & Ether

nH n X nN
Solution: Double bond equivalent (DBE) = nC – –  1
2 2 2
where nC = no. of carbon atoms
nH = no. of Hydrogen atoms,
nX = no. of halogen atoms
nN = no. of nitrogen atoms
14
For compound (A), DBE = 6 – +1=0
2
 (A) is a saturated compound but cannot be an alcohol, because it does not react with Na.
Hence, (A) is an ether.
Now, C3H7I has only two possible isomers:

CH3
CH3CH2CH2(I) and CH(I)
CH3
(B) (C)

Hot HI cleaves (A) to (B) and (C)

CH3
Hence, (A) is CH3CH2CH2 — O — CH
CH3

Example 11. Identify the products, giving the mechanism

NaOCH3
(a) CH3CH2CH — CH2 ?
CH3OH, 
O

H+
(b) CH3CH2CH — CH2 ?
CH3OH, 
O
Solution: The reactions involved are the cleavage of the expoxide ring.
(a) This is a base-catalysed ring opening.
 The mechanism is SN2 and the nucleophilic attack is on the less-crowded carbon.

OCH3 H+
CH3CH2CH — CH2 CH3CH2CHCH2OCH3 CH3CH2CHCH2OCH3
O O– OH
(Product)

1-Methoxybutan-2-ol

(b) This is an acid-catalysed ring opening; therefore, mechanism is SN1 and nucleophilic attack
is on the more-substituted carbon.
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 JEE

CH3CH2CH — CH2 H+
CH3OH CH3CH2CHCH2OH
O
OCH3 (3, methoxybutanol) (Product)

Example 12. An organic compound (A) has 76.6% C and 6.38% H. Its vapour density is 47. It gives
characteristic colour with FeCl3 solution. (A) when treated with CO2 and NaOH at 140°C
under pressure gives (B) which an acidification gives (C). (C) reacts with acetyl chloride to give
(D) which is a well-known painkiller. Identify A, B, C and D and also explain the reactions
involved.
Solution: Molar mass of A = 2  V.D = 2  47 = 94 g/mol
The ratio of atoms is
76.6 6.38 17.02
C:H:O = : :
12 1 16
= 6.38 : 6.38 : 1.064
=6:6:1
Hence, the empirical formula of A = C6H6O
Since empirical formula mass = 94 = molar mass of A
Therefore, the formula of A is C6H6O.
Since (A) gives characteristic colour with FeCl3 it should be phenol. The reactions involved are

NaOH H+
OH + CO 2 OH OH
140°C, high P
COO – Na+ COOH
(A) (B) (C)
Salicylic Acid

O O

OH + CH 3CCl O — C — CH 3

COOH COOH
(D)
(C)
Aspirin (pain-killer)

Example 13. An optically active alcohol (A), (C6H10O), absorbs two moles of hydrogen per mole of (A) upon
catalytic hydrogenation and gives a product (B). Compound (B) is resistant to oxidation by CrO3
and does not show any optical activity. Identify (A) and (B).
10
Solution: D.B.E of A = 6 – +1=2
2
(A) must have following characteristics:
(i) is an alcohol (ii) contains two  bonds
(iii) has an asymmetric carbon
(iv) is a tertiary alcohol being resistant to oxidation by CrO3
 A is
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 Alcohol, Phenol & Ether

OH

CH3 C C CH 3–Methyl pent –1–yn–3–ol

CH2CH3 OH

And, B is CH3 C C 2H5

CH2CH3

Al2O3 (i) HI Al2O3 (i) B2H6

Example 14. (A) . (B) (C) (B) (ii) H O , OH– (A)
250° (ii) AgOH 150°C 2 2

(A) and (C) are isomers. (B) has a formula of C5H10 which can also be obtained from the
product of reactions of CH3CH2MgBr and acetone. Identify (A), (B), and (C).
Solution: (B) [M.F = C5H10] can be obtained as

CH2CH3 CH3
H+
CH3CH2MgBr + CH3CCH3 CH3CCH3 C2H5 — C — CH3

O OMgBr OH


CH3CH = C(CH3)2
(B)

Since (B) is formed by heating (A) with Al2O3, (A) must be an alcohol. Moreover, (A) and (C) are
isomers. Hence

CH3

(A) is CH3CH — CHCH3 ; (B) is CH3CH = C — CH3 ; (C) is CH3 — C — CH2CH3

CH3 OH CH3 OH

Example 15. Compound (A), C10H12O gives off hydrogen on treatment with sodium metal and decolourises
Br2 in CCl4 to give (B), C10H12OBr2. (A) on treatment with I2 in NaOH gives iodoform and an
acid (C) after acidification. Give the structures of (A) to (C) and also of all geometrical and
optical isomers of (A).
12
Solution: D.B.E. of (A) = 10 – +1=5
2
Since (A) decolouries bromine water and adds only a molecule of bromine, (A) should have a
double bond.
D.B.E. of A = 5; it should also have a benzene ring.
(A) gives positive iodoform test and should have structure of the type

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 JEE

R — CHCH3 (R = alkyl/aryl group)

OH

CH = CHCHCH 3 CHBrCHBrCH(OH)CH 3
OH Br 2
Hence, (A) = (B) =
CCl 4

CH = CHCHCH 3 CH = CHCOOH
OH I2
CHI 3 +
NaOH Iodoform
(A) (C)
(A) has a chiral carbon and exists in two enantiomeric forms:

CH = CHC6H5 CH = CHC6H5

H OH HO H

CH3 CH3

(A) has two geometrical isomers:

C6H5 H
CH(OH)CH3 CH(OH)CH3
C=C C=C
H H C6H5 H

(cis) (trans)

Example 16. Two different Grignard reagents (X) and (Y) produce C6H5CH2C(CH3)2OH on reaction with
(P) and (Q) respectively. Give the structures of (X), (Y), (P), and (Q).

CH3

Solution: The compound C6H5CH2 — C — CH3 can be synthesised as

OH
C6H5CH2 CCH3 + CH3MgX
(X)
OH
(P)
O
C6H5CH2 — C — CH3
O
CH3
CH3 C CH3 + C6H5 CH2 MgX
(Q) (Y)

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 Alcohol, Phenol & Ether
Example 17. A phenolic compound (A), C7H8O2 on mild oxidation gives a highly volatile oil (B). (A) forms (C)
on reaction with dimethyl sulphate in alkali. The oxidation of (C) with hot KMnO4 gives (D)
which then reacts with bromine water to give (E), containing about 72% bromine. Identify (A) to
(E) with proper reasoning.
Solution: D.B.E. of [A] = 7 – 4 + 1 = 4
D.B.E. = 4 indicates that [A] might contain a benzene ring.
[A] should contain a benzene ring as well as a phenolic group.
The molecular formula will be C6H5OH – CH2O.
Since (A) undergoes mild oxidation, the ring should contain a CH2OH group and since on oxidation
a hightly volatile oil is obtained, this group should be at ortho-position.

OH OH
CH 2OH CHO
mil
oxidation
(A) (highly volatile due to
intra-molecular H-bonding)
Etherfication (CH 3)2SO4/OH –

OCH 3 OCH 3 OCH 3

CH 2OH COOH Br Br
hot Bromine
KMnO4 Water
Br
(C) (D) (E)

Percentage of Br in [E] = 69.56 % (

Example 18. An organic compound (A) on treatment with CHCl3 and KOH gives (B) and (C), both of which,
in turn, give the same compound (D) when distilled with Zn dust. The oxidation of (D) yields (E)
of formula C7H6O2. Sodium salt of (E) on heating with soda-lime gives (F) which can also be
obtained by distilling (A) with zinc dust. Identify (A) to (F).
Solution: The summary of reactions is
CHCl3
[A] [B] + [C]
KOH
Zn-dust Zn-dust

(i) NaOH [O]

[F] [E] [D]
(ii) soda -lime C7H6O2

6
D.B.E. of E(C7H6O2) = 7 – +1=5
2
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JEE
[E] should contain a benzene ring and it undergoes decarboxylation with soda-lime.

[E] can be benzoic acid COOH

[F] can be benzene (C6H6)

[A] is undergoing Reimer-Tiemann reaction; thus, [A] is phenol.
The reactions involved are

CHCl 3
OH OH + OHC OH
KOH
(A) (B) CHO (C)
Zn-Dust
Zn-Dust

(i) NaOH [O]

COOH CHO
(ii) Soda-sime
(F) (E) (D)

****

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 Alcohol, Phenol & Ether

EXERCISE # 1(A) (Level 1 – Beginner)

1. Which of the following is produced when an aqueous solution of butan-2-ol is refluxed with dilute
acidic KMnO4?
(A) butanol (B) butanoic acid
(C) potassium butanoate (D) butanone
PCl alc.
2. Consider the reaction: CH3CH2CH2OH 
5
 A 
KOH
 B . The compound ‘B’ is
(A) propane (B) propene (C) propyne (D) propanal
3. Which of the following has the lowest solubility in water?

CH3
(A) CH3CH2CH2CH2OH (B) CH3—CHCH2OH

(C) HOH2C — CH2OH (D) C6H5CH2CH2OH

4. Chlorine reacts with ethanol to give
(A) ethylchloride (B) chloroform (C) chloral (D) acetaldehyde
5. Ethanol is heated with concentrated H2SO4. The product formed is

(A) CH 3  CH – O  C2 H 5 (B) C2H6

|
OH
(C) C2H4 (D) C2H2
6. Which of the following is also known as ‘picric acid’?
(A) phenol (B) carboxylic acids (C) trinitrophenol (D) nitroalkane
7. Which of the following has the highest value of pKa?
(A) CH3 — CH2OH (B) Cl — CH2 — CH2OH
(C) F3C — CH2 — OH (D) CH3 — CH — CH2OH

CH3

8. Which of the following has the highest boiling point?

(A) CH3 — CH2 — CH — CH3 (B) CH3 — CH2 — CH2 — CH2OH

OH

CH3

(C) CH3 — CH — CH2OH (D) CH3 — C— OH

CH3 CH3

9. Wood spirit contains

(A) only methanol (B) only ethanol
(C) methanol + ethanol (D) a mixture of a number of alcohols
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10. The compound which reacts faster with Lucas reagent at room temperature is
(A) butan–1–ol (B) butan–2–ol
(C) 2–methyl propan–1–ol (D) 2–methyl propan–2–ol
11. Lucas test is used to determine the type of
(A) amines (B) alcohols (C) acids (D) phenols
12. When glycerol is heated with oxalic acid, the compound formed is
(A) allyl alcohol (B) formic acid
(C) tartaric acid (D) formic acid and allyl alochol
13. Salol is prepared from
(A) Salicylic acid and phenol (B) Salicylic acid and methanol
(C) both (A) and (B) (D) phenol and methylchloride
14. Separation of a higher phenol and an aromatic carboxylic acid can be easily carried out by
(A) NaOH (B) Na2CO3 (C) lime (D) NaHCO3
15. A compound ‘A’ reacts with sodium metal and also undergoes iodoform reaction. ‘A’ is
(A) phenol (B) methanol (C) n-propanol (D) iso-propanol
16. Which of the following pairs gives the same compound on heating with zinc dust?

OH OH OH OH
CH3 CHO
(A) and (B) and

CHO

(C) CH3CH2CH2OH and CH3CHOHCH3 (D) 1- butanol and 2-butanol

17. Which of the following ethers is cleaved even by HCl at room temperature?
(A) C6H5OCH2CH3 (B) CH3CH2OCH2CH3
(C) (CH3)3COCH2CH3 (D) (CH3)3COC(CH3)3
18. The reaction between sodium ethoxide and bromoethane yields
(A) methyl ethyl ether (B) dimethyl ether
(C) diethyl ether (D) propane
19. Diethyl ether on heating with concentrated HI gives two moles of
(A) ethanol (B) iodoform (C) ethyl iodide (D) methy liodide
20. Major product of the given reaction will be-
OH OH H2SO4
Ph
Ph

O O O O
Ph Ph Ph Ph
(A) Ph (B) (C) Ph (D) Ph
Ph
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 Alcohol, Phenol & Ether

OH OH

21. PCC (1) MeMgBr NaBH 4 , EtOH

(A) OH OH (B)  +
(C)   (D)
(2) H 3O

Product (D) in above reaction is:

OH OH HO OH OH OH OH

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

OH

22. What is the rearranged product of given compound ?

OH OH
Ph—C—C—Ph
Ph CH 3

Ph O Ph O
(A) Ph—C—C—CH 3 (B) Ph—C—C—CH 3
H Ph

CH 3O CH 3O
(C) Ph—C—C—CH 3 (D) CH 3—C—C—Ph
CH 3 CH 3

OH
H 2SO 4
23. Identify the major product  Product.

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

24. By which of the following sequence of steps can the alcohol RCH2CH2OH(X) be converted into
RCH2CH2COOH(Y)?

PBr3 KCN H3O
(A) X     Y
PBr KCN H /Pt
(B) X 
3
  
2
Y

KCN
(C) X  H3O
  Y

HCN PBr H O
(D) X   
3
 
3
Y

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25. Non–occurence of the following reaction Br– + CH3OH  BrCH3 + OH– , is due to :
(A) Attacking nucleophile is stronger one
(B) Leaving group is a strong base
(C) Alcohols are not good substrate
(D) Hydroxide ions are weak bases
26. The end product of which of the following reaction is not the alcohol or isomer of alcohol –

(A) C 2 H 4 
B2 H 6
 A 
H2O2
NaOH
Z

(B) CHI3   A   B  Z

Ag dil. H 2SO4 Reduction
 Hg 2

(C) C 2 H 4 
HI
 A 
aqueous KOH
 B 
Conc. H 2SO 4
170 C
Z

(D) CH 3 MgBr 

CH 2 O
 A 
H2O
Z
27. Vapour of t-butyl alcohol is passed over copper heated at 300ºC. The product formed is -
(A) CH3COCH3 (B) (CH3)3COC(CH3)3
(C) (CH3)2C=CH2 (D) (CH3)3 C–O–O–C(CH3)2
28. Which of the following pairs can be distinguished by iodine and dilute NaOH -
(A) n-Propyl alcohol and n-butyl alcohol
(B) t-Butyl alcohol and s-butyl alcohol
(C) Benzyl alcohol and cyclohexanol
(D) n-Propyl alcohol and ethyl methyl ether
29. The correct order of boiling points of n-pentane, butyraldehyde, diethyl ether and n-butyl alcohol is
(A) n-Pentane > butyraldehyde > diethyl ether > n-butyl alcohol
(B) n-Pentane > diethyl ether > butyraldehyde < n-butyl alcohol
(C) n-Butyl alcohol > butyraldehyde > n-pentane > diethyl ether
(D) n-Butyl alcohol > diethyl ether > n-pentane > butyraldehyde

OH
O
30. CH2 OH ; Above transformation can be carried out by:



(A) H+/, Zn (Hg), HCl (B) HIO4, LiAlH4

(C) HIO4, H+/ (D) H+/, HIO4

*****

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 Alcohol, Phenol & Ether

EXERCISE # 1(B)(Level 2 – Learner)

1. The compound that does not change the orange colour of chromic acid to blue green is
(A) 2° alcohol (B) 1° alcohol (C) 3° alcohol (D) none of the above
2. HBr reacts the fastest with
(A) 2-methyl propan-2-ol (B) propan-1-ol
(C) propan-2-ol (D) 2-methyl propan-1-ol
3. A compound ‘X’ on oxidation gave ‘B’ and then again on oxidation gave an acid. After the first
oxidation, it reacted with ammoniacal silver nitrate to produce a black precipitate. ‘X’ is
(A) a primary alcohol (B) a tertiary alcohol (C) acetaldehyde (D) acetone
4. Phenol forms benzene on reaction with
(A) NaHCO3 (B) NaOH (C) HCl (D) zinc
5. Which of the following statements is correct?
(A) phenol is acidic in nature, gives effervescence with NaHCO3
(B) phenol is basic in nature due to the presence of OH
(C) phenol gives violet colour with neutral FeCl3
(D) phenol as well as ethanol can be reduced to corresponding alkanes by heating with zinc dust
6. Reimer-Tiemann reaction is/are
anhydrous
(A) C6H6 + CH3Cl 
AlCl
 C6H5CH3 + HCl
3

(B) CH3COOAg + Br2 

 CH3Br + AgBr + CO2
Ni
(C) CH2 = CH2 + H2   CH3 – CH3
OH
(D) C6H5OH + CHCl3 + 3KOH 
 C6H4 + 3KCl + 3H2O
CHO
7. The following reaction

OH OH
anhydrous
+ HCl + HCN  
ZnCl
 is
2
CHO
(A) Perkin reaction (B) Gattermann reaction
(C) Kolbe reaction (D) Gattermann koch reaction
8. Which of the following has a higher pH?
(A) phenol (B) o-cresol (C) p-nitrophenol (D) glycerol
9. Which of the following alcohols is a stronger acid?
(A) CH3OH (B) CH3 – CH2 – OH

CH3 CH3

(C) CHOH (D) CH3 — C — OH

CH3 CH3

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JEE
10. The reaction of anisole with HI leads to the formation of
(A) phenol and methanol (B) phenol and methyl iodide
(C) iodobenzene and methanol (D) iodobenzene and methyl iodide
11. Which of the following compounds is resistant to nucleophilic attack by hydroxyl ions?
(A) methyl acetate (B) acetonitrile (C) dimethyl ether (D) acetamide
12. Diethyl ether absorbs oxygen to form
(A) a red-coloured sweet-smelling compound (B) acetic acid
(C) ether suboxide (D) ether peroxide
13. On boiling with concentrated HBr, phenyl ethyl ether will yield
(A) phenol and ethyl bromide (B) bromobenzene and ethanol
(C) phenol and ethane (D) bromobenzene
14. Which of the following reactions leads to formation of 2-propanol ?

(A) CH3CH2MgI + HCHO 
 Adduct H3O
(B) CH3MgBr + CH3CHO  H 3O 
 Adduct  
(C) CH3MgBr + CH2–CH2 
 Adduct
O
(D) CH3COCH3 + Mg-amalgam + conc HCl 

15. Ether in contact with air for a long time form peroxides. The presence of peroxide in ether can be
tested by adding Fe2+ ion in it and then adding -
(A) KCNS (B) SnCl2 (C) HgCl2 (D) KI
16. When phenol is reacted with CHCl3 & NaOH followed by acidification, salicyladehyde is obtained.
Which of the following species are involved in the above mentioned reaction as intermediates -

O OH O
H CHCl 2 H
(A) CHCl 2 (B) (C) CCl 2 (D) Both (A) and (B)
OH
17. Given :
Four alcohols Number of a–hydrogen Number of b–hydrogen
A 3 0
B 2 3
C 1 6
D 0 9
Which alcohol will give blue colour with Victor Meyer reagent ?
(A) C (B) B (C) D (D) A
18. Ether does not form oxonium salt on reaction with -
(A) Cold conc. H2SO4 (B) Cold conc. HCl
(C) Conc. HI (D) None of the above
19. The presence of -OH on adjacent carbon atoms of an alcohol can be detected by the reaction of the
compound with -
(A) Conc. H2SO4 (B) Conc. HNO3 (C) HIO4 (D) Acidic KMnO4
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 Alcohol, Phenol & Ether
20. Among the following the one that gives positive iodoform test upon reaction with I2 and NaOH is-
(A) CH3CH2CH(OH)CH2CH 3 (B) C6H5CH 2CH 2OH
CH3
(C) CH3–CHCH2–OH (D) PhCHOHCH 3
21. The decomposition of ethers by HI or HBr is called -
(A) Zerewitinoff’s reaction (B) Ziesel’s method
(C) Williamson’s method (D) Hell-Volhard-Zelinsky reaction
22. Which of the following will not be soluble in sodium carbonate solution –

OH
O 2N NO2 OH SO2OH
NO2
(A) (B) CH3CH2OH (C) (D)
NO2

23. The oxidation of a secondary alkanol with Cr (VI) leads to the formation of :
(A) An alkanone and Cr (II) (B) An aldehyde and Cr (III)
(C) An alkanone and Cr (III) (D) An aldehyde and Cr (II)
24. Ether is not formed in this reaction -

(A) 2C2H5OH  

Conc.H 2SO 4
140
(B) (CH3)3C–Cl + C2H5ONa 
(C) C2H5Cl + (CH3)3C–ONa  (D) CH3ONa + CH3I 
25. The order of reactivity of the following alcohols with a given halogen acid, say HBr, is-
(A) CH3CH2CHOHCH3 > CH3CH2CH2CH2OH > (CH3)3COH
(B) (CH3)3COH > CH3CH2CHOHCH3 > CH3CH2CH2CH2OH
(C) CH3CH2CH2CH2OH > CH3CH2CHOHCH3 > (CH3)3COH
(D) (CH3)3COH > CH3CH2CH2CH2OH > CH3CH2CHOHCH3

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 JEE

EXERCISE # 2(A)(Adept – JEE Main PYQs)

1. An unknown alcohol is treated with the “Lucas reagent” to determine whether the alcohol is
primary,secondary or tertiary. Which alcohol reacts fastest and by what mechanism:
(JEE Main 2013)
(A) tertiary alcohol by SN1 (B) tertiary alcohol by SN2
(C) secondary alcohol by SN2 (D) secondary alcohol by SN1
2. Sodium phenoxide when heated with CO2 under pressure at 125oC yields a product which on
acetylation produces C. (JEE Main 2014)
ONa
125° H+
+ CO2 B C
5 atm Ac2O
The major product C would be:
OH
OH COCH 3 OCOCH 3 OCOCH 3
COOCH 3 COOH
(A) (B) (C) (D)
COCH 3 COOH

3. The product of the reaction given below is: (JEE Main 2016)

1. NBS/hv
X
2. H2O/K 2CO 3

CO 2H OH O

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

4. The major product fromed in the following reaction is: (JEE Main 2018)

O HI
Heat
O

OH I OH I
(A) (B) (C) (D)
OH I I OH
5. The major product of the following reaction is : (JEE Main 2019)
OCH 3 Conc HBr (excess)
heat
CH=CH 2

Br OH Br OH
(A) (B) (C) (D)

Br–CHCH 3 Br–CHCH 3 CH 2CH3Br CH 2CH3Br

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 Alcohol, Phenol & Ether
6. Which is the most suitable reagent for the following transformation? (JEE Main 2019)
OH
|
CH 2  CH  CH  CH 2  CH  CH3  CH 3  CH  CH  CH 2 CO 2 H
(A) Tollen’s reagent (B) I2/NaOH
(C) CrO2Cl2/CS2 (D) alkaline KMnO4
7. What will be the major product when m-cresol is reacted with propargyl bromide (HC  C  CH 2 Br)
in presence of K2CO3 in acetone ? (JEE Main 2019)

O OH OH OH

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

CH3 CH3 H3C H3C

8. The major product [B] in the following reactions is: (JEE Main 2020)

CH3
|
HI H 2SO 4
CH3 –CH 2 – CH –CH 2 –OCH 2 –CH3 
Heat
[A]alcohol Δ
[B]

CH3
|
(A) CH 2CH 2 (B) CH3 –CH = C – CH3

CH3
|
(C) CH3 –CH 2 – C = CH 2 (D) CH 3  CH 2  CH  CH  CH3
9. The major product [B] in the folowoing sequence of reaction is: (JEE Main 2020)
(i) B H dil.H 2SO4
CH3 – C = CH–CH 2 CH3  2 6
[A]  [B]
(ii) H 2O 2 ,OH Δ
|
CH(CH3 ) 2

(A) CH 2 = C – CH 2 CH 2 CH3 (B) CH 3  C  CH 2CH 2CH 3

| ||
CH(CH3 ) 2 C
H 3C CH 3

(C) CH3 – C = CH–CH 2 CH 3 (D) CH 3 – C – CH=CH – CH 3

| |
CH(CH3 ) 2 CH(CH 3 )2
10. The major aromatic product C in the following reaction sequence will be: (JEE Main 2020)
O
HBr (excess), (i) KOH (Alc.) O


 A 
  B 
3
 C
(ii) H Zn/H3O

OH OH Br Br
(A) (B) CO2H (C) CO2H (D)
CHO CHO

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JEE

OH
Conc. H2SO4
11. +

A B
Consider the above reaction, and choose the CORRECT statement: (JEE Main 2021)
(A) The reaction is not possible in acidic medium
(B) Both compound A and B are formed equally
(C) Compound A will be the major product
(D) Compound B will be the major product
12. The major product formed in the following reaction is: (JEE Main 2021)

CH3
|
conc. H 2SO4
CH 3  C— CH  CH 3 
a few drops
 Major product
| |
CH 3 OH

CH 3 CH3

(A) CH 3  C  CH  CH 2 CH 3 (B)
H3C CH3
CH 3
(C) C = CH – CH3 (D) CH 3 – C – CH = CH 2
CH 3 |
CH3
13. The major product of the following reaction is: (JEE Main 2022)
OCH 3
O2N (i) Na/liq.NH 3
(ii) CH 3CH2OH

OCH 3 OCH 3 OH OCH 3

H H H
(A) O2N (B) H2N (C) O2N (D) O2N

(i) NaI, H3PO4

(ii) Mg, Dry ether
14. H 3C – CH 2 – CH – CH3 
(iii) D 2O
[X] (JEE Main 2023)
| Product
OH
Product [X] formed in the above reaction is:

H
|
(A) H3C – CH 2 – C H – CH3 (B) H 3C – CH 2 – C – CH 3
| |
D OH

(C) H 3C – CH 2 – CH = CH 2 (D) H 3C – CH = CH – CH3

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 Alcohol, Phenol & Ether
15. Incorrect method of preparation for alcohols from the following is: (JEE Main 2023)
(A) Ozonolysis of alkene.
(B) Reaction of Ketone with RMgBr followed by hydrolysis.
(C) Hydroboration-oxidation of alkene.
(D) Reaction of alkyl halide with aqueous NaOH.
16. Find out the major product for the following reaction: (JEE Main 2023)
CH3
H 3O +
Major Product

OH

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

17. Compound ‘B’ is- (JEE Main 2023)

NaNO2 NH 4SH
A B
HCl H2O Major
OH

H2N
(A) (B)
OH

HS
(C) (D)
SH OH

18. A compound ‘X’ when treated with phthalic anhydride in presence of concentrated H 2SO 4 yields '
‘Y’. ‘Y’ is used as an acid/base indicator. ‘X’ and ‘Y’ are respectively: (JEE Main 2023)
(A) Carbolic acid, Phenolphthalein (B) Anisole, methyl orange
(C) Salicylaldehyde, Phenolphthalein (D) Toludine, Phenolphthalein
19. The strongest acid from the following is: (JEE Main 2023)
OH OH OH OH

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

NO 2 Cl CH 3
20. Decreasing order of dehydration of the following alcohols is- (JEE Main 2023)

OH OH OH OH
(A) (B) (C) (D)
(A) D > B > C > A (B) A > D > B > C (C) B > A > D > C (D) B > D > C > A
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JEE
21. An organic compound ‘A’ with empirical formula C6 H 6 O gives sooty flame on burning. Its reaction
with bromine solution in low polarity solvent results in high yield of B. B is- (JEE Main 2023)

OH
CH 2CH2Br Br CH 2CH 3 Br
OH
(A) (B) (C) Br (D)
Br
22. In the cumene to phenol preparation in presence of air, the intermediate is- (JEE Main 2023)

O
O O–O–H
O CH3
(A) (B) (C) (D)

23. Suitable reaction condition for preparation of Methyl phenyl ether is: (JEE Main 2023)
(A) Ph  Br, MeO  Na  (B) PhO  Na  , MeOH

(C) PhO Na  , MeBr (D) Benzene, MeBr

24. ‘A’ and ‘B’ formed in the following set of reactions are- (JEE Main 2023)
OH OH
HBr HBr
A; B
 
CH 2OH OCH 3
Br Br OH Br
(A) A = , B= (B) A = , B=

CH 2OH Br CH 2OH OCH 3

OH OH OH OH
(C) A = , B= (D) A = , B=

CH 2Br Br CH 2Br OH

25. C2 H5OH
CH3  CH 2  CH 2  Br  NaOH   Product ‘A’’ (JEE Main 2024)

H2O, H+
Product B
Product A
Diborane
Product C
H2O, H2 O2 , OH
Consider the above reactions, identify product B and product C.
(A) B = 1-Propanol C = 2-Propanol (B) B = C = 2-Propanol
(C) B = 2-Propanol C = 1-Propanol (D) B = C = 1-Propanol
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 Alcohol, Phenol & Ether
26. Identify compound in the following reaction sequence. (JEE Main 2024)
Cl
623 K HCl Conc. HNO
 NaOH 
 X 
 Y 
3
Z
300 atm

OH OH
O2 N NO2 NO2
(A) (B)

NO2 NO2

OH OH
NO2
(C) (D)

NO2
27. Consider the given reaction, identify the major product P. (JEE Main 2024)
(i) LiAlH (ii) PCC (iii) HCN/OH
CH3  COOH 
4
'P '
(iv) H 2O/OH,

O
||
(A) CH3  CH 2  C  NH 2 (B) CH 3  CH 2  CH 2  OH

OH O
| ||
(C) CH3  CH  COOH (D) CH3  C  CH 2CH3
28. The major products formed: (JEE Main 2024)
OCH3

HNO ,H SO Br (excess)

3 2 4
 'A' 
2

 'B'
Fe

A and B respectively are:

OCH3 OCH3 OCH3 OCH3

Br Br NO2 NO2
(A) and (B) and

NO2 NO2 Br

OCH3 OCH3 OCH3 OCH3

Br NO2 Br NO2
(C) and (D) and

NO2 NO2 Br

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JEE
29. Match List - I with List - II. (JEE Main 2024)
List-I (Reaction) List-II (Reagent(s))
OH OH
COOH
(A) (I) Na 2 Cr2 O 7 , H 2SO 4

OH OH
CHO
(B) (II) (i) NaOH (ii) CH3Cl

OH O

(C) (III) (i) NaOH, CHCl3, (ii) NaOH (iii) HCl

O
OH

(D) OCH3 (IV) (i) NaOH (ii) CO2, (iii) HCl

Choose the correct answer from the options given below:

(A) (A)-(IV), (B)-(I), (C)-(III), (D)-(II)
(B) (A)-(II), (B)-(III), (C)-(I), (D)-(IV)
(C) (A)-(II), (B)-(I), (C)-(III), (D)-(IV)
(D) (A)-(IV), (B)-(III), (C)-(I), (D)-(II)
30. Salicylaldehyde is synthesized from phenol, when reacted with (JEE Main 2024)

(A) H Cl , NaOH (B) CO 2 , NaOH

(C) CCl4 , NaOH (D) HCCl3 , NaOH

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 Alcohol, Phenol & Ether

EXERCISE # 2(B)(Scholar – JEE Main PYQs)

1. The number of chiral centres present in [B] is ____. (JEE Main 2020)

(i) C H MgBr (i) CH MgBr

CH –C  N 
2 5
 [A]  3
[B]
| (ii) H3O + (ii) H 2O

CH 3

2. To synthesise 1.0 mole of 2-methylpropan-2-ol from Ethylethanoate ______ equivalents of CH3

MgBr reagent will be required. (Integer value) (JEE Main 2021)
3. A 1.84 mg sample of polyhydric alocoholic compound ‘X’ of molar mass 92.0 g/mol gave 1.344 mL
of H2 gas at STP. the number of alocoholic hydrogens present in compound ‘X’ is ____.
(JEE Main 2022)
4. A 100 mL solution of CH3CH2MgBr on treatement with methanonal prodcues 2.24 mL of a gas
STP. The weight of gas produced is ____ mg. (nearest integer). (JEE Main 2022)
5. A sample of 4.5 mg of an unknown monohydric alcohol, R–OH was added to methylmagnesium
iodide. A gas is evolved and is collected and its volume measured to be 3.1 mL. The molecular
weight of the unknown alcohol is ____ g/mol. (Nearest integer) (JEE Main 2022)

6. The number of chiral alcohol(s) with molecular formula C 4 H10 O is ___. (JEE Main 2022)
7. Consider the given chemical reaction sequence: (JEE Main 2024)

OH

Conc. H SO Conc. HNO


2 4
 Product A 
3
 Product B

Total sum of oxygen atoms in Product A and Product B are _______.

*****

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 JEE

EXERCISE # 3(A)(Proficient – JEE Advanced Level Questions)

1. Reaction of tertiarty butyl alcohol with hot Cu at 350°C produces
(A) Butanol (B) Butanal (C) 2-Butene (D) 2-methylpropene
2. The product (B)in the following sequence of reaction is:

C6H5CO 3H HCl
A B
CH 2

OH Cl O
O
(A) (B) (C) (D)
Cl OH OH

2 Br Aq.KOH con.
3.  ethene 
 A  B  C 
D
 H2SO4

O
O
O CHO
(A) (B) (C) H (D)

Jone's
4. CH3 – CH = CH – CH(OH) – CH3 
reagent
 X, Product X is
(A) CH3CH2CH2CH(OH)CH3 (B) CH3CH = CHCOCH3
(C) Both (A) and (B) are correct (D) CH 3CH 2CH 2COCH 3
5. One mole of t-butyl methyl ether on being heated with 1 mole of concentrated hydriodic acid gives-
(A) CH3OH (1 mole) and (CH3)3CI (1 mole) (B) CH3I (1 mole) and (CH3)3COH (1 mole)
(C) CH3I (1 mole) and (CH3)3CI (1 mole) (D) CH3OH (1 mole) and (CH3)3COH (1 mole)
conc. H 2SO 4
6. The reaction 2C 2 H 5 OH   (C 2 H5 ) 2 O  H 2 O is an example of
140C

(A) an elimination reaction (E2) (B) an electrophilic substitution (SE2) reaction

(C) a nucleophilic substitution (SN1) reaction (D) a nucleophilic substitution (SN2) reaction
7. Pinacol vapour is passed over alumina heated at about 350ºC.

CH 3 CH 3
| |
CH 3 — C — C —– CH 3
| |
OH OH
The major product formed in the reaction is:

CH3 CH3
| |
(A) CH 3COC(CH 3 )3 (B) CH 2  C — C  CH 2

(C) (CH 3)2C — C(CH 3)2 (D) (CH 3 ) 2 CHOCH(CH3 ) 2

O
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 Alcohol, Phenol & Ether
Al2O3
8. In the reaction; 2C 2 H 5OH  (C 2 H5 ) 2 O  H 2 O alumina acts mainly as
240 C

(A) an absorbent of water

(B) a provider of hot solid surface
(C) a Lewis acid to coordinate (C2H5)2O formed
(D) a Lewis acid catalyst to increase the leaving group ability of the –OH group by coordination at
oxygen.
9. Reaction of t-butyl bromide with sodium methoxide produces
(A) isobutane (B) isobutylene
(C) sodium t-butoxide (D) t-butyl methyl ether
10 . In the reaction
(CH 3 )3 C  O  CH 2 CH 3  HI 
heat

(1mole)

the product(s) formed is (are)

(A) (CH3)3 C—OH and CH3CH2I (B) (CH3)3 C—I and CH3CH2OH
+
(C) (CH3)3 C—I and CH3CH2I (D) (CH 3 )3 C  O  CH 2 CH3 I 
|
H
11. The order of reactivity of the following alcohols towards conc. HCl is

CH3 H3C CH3

F CH3 Ph OH
F OH HO OH
(I) (II) (III) (IV)

(A) I > II > III > IV (B) I > III > II > IV (C) IV > III > II > I (D) IV> III > I > II
12. Consider the following sequence of reactions;
H PO 1. O . heat
C6 H6  CH3CH  CH 2 
3 4
heat
 A 
2
 B  C
2. H3O , heat

The product (B) and (C) are -

(A) benzaldehyde and acetaldehyde (B) benzoic acid and acetic acid
(C) phenol and propionaldehyde (D) phenol and acetone

13. The reaction O CH2 + HI Produces

(A) CH2I and I (B) OH and CH2I

(C) OH and CH2OH (D) CH2OH and I

14. Denaturation of ethyl alcohol refers to:

(A) Mixing of methyl alcohol with it. (B) Mixing some copper sulphate and pyridine.
(C) Heating of ethyl alcohol (D) Sudden cooling of ethyl alcohol.

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JEE
15. Which of the following statement is incorrect ?
(A) PCC oxidises 1° alcohol to aldehyde and 2° alcohol to ketone.
(B) H2CrO4 (chromic acid) oxidises 1° alcohol to aldehyde.
(C) CrO3·H2SO4/acetone oxidises 2° alcohol to ketone.
(D) Jones reagent oxidises 1° alcohol to carboxylic acid and 2° alcohol to ketone without affecting
double bond
16. Order of boiling point for the following compounds is -
OH OH OH OH
OH

OH OH
OH
(I) (II) (III) (IV)
(A) (I) < (II) < (III) < (IV) (B) (I) < (II) < (IV) < (III)
(C) (IV) < (I) < (II) < (III) (D) (II) < (I) < (III) < (IV)
17. On acid catalysed hydration, 2 phenyl propene gives:
(A) 3 phenyl 2 propanol (B) 2 phenyl 1 propanol
(C) 1 phenyl 3 propanol (D) 2 phenyl 2 propanol

Me NH CH 3
18. (i) Br2/Fe
O P (ii) Mononitration
Q
NO 2

H5C 6 Anh.AlCl 3 mononitration

(iii) + Cl R S
O
Where P, Q, R and S are all major products of the respective reactions:
Now choose the correct choice (s) from the following:

Me
O
O Br and
(A)
(P) (R)

O O

NH CH 3 NH CH3
O2N O
or and
(B) NO 2 NO 2 NO2
NO2
(Q) (S)

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 Alcohol, Phenol & Ether

Br
Me O
O and
(C)
(P) (R)

Br
Me
O
O and
(D) NO2
(P) (S)
19. Which of the following is / are the correct order of acidic strength?
(A) R — OH > H2O > HF
(B) PhOH> H2O > R — OH
(C) RCOOH > PhOH > R — OH
(D) m-Nitrophenol> Phenol > m-chlorophenol
O O
(i) CH 3MgBr (i) CH 3MgBr
20. H3C CH3  (A); H CH 3  (B)
(ii) H (ii) H
Which of the following reagent can be used to differentiated between A and B?
(A) FeCl3 (B) Active metal Na (C) Lucas reagent (D) K 2Cr 2O 7
21. Which of the following compounds do/does not react with NaHCO3 ?

OH
OH OH

(A) (B) (C) (D) CH 3  C  C  H

CH 3
22. Which of the following reaction(s) are correctly matched with major product?
(A) H 3C  O  CH 2  CH 3  PCl5  H 3C  Cl  Et  Cl
(B) CH 3COOH  PCl5  CH 3 COCl
(C) MeCOMe  PCl5  MeCH(Cl)Me
(D) Cyclohexanol  PCl5  Cyclohexylchloride
23. Which of the following will produces methylcyclohexene on heating with conc. H2SO4 ?
(A) 2-cyclopentylethanol
(B) methylcyclohexanol
(C) ethylcyclopentanol
(D) cyclohexylmethanol

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JEE
24. Which of the following reaction(s) follow the same pattern of energy graph for the formation of
major product only?

P.E.

Reaction progress

OH

(A) H


OH

(B) H

OH

H
(C)

CH3 CH3
H
(D) CH CH CH 2 OH

25. Which of the following reaction proceeds via formation of cabrocation?
(A) Dehydration of alcohols (B) Pinacol-Pinacolone rearrangement
(C) Diazotisation of aliphatic amines (D) Photo halogenations of alkanes

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 Alcohol, Phenol & Ether

EXERCISE # 3(B)(Amateur - Variety of JEE Advanced Level Questions)

Comprehension Based Questions:
Paragraph # 1 for (Ques. 1 to 2)

|
|| |
|||
H H

|||
|
(P)

H /Pd/CaCO / Quinoline
1. P 
2 3
 Product(s)
The number of isomeric product(s) obtained in this reaction is :
(A) 1 (B) 2 (C) 4 (D) 8
Na / NH (  )
2. (P)  3
 Product(s)
The product(s) has/have degree of unsaturation and number of isomeric product(s) formed are
respectively:
(A) 1, 4 (B) 4, 2 (C) 4, 1 (D) 2, 4
Paragraph # 2 for (Ques. 3 to 4)
Alexander Williamson prepared diethyl ether by a simple method, now called as Williamson’s ether
synthesis. In this method an alkyl halide is treated with sodium alkoxide prepared from sodium and
alcohol.

R  O  R   x  R  O  R   x 
This reaction is used in the synthesis of symmetrical and unsymmetrical ethers.
It may be noted that for preparing unsymmetrical ethers, the halide used should preferably be primary
because secondary and tertiary alkyl halides may form alkenes as major product due to elimination
process.

CH3 CH3
| |
CH3  C – Br  Na  O   C 2 H5  CH3  C  CH 2  C 2 H5 OH  NaBr
| Sodium ethoxide 2-methyl propene
CH3
Aryl ethers or phenolic ethers can be prepared by using sodium phenoxide and alkyl halides. However,
aryl halides and sodiumalkoxide cannot be used for preparing phenolic ethers because aryl halides
are less reactive towards nucleophilic substitution reactions.
3. Arrange the following halides in decreasing order of reactivity towards Williamson’s ether synthesis:
CH3CH2CH2Cl (u) CH3CH2CH2Br (v)
(CH3)3 C–CH2Br (w) CH2 = CH —CH2Br (x)
(A) (x) > (v) > (u) > (w)
(B) (u) > (v) > (w) > (x)
(C) (w) > (x) > (v) > (u)
(D) (v) > (w) > (x) > (u)
4. To which of the following mechanisms does the reaction (Williamson’s ether synthesis) belong?
(A) SN1 (B) SN2 (C) E 1 (D) E 2

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 JEE
Paragraph # 3 for (Ques. 5 to 6)
HI alc. KOH
C5 H10 O 
Excess
 C5 H10 I2  C5 H8
(X) (Y) (Z)
Optically Optically Conjugated
active active diene

5. Structure of ‘X’ is
O O O O
(A) (B) (C) (D)

6. Structure of ‘Z’ is

(A) H2C=CH–CH=CH2–CH3 (B)

(C) (D)
Matrix Match type Questions:
7. Match the reagent of Column – II with the reactions of Column–I
Column – I Column – II

O O

H Cl HO OH
(A) (P) LiAlH4

O OH
O

OH OH

(B) O OH (Q) NaBH4

OH
HO O HO
O OH
O O

(C) O O (R) Na/EtOH

O O
O

Cl OH

(D) (S) H2/Ni

H O HO OH

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 Alcohol, Phenol & Ether
8. Match the column-I and Column-II
Column-I Column-II (reagents used for the desired
product in major amount)
OH OH

(A) (P) CHCl3/NaOH

COOH
OH OH
COOH
(B) (Q) CCl4/NaOH

Cl
..
(C) N N (R) NaOH followed by CO2
H
OH OH
CHO
(D) (S) KOH followed by CO2

9. Observe the following compound and match the reagents of List - I and List – II
(x)
O
(y)
HO CHO
(z) O
HOH 2C (w) CH
3
O
Reagents-I Functional group oxidised/reduced-II
(A) CrO3 / Pyridine / CH2Cl2 (P) w
(B) NaBH4 (Q) z
(C) Na / C2H5OH (R) x
(D) CrO3 / H+ (S) y

Integer Type Questions:

10. Following conversion can be done in four steps using four reagents one after the other. These four
reagents are listed below with some other reagents.
Write the number of most suited reagent in order you want to use them and present the four
digit number in OMR sheet. For example if you want to use (1) than (2) than (3) than (4) fill
1234 in OMR sheet.
OH

OH

(1) O3 / Zn / H2O (2) O3 / H2O (3) conc. H2SO4 / 

(4) aq. KOH /  (5) H2 / Zn (6) Zn – Hg / HCl
(7) NH2 – NH2 / EtOK (8) H 3O + (9) NaOH / CaO / 

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JEE
11. Sum of molecular mass of iodides produced in following reactions is:
(a) conc. HI
O
anyhydrous
(b)
O HI
(c) Ph – O – Me
If answer of part (a) is x, part (b) is y and part (c) is z then present sum of x+y+z in the OMR
sheet. For example if answer of (a) is 12, (b) is 13 and (c) is 3 you will fill 0028 in OMR sheet.

OH
HI (excess)
14 OH Product
12.

OH
(major)

(a) Number of organic products obtained in more than 5% yield.

(b) Number of moles of HI consumed
(c) Number of moles of I2 generated
(d) Number of fractions which can be obtained on fractional distillation of organic product from
mixture of products.
Write answer of part (a), (b), (c) and (d) in the same order and present the four digit number
as answer in OMR sheet. For example: If all these answers are 9 then fill 9999 in OMR sheet.
13. Find out the number of 1-2-shifts during the conversion of
conc. H2SO4
OH 
14. How many out of the following reagents will change 1-propanol into propanaldehyde?
(a) H /KMnO4 /  (b) TsCl/DMSO  NaHCO3
(c) P.C.C. (Pyridinium chloro chromate) (d) Bendict solution
(e) Red hot Cu tube (f) H /K 2Cr2O7 / 

(g) NBS/  (h) SeO2 / 

15. How many moles of Grignard’s reagent will be consumed per mole of following compound?

O
HS C–Cl Cl
OMe

C OMe
HC C
O
O NO2
OH

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 Alcohol, Phenol & Ether

Cl Cl O O

O RMgCl
16. Cl (excess)

OMe SH
Number of moles of Grignard reagent consumed per mol.
17. Number of mole of Grignard consumed per mole in given molecule. (When Grignard reagent is in
excess)
ONH 2
O
O
O NHCl
18. How many number of mole of Grignard reagent consumed per mole for one mole of following
compound?

O
||
O O O O C–O–Et

Cl Br CH2–Cl
OH
19. What is the number of compounds having a benzene nucleus can have the molecular formula C7H8O?
20. What is the number of optical isomers possible for the compound
H3C  CH  CH 2 CH  CH 2 CH 2 CH  CH 2
| | | |
OH CH3 OH OH
21. Compounds are not oxidized by HIO4
(A) CH 3–CH–OH (B) CH 2–CH 2–CH2
| | |
CH 2–OH OH OH

CHO CH 2–OH
| |
(C) (CHOH) 4 (D) CH–OH
| |
CH 2OH CH 2–OH

CH 2–OH
(E) CH2–OH (F)
OH
OH

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JEE

O
+
H
22. (P) ?

How many benzylic hydrogen are present in product

OH

23. H+
Product

Total number of possible products are (no stereoisomer)
24. How many moles of formaldehyde is formed by the complete hydrolysis of following compound
with H3O+.
O O O O O O O O OH

25. Write mechanism for the following reaction:

CH2OH
H+
(a)

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 Alcohol, Phenol & Ether

EXERCISE # 4(A)(Expert – JEE Advanced PYQs)

HBr
1. In the reaction OCH 3 the products are (JEE Adv. 2010)

(A) Br OCH 3 and H2 (B) Br and CH3Br

(C) Br and CH3OH (D) OH and CH3Br

OH
NaOH(aq.)/Br 2
2. In the reaction the intermediate(s) is/are (JEE Adv. 2010)

 
O O O 
O
Br
(A) (B) (C) (D)

Br Br Br Br Br
3. In the following reaction, the product(s) formed is(are) (JEE Adv. 2013)
OH
CHCl 3
–
?
OH
CH3

OH O OH OH
OHC CHO CHO

H3C CHCl 2 H3C CHCl 2

CH 3 CH 3
(P) (Q) (R) (S)
(A) P(major) (B) Q(minor) (C) R(minor) (D) S(major)
4. The major product(s) of the following reaction is (are) (JEE Adv. 2013)
OH
aqueous Br2 (3.0 equivalent)
?

SO3H
OH OH OH OH
Br Br Br Br Br

Br Br Br Br Br
SO3H Br Br SO3H
(P) (Q) (R) (S)
(A) P (B) Q (C) R (D) S
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 JEE
5. Match the chemical conversions in List-I with the appropriate reagents in List-II and select the
correct answer using the code given below the lists- (JEE Adv. 2013)
List-I List-II
(P) Cl (1) (i) Hg(OAc)2; (ii) NaBH4

(Q) ONa OEt (2) NaOEt

OH
(R) (3) Et-Br

(Q) (4) (i) BH3; (ii) H2O2/NaOH

OH
(A) P  2; Q  3; R  1; S  4 (B) P  3; Q  2; R  1; S  4
(C) P  2; Q  3; R  4; S  1 (D) P  3; Q  2; R  4; S  1
6. The acidic hydrolysis of ether (X) shown below is fastest when (JEE Adv. 2014)

base
OR OH + ROH

(A) one phenyl group is replaced by a methyl group.

(B) one phenyl group is replaced by a para-methoxyphenyl group.
(C) two phenyl groups are replaced by two para-methoxyphenyl groups.
(D) no structural change is made to X.
7. The major product U in the following reactions is (JEE Adv. 2015)
CH2 = CH – CH 3, H+ radical initiator, O 2
T U
high pressure, heat

H
O H3C CH 3
O O
(A) (B) O H
CH 3

H
O CH 2
O O H
(C) CH2 (D) O

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 Alcohol, Phenol & Ether
8. LIST-I contains reactions and LIST-II contains major products. (JEE Adv. 2018)
List-I List-II

(P) + (1)
ONa Br OH

(Q) + HBr (2)

OMe Br

(R) + NaOMe (3)

Br OMe

(S) + MeBr (4)

ONa
O
(5)

Match each reaction in LIST-I with one or more products in LIST-II and choose the correct option.
(A) P  1,5; Q  2; R  3; S4
(B) P  1,4; Q  2; R  4; S3
(C) P  1,4; Q  1,2; R  3,4; S4
(D) P  4,5; Q  4; R  4; S  3,4

9. Aniline reacts with mixed acid (conc. H2SO4 and conc. HNO3) at 288 K to give P (51 %), Q (47%)
and R (2%). The major product(s) of the following reaction sequence is (are) (JEE Adv. 2018)

(1) Ac2 O, pyridine (1)Sn/HCl

(2) Br2 ,CH3CO2 H (2) Br2 , H 2 O(excess)
R 
+
 S   major product(s)
(3) H 3O (3) NaNO2 , HCl/273–278K
(4) NaNO2 , HCl/273–278K (4) H 3PO2
(5) EtOH,Δ

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

Br
Br

(C) (D) Br
Br
Br Br Br

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JEE
10. In the following reaction sequence, the correct structure(s) of X is (are) (JEE Adv. 2018)

(1) PBr3 , Et 2 O Me N3
X  

(2) NaI, Me2 CO
(4) NaN3 , HCONMe 2 enantiomerically pure

Me OH Me OH
(A) (B)

(C) (D)
Me OH Me OH
11. In the given reaction scheme, P is a phenyl alkyl ether, Q is an aromatic compound; R and S are the
major products.
(i) NaOH
HI (ii) CO 2 (i) (CH CO) O
P  Q 
  R 
3

2
S
(iii) H 3O (ii) H 3O

The correct statement about S is (JEE Adv. 2023)

(A) It primarily inhibits noradrenaline degrading enzymes.
(B) It inhibits the synthesis of prostaglandin.
(C) It is a narcotic drug.
(D) It is ortho-acetylbenzoic acid.
12. Reaction of iso-propylbenzene with O2 followed by the treatment with H3O+ forms phenol and a by-
product P. Reaction of P with 3 equivalents of Cl2 gives compound Q. Treatment of Q with Ca(OH)2
produces compound R and calcium salt S. (JEE Adv. 2024)
The correct statement(s) regarding P, Q, R and S is(are)

HO CCl3
(A) Reaction P with R in the presence of KOH followed by acidification gives
H3C CH3

(B) Reaction R with O2 in the presence of light gives phosgene gas

(C) Q reacts with aqueous NaOH to produce Cl3CCH2OH and Cl3CCOONa
(D) S on heating gives P

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 Alcohol, Phenol & Ether

EXERCISE # 4(B)(Conqueror - Variety of JEE Advanced PYQs)

1. The number of hydroxyl group(s) in Q is: (JEE Adv. 2015)

H H+ aqueous dilute KMnO4 (excess)

P Q
heat 0°C
HO
H3C CH 3

2. Total number of isomers, considering both structural and stereoisomers of cyclic ethers with the
molecular formula C4H8O is ____. (JEE Adv. 2019)
3. An organic compound (C8H10O2) rotates plane-polarized light. It produces pink colour with neutral
FeCl3 solution. What is the total number of all the possible isomers for this compound ?
(JEE Adv. 2020)

OH
red phosphorous
4. Consider the following reaction R (major product)
Br2
Br

On estimation of bromine in 1.00 g of R using Carius method, the amount of AgBr formed (in g) is_.
[Given: Atomic mass of H = 1, C = 12, O = 16, P = 31, Br = 80, Ag = 108] (JEE Adv. 2022)
5. Number of compounds giving (i) red colouration with ceric ammonium nitrate and also (ii) positive
iodoform test from the following is (JEE Adv. 2023)

O
O OH
CH3, , , O ,
OH H ,

OH OH
, ,
OH

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 JEE

JEE MAIN YEARLONG REVISION EXERCISE

1. Phenol, when it first reacts with concentrated sulphuric acid and then with concentrated nitric acid,
gives - (JEE Main 2008)
(A) o-nitrophenol (B) p-nitrophenol
(C) 2,4,6-trinitrobenzene (D) nitrobenzene
2. The major product obtained on interaction of phenol with sodium hydroxide and carbon dioxide is-
(JEE Main 2009)
(A) salicylaldehyde (B) salicyclic acid
(C) phthalic acid (D) benzoic acid
3. From amongst the following alcohols the one that would react fastest with conc. HCl and anhydrous
ZnCl2, is- (JEE Main 2010)
(A) 2–Butanol (B) 2–Methylpropan–2–ol
(C) 2–Methylpropanol (D) 1–Butanol
4. Phenol is heated with a solution of mixture of KBr and KBrO3. The major product obtained in the
above reaction is (JEE Main 2011)
(A) 3-Bromophenol (B) 4-Bromophenol
(C) 2,4,6-Tribromophenol (D) 2-Bromophenol
5. Aspirin is known as : (JEE Main 2012)
(A) Acetyl salicylic acid (B) Phenyl salicylate
(C) Acetyl salicylate (D) Methyl salicylic acid
6. Ortho–Nitrophenol is less soluble in water than p– and m– Nitrophenols because:
(JEE Main 2012)
(A) o-Nitrophenol is more volatile in steam than those of m – and p–isomers
(B) o-Nitrophenol shows Intramolecular H–bonding
(C) o-Nitrophenol shows Intermolecular H–bonding
(D) Melting point of o-Nitrophenol is lower than those of m and p-isomers
7. Given below are two statement: (JEE Main 2024)
Statements I: Bromination of phenol in solvent with low polarity such as CHCl3 or CS2 requires
Lewis acid catalyst.
Statements II: The Lewis acid catalyst polarises the bromine to generate.
In the light of the above statements, choose the correct answer from the options given below:
(A) Both Statement I and Statement II are true (B) Statement I is true but Statement II is false
(C) Statement I is false but Statement II is true (D) Both Statement I and Statement II are false
(i) Jone's Reagent
8. CH3CH 2  OH  P (JEE Main 2024)
(ii) KMnO 4
(iii) NaOH,CaO,
Consider the above reaction sequence and identify the major product P.
(A) Methoxymethane (B) Methanoic acid
(C) Methanal (D) Methane
9. Which one of the following reactions is NOT possible? (JEE Main 2024)

OCH3 OH OCH3 OCH3

HBr Cl2/AlCl 3
(A) (B)

Cl OH Cl
OH Cl
NaOH HCl
(C) High Temp. H + (D)

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 Alcohol, Phenol & Ether
10. Statement-I : Piciric acid is 2,4,6 - trinitrotoluene. (JEE Main 2024)
Statement II: Phenol-2, 4-disulphonic acid is treated with Conc. HNO3 to get picric acid.
In the light of the above statements, choose the most appropriate answer from the options given
below:
(A) Statement I is incorrect but Statement II is correct
(B) Both Statement I and Statement II are incorrect
(C) Statement I is correct but Statement II is incorrect
(D) Both Statement I and Statement II are correct
11. In Reimer - Tiemann reaction, phenol is converted into salicylaldehyde through an intermediate. The
structure of intermediate is ____. (JEE Main 2024)

ONa+ ONa+ ONa+ OH

CHCl2 CHO CH3 CHCl2
(A) (B) (C) (D)

Cl
CH3
12. H 2O
+ NaOH   Major Product ‘A’’ (JEE Main 2024)

Consider the above chemical reaction. Product "A" is:

CH3 CH3
(A) OH (B)
OH

OH
CH3 CH3
(C) (D)
OH
13. Identify the major products A and B respectively in the following set of reactions.

CH COCl
CH3
Conc.H 2SO 4

B
3
OH  A (JEE Main 2024)
Pyridine Δ

CH3 CH3
(A) A = and B = OH
CH3CO

CH2 CH3
(B) A = and B = COCH3

CH2 CH3
(C) A = and B = OH
COCH3

CH3 CH3
(D) A = and B = OCOCH3

14. Which one the following compounds will readily react with dilute NaOH ? (JEE Main 2024)
(A) C2 H5OH (B) C6 H 5OH (C) C6 H 5CH 2 OH (D) (CH 3 )3 COH
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JEE
15. Match List - I with List - II. (JEE Main 2024)
List-I (Reactants) List-II (Products)
(A) Phenol, Zn/Δ (I) Salicylaldehyde
(B) Phenol, CHCl3 , NaOH, HCl (II) Salicylic acid
(C) Phenol, CO 2 , NaOH, HCl (III) Benzene
(D) Phenol, Conc. HNO3 (IV) Picric acid
Choose the correct answer from the options given below.
(A) (A)-(IV), (B), (II), (C)-(I), (D)-(III)
(B) (A)-(IV), (B)-(I), (C)-(II), (D)-(III)
(C) (A)-(III), (B)-(I), (C)-(II), (D)-(IV)
(D) (A)-(III), (B)-(IV), (C)-(I), (D)-(II)
16. Given below are two statements: (JEE Main 2024)
Statement (I) : p-nitrophenol is more acidic than m-nitrophenol and o-nitrophenol.
Statement (II) : Ethanol will give immediate turbidity with Lucas reagent.
In the light of the above statements, choose the correct answer from the options given below :
(A) Statement I is true but Statement II is false (B) Both Statement I and Statement II are true
(C) Both Statement I and Statement II are false (D) Statement I is false but Statement II is true
17. Phenolic group can be identified by a positive: (JEE Main 2024)
(A) Phthalein dye test (B) Lucas test (C) Tollen's test (D) Carbylamine test
18. Major product formed in the following reaction is a mixture of: (JEE Main 2024)
CH3
HI
O C CH3 Major Product
CH3

I I

(A) and (CH3)3Cl (B) and (CH3)3COH

OH OH
CH3
(C) and (CH3)3COH (D) and CH3 C I
CH3
19. Phenol treated with chloroform in presence of sodium hydroxide, which further hydrolysed in presence
of an acid results (JEE Main 2024)
(A) Salicyclic acid (B) Benzene-1,2-diol
(C) Benzene-1, 3-diol (D) 2-Hydroxybenzaldehyde
20. Given below are two statements: One is labelled as Assertion A and the other is labelled as Reason
R: (JEE Main 2024)
Assertion A: Alcohols react both as nucleophiles and electrophiles.
Reason R: Alcohols react with active metals such as sodium, potassium and aluminum to yield
corresponding alkoxides and liberate hydrogen.
In the light of the above statements, choose the correct answer from the options given below:
(A) A is false but R is true.
(B) A is true but is R false.
(C) Both A and R are true and is the correct explanation of A.
(D) Both A and R are true but R is NOT the correct explanation of A.

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 Alcohol, Phenol & Ether
21. Given below are two statements: One is labelled as Assertion A and the other is labelled as Reason
R: (JEE Main 2024)
Assertion A: pKa value of phenol is 10.0 while that of ethanol is 15.9.
Reason R: Ethanol is stronger acid than phenol.
In the light of the above statements, choose the correct answer from the options given below:
(A) A is false but R is true.
(B) A is true but is R false.
(C) Both A and R are true and is the correct explanation of A.
(D) Both A and R are true but R is NOT the correct explanation of A.
22. How would you get racemic mixture of 1,2 butane diol from cis 2-butene.
OH
(i ) A
|
CH3CH = CHCH3  CH 3  CH  CH  CH 3 , A & B are
( ii ) B
|
OH
(A) A = KMnO4/OH– , B = H2O (B) A = CF3CO3H, B = H2O
(C) A = OsO4/OH–, B = H2O (D) A = O3/H2O, B = Ph3P
CH 3
|
CH 3  CH — C — CH 2  NH 2 HNO
23. | | 2  (X) (major)
CH 3 CH 3
Major product of above reaction is

(A) (B)

(C) (D)

18
O H  /MeOH
24. NO2 – CH – CH2 
 'A'
O
Product 'A' is:

18
OH OH
| |
(A) NO 2  CH  CH 2 (B) NO 2  CH  CH 2
| |
OH OH
18

18
OH OH
| |
(C) NO 2  CH  CH 2 (D) NO 2  CH  CH 2
| |
OH OH
18

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JEE
25. In the following reaction, final product is
14
ClCH 2 CH  C H 2 NaOC H
 25 
\ /
O
14 14
(A) ClCH 2CH C H 2OC 2 H 5 (B) ClCH 2CH C H 2ONa
| |
OH OC 2 H 5
14 14
(C) C H 2 CHCH 2 OC 2 H 5 (D) C H 2 CHCH 2 OC 2 H 5
O O
18
(i ) H 3C C O  OH
||
O
26.     
 Product(s)
( ii ) OH ¯/ H 2O

18
OH OH

(A) + en (B) + en
18 18
OH OH
OH

(C) + en (D) + en
18
OH OH

27. H/
H 2O
 J (Major)
J is
OH
OH OH OH
(A) (B) (C) (D)

28. Br / H 2O / NaCl

2   
Which product(s) can not form during above reaction?
CH3 CH3
OH Br
Br Br
(A) H + en (B) H + en

CH3 CH3
Cl OH
Br Cl
(C) + en (D) H + en
H

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 Alcohol, Phenol & Ether

Et Et O
|| 18
( i ) CH3 CO O H
29.     
( ii ) H  / H 2O
D D
Major product(s) of the above reaction is :
Et 18 Et
D OH D OH
(A) + en (B)
18
+ en
HO D D OH
Et Et

Et
D OH Et
D OH
(C) D (D) + en
OH
HO D
Et
Et
30. The alcohol manufactured from water gas is
(A) CH3OH (B) C2H5OH
(C) CH3–CH2–CH2–OH (D) (CH3)2CHOH
31. Which of the following enzyme is used for the preparation of ethanol by following reaction.
C6H12O6  2C2H5OH + 2CO2
(A) Invertase (B) Maltase (C) Zymase (D) Diastase
O OH
I / NaOH  
32. CH3 
2
 H  A, A is


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

33. Ethanol on reaction with acetic anhydride gives

(A) Acetic ester (B) Formic ester
(C) Ethanoic acid (D) Acetic ester and Ethanoic acid both

34. Glycerol KHSO


LiAlH 4
4  A    B

A and B are :
(A) Acrolein, allyl alcohol (B) Glyceryl sulphate, acrylic acid
(C) Allyl alcohol, acrolein (D) Only acrolein (B is not formed)

35. Alc
. KOH
 Major product is

(A) (B)

(C) (D)

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JEE
36. How many products are obtained in the given reaction :
Et Ph CH3 Ph
4H SO
HO OH + HO OH 2  

Et Ph CH3 Ph
(A) 1 (B) 2 (C) 3 (D) 4
OH OH

Et Me

37. H ? Product is:

Et Me Me O O Et
Et Me
(A) (B) (C) (D)

CH3 Et
38. What is most favourable combination of alkoxide and halide to prepare H O CH3 by
D D
Williomson's ether synthesis ?
CH3 Et CH3 Et

(A) H Br + ¯O CH3 (B) H O¯ + Br CH3

D D D D

CH3 Et CH3 Et

(C) H O¯ + H3C Br (D) Br H + ¯O CH3

D D D D

CH3
TsCl NaBr P
39. H OH
DMSO

Et PBr3
Q
P and Q are
(A) Identical (B) Enantiomer (C) Diastereomer (D) Positional isomer

(379)
 Alcohol, Phenol & Ether

CH2 OH O
OH
HO
40. CH
3OH (1eq.)
 Product(s)
OH HCl
HO
Product(s) is / are
CH2OH O CH2OCH3 O
OCH3 OH
HO HO
(A) OH (B) OH
HO HO
CH2OH O
HO
(C) OH (D) Both (A) and (C)
HO OCH3

conc.H2SO4 DBr
41. OH

Final major product is :
D
D Br
(A) (B)
Br
D

(C) (D)
D Br Br
OH
(P) (i) CH3MgCl/ether
42. CH2 – OH A + CH – CH3
(ii)H3O
Choose the compound A & reagent P.

(A) Cu/, CHO (B) John’s reagent , COOH

(C) KMnO4, COOH (D) Na2Cr2O7/H+, COOH

OH MnO2 (i) (CH3)2 CuLi

43. + P (Major Product) :
(ii) H3O

CH3
O
(A) (B) OH
CH3
CH3
C
(C) O (D) None of these

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JEE

44. . In this diol

(A) OH at C2 is more basic than that of at C5 (B) OH at C2 is more acidic than at C5.
(C) both have same basicity (D) both have same acidic strength
45. Boiling point of alcohol is comparatively higher than that of corresponding alkane due to
(A) Intermolecular hydrogen bonding (B) Intramolecular hydrogen bonding
(C) Volatile nature (D) None of these
46. Methanol & Ethanol are miscible in water due to
(A) Covalent character (B) H-bonding (C) Ionic character (D) None of these
47. Choose the correct option for following sets of compounds in order of their increasing boiling points:
(I) Ethanol (II) Methoxymethane (III) Propane
(A) I > II > III (B) II > I > III (C) III > II > I (D) I > III > II
48. Which of the following compounds will react with sodium hydroxide solution in water?
(A) Ph–OH (B) (CH3)3–OH (C) Ph – CH2 – OH (D) C2H5 –OH
49. Ph CH2 CH CH3 
K C 2 H5
   (A); Product (A) in the reaction is:
OH
(A) Ph CH2 CH CH3 , (inversion) (B) Ph CH2 CH CH3 , (retention)
OEt OEt
(C) Ph CH2 CH CH3 , (racemic) (D) Ph CH CH CH3
OEt
50. Match List-I with List-II and then select the correct answer from the codes given below the
lists:
List-I List-II

(I) CH3MgI + CH3CHO 
H 3O
 (a) Shows optical isomerism
(II) (CH3)2C = CH2  Dil.H 2SO 4
(b) A secondary alcohol giving iodoform test

(III) CH3COOC2H5  
Na
alcohol
(c) Product is a tertiary alcohol
(IV) CH3CHOHC2H5 (d) Product is primary alcohol
(A) I-b, II-d, III-c, IV-a (B) I-b, II-c, III-d, IV-a
(C) I-b, II-c, III-a, IV-d (D) I-b, II-a, III-d, IV-c
CHO
51. (CH OH)3 + 4HIO4 

CH2 OH
Aldo pentose

(A) 4HCO2H, HCHO (B) 4CH2O, HCO2H

(C) CO2, 4HCHO (D) CO2, 3HCO2H, HCHO
Cl O
52. 


Sequence of reagents for the above conversion will be.

(A) BH3/THF, H2O2/OH–, NaOH (B) Hg(OAc)2, NaBH4, NaOH
(C) NaOH, H2O2/OH , NaOH
–
(D) H+/OH–, H2O2/OH–, NaOH
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 Alcohol, Phenol & Ether
53. Identify the final product (B) in the following sequence of reactions:
CH3
conc. H 2SO 4 C2 H5OH
CH3 C CH2 0ºC
 A  B
(A) (CH3)3 C – OSO3H (B) C2H5OC2H5
(C) (CH3)3COC2H5 (D) (CH3)2CHCH2OC2H5
54. Consider the following reactions:
HBr CH ONa
CH3CH = CH2 
(C H CO) O
 A 
3
 B.The major end product (B) is:
6 5 2 2

CH3
(A) CH3 CH OCH3 (B) CH3CH2CH2OCH3
(C) CH3CH CH 2Br (D) CH3CH CH2OCH3
OCH3 Br
55. Predict the major product:

+ excess HI 
O
(A) HO – CH2 – CH2 – CH2 – CH2 – I (B) HO – CH2 – CH2 – CH2 – CH2 – OH
(C) I – CH2 – CH2 – CH2 – CH2 – I (D) No reaction
56. Ethylene glycol, on heating with concentrated H2SO4 given mainly:
(A) HOCH 2CH 2OCH 2CH 2OH (B) CH2 CH2
O
O
(C) (D) CHO – CHO
O
57. Consider the following sequence of reactions:
1. KH 1. B2 H6
OH   A   B
2. PhCH Br 2 2. H 2O 2 /OH
The end product (B) is
(A) O Ph (B) HO O Ph
OH
(C) O Ph (D) Ph OH
58. Dimethyl ether, Me2O, is highly soluble in water while diethyl ether, Et2O, is only sparingly soluble
because:
(A) Me2O reacts with water efficiently due to its small sized methyl groups but Et2O does not
(B) Hydrogen bonding between Et2O and H2O is less efficient due to steric crowding around oxygen
of Et2O while the hydrogen bonding between Me2O and H2O is much efficient due to small size of
the methyl groups
(C) C2H5 – groups has a stronger +I effect than CH3 – group
(D) Hyperconjugation of C – H bond is greater in Me2O than in Et2O
59. Ethyl methyl ether on heating with PCl5 produces:
(A) Ethyl chloride and methyl alcohol (B) Acetyl chloride and methyl chloride
(C) Ethylidene dichloride and methylene dichloride (D) Ethyl chloride and methyl chloride
60. When phenol is treated with bromine water in excess, it gives
(A) m-bromophenol (B) o-and p-bromophenol
(C) 2, 4–dibromophenol (D) 2, 4, 6–tribromophenol

*****

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 JEE

JEE ADVANCED YEARLONG REVISION EXERCISE

Paragraph for question nos. 1 to 3

1. Compound 'B' is?

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

2. Organic compound A does not undergo de carboxylation reaction because?

(A) Intermediate does not follow Saytzeff'n rule
(B) Intermediate does not follow Hofmann's rule
(C) Intermediate does not follow Bredt's rule
(D) Intermediate does not follow MarkwoniKoffs rule
3. Total No. of stereoisomers of B are?
(A) 2 (B) 4 (C) 3 (D) 6
4. HBO, oxymercuration-demercuration and acid catalysed hydration will not give same product in

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

Cl

5. (
i ) aq.KOH
  P
(ii ) PCC

P is

O COOH CHO

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

6. Dehydration of alcohols take place more rapidly with POCl3 than with H2SO4. Select the correct
statement(s) about the following dehydration reaction.

POCl
3 
pyridine

(A) It does not involve carbocation.

(B) It involves R–OPOCl2 with – OPOCl2 as a better leaving group.
(C) It involves E2 mechanism as pyridine base abstracts proton from the adjacent carbon as the
same time at which – OPOCl2 is leaving.
(D) It is E1 reaction without formation of carbocation.

(383)
 Alcohol, Phenol & Ether
7. Which of the following will get oxidised by Br2 / KOH into carboxylic acid?

(A) CH3–CH2–OH (B) CH  CH 3

|
OH

(C) CH2OH (D)

8. Diethyl ether reacts with PCl5 to form

(A) Ethyl chloride (B) Phosphorous oxy trichloride
(C) 1,2-dichloro ethane (D) Ethene
9. Which reaction(s) do(es) not represents correct major product.
Cl CN

(A) HBr (B) KCN


OH 
 Br

CH3 CH3 CH3

H OH H Br Br H
(C) HBr +
H Br
 
H Br H Br
CH3 CH3 CH3

OCH3
(D) 
 OCH3 + Cl
Cl
10. Select option which is having correct major product mentioned.
OH I

(A) Red P+I2

HI
(B) CH3–CH2–OH  CH3–CH2–I


(C) CH3 – CH2 – CH2 – OH HI Re d P
 CH3–CH2–CH3
Me Me
SOCl2
(D) H OH H Cl
D D

11. OH conc.H2SO4/

Possible alkene(s) formed in above reaction is/are :

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

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JEE
12. Choose the correct option?
(A) Boiling point of alcohols and phenols increase with increase in the number of carbon atoms.
(B) In alcohols boiling point decrease with decrease in surface area
(C) In alcohols boiling point increase with increase of branching in carbon chain.
(D) Vander waals forces decrease with increase of branching in carbon chain.
13. When the alcohols and phenols are dissolved in water then
(A) Solubility increase with increase in size of Alkyl / Aryl group.
(B) Solubility decrease due to hydrophobic nature of Aryl / Allyl groups.
(C) Solubility increase due to H-bonding with water molecules
(D) Solubility increase due to branching chain of carbon.

HO

14. Which alcohol(s) react(s) more rapidly than towards dehydration reaction?

HO
HO HO HO

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

NO2
CH3
15. Lucas test is used to make distinction between 1°, 2° and 3° alcohols
ROH + HCl anhydrous ZnCl
   2  RCl  + H2O
conc.
White turbidity

This shows that

(A) ROH behaves as a base
(B) greater the value of pKa (alcohol), greater the reactivity with conc. HCl and thus sooner the
formation of white turbidity.
(C) alcohol which reacts fastest with Na metal, will give turbidity at fastest rate
(D) alcohol which gives red colour during Victor Mayor test, will always give turbidity at slower rate
than those giving blue or white colour during Victor Mayor test.
16. End-product of which of following reaction give positive Iodoform test.
O O
|| (i ) CH MgBr ( excess ) || (i ) CH MgBr ( excess )
(A) H  C  Cl  3   
  (B) Ph  C  O  Et  3   
 
(ii ) H (ii ) H

O O
|| || (i ) CH MgBr ( excess )
(C) H  C  O  Et (
i ) CH 3MgBr ( excess )
     (D) CH 3  C  H  3   
 
(ii ) H  (ii ) H

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 Alcohol, Phenol & Ether
17. Column-I (Reaction) Column-II (Major product)

(A) H/
H 2O
 (P) OH

(i) Hg(OAc) /H O
(B) 
2
Θ
2
 (Q) OH
(ii) NaBH 4 / O H

OH

(C) (
i ) BH 3 / THF
  (R)
( ii ) H 2 O 2 / OH

OH
(S)

18. Column-I (Compound) Column-II (pKa)

(A) o-Nitrophenol (P) 8.3
(B) m-Nitrophenol (Q) 7.1
(C) p-Nitrophenol (R) 7.2

CHCH 3
||
H3O
19. CH3  CCH = CHCH 3 
Major product of this reaction :
(A) will show optical isomerism (B) gives white turbidity with HBr immediately
(C) is dehydrated easily (D) all correct
MnO
20. H 2C  CH  CH  CH 2 CH 2 OH 
2
A . is
|
OH

(A) H 2 C  CH  C CH 2  CH 2OH (B) H 2C  CH  CH – CH 2 OH

|| |
O OH

(C) H 2 C  CH  C CH 2  COOH (D) H 2C  CH  C CH 2  CHO

|| ||
O O
21. An organic compound having the molecular formula C8H10O on being heated with I2 and dilute
NaOH gives a yellow precipitate. The compound is expected to be -

(A) C6H5CH2CH2OH (B) CH3 CH2OH (C) H3C OH (D) CHOHCH3

CH3

22. Sequence of reagents used in Victor–Meyer method of detection of primary, secondary and tertiary
alcohol:
(A) P/I2, AgNO2, NaNO2/H+, NaOH (B) AgNO2, P/I2, NaOH, NaNO2/H+
(C) NaNO2/H+, NaOH, P/I2, AgNO2 (D) P/I2, NaNO2/H+, AgNO2, NaOH

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JEE
23. In which of the following reactions 3° alcohol will obtained as a product ?
O
||
H+
(A) CH3MgBr (excess) + H – C – Cl  

O
||
H+
(B) PhMgBr (excess) + CH3 – C – Cl  

O O
|| ||
H+
(C) CH3MgBr (excess) + CH3 – C – O – C – CH3  

O
||
H+
(D) CH3MgBr (excess) + Cl – C – O – Et  
24. Product of the following reaction are:
Me Me
PCl5
H O H
D Et
Me Me Me Me
(A) H Cl (B) Cl H (C) Cl H (D) H Cl
D D Et Et
25. Compounds which can give periodic cleavage are:
O OH OH
O
(A) (B) (C) (D)
OH O OH OH
26. Product of following reaction can be:
18
H3 O
O

18
(A) OH (B) 18 (C) OH (D) OH
OH
SOCl2
27. Product is/are:
OH

(A) (B)
Cl Cl

(C) (D)
Cl Cl
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 Alcohol, Phenol & Ether
28. Select reaction with correct major products:
Cl 2 Cl
(A) O O
hv
Mg
(B) HOCH 2CH 2 CH 2 CH 2  Br  
Et O 2 O
O
CO+BF 3
(C) O O
/high P
H2S
(D) OH – SH
ThO 2
29. Which of the following compound(s) will give red colour with FeSO4 + KCNS after keeping open in
sunlight for sometime ?
O
O O
(A) (B) (C) (D) Ph – O – Ph

Paragraph # 2 for (Ques. 30 to 32)

CH 3 CH3
CH 3 CH3 CH3
H OH H OH
H OH H OH H OH
CH 2 CH2
OH H H
H OH H HO HO HO H
CH 3 CH 3 CH3 CH2 –CH 3 CH3
(I) (II) (III) (IV) (V)
Mrs. Aishwarya had worked for several days to prepare the above diols in her laboratory. She
carefully labeled them and went to abroad for her PhD interview. When she returned she found that
the labels had fallen off from the bottles. She get puzzled but her guide in the office told her that the
diols could be easily distinguished by these experiments.
Mrs. Aishwarya follow her guide instruction and obtained the following results:
1. Compound P, Q,T are optically inactive while R and S are optically active.
2. Only one product is obtained from Q & R with HIO4 oxidation.
3. Two products are obtained from S with HIO4 oxidation.
4. P and T did not react with HIO4 oxidation.
30. Compound Q and R are :
(A) I & II (B) II & III (C) I & V (D) III & IV
31. When S is subjected to react with HIO4 then the product are :
(A) Both CH3CHO (B) CH3–CH=O and CH3CH2CHO
(C) Both CH3CH2CHO (D) HCHO and CH3CH2CHO
32. Which of the following is/are best reagent to obtain compound (Q) from the 2-butene ?
(A) Dil cold KMnO4 (B) Peroxy benzoic acid followed by hydrolysis
(C) Hot KMnO4 solution (D) Concentrate hot KMnO4
33. Match the Column– I with Column – II and select the correct.
Column-I (Reagents) Column-II (Reactions involved)
(A) OsO4, NaHSO3.H2O (P) Reduction of carbonyl groups
(B) BH3.THF; CH3CO2H (Q) Oxidation of –OH group from allylic/benzylic position
(C) MnO2 (R) Reduction of alkene
(D) LiAlH4 ether; H2O (S) Hydroxylation of alkene

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JEE
34. If ‘X’ litres of ethene would be produced when 2.62 gm of vinyl magnesium bromide is treated with
224 ml of ethyne at STP. Then what is the value of “1000 X”?
35. Complete the following reactions:
HI(excess)
(a) (CH3)2CHOCH3 
Two products
Hg2+ (CH3CO)2O
(b) [A] CH3CHO [B]
dil. H2SO4
CHO
?
(c) OH OH

OH
CH3MgBr ?
(d) H3C — CHO ? H3C — C — CH3

moist H2SO4 C2H5OH

(e) C2H5I (A) (B) (C)
Ag2O 140°C

NO2
(C2H5)2SO4 Zn, HCl NaNO 2, HCl C6H5OH
(f) – [A] [B] [C] [D]
OH 5°C

OH

H
(g) ?
OH



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 Answer Key

ANSWER KEY
CHAPTER-4 (Stereoisomerism)

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

MLE-20
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A B B D A C D C B C C A D D C
MLE-21
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. B D D D D C B A D D D A C B A
Que. 16
Ans. B

MLE-22
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A A A D B A B D C A A C C B A
Que. 16 17 18
Ans. D B D
MLE-23
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C A B D B C D B C B B B D A C

MLE-24
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. B C D C A C D A B B B B A D C
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JEE

EXERCISE # 1(A) (Level 1 – Beginner)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. B A C B D C C B B C B B B D D
Que. 16 17 18 19 20 21 22 23 24 25
Ans. D A A C D D D B D A

EXERCISE # 1(B)(Level 2 – Learner)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C C B A A A B A D B D C C C C
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29
Ans. B B A B B A A C A B B C B C

EXERCISE # 2(A)(Adept – JEE Main PYQs)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. D B A A B A A A D D C C C C C
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28
Ans. C A B C D D D C B A C C C

EXERCISE # 2(B)(Scholar – JEE Main PYQs)

Que. 1 2 3 4 5 6 7 8 9
Ans. 5 6 2 6 5 3 1 42 60

EXERCISE # 3(A)(Proficient – JEE Advanced Level Questions)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. B A B B B D C B C AD C ACD AC AD ACD
Que. 16 17 18 19 20 21 22 23 24 25
Ans. D C ABC CD A ACD BCD ACD AC B

EXERCISE # 3(B)(Amateur - Variety of JEE Advanced Level Questions)

Que. 1 2 3 4 5 6 7 8 9 10
Ans. D C C A C D A C D (A)-P; (B)-R; (C)-Q; (D)-R
Que. 11 12 13
Ans. (A)-R; (B)-P; (C)-Q (A)-IV-iii; (B)-III-iv; (C)-II-ii; (D)-I-i (A)-R; (B)-Q; (C)-S; (D)-P
Que. 14 15 16
Ans. (A)-Q; (B)-T; (C)-S; (D)-P,S; (E)-P;R (A)-Q; (B)-P; (C)-R; (D)-S (I)-4, (II)-3, (III)-4
Que. 17 18 19 20 21 22 23 24 25
Ans. 8 4 3 8 8 7 4 9 (a)-4, (b)-4

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 Answer Key

EXERCISE # 4(A)(Expert – JEE Advanced PYQs)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A A B C C A A D D B D B C C BCD
Que. 16 17 18 19 20 21 22 23 24 25
Ans. AD AD C BD BC ABC C C CD B

EXERCISE # 4(B)(Conqueror - Variety of JEE Advanced PYQs)

Que. 1 2
Ans. 2 2

JEE MAIN YEARLONG REVISION EXERCISE

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A D B D A A C B A D D C D A C
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. C A A C D B B C C B C C D D B
Que. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
Ans. C A C B D C D D C C C C A C A
Que. 46 47 48 49 50 51 52 53 54 55 56
Ans. C C C B D D C C B A A

JEE ADVANCED YEARLONG REVISION EXERCISE

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. AD ACD AC AD AC D B A B B B BCD AD AB D
Que. 16 17 18 19 20 21
Ans. C A B A (a) ii (b) v (c) iv (d) i, iv (e) i, iii (A)-Q (B)-Q (C)-S (D)-P
Que. 22 23 24
Ans. (A)-Q, (B)-P, (C)-R, (D)-S (A)-PS, (B)-QRS, (C)-QR, (D)-PS (A)-R, (B)-R, (C)-P, (D)-S
Que. 25 26
Ans. (A)-PQ, (B)-PQ, (C)-PQ, (D)-PR (A)-QR, (B)-QS, (C)-PQ, (D)-QS
Que. 27 28
Ans. (A)-RS, (B)-PQ, (C)-RS, (D)-PRS achiral : I, III, IV; chiral : II,V, VI, VII

29. (a) Enantiomers, (b) Identical, (c) Geometrical isomers & Diastereomers,
(d) Positional, (e) Optical (Diastereomers),
(f) Diastereomers, (g) Enantiomers, (h) Identical,
(i) Geometrical isomers (Diastereomers)
30. (i) 25 , (ii) 24 , (iii) 2 , (iv) 4 , (v) 3, (vi) 8

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JEE
CHAPTER-5 (Hydrocarbon)

MLE-25
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C C D A C D B D A D C C A D C
Que. 16
Ans. B

MLE-26
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. B A B C D B B A C C B B D A A
Que. 16 17
Ans. B A

MLE-27
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A B B A A B B A B B D C B C D

MLE-28
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. D D D A B C D A A B A C C C D
Que. 16
Ans. C

MLE-29
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A B C C C B C C A C D C C A A
Que. 16 17 18
Ans. B D A

MLE-30
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. D B B A C A D C D A C B C A D
Que. 16
Ans. B

MLE-31
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C B D A A C D B D C B B B B C
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 Answer Key

MLE-32
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. D D A C B C B C C D C B D D D

MLE-33
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C C D A D C A C D C C B B D C

MLE-34
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C A B A B B C B C B C A C C B
EXERCISE # 1(A) (Level 1 – Beginner)
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A B D B A A C B B D C C C A D
Que. 16 17 18 19 20 21 22 23 24 25 26 27
Ans. B C B B C B D C C A C D

EXERCISE # 1(B) (Level 2 – Learner)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C B C D C D B A C C B B A B D
Que. 16 17 18 19 20 21 22 23 24 25
Ans. D A B B A B A C D A

EXERCISE # 2(A)(Adept – JEE Main PYQs)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C B B C D D C A A A C B D D B
Que. 16 17 18 19 20 21 22 23 24 25
Ans. A C C A D D A B D C
EXERCISE # 2(B) (Scholar – JEE Main PYQs)
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. 2 10 7 8 4 2 9 3 3 4 70 6 4 1 3
Que. 16
Ans. 6

EXERCISE # 3(A) (Proficient – JEE Advanced Level Que stions)

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. A C B D B B B B C A D A D D C
Que. 16 17 18 19 20 21 22 23 24 25 26 27
Ans. BC CD ABCD CD ACD AB ABD ACD AC BD AC AB
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JEE
EXERCISE # 3(B)(Amateur - Variety of JEE Advanced Level Questions)
Que. 1 2 3 4 5 6 7 8 9 10
Ans. B C B B B B AB C A (A)-Q, S ; (B)-Q, R ; (C)-P; (D)-Q,R,S
Que. 11 12 13
Ans. (A) - Q; (B) - R; (C) - S; (D) - P (A) - Q; (B) - P; (C) - S; (D) - R (A)-S; (B)- Q,S; (C)-S; (D)-P,S
Que. 14 15 16
Ans. (A) - P; (B) - R; (C) - S; (D) - Q (A)-S; (B)-R; (C)-Q; (D)-R, S (A)-R; (B)-PS; (C)-PS; (D)-Q
Que. 17 18 19 20 21 22 23 24 25
Ans. (A) - Q; (B) - R; (C) - P 1 (i)-3, (ii)-3, (iii)-3, (iv)-2 3 4 10 1 8 9

EXERCISE # 4(A) (Expert – JEE Advanced PYQs)

Que. 1 2 3 4 5 6 7
Ans. D C D BD AC BC B

EXERCISE # 4(B) (Conqueror - Variety of JEE Advanced PYQs)

Que. 1 2 3 4 5 6
Ans. 7 4 13 0 2 0

JEE MAIN YEARLONG REVISION EXERCISE

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

JEE ADVANCED YEARLONG REVISION EXERCISE

Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. C A B A C D D D C A D D B B D
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. A A A D A C AC ABC ABC BD ABD ABCD ABCD ABC BCD
Que. 31 32 33
Ans. ABD ACD AB



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