JEE - MODULE 2 - CHEM - Organic Chemistry 1

Published by
Vedantu Innovations Private Limited

D. No. 1081, 3rd Floor, Vistar Arcade,
14th Main Rd, Sector 3, HSR Layout
Bangalore, Karnataka, India 560 102
www.vedantu.com
Vedantu Innovations Private Ltd.
All rights reserved. No part of this book may be reproduced or utilized in any form or
by any means, electronic or mechanical including photocopying, recording or by
any information storage and retrieval system, without permission in writing from the
publishers.
Notice : Vedantu is committed to serving students with the best of the resources and
knowledge. Bearing that in mind, we have obtained all the information in this book
from sources regarded as reliable, and taken utmost care in editing and printing this
book. However, we as authors and publishers are not to be held responsible for unin-
tentional mistakes that might have crept in. Having stated that, errors (if any) brought
to our notice shall be gratefully acknowledged and rectified in upcoming editions.
Printed by
Colours Imprint
475C, Adugodi Main Road,
8th Block, Koramangala, Bengaluru 560 095
www.coloursimprint.com
4
Founder’s Message
Dear Student,
It gives me immense pleasure to present to you a Ready Reckoner and Practice booklet by Vedantu
- ‘TATVA’. Tatva in Sanskrit, means a collection of “Core” content/truth and isn’t that what Vedantu
brings to your table - the Core? Vedantu, at all times, ensures that you have easy accessibility to
a collection of essential concepts, theory, derivations, definitions, solved examples, concept videos,
and practice questions, important questions from competitive examinations and I am pleased
to say that all questions in ‘Tatva’ come with detailed solutions.
Tatva is the result of the constant endeavour and research done by our highly experienced team
of teachers and subject experts who compiled relevant content for you so that you come out
with flying colours in IIT JEE/NEET and Olympiads. We strongly believe and vouch for the
effectiveness and relevance of this booklet to grab the desired rank in IIT JEE/ NEET.
Key Points on ‘How to obtain optimal benefits from ‘Tatva’ ?

* We suggest starting with the Practice of ‘Tatva questions’ at the end of a chapter after
revision and Practice of basic questions.
* For daily practice of questions, we strongly recommend attempting session assignments
along with Vedantu live sessions
* Tatva equips you with Theory, Concept Videos, and Solved examples to help you revise
concepts, mark your notes, walk you through the entire summary and eventually clear all
your conceptual doubts all by yourself.
* Attempt Tatva questions post revision of 11th and 12th Grade topics. Take one topic at a
time to solve. Attempt any revision test series for NEET/JEE once you have solved Tatva
questions. Following this will not only help you during revision but also give a major boost
to your confidence.
* First solve basic level questions and gradually progress to the advanced level.
* Practice basic level questions regularly all through your journey of preparation.
* Your success is our dream-come-true
I wish you all the best.
Anand Prakash
Founder, Academic Head
Vedantu
Anand Prakash Sir has been a pioneer in producing

Top Ranks in JEE/NEET and Olympiads. He has
personally taught and mentored AIR 1,6,7 (JEE
ADVANCED) and AIR-1, 7, 9 (AIIMS), and thousands
of more students who have successfully cleared
these competitive exams in the last few years.
5
Credits
“Happiness lies in the joy of achievement
and the thrill of creative effort.”
—Theodore Roosevelt
Tatva is the brainchild of the creative Vedans who The managers who understood every aspect of what
strived tirelessly to weave success stories for you. the leadership were trying to accomplish and
Our heartfelt thanks to the Super Vedans who give brought so much of their own to the table and
wings to the vision of Vedantu. managed the execution of ‘Tatva’ immaculately.
Our leaders who have been our guiding light and Kiran Kumari Sushmitha M D
encouragement in every step: Harish Rao Akshatha J
Vamsi Sir, Anand Prakash Sir and Pulkit Sir Bhavya Bangera J Charubak Chakrabarti
Shraddha R Shetty
Our gratitude to the insightful leadership and
guidance of our leaders who dreamt about ‘Tatva’,
steered the project in the right direction and were
instrumental in making this dream into a reality:
Sahil Bhatia Sudhanshu Jain
Shubam Gupta Ajay Mittal
Arshad Shahid Jaideep Sontakke
Chemistry Team
Our true appreciation for all the Master Teachers of Assistant Teachers
Vedantu whose relentless efforts helped us in Suresh Avvari Ashok Kumar
accomplishing this vision into reality. Our heartfelt Rashmi G S Attal Sharma
gratitude to our creative content developers, and Waquas Ahmad Hefseeba Joseph
the DTP team who have put in their hard work, SME
insights, eagerness to execute and nurture Tatva Seema Agarwal (Team Lead) Garima Bhutani
into ‘your ready handbook’ and to bring positive Malika Arora Nikhil Sharma
learning experience to you. Priyanka Kumari Sumit Pareek
DTP
Neelima Thakur
A loud shout out for our media team - a bunch of creative minds with contagious energy. We cannot
thank them enough.
Suraj Bhan Singh

Gadde Ranjith
Ranjeeth Ramesh
Sreyoshi Biswas
Devika Ramachandran
Special thanks and appreciation for the enthusiastic support provided by Arunima Kar, Savin Khandelwal,
Dipshi Shetty and Mohamed Anzar.
The journey of the imagination to the reality of ‘Tatva’ would not have been possible without our enthusiastic
Operations Team, our amazing Academic Team, our dedicated team of Teachers and our talented Tech
Team.
TABLE OF CONTENTS
GENERAL ORGANIC CHEMISTRY-2
Theory ................................................................................................................................................ 8
Solved Examples ............................................................................................................................... 34
Exercise - 1 : Basic Objective Questions........................................................................................... 39
Exercise - 2 : Previous Year JEE MAIN Questions ............................................................................ 47

Exercise - 3 : Advanced Objective Questions ................................................................................. 50
Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 61
Answer Key ........................................................................................................................................ 190
REAGENTS AND MECHANISM AND ALKYL HALIDES
Theory ................................................................................................................................................ 66
Solved Examples ............................................................................................................................... 80
Exercise - 1 : Basic Objective Questions........................................................................................... 88
Exercise - 2 : Previous Year JEE MAIN Questions ............................................................................ 108
Exercise - 3 : Advanced Objective Questions ................................................................................. 114
Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 134
Answer Key ........................................................................................................................................ 193

ALCOHOLS, PHENOLS AND ETHERS
Theory ...................................................................................................................................................... 138

Solved Examples ..................................................................................................................................... 156
Exercise - 1 : Basic Objective Questions.................................................................................................. 163
Exercise - 2 : Previous Year JEE MAIN Questions ................................................................................... 170

Exercise - 3 : Advanced Objective Questions ....................................................................................... 178
Exercise - 4 : Previous Year JEE Advanced Questions ....................................................................... ... 185
Answer Key .............................................................................................................................................. 196

01
Chapter 01 9
1. Introduction General Organic Chemistry is the detailed study of the

basic concepts and factors that govern the progress and
In 1807, Berzelius proposed the term ‘Organic Chemistry’ outcome of reactions.
for the study of compounds derived from natural sources.
This was based on the theory of vitalism which said that
NOTES :
all living systems possessed a ‘vital force’ which was absent
in non-living systems. Compounds derived from living
natural sources (organic) were thought to be fundamentally The making and breaking of bonds usually occurs in several
different from inorganic compounds. discrete steps before transforming into products. The detailed
sequential description of all the steps is called the mechanism
of the reaction.
2. Hybridization
Hybridisation is a process in which two or more atomic

The vital force could be philosophically thought as the orbitals of comparable energy of the valence-shell of an
mysterious force God instilled in the living systems. atom (central atom of the molecule or ion) either in its
In 1823, Friedrich Wohler joined Berzelius as his student. ground state or in its excited state mix together and give
In 1828, Wohler made a discovery which changed the rise to the formation of new degenerate orbitals which are
definition of organic chemistry. Wohler conducted the called hybrid orbitals.
following experiment.
2.1 Applications of Hybridization
Wohler successfully synthesized an organic compound

starting from an inorganic compound. Following this, many
others synthesized organic compounds starting from
inorganic compounds. Thus, the theory of vitalism and the
definition of organic chemistry lost its meaning.
But what was common in all the above compounds
synthesized was the presence of carbon. Carbon shows a
special property catenation. Carbon can connect with other
carbon atoms to form long chains and rings (self-
catenation) and can connect with atoms of many other  Size of Hybrid Orbitals
elements in the periodic table (cross-catenation). Because As % s-character increases, size of hybrid orbital decreases.
of this reason, carbon can form a wide variety of Therefore
3 2
compounds. Therefore, the modern definition of organic Size of Hybrid Orbital : sp > sp > sp
chemistry is the study of carbon compounds.  Electronegativity of Hybrid Orbitals
Probably, the vital force can be explained by the fact that As % s-character increases, electronegativity of hybrid
most of the life-giving and life-sustaining functions are orbital increases. Therefore
2 3
performed by carbon compounds, for example, the human EN of Hybrid Orbital : sp > sp > sp
tissues and skin are formed by proteins, respiration is
possible due to haemoglobin, the information in our genes
is carried out in the form of DNA/RNA etc.
SCAN CODE
General Organic Chemistry-2
10
2.2 Dienes (a) Isolated Diene

3
In this case, double bonds are separated by atleast one sp
Dienes are organic compounds containing two double carbon.
bonds. There are three types of dienes :
(a) Isolated (b) Conjugated (c) Cumulated
Table : Hybridization of Common Molecules.
(b) Conjugated Diene

NOTES :
Double bonds are separated by only one single bond (or 4
2 3
sp carbons in a row). Diamond - Each C is sp . Tetrahedral solid.
2
Graphite - Each C is sp . Layered solid with weak van der
Waal’s forces between layers.
Calcium Carbide - Each C is sp.
2
Fullerene - Each C is sp .
(c) Cumulated Diene
Both sets of double bonds are at the same carbon. 3. ELECTRONIC DISPLACEMENT EFFECT
A substituted allene
An allene is
Stability of Dienes
The relative stabilities of dienes follows the order
Conjugated > Isolated > Cumulated
Important :
1
Stability 
Energy Content of the molecule 3.1 Inductive effect
When two unlike atoms form covalent bond, the electron-
pair forming the sigma bond is never shared equally
between the two atoms but is shifted slightly towards the
more electronegative species.
SCAN CODE
11
(A) Characterstics of Inductive Effect (b) Applications of Inductive Effect
 Effect on Acidic/Basic Strength

EWG increases acidic strength and decreases basic
strength. ERG decreases acidic strength and increases basic
strength.
Example
There are broadly three types of groups/atoms that may be Compare the acidic strength :
attached to carbon as illustrated. Although C is more
electronegative than H, the electronegativity difference is (I) (II)
small and the bond is generally consider non-polar.
 Nature of Inductive Effect

Inductive effect is a permanent effect and can be directly (III)
correlated to its dipole moment.
It is a weak effect as the shifting of electrons takes place Solution :
only through sigma bonds. An alkyl group is donating only if no other EWG is present
on it. Therefore, groups like –CH2Cl and –CH2F become
 Effect of branched carbon chain electron withdrawing groups.
An illustration has been marked for operation of inductive Order of Acidic Strength : III > II > I
effect which is self-explanatory.
 Effect of Distance
If the ERG/EWG moves away, the inductive effect
diminishes.
Example
(a) Compare the acidic strength of :

More the number of , lesser the effect
(I)
 Electron Donating and Electron withdrawing Groups (II)
Inductive effect may be due to single atom or a group of
atoms. Relative inductive effects are measured with
reference to hydrogen. Those which donate electrons to (III)
carbon chain are called electron-donating groups (EDG)
or electron-releasing groups (ERG) and are said to exert
+I effect. Those which withdraw electrons from carbon (IV)
chain are called electron-withdrawing groups (EWG)
and are said to exert –I effect.
Important : Solution :
1. I.E. of alkyl groups : 3° > 2° > 1° > CH3–
(a) (I)
2. In general, greater is the number of carbons in an alkyl group,
greater is its +I effect.
3. For problem-solving, we take electronegativity of sp- (II)
3
hybridized carbon to be more than sp hybridized nitrogen.
SCAN CODE
12
(III) (IV)
Order of acidic strength : II > III > IV > I
Series of +I and –I groups in order of their strength
–I Series (EWG)
+I Series (ERG)
 Basicity of Amines Example

The order in gaseous or liquid phase is :
3° > 2° > 1° > NH3 Example
To determine the basic strength of amines in aqueous

phase. We have to consider inductive effect, solvation
effect and steric hinderance. The order of basic strength
is therefore experimental in aqueous state as we can’t give
priority to stability provided by any one factor. Two results
are important for aqueous phase :
(a) (CH3)2NH > CH3NH2 > (CH3)3N > NH3
i.e. 2° > 1° > 3° > NH3 (R = CH3)
(b) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
i.e. 2° > 3° > 1° > NH3 (R = C2H5)
RESONANCE
(2) Pi alternate Positive Charge
Molecules are generally represented by simple lewis Example
structures but some molecules can not be represented by
just one Lewis structure. This led to the discovery of
resonance. Resonance refers to the delocalization of
electrons (generally -electrons).
(A) Conjugated Systems
(1) Pi alternate Pi
SCAN CODE
13
(3) Pi alternate Negative Charge (C) Criteria for Major/Minor Contributors
Example Resonance forms can be compared using the following

criteria in the following order :
1. Complete octate (a neutral molecule is always more stable
in which its octet is complete).
2. More number of  bonds more will be stability.
(4) Pi alternate Odd Electron
3. Negative charge on more electronegative atom is stable.
Example 4. Charge separation.
(a) Similar charges - Keep them as FAR as possible to
minimize repulsion and instability.
(b) Opposite charges - Keep them as NEAR as possible to
(5) Pi alternate Lone Pair maximize attraction and stability.
This case is similar to ‘pi alternate negative charge’ as lone Example
pair and negative charge are treated similarly.
Which of the following structures is more stable ?
Example
Solution :
II is more stable as all the octets are complete.
Example
(6) Lone Pair and Positive Charge on Adjacent Atoms Which of the following is more stable in the following
Example pairs ?
(a)
(B) Rules for Validity of Lewis Structures
Rule-1 :
All the lewis structures must conform to lewis octet rule. (b)
Rule-2 :
Position of atoms in all resonating structures must be the
Solution :
same. Only the electrons move.
(a) In II, all octets are complete. Therefore, II is more stable.
Rule-3 :
(b) I and II are tied on octets and number of  bonds but negative
All the resonating structures must have the same number
charge is more stable on more electronegative atom. Hence,
of paired and unpaired electrons, i.e. sum of bond pairs
II is more stable.
and lone pairs must be constant.
Rule-4 : Example
All the atoms participating in resonance in a molecule must
Give the order of stability of following resonating structures
be coplanar. This is required for the effective overlap of
p orbitals and the delocalization of electrons, for eg, (I)
buta-1,3-diene.
(II)
SCAN CODE
14
(ENZ > ENY)

(III)
 Dual Behaviour
Groups such as are both electron-releasing and
(IV) electron-withdrawing as illustrated.
Example
(V)
Solution : As electron releasing group
In (I), there are maximum number of pi bonds. Therefore,
it is most stable. In (II) and (V), the number of pi bonds is
equal but charge separation is greater in (V). Therefore, (II)
As electron withdrawing group
is more stable than (V). In (III) and (IV), there is maximum
charge separation but (III) is highly unstable due to
electrostatic repulsion. Hence, the order of stability is :
I > II > V > IV > III Which behaviour dominates and which is used in a
particular context will be discussed later in Electrophilic
3.2 MESOMERIC EFFECT Aromatic Substitution later.
Resonance Effect does NOT depend upon distance
The permanent polarization, due to a group conjugated unlike inductive effect.
with a  bond or a set of alternate bonds, is transmitted
(b) Applications of Mesomeric Effect
through the  electrons of the system-resulting in a different
distribution of electrons in the unsaturated chain.
(1) Effect on Acidic Strength of Carboxylic Acids and
This kind of electron redistribution in unsaturated
Phenols
compounds conjugated with electron-releasing or electron-
withdrawing groups (or atoms) is called Mesomeric Effect The resonating structure of carboxylic acid leads to charge-
or Resonance Effect. separated structure which is less stable than the carboxylate
This effect is permanent and is indicated by the dipole ion in which charge is delocalized. Therefore, carboxylic

moment. acid readily loses proton (H ) to form a carboxylate ion.
(a) Electron-Releasing and Electron-Withdrawing Groups
Groups which release or withdraw electrons by resonance

are said to exert M or R effect.
 Electron-Releasing Groups (+R or +M effect)
The common thing about all the groups listed is that the
atom connected with the conjugated system has a lone pair
to donate. Therefore, a generic representation can be
 Electron-Withdrawing Groups (–R or –M effect)
The common thing about all the groups listed is that the atom
connected with the conjugated system has a  bond with Similarly, in phenol, resonance leads to charge separation
another more electronegative atom which withdraws the which increases the rate of ionization and forms phenoxide
ion which is stabilized by charge delocalization.
electrons or directly has a positive charge on them. Therefore,
a generic representation can be
SCAN CODE
15
EWG increases the acidic strength and decreases the basic

strength.
ERG decreases the acidic strength and increases the acidic
strength.
Example
Arrange the following in the order of decreasing acidic

strength :
Solution :
NOTES :
Order of acidic strength

RSO3H > RCOOH > PhOH > CH3OH > H2O >
ROH > HCCH > NH3 > CH4
(2) Effect on Reactivity of Carboxylic Acid Derivatives
A typical nucleophilic reaction is represented as :
The order of acidic strength is : II > V > I > III > IV

In the previous example, let’s also discuss the stability of
phenoxide ions corresponding to (II) and (IV).
The stronger is the bond between C and Z, the difficult it

is for a nucleophile to break a bond and therefore, lower
reactivity.
Reactivity order of carboxylic acid derivatives towards

nucleophilic acyl substitution is :
Acyl Chloride > Acid Anhydride > Ester > Amide
(3) Effect of ERG/EWG on Acidic/Basic Strength
SCAN CODE
16
Now, greater the number of -H, greater the number of

hyperconjugating structures and more is the electron
donation of alkyl group to  bond.
The order of electron-donation of alkyl groups based on
hyperconjugation is :
3.3 HYPERCONJUGATION Methyl > 1° > 2° > 3°

Note : More is the number of -H, more is the bond
Hyperconjugation is the ability of the  bond electrons of delocalized. This implies that more will be the stability
an  bond to undergo conjugation with the adjacent of alkene and less will be the heat of hydrogenation and
 electrons. It is also known as Baker-Nathan Effect, No- more is the no-bond resonance energy.
Bond Resonance and - Effect.
(c) Applications of Hyperconjugation
(a) -Carbon and -Hydrogen
We have already discussed the , ,  nomenclature. Let’s 1. Stability of Alkenes
take an example : More is the number of -hydrogen, more is the number of
hyperconjugating structure and therefore more stability and
greater no bond resonance.
Example
Which alkene is more stable ?
-Carbon is the carbon attached to a functional group such

as . The hydrogen attached to -carbon is called -
hydrogen. For an  bond to be eligible for Solution :
3
hyperconjugation,  C must be sp hybridized.
(b) Mechanism of Electron Donation in Hyperconjugation
I is more stable than II.

2. Acidic Character of Alkenes
The hybrid formed by these resonating structures better Hyperconjugation weakens the  C-H bond in
known as hyperconjugating structures is : hyperconjugation hybrid (partial single bond) and therefore
H can be lost easily.
SCAN CODE
17
Resonance/Mesomeric Effect is a - interaction and acts

through weak pi bonds.
Hyperconjugation is a - interaction and acts through a
strong sigma and a weak pi bond.
Therefore, the order of importance is :
3. Stability of Carbocations
Resonance > Hyperconjugation > Inductive
2. STERIC INHIBITION OF RESONANCE (SIR)

When both the ortho positions of a bulky functional
group are occupied by bulky substituents, all the three
groups are out of plane of the benzene ring.
The positive charge on C is delocalized over H to give
stability to the carbocation. More is the number of H,
more is the stability of carbocations.
Stability of Carbocations
Example
Mark the order of basic strength :
3.4 ELECTROMERIC EFFECT
Electromeric effect is observed only in the presence of a

reagent and is therefore, a temporary effect. When a reagent
approaches a molecule, the multiple bond such as Solution :
or is polarized by the complete transfer of  In (II) and (III), the lone pair of N is in conjugation with the
electrons. benzene ring and is not available for donation. (II) is less
basic than (III) due to –I and –M of –NO2 group. It may
seem that (I) is least basic due to presence of 2 –NO2 groups
but –NO2 and –N(CH3)2 are all bulky groups. This is a case
of steric inhibition of resonance due to which the lone pair
When the multiple bond is between two unlike atoms, the of N is not in conjugation and is readily available for electron
shift of electrons takes place towards more electronegative donation. Hence, the order of basic strength is :
atom. (I) > (III) > (II)
Example
Mark the order of bond lengths in the given molecule.
SOME IMPORTANT POINTS:

1. COMPARISON OF INDUCTIVE, HYPERCONJUGATION
AND RESONANCE EFFECTS
Inductive Effect is a - interaction and acts through
strong sigma bonds.
SCAN CODE
18
Solution :
–I, –NO2 are bulky groups and is case of steric inhibition
of resonance. Therefore, the –NO2 groups ortho to –I are
out of conjugation while the –NO2 group para to –I will be
in conjugation with the benzene ring. Therefore, bonds ‘a’
and ‘b’ will always have single bond character while ‘c’
has double bond character. Therefore :
c<a=b
4. REACTIVE INTERMEDIATE
4.1 CARBOCATION
(a) Definition
Carbocation is the intermediate of carbon containing

positive charge. It has six electrons in the valence shell.
(b) Geometry and Hybridization

 2
Hybridization of C = sp

Geometry of C = Trigonal Planar
(d) Stability of Carbocations

There are three factors contributing to the stability of
carbocations :
(a) Inductive Effect
(b) Hyperconjugation
(c) Resonance
(c) Classification of Carbocations
Order of stability :
This classification will also be used for carbanions and
carbon free radical and will be studied only in this section.
Methyl Carbocation
1° Primary Carbocation
2° Secondary Carbocation
3° Tertiary Carbocation
SCAN CODE
19
Example (b) Leaving group accepts the pair of electrons that were shared
in the covalent bond.
Rank the stability of carbocations in each case :
Rate of formation of carbocation depends on :
(a) The stability of carbocation formed.
(b) The nature of the leaving group. Weaker the base better
the leaving group. This is because weaker leaving group
implies a stable compound and its formation will therefore
(a)
be favoured.
 Addition of Proton to a  bond
Solution :
Rate of carbocation formation depends on :

(a) Stability of carbocation formed.
(b) Strength of the electrophile.
(f) Reactions of Carbocations
There are three important reactions of carbocations :

(a) (a) Capture a Nucleophile
(b) Lose a proton to form a  bond.
(c) Rearrangement
1. Capture a Nucleophile
2. Loose a proton to form a  bond
Example
Form the products from the following reaction :
Solution :
Step-1 : Protonation
Order of stability : III > I > II
(e) Formation of Carbocations
 Ionization of Carbon-Leaving Group Bond

Step-2 : Formation of Carbocation
In this method :
(a) Bond between carbon and leaving group ionizes.
SCAN CODE
20
 Cyclic Rearrangement/Ring Expension

Ring expension will take place only when positive charge
is on carbon adjacent to the ring.
Example
Draw the products of the following reaction :

Step-3 : Deprotonation
Solution :
When carbocation deprotonation can lead to more than one

product, all products are formed and the most stable product
is the major product.
3 Carbocation Rearrangement
A carbocation can become more stable by rearrangement.
Bonding electrons of carbocation may shift between Even though the hydride shift leads to more stable
adjacent atoms to form more stable carbocation. There are carbocation, ring expansion is preferred.
two kinds of shifts that take place in order to gain stability.
(a) Hydride Shift (b) Alkyl Shift
Example
In the above example, both hydride and methyl shifts are

possible leading to more stable carbocation but only that
shift is preferred which leads to more stable
carbocation. In this example, hydride shift will take place.
Important : The shift takes place in the form of
SCAN CODE
21
4.2 CARBANIONS Solution :

As s-character increases, electronegativity of C increases
(a) Definition and therefore negative charge will become more stable.
Therefore, order of stability is :
Carbanion is the intermediate of carbon containing negative
charge. It has eight electrons in the valence shell. III > II > I

(d) Formation of Carbanion
3
Hybridization of : sp
There are two methods for the formation of carbanion :
Geometry : Trigonal Pyramidal
(A) Partial formation via Grignard Reagent
Carbanion and ammonia are isoelectronic species having
same structure (B) Formation from Carbonyl Compounds
We will discuss these methods in the subsequent section
 Formation via Grignard Reagent
(c) Stability
ERG will increase the electron density at carbon and will

make it unstable. EWG will decrease the electro density at
Note :
carbon and will make it stable.
Order of Stability : 1. Carbanion is never formed as an intermediate that can be
isolated in the case of Grignard Reagent. It directly participates
in the reaction.
2. Dry ether is used in this formation as it is inert to Grignard
reagent. For the formation of Grignard reagent from aryl
halides, we use tetrahedrofuran (THF) as solvent.
 Formation from Carbonyl Compounds
Example
Give the order of stability of :
SCAN CODE
22
There are three reasons for the easy formation of carbanion Mechanism :
from carbonyl compounds
(a) Resonance - stabilization of carbanion which is the
conjugate base of carbonyl compound.
(b) Hyperconjugation makes the C-H bond acidic.
(c) –I of increases the acidic strength of C–H bond.
(e) Reactions of Carbanion
The reactions of carbanion are very fast as electropositive

carbon carries negative charge.
 Grignard Reagent as a Base
In this reaction it captures acidic hydrogen.
is never added along with the first step as Grignard
Reagent will react with to give as in previous

reaction.
 Aldol Condensation
This reaction is shown by carbonyl compounds containing
atleast one H in presence of dilute base such as dilute
NaOH.
Mechanism :
In (d), the reaction with terminal alkyne also takes place

as sp-hydridized carbon is highly electronegative and
therefore H attached to it is fairly acidic.
 Grignard Reagent as a Nucleophile

Grignard Reagent reacts with carbonyl compounds to form
alcohols. This is a very important method for the synthesis
of alcohols.
SCAN CODE
23
(d) Formation of Carbon Free Radical

4.3 CARBON FREE RADICALS
Carbon Free Radicals are formed by homolytic cleavage of
(a) Definition bonds. They are formed :
(a) at high temperature in the gas phase
Carbon Free Radical is the intermediate of carbon having
an odd electron. It is neutral and has seven electrons in the (b) in non-polar solvents
valence shell. It is highly reactive as it requires only one (c) by ultraviolet light
electron to complete its octet and therefore, is short-lived.
(d) by addition of other radicals
(e) Reactions of Carbon Free Radical
The most common reactions in which free radical is

involved are :
(a) Halogenation of alkanes.
(b) Addition of HBr in the presence of peroxides to alkenes.
(Anti-Markonikov Rule)
(c) -Halogenation of alkenes.
(d) Wurtz Reaction
(e) Decarboxylation reaction
 Free Radical Halogenation of Alkanes

The hybridization of carbon free radical was proposed after
The typical reactions of free radical are chain reaction
experimental verification of structure of different radicals.
• mechanisms. There are three steps in a chain reaction
It wasproposed that when ERG areplaced on C , it has sp2 mechanism : initiation, propagation and termination.
3
hybridization and when EWG are placed on C•, it has sp
hybridization.
Mechanism
(I) Chain Initiation
There are two choices :
(a)
(c) Stability
ERG increase stability while EWG decrease stability. (b)

(I) (b) will take place as it is energetically feasible.
(II) Chain Propagation
(a)
SCAN CODE
24
(b)
(III) Chain Termination

The various free radicals in the progress of reaction are :
There is a side-product that is formed in this
Cl•, CH3•. There are ways in which free radicals from reaction. Besides these, a number of other side-products such
different chains may combine to terminate the reaction. as CH2Cl2, CHCl3 and CCl4 have also been observed.
These get formed since carbon free radical is highly
reactive. It randomly reacts with other species that make
it stabler.
5. FUNCTIONAL GROUPS
Class Formula Prefix Suffix
Acid Halide COX Halocarbonyl – carbonyl halide
(C)OX – – oyl halide
Alcohols OH Hydroxy – ol
Aldehydes CHO Formyl – carbaldehyde
(C)HO Oxo – al
Amides CONH2 Carbamoyl – carboxamide
(C)ONH2 – – amide
Amines NH2 Amino – amine
Class Formula Prefix Suffix
Carboxylates Carboxylato – carboxylate
– – oate
Carboxylic Acid COOH Carboxy– – carboxylic acid
(C)OOH – – oic acid
Ethers OR Alkoxy– –
SCAN CODE
25
Esters of COOR Alkoxy carbonyl Alkyl .. carboxylate
Carboxylic Acid (C)OOR – Alkyl ... oate
Ketones Oxo– – one
Cyanides (Nitriles) C  N Cyano – carbonitrile
(C )  N – – nitrile
Salts of Carboxylic – Cation ... carboxylate
Acids – Cation ... oate
Sulphonic Acids Sulfo– – sulfonic acid
Thiols SH Mercapto – thiol
The order of decreasing priority for functional groups is :
, , C O  C , , , , , , , , ,
|| ||
O O
, ,
Important :
(a) The –R, –C6H5, halogens, nitro and alkoxy groups are always treated as substituents.
(b) If more than one functional group of same type is present, its number is indicated by adding di-, tri- etc.
(c) When C is marked in parenthesis, the carbon of the functional group is counted as part of the parent chain and the numbering
will always begin from this carbon and its position need not be marked in the name.
SCAN CODE
26
(6). ISOMERISM IN ORGANIC CHEMISTRY
In organic chemistry, a number of organic compounds having

Since the isomers are constituted of the same number of
different physical and chemical properties can be represented
atoms, so it is clear that the difference in their properties
by the same molecular formula. The property by virtue of
must be due to the difference in the relative arrangement of
which organic compounds possessing different physical and
the atoms within the molecules.
chemical properties and having the same molecular formula
is known as isomerism and the different compounds are
known as isomers.
STRUCTURAL ISOMERISM Example

(i) CH3–CH2–CH=CH2 CH3–CH = CH–CH3
If the isomers have the same molecular formula but they But–1–ene But–2–ene
differ in the relative arrangement of atoms, it is called (ii) C6H4(NO2)2 exhibits following three positional isomers.
structural isomerism. In structural isomers, the structural
formula of the isomers differ whereas the molecular formula
remains same. This type of isomerism is further divided into
various types.
Chain or Nuclear Isomerism
This type of isomerism arises due to the difference in the Functional Isomerism
structure of carbon chain. The difference may be in the length
of the carbon chain or in the size of the carbon ring. These isomers have same molecular formula but they differ
only in the presence of different functional groups.
Example
n–Butane and isobutane are chain isomers.

CH3–CH2–CH2–CH3
n–butane isobutane
Positional Isomerism
This isomerism arises due to the difference in position of
either substituent or functional group in the same carbon
chain.
SCAN CODE
27
Example
(i)
(ii) C3H6O exhibits the following functional isomers.
NOTES :
Test for Enols

In those equilibria where the enol content ishigher than the
keto form, the solution produces red/green/blue colour with
neutral FeCl3 solution. The appearance of such a colour on
addition of neutral FeCl3 solution is a test for any enol. Phenol
also responds to this test.
Tautomerism
Example
This is a special type of functional isomerism where functional
isomers exist in equilibrium with each other. Such isomers
are called tautomers.
The necessary condition for this type of isomerism is the Keto end
presence of –hydrogen to the carbonyl group (a hydrogen
on a carbon adjacent to carbon of functional group). Example
 A very common form of tautomerism is that between a

carbonyl compound containing an hydrogen and its enol
form. This type of isomerism is also known as keto–enol
isomerism.
less stable more stable

Example
In general, the keto form is more stable than the enol form
but in some cases the enol form is more stable.
Cases when the enol form is more stable than the keto form :
3
(1) Enol form has resonance stabilization by forming a conjugated This cannot show tautomerism as no sp hybridized –
system and has intra-molecular hydrogen bonding. carbon is present.
Example NOTE :
The tautomers are not counted while finding the total number
of isomers for a given molecular formula.
Acetoacetic ester
(2) Enol form has aromatic stabilization.
SCAN CODE
28
Metamerism (b) Groups attached to the doubly bonded carbon or nitrogen must
be different. Lone pair is also considered as a different group.
It is caused by the attachment of different alkyl/groups to a
polyvalent atom or group (an atom having more than one Cis-Trans Isomerism
valency). A metamer can be obtained by shifting one or more Geometrical Isomerism in
CH2 group from one side of the polyvalent functional group to
Example
the other side. Metamerism is found to occur in amines, ethers,
ketones, esters, etc. Same atoms or groups on same side. So geometrical
Example isomerism is not possible.
C4H10O exhibits three metamers.
Example
Syn-Anti Isomerism
Geometrical isomerism in and
Example
STEREO ISOMERISM
In this type of isomerism, the compounds possessing same

molecular formula differ in their properties due to the
difference in the arrangement in space of their atoms or
groups in the molecule.
Example
(a) Geometrical Isomerism
It is the type of isomerism in which the compounds possessing

same molecular formula differ in their properties due to the
difference in their geometry that is, due to the difference in
the direction of attachment of same atoms or groups in their
molecule. It is not shown by single bonded compounds like
(C – C) due to free rotation. E-Z Nomenclature of Geometrical isomers
It is shown by C = C, C = N, N = N and cycloalkanes.
Conditions for exhibiting Geometrical Isomerism When C = C contain three or four different groups, it is
(a) There must be restricted rotation in the molecule. difficult to assign cis or trans configuration to the geometrical
isomers.
SCAN CODE
29
Example 2. In case of isotopes, check the atomic mass of that atom.

Example : H, D
3. Chain Method
Example
To deal with such problems, E–Z nomenclature is used.
Cahn - Ingold - Prelog (CIP) Rules
1. Higher atomic number group is assigned higher priority.
For determining priority, use the following method light is called optical activity and the compound that rotates
the plane of polarized light is called optically active
compound. The angle by which plane polarized light is rotated
is called the specific rotation of the compound and is
measured by polarimeter.
Chirality
Chirality means unsymmetricalness. A molecule that is non-

superimposable on its mirror image is chiral. A molecule
that is superimposable on its mirror image is achiral. Chirality
is the necessary and sufficient condition for a compound to
show optical activity.
(b) Optical Isomerism  Chiral Carbon and Chiral Compound
Optical isomers differ in their interaction with the plane When a carbon atom is bonded to four different atoms (or
polarized light. The property of rotating the plane polarized groups)
SCAN CODE
30
NOTES :
It is not necessary for a chiral compound to contain chiral

S
carbon.
CWXYZ, it is chiral and is denoted as C*.

 The configuration is assigned for a stereoisomer based on
Cahn-Ingold-Prelog rules by assigning priority to the groups
attached to the chiral carbon.
 The rules that are used for EZ isomerism are used in the same
Example way here as well.
A compound which is non-superimposable on its mirror  The lowest priority group should be behind the plane while
image is called a chiral compound. deciding the configuration.
Example  If the direction of priorities assigned to groups is clockwise, the
compound has R configuration. If the direction of priorities assigned
to groups is anti-clockwise, the compound has S configuration.
Example
Example
Fischer Projection
It is the two dimensional representation of a tetrahedral carbon.

The method to draw Fischer projection of a molecule has been
illustrated.
R/S Configuration
The arrangement of atoms that characterizes a particular

stereoisomer is called its configuration.
 The groups present on the vertical line in Fischer projection

are behind the plane whereas the groups present on the horizontal
line are outside the plane.
31
 R/S configuration is assigned in a Fischer projection by keeping

NOTES :
the lowest priority group on the vertical line (behind the plane).
Example R and S configurations are mirror images of each other.
Example
 If the lowest priority group is not behind the plane or on the

vertical, exchange it with the group that is behind the plane.
 When two groups are exchanged, the configuration of that atom
is inversed. Case II : Chiral compounds containing more than chiral
carbon are chiral only if they do not satisfy any symmetry
Example condition such as plane of symmetry or centre of symmetry.
If any symmetrical condition is satisfied, the compound is

achiral.
Example
Exchange H and NH2 and we get :
Example
Therefore, after the exchange, we get S configuration which Example

means the given molecule has R configuration.
Chiral Compounds with Chiral Carbons
Case I : Compounds with only one chiral carbon are always

chiral, i.e. optically active.
SCAN CODE
32
Example Specific Rotation and Nature of Rotation
NOTES :
The d configuration is relative to the optical activity

experiment whereas R/S configuration is absolute configuration
which is assigned based on priority of groups according to
CIP rules.
Optical activity is the ability to rotate the plane-polarized

Example light. The optically active isomers are of two types
1. Dextrorotatory : The isomer that rotates the plane-
polarized light to the right (clockwise) is called
‘Dextrorotatory’. It is denoted as ‘d’ or (+).
2. Laevorotatory : The isomer that rotates the plane-
polarized light to the left (anticlockwise) is called
‘Laevorotatory’. It is denoted as ‘’ or (–).
Enantiomers, Diastereomers, Optical rotation is measured by polarimeter in terms of specific

Meso Compounds and Racemic Mixture rotation.
observed
Enantiomers are compounds that are non-superimposable  T 
mirror images of each other. c
Meso compounds are compounds which satisfy any  = specific rotation

symmetry condition will be optically inactive due to internal observed = observed value of rotation
compensation of rotation.
 = length of solution
Diastereomers are stereoisomers which are non-mirror
images of each other. c = concentration of solution.
Racemic Mixture are equimolar mixture of enantiomers. Specific Rotation depends upon :
They are optically inactive due to external compensation of (a) Nature of solute and solvent.
rotation. (b) Wavelength of light during the experiment.
Resolution is the process of separation of racemic mixture (c) Temperature during the experiment.
into optically active enantiomers.
(d) Length and concentration of solution.
Example
(c) Conformers
The different spatial arrangements of the atoms that result

from rotation about a single bond are called conformations.
A specific conformation is called a conformer.
When rotation occurs about the carbon-carbon bond of
ethane, two extreme conformations can result-a staggered
conforamtion and an eclipsed conformation. An infinite
number of conformations between these two extremes are
also possible.
SCAN CODE
33
The staggered conformation, therefore, is the most stable

conformation of ethane because the C–H bonds are as far
away from each other as possible. The eclipsed conformation
is the least stable conformation because in no other
conformation are the C–H bonds as close to one another.
The extra energy of the eclipsed conformation is called
torsional strain.
Conformations of Ethane
Order of stability of conformers of Butane :

Anti > Gauche > Eclipsed > Totally Eclipsed
Conformations of Butane
SCAN CODE
GENERAL ORGANIC CHEMISTRY-2 34
SOLVED EXAMPLES
Example – 1
Which one of the following acids does not exhibit optical Example-4
isomerism ? The alkene that exhibits geometrical isomerism is
(a) Lactic acid (b) Tartaric acid (a) propene (b) 2-methyl propene
(c) Maleic acid (d) -amino acids (c) 2-butene (c) 2-methyl-2-butene
Ans. (a) Ans. (c)
Sol. Sol. 2-Butene may exist as cis and trans isomers. The cis-isomer
HOOC OH has the two methyl groups on the same side and the trans-
isomer has the two methyl groups on opposite sides. Due
COOH HOOC COOH to restricted rotation around double bond it exhibits
geometrical isomerism.
OH
maleic acid
Tartavc acid Example-5
The number of stereoisomers possible for a compound
of the molecular formula
CH 3  CH  CH  CH(OH)  Me is
(a) 3 (b) 2
(c) 4 (d) 6
Ans. (c)
Sol. d and l for cis form.
d and l for trans form.
maleic acid has no chiral centre, so optically inactive. So, a total of 4 isomers are possible.
Example-2
Identify the compound that exhibits tautomerism
(a) 2-butene (b) lactic acid
(c) 2-pentanone (d) phenol
Ans. (c)
Sol. Tautomers are isomers of a compound which differ only in
the position of the protons and electrons. The carbon
skeleton of the compound is uncharged. A reaction which
involves simple proton transfer in an intramolecular fashion
is called tautomerism. So the correct option is 2-Pentanone.
Example-3
Out of the following, the alkene that exhibits optical
isomerism is
(a) 3-methyl-2-pentene (b) 4-methyl-1-pentene
(c) 3-methyl-1-pentene (d) 2-methyl-2-pentene
Ans. (c)
Sol. Optical isomerism is shown by the carbon compounds
which possess at least one chiral carbon. Since none of
the given compounds in the options has a chiral carbon
so it will not exhibit optical isomerism.
Example-6 Example-9
The absolute configuration of Increasing order of stability among the three main
conformations (Eclipse, Anti, Gauche) of 2–fluoroethanol
is
(a) Eclipse, Gauche, Anti (b) Gauche, Eclipse, Anti
(c) Eclipse, Anti, Gauche (d) Anti, Gauche, Eclipse
Ans. (c)
(a) S, S (b) R, R Sol. Eclipse < Gauche < Anti
(c) R, S (d) S, R In the case of Anti, the two electronegative atoms (F- and
OH-) are oppositely placed and the repulsive forces are
Ans. (b) minimum making the conformation more stable, whereas
Sol. Four different groups attached to the chiral center are in eclipsed the groups are closely placed, thereby showing
arranged in decreasing order of priority. The lowest priority maximum steric forces, making the conformation less stable.
group is placed below the plane of paper. When the
remaining 3 groups in decreasing order of priority are in
clockwise direction, the configuration is R and when the Example-10
direction is counterclockwise, the configuration is S. Which types of isomerism is shown by 2,3–dichlorobutane ?
(a) Structural (b) Geometric
Example-7 (c) Optical (d) Diastereomerism
Which one of the following conformations of cyclohexane Ans. (c)
is chiral ? Sol. As shown in the figure 2,3-dichlorobutane has four optical
(a) Twist boat (b) Rigid isomers.
(c) Chair (d) Boat
Ans. (a)
Sol. Twist boat form is chiral as it lacks plane of symmetry
Example-11
Example-8 Which of the following compounds is not chiral ?
Which of the following molecules is expected to rotate the (a) 1–Chloropentane (b) 2–Chloropentane
plane of polarised light ?
(c) 1–Chloro–2–Methyl Pentane
(d) 3–Chloro–2–Methyl Pentane
(a) (b) Ans. (a)
Sol. 1-chloropentane does not contain any asymmetric carbon
atom, Thus it is not a chiral compound.
(c) (d) Example-12

Amongst the following compounds, the optically active
alkane having lowest molecular mass is
Ans. (a) (a) CH3 –– CH2 –– CH2 –– CH3
Sol. For A :The molecule, which is optically active, has a chiral
centre, is expected to rotate the plane of polarised light.
(b)
(c) (d)
Ans. (c)
It is true that
Sol. (a) There is no stereo center.
(a) all four are chiral compounds
(b) There is no stereo center as there are two same (-CH3)
groups on carbon. (b) only I and II are chiral compounds
(c) The is one stereo center. All atoms attached to carbon (c) only III is a chiral compound
atom are different as you can see in the diagram. So, it is (d) only II and IV are chiral compounds
optically active. Ans. (d)
(d) There is no stereo center. Sol. Structure I and III do not have any chiral carbon but II and
IV have one chiral carbon each. So, II and IV are chiral.
Example-13
Which of the following will have a meso-isomer also ? Example-16
(a) 2–Chlorobutane Following types of compounds (as I, II)
(b) 2, 3–Dichlorobutane
(c) 2, 3–Dichloropentane
(d) 2–Hydroxypropanoic Acid
are studied in terms of isomerism in
Ans. (b)
(a) chain isomerism (b) position isomerism
Sol. The compound 2, 3-dichlorobutane contains a plane of
symmetry. Hence, It is superimposable on its mirror images. (c) conformers (d) stereoisomerism
Thus, It has a meso isomer. Ans. (d)
Sol. These all compounds show stereoisomerism
Example14
For which of the following parameters the structural Example-17
isomers C2H5OH and CH3OCH3 would be expected to Racemic mixture is formed by mixing two
have the same values ? (Assume ideal behaviour) (a) isomeric compounds
(a) Heat of vaporisation (b) chiral compounds
(b) Vapour pressure at the same temperature (c) meso compounds
(c) Boiling points (d) enantiomers with chiral carbon
(d) Gaseous densities at the same temperature and Ans. (a)
pressure
Sol. The racemic mixture is generally formed when two chiral
Ans. (d) compounds which are having different rotation to plane
Sol. Since both isomers have the same molecular mass and polarised light are mixed in certain proportions. Chiral
hence their densities will be the same at same temperature compounds are optically active compounds.
and pressure.
Example-18
Example-15 Which one of the following acids does not exhibit optical
Among the following four structures I to IV isomerism?
(a) Maleic acid (b) Tartaric acid
(c) Lactic acid (d) -amino acid
Ans. (a)
Sol. HOOC COOH

Example-22
The compound which is not isomeric with diethyl ether
H H
is
Maleic acid do not have chiral centre & it has plane of (a) n-Propyl Methyl Ether (b) Butan–1–ol
symmetry so it is optically in-active. (c) 2–Methyl Propan–2–ol (d) Butanone
Ans. (d)
Example-19 Sol. Diethyl ether (C2H5OC2H5) will be isomeric will all 4-carbon
saturated alcohols, Butanone (CH 3 CH 2 COCH 3 ) is
Which one of the following substituents at para-position unsaturated, has two hydrogen less than the diethyl ether.
is most effective in stabilizing the phenoxide
Example-23
ions ? Which of the following compounds will exhibit cis-trans
(geometrical) isomerism ?
(a) But–2–ene (b) But–2–yne
(a) –OCH3 (b) –CH2OH (c) Butan–2–ol (d) Butanal
(c) –CH3 (d) –COCH3 Ans. (a)
Ans. (d)
Sol. Electron withdrawing group  es stability of phonoxide
ion. So –COCH3 shows, – I and –R effect.
Sol.
Example-20
Which one of the following compounds will not be soluble
in sodium bicarbonate ?
Example-24
(a) 2, 4, 6 – Trinitrophenol
An isomer of ethanol is
(b) Benzoic acid
(a) methanol (b) diethyl ether
(c) o – Nitrophenol
(c) acetone (d) dimethyl ether
(d) Benzene sulphonic acid
Ans. (d)
Sol. The acid weaker than H2CO3 is not soluble in NaHCO3. so
it is o-nitrophenol. Sol. Ethers and alcohols (saturated, acyclic) with same number
of carbons are always isomeric.
CH3 – O – CH3 and CH3 – CH2 – OH are functional isomers.
Example-21
The correct IUPAC name of the following compound :
Example-25
Which of the following will have least hindered rotation
about carbon-carbon bond ?
is (a) Ethane (b) Ethylene
(c) Acetylene (d) Hexachloroethane
Ans. (a)
(a) 4 – methyl – 3 – ethylhexane
(b) 3 – ethyl – 4 – methylhexane
(c) 3, 4 – ethylmethylhexane
(d) 4 – ethyl – 3 – methylhexane Sol.
Ans. (b)
Ethane has the smallest sized group (H) bonded to
2 3 6 carbons, hence there will be least hindered rotation about
3– ethyl –4– methylhoxgne
4 C – C bond.
Sol. 1 5
Example-26 (b) pH in organic solvent
The enolic form of acetone contains (c) optical rotation and is derived from D-(+)-glyceraldehyde
(a) 9 sigma bonds, 1 pi bond and 2 lone pairs (d) optical rotation when substituted by deuterium
(b) 8 sigma bonds, 2 pi bonds and 2 lone pairs Ans. (c)
(c) 10 sigma bonds, 1 pi bond and 1 lone pair
(d) 9 sigma bonds, 2 pi bonds and 1 lone pair Sol. The ‘D’ term in name is derived from D-glyceraldehyde.
Ans. (a)
Sol.
It has 9  (6 with H, two C – C and one C – O), one  -

bond and two lone-pairs
Example-27
Isomers which can be interconverted through rotation
around a single bond are
(a) conformers (b) diastereomers
(c) enantiomers (d) positional isomers
Ans. (a)
Sol. Conformers can be intercoverted through rotation about
C-C bond.
Example-28
How many optically active stereoisomers are possible for
butane–2, 3–diol ?
(a) 1 (b) 2
(c) 3 (d) 4
Ans. (b)
M
CH3 CH3 CH3
H HO HO H H HO
HO H H HO H HO
Sol.
CH3 CH3 CH3
I II III
I and II are optically active while III is optically inactive

(meso form).
Example-29
The optically active tartaric acid is named as D-(+)-tartaric
acid because it has a positive
(a) optical rotation and is derived from D–glucose
EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Introduction Structural Isomerism
1. What is the IUPAC name of the following compound ? 6. Only two isomeric monochloro derivative are possible for
(a) n–Butane (b) 2, 4–Dimethylpentane
(c) Benzene (c) 2–Methyl propane
7. The number of isomers–1of dibromo derivative of an alkene

(molar mass 186 g mol ) is
(a) two (b) three
(a) (Z)-2-Methylpent-2-enoic acid (c) four (d) six
(b) (E)-2-Methylpent-2-enoic acid
(c) (Z)-2-Methylpent-2-ene carboxylic acid 8. Meso form of tartaric acid is :
(d) (E)-2-Methylpent-2-ene carboxylic acid (a) Dextorotatory
(b) Laevorotarory
2. If unsaturation factor is two, then it means that the struc- (c) Neither Laevo nor dextro rotatory due to internal
ture should have compensation
(a) either two -bonds or two rings or one ring with a - (d) A mixture of equal quantities of dextro and levo rotatory
bonds. forms
(b) only two -bonds
O
(c) only two rings
(d) both two -bonds and two rings
9. I ` II
3. The unsaturation factor of the molecular formula C5H8O is
(a) 1 (b) 2
(c) 3 (d) 4
4. Of the following compounds, which will have zero dipole

moment ?
(a) 1, 1-Dichloroethylene
(b) cis-1, 2-Dichloroethylene OH
(c) trans-1, 2-Dichloroethylene
(d) None of these compounds
III
5. Ease of ionization to produce carbocation and bromide ion
under the treatment of Ag will be maximum in which of Stability order among these tautomers is
the following compounds? (a) I > II > III (b) III > II > I
O (c) II > I > III (d) II > III > I
(a) (b) 10. The molecular formula of a saturated compound is C2H4Cl2.

The formula permits the existence of two
(a) functional isomers (b) position isomers (c) optical
Br isomers (d) cis-trans isomers
Br
11. Which of the following statements is true about these two
structures ?
(c) (d)
Br Br
(a) I and II are a pair of enantiomers
(b) I and II are a pair of diastereomers 20. Which of the following compound will not exhibit
(c) I and II are a pair of conformers geometrical isomerism ?
(d) I and II are a pair of structural isomers (a)
(b)
12. Which of the following is an example of functional (c)
isomerism ?
(a) Isopentane and Neopentane
(b) Glucose and Fructose (d)
(c) Diethyl Ether and 2–Methoxy Propane
(d) –Naphthol and –Naphthol
21. Which of the following can exist as cis and trans isomers ?
Geometrical Isomerism
(a) (b)
13. Maleic acid and fumaric acid are (c) (d)
(a) Position isomers (b) Geometrical isomers
(c) Enantiomers (d) Functional isomers 22. The correct configuration name of
14. Which is a pair of geometrial isomers ?
(a) (2E, 5E) (b) (2Z, 5Z)

(c) (2E, 5Z) (d) (2Z, 5E)
(a) I and II (b) I and III
(c) II and IV (d) III and IV H3C Cl
23. C C
15. Geometrical isomerism will be exhibited by Br
H
(a) Pent–1–ene This compound can be named as
(b) 3–Methylbut–1–ene (a) only cis-1-bromo-1-chloro-propene
(c) Pent–2–ene (b) only trans-1-bromo-1-chloro-propene
(d) All of these compounds (c) trans-1-bromo-1-chloro-propene as well (z)-1-bromo-
1chloro-propene
16. Which of the following compounds can show geometrical (d) only (E)-1-bromo-1-chloropropene
isomerism ?
(a) Vinyl chloride (b) 1, 1–Dichloroethene 24. What is the configuration of the given molecule ?
(c) 1, 2–Dichloroethene (d) Trichloroethene
17. Which of the following compounds does not exhibit

geometrical isomerism ?
(a) 1, 1–Dichlorobut–2–ene
(b) 1, 2–Dichlorobut–2–ene (a) (1E,3Z) (b) (1E,3E)
(c) 1, 1–Dichlorobut–1–ene (c) (1Z,3Z) (d) (1Z,3E)
(d) 2, 3–Dichlorobut–2–ene
25. What is the IUPAC name of the following compound ?
18. Which of the following compounds can exhibit geometrical
isomerism ?
(a) Hex–1–ene (b) 2–Methylpent–2–ene
(c) 3–Methylpent–1–ene (d) Hex–2–ene
19. Each of the following compounds show geometrical

isomerism except
(a) But–2–en–1, 4–dioic acid
(b) But–2–yn–1, 4–dioic acid
(c) But–2–ene
(d) 3–Chlorohex–2–ene
(a) (1Z,3E)-4-Bromo-1-chloro-4-fluoro-1-iodobuta-1,3-diene
(b) (1E,3Z)-4-Bromo-1-chloro-4-fluoro-1-iodobuta-1,3-diene
(c) (1Z,3E)-1-Bromo-4-chloro-1-fluoro-4-iodobuta-1,3-diene (b)
(d) (1E,3Z)-1-Bromo-4-chloro-1-fluoro-4-iodobuta-1,3-diene
26. The number of geometrical isomers of the given compound

Br
is
(a) 2 (b) 3
(c) 4 (d) 5 (c)
Optical Isomerism
Br
27. Number of stereoisomers of the compound, 2-chloro-4-
methylhex-2-ene is O
(a) 2 (b) 4
(c) 8 (d) 16
(d)
28. The compound, whose stereochemical formula is written
below, exhibits x geometrical isomers and y optical isomers
Br
34. Number of chiral carbon atom in

The values of x and y are :
(a) 4 and 4 (b) 2 and 2 (a) 2 (b) 4
(c) 2 and 4 (d) 4 and 2 (c) 3 (d) 1
29. The number of stereoisomers for pent-3-en-2-ol is
(a) 2 (b) 3 35. Consider the following organic compound.
(c) 4 (d) 5
30. When an optically active compound is placed in a 10 dm To make it a chiral compound, the attack should be on carbon
tube, is present 20 g in a 200 mL solution rotates the plane (a) 1 (b) 3
polarized light by 30o. Calculate the angle of rotation and (c) 4 (d) 7
specific angle of rotation if above solution is diluted to 1 L.
(a) 16o and 36o (b) 6o and 30o 36. A stereo-center is
(c) 3o and 30o (d) 6o and 36o (a) An atom in which an interchange of any two group will
result in a new stereoisomer
31. Which of following have asymmetric carbon atom ? (b) A chiral carbon atom
(c) Both of these
(a) CH2Cl–CH2Br (b) CH3CHCl2
(d) none of these
(c) CH3CH2Cl (d) CH2Br–CHOH–CH3
37. Which of the following compounds has asymmetric
32. How many asymmetric carbon atoms are present in : centre ?
(i) 1, 2–dimethyl cyclohexane
(ii) 3–methyl cyclopentene Br
(iii) 3–methyl cyclohexene O
(a) two, one, one (b) one, one, one
(c) two, none, two (d) two, none, one (a) (b)
33. Which of the following compounds has asymmetric centre ?

(a) CH2 CH CH CH CH2 Br
(c) (d) both (b) and (c)
Br
Br
38. Which of the following compounds has asymmetric C2–C3 bond by 180° seems to produce II. Which of the
centre ? following statements is correct ?
(a) I and II are a pair of enantiomers
O O O
(b) I and II are a pair of diastereomers
(a) (b) (c) I and II are a pair of conformers
(d) I and II are identical
O
43. The correct statement about the compound A, B and C
OH OH
(c) Br (d)
Br
39. The compound has:
(a) A and B are identical

(b) A and B are diastereomers
(c) A and C are enantiomers
(a) plane of symmetry (b) axis of symmetry (d) A and B are enantiomers
(c) center of symmetry (d) no symmetry
44. The number of enantiomers of the compound
40. Which of the following structures is chiral? CH3CHBrCHBrCOOH is
(a) 1 (b) 2
(c) 3 (d) 4
(a) (b)
45.
I II
(c) (d)
III IV
Which of the following statements is true about these
molecules?
41. A pair of optically active compounds which are not the (a) I is a mesomer
mirror images are called (b) I and II are identical
(a) Mesomers (b) Anomers (c) III and IV are a pair of enantiomers
(c) Epimers (d) Diastereomers (d) all of these
46. The possible number of alkynes with the formula C5H8 is

42. (a) 2 (b) 3
(c) 4 (d) 5
47. How many isomers are possible with trisubstituted

benzene with all the three groups same ?
(a) 3 (b) 4
(c) 5 (d) 6
Holding C–2 unit of I in hand, rotation of C–3 unit about
48. The number of isomers for the aromatic compound C7H8O 55. Which of the following compound may exhibit optical activity ?
(containing benzene ring) are
(a) 2 (b) 3
(c) 4 (d) 5 (a)
49. The number of optical active isomers possible for

is (b) (CH3)2C(OH)CN
(a) 2 (b) 3
(c) 6 (d) 8
H (c) (d)
50. H2O  Alkene  F 
CH3CH2CH(OH)CH3 
Br2 /CCl4
  C4H8Br2(5 products are possible).
How many structures of F are possible ?
(a) 2 (b) 5 56. Which of the following will not show optical activity ?
(c) 6 (d) 3 C2H5
|
51. CH3 CH CH CH2 (a) CH3 — C — CH2 — CH = CH2
|
OH H
How many geometrical and optical isomers are possible in H
this compound ? |
(a) 0, 2 (b) 0, 3 (b) —C—
(c) 2, 0 (d) 2, 2 |
52. Number of Stereoisomers for CHO – CHOH – CHOH –

CH2OH is (c) CH3CH2CH2CH2OH
(a) 2 (b) 4
(d) CH3 — CH2 — CH — CH3
(c) 6 (d) 8
|
OH
53. Rotation of polarised light can be measured by
(a) Monometer (b) Galvanometer 57. An organic compound C4H8O, is found to be optically
(c) Polarimeter (d) Viscometer active. Which of the following could it be ?
(a) CH3 –– CH2 –– CH2 –– CHO
Chiral Compounds (b) CH2 –– CO –– CH2 –– CH3
(c)
54. Consider following structures and write correct statements
(d) (CH3)2CH –– CHO
Optical Activity
(1) (2)
58. Rotation of polarised light can be measured by
(a) Monometer (b) Galvanometer
(c) Polarimeter (d) Viscometer
(3) (4)
59. Optical rotation produced by is 36°,
where R1 R2 R3 R4
(a) Only 4 shows optical isomerism
(b) 1 and 2 show optical isomerism
(c) 1, 2 and 4 show optical isomerism
(d) All show optical isomerism then that produced by is
(a) – 36° (b) 0°

(c) + 36° (d) unpredictable
60. From the structure of the three stereoisomers of tartaric 65. CH3 CH CH CH3
acid, which statement should be true ?
OH OH
How many optical isomers are possible in this compound ?

(a) 2 (b) 3
(c) 4 (d) 5
66. Which of the following shows optical isomerism ?

(a) 1 is (+), 2 is (–), and 3 is optically inactive (a) cis–1, 2–Dimethyl cyclohexane
(b) 1 is (–), 2 is (+), and 3 is optically inactive (b) trans–1, 3–Dimethyl cyclohexane
(c) 1 is (+), 2 is (–), and 3 is meso (c) trans–1, 4–Dimethyl cyclohexane
(d) 3 is optically inactive, but nothing can be said about 1 (d) All of the above
and 2
67. Which of the following is optically active ?
Stereoisomers
61. The following compound can exhibit :
(a) (b)
(a) geometrical isomerism

(b) geometrical and optical isomerism
(c) optical isomerism
(d) tautomerism
(c) (d) All of these
62. The two structures (I) and (II) represented below are
68. Which of the following is optically active ?
(a) enantiomers
(b) diastereomers (a) (b)
(c) two representations of the same molecule
(d) functional isomers
63. are _______ isomer.. (c) (d)
(a) Position (b) Optical Resolution

(c) Geometrical (d) Diastereomers
69. An enantiomerically pure acid is treated with racemic
mixture of an alcohol having one chiral carbon. The ester
64. CH3 CH CH CH2 CH3 formed will be
(a) Optically active mixture
OH OH (b) Pure enantiomer
(c) Meso compound
How many optical isomers are possible in this compound ? (d) Racemic mixture
(a) 2 (b) 3
(c) 4 (d) 5
R/S Configuration 75. The structure of (S)-2-fluorobutane is best represented by:
70. Rank of the following groups in decreasing order of R, S

precedence. (a) (b)
–CH(CH3)2 –CH2CH2Br –CH2Br –C(CH3)3
1 2 3 4
(a) 3 2 4 1
(b) 1 4 2 3
(c) 3 4 1 2
(d) 3 4 2 1
(c) (d)
71. The absolute configurations of the two centres in the fol-

lowing molecules are:
1
COOH Racemization
2
H Br 76. Which one of the following alkene, when reacted with HCl
3 produces racemic mixture ?
H CN
OH (a) (b)
(a) 2(R), 3(S) (b) 2(R), 3(R)

(c) 2(S), 3(S) (d) 2(S), 3(R)
(c) (d)
72. The configuration at C-2 and C-3 of the compound given:
77. The conversion of dextro- or laevo- form into racemic
CH3 mixture is called
H Cl (a) Resolution (b) Racemisation
(c) Dehydration (d) Revolution
Cl H
78. The process of separation of racemic mixture into d and 
C2H5 enantiomers is called
(a) resolution (b) racemisation
(a) 2R, 3S (b) 2S, 3R (c) filtration (d) distillation
(c) 2S, 3S (d) 2R, 3R
Conformers
73. Correct configuration of the following molecule is:
79. The Baeyer’s angle strain is expected to be maximum in
CH3
(a) cyclopentane (b) cyclodecane
H OH (c) cyclooctane (d) cyclohexane
CH3 OH 80. The most stable conformation of 1,2-diphenylethane is

H
(a) 1S, 2S (b) 1S, 2R

(c) 1R, 2S (d) 1R, 2R (a) (b)
74. Determine the absolute configurations of the chiral cen-
tres in the following compound.
(c) (d)
(a) a=R; b=S (b) a=R; b=R

(c) a=S; b=S (d) a=S; b=R
81. Which of the following is a conformer of isobutane?
(a) (b)
(c) (d)
82. The most stable conformation of ethylene glycol is

(a) anti (b) gauche
(c) fully eclipsed (d) partially eclipsed
83. The Newman projection below represents
(a) A staggered form of 2-methyl propane

(b) A gauche form of butane
(c) An eclipsed form of 2-methyl propane
(d) A most stable conformation of 2-methyl butane
84. Which conformation of ethane has the lowest potential

energy ?
(a) Eclipsed
(b) Skew
(c) Staggered
(d) All will have equal potential energy
EXERCISE - 2 : PREVIOUS YEAR JEE MAIN QUESTIONS

1. The optically inactive compound from the following is 6. The “N” which does not contribute to the basicity for the
(2015) compound is : Online 2016 SET (2)
(a) 2-chloropropanal (b) 2-chloropentane
(c) 2-chlorobutane (d) 2-chloro-2-methylbutane
2. The number of structural isomers for C6H14 is :

Online 2015 SET (1)
(a) 4 (b) 3
(c) 6 (d) 5
3. Match the organic compounds in column-I with the

(a) N 7 (b) N 9
Lassaigne’s test results in column-II appropriately :
(c) N 1 (d) N 3
Column-I Column-II
(A) Aniline (i) Red colour with
7. Which of the following compounds will be suitable for
FeCl3
Kjeldahl's method for nitrogen estimation ? (2017)
(B) Benezne sulfonic (ii) Violet colour with
acid sodium nitroprusside
(C) Thiourea (iii) Blue colour with
hot and acidic
(a) (b)
solution of FeSO4
Online 2015 SET (1)
(a) A– (ii); B– (iii); C– (i) (b) A– (iii); B– (i); C– (ii)
(c) A– (iii); B– (ii); C– (i) (d) A– (ii); B– (i); C– (iii)
4. Which of the following statements is not true about (c) (d)

partition chromatography ? (2016)
(a) Mobile phase can be a gas.
(b) Separation depends upon equilibration of solute 8. The number of geometrical isomers in the following
between a mobile and a stationary phase. compound
(c) Paper chromatography is an example of partition
chromatography. CH3—CH=CH—CH=CH—C2H5 is
(d) Stationary phase is a finally divided solid absorbent. Online 2017 SET (1)
(a) 4 (b) 3
5. The configuration of the chiral centre and the geometry (c) 2 (d) 5
of the double bond in the following molecule can be
described by Online 2016 SET (1) 9. Which of the following statements is not true about
partition chromatography ?
Online 2017 SET (1)
(a) Mobile phase can be a gas
(b) Stationary phase is a finely divided solid adsorbent
(c) Separation depends upon equilibration of solute
between a mobile and a stationary phase
(d) Paper chromatography is an example of partition
chromatography
10. The IUPAC name of the following compound is :
(a) R and E (b) S and E

(c) R and Z (d) S and Z
Online 2017 SET (1)

(a) 1, 1-Dimethyl-2-ethylcyclohexane 14. Among the following compounds, the increasing order of
(b) 2-Ethyl-1, 1-dimethylcyclohexane their basic strength is : Online 2017 SET (2)
(c) 1-Ethyl-2, 2-dimethylcyclohexane
(d) 2, 2-Dimethyl-1-ethylcyclohexane
11. Which of the following compounds is most reactive to an

aqueous solution of sodium carbonate ?
Online 2017 SET (2)
(a) (b)
(a) (I) < (II) < (IV) < (III) (b) (I) < (II) < (III) < (IV)
(c) (II) < (I) < (IV) < (III) (d) (II) < (I) < (III) < (IV)
(c) (d)
15. The IUPAC name of the following compound is :
Online 2018 SET (1)
12. In the following structure, the double bonds are marked
as I, II, III and IV
(a) 4-methyl-3-ethylhex-4-ene
(b) 3-ethyl-4-methylhex-4-ene
(c) 4-ethyl-3-methylhex-2-ene
(d) 4, 4-diethyl-3-methylbut-2-ene
16. Two compounds I and II are eluted by column

chromatography (adsorption of I > II). Which one of
following is a correct statement ?
Online 2018 SET (2)
Geometrical isomerism is not possible at site (s) : (a) I moves faster and has higher Rf value than II
Online 2017 SET (2) (b) II moves faster and has higher Rf value than I
(a) III (b) I
(c) I moves slower and has higher Rf value than II
(c) I and III (d) III and IV
(d) II moves slower and has higher Rf value than I
13. Which of the following compounds will show highest
dipole moment Online 2017 SET (2) 17. The increasing order of the acidity of the following
carboxylic acids is : Online 2019 SET (1)
(a) I (b) II (a) I<III<II<IV (b) IV<II<III<I

(c) III (d) IV (c) II<IV<III<I (d) III<II<IV<I
18. In the following compounds, the decreasing order of basic

strength will be : Online 2019 SET (3)
(a) C2H5NH2 > NH3 > (C2H5)2 NH
(b) NH3 > C2H5NH2 > (C2H5)2 NH
(c) (C2H5)2 NH > C2H5NH2 > NH3
(d) (C2H5)2 NH > NH3 > C2H5NH2
19. Which of these factors does not govem the stability of a

conformation in acyclic compounds ?
(2019-04-10/Shift-2)
(a) Torsional strain (b) Angle strain
(c) Steric interactions (d) Electrostatic forces of
interaction
20. In the following skew conformation of ethane, H'–C–C–

H" dihedral angle is : (2019-04-12/Shift-2)
(a) 58 (b) 120

(c) 149 (d) 151
21. Among the following compounds, geometrical

isomerism is exhibited by :
(2020-09-05/Shift-2)
(a) (b)
(c) (d)
EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Single Choice Questions
1. The degree of unsaturation or index of hydrogen 9. The molecular formula of diphenyl methane
deficiency in the following is:
(i) C6H14 (ii) C4H6 (iii) C6H6 is C13H12.
(a) 0, 2, 4 (b) 1, 0, 2
(c) 4, 1, 0 (d) 2, 0, 4
How many structural isomers are possible when one of
2. Among the following alkenes the hydrogen is replaced by a chlorine atom ?
(I) 1–Butene (a) 4 (b) 6
(II) cis–2–Butene (c) 7 (d) 8
(III) trans–2–Butene
the decreasing order of stability is 10. The enolic form of acetone contains
(a) III > I > II (b) I > II > III (a) 9 sigma bonds, 1 pi bond and 2 lone pairs
(c) II > I > III (d) III > II > I (b) 8 sigma bonds, 2 pi bonds and 2 lone pairs
(c) 10 sigma bonds, 1 pi bond and 1 lone pair
(d) 9 sigma bonds, 2 pi bonds and 1 lone pair
3. Write the correct order of acidity:
11. Which one of the following compounds cannot show
tautomerism ?
(P) (Q)
(a) (b)
(R) (S)
(a) P > Q >R > S (b) Q > P > R > S
(c) Q > R > S > P (d) S > R > Q > P (c) (d)
4. Number of isomers which can be obtained theoretically
on monochlorination of 2–methylbutane is
(a) 2 (b) 3 12. Which can not exhibit tautomerism here
(c) 4 (d) 5
5. How many structural (including stereoisomers) isomers

could be obtained by replacing one hydrogen of propene
with chlorine ? (a) (b)
(a) 2 (b) 3
(c) 4 (d) 5
6. The compound which is not isomeric with diethyl ether

is
(a) n-Propyl Methyl Ether (b) Butan–1–ol
(c) 2–Methyl Propan–2–ol (d) Butanone
7. An isomer of ethanol is (c) (d)

(a) methanol (b) diethyl ether
(c) acetone (d) dimethyl ether
8. How many possible carboxylic acids and esters are for a

compound with molecular formula C4H8O2 ?
(a) four (b) six
(c) five (d) eight
18. Which of the following combinations amongst the four
13. – CHO – COOH – CN – NO2 Fischer projections represents the same absolute con-
I II III IV figurations?
Among these groups, which of the following orders is
the correct priority order in accordance with sequence
rule?
(a) IV > III > II > I (b) IV > II > I > III
(c) II > I > III > IV (d) III > IV > II > I
I II
14. Which of the following compounds will exhibit cis-trans
(geometrical) isomerism?
(a) But–2–ene (b) But–2–yne
(c) Butan–2–ol (d) Butanal
15. The Fischer projection that represent enantiomer of the

given sawhorse projection is III IV
(a) II and III (b) I and IV

(c) II and IV (d) III and IV
19. Which of the Fischer projection formula correspond to

the following stereostructure?
(a) (b)
(a) (b)
(c) (d)
16. Which of the following swithing or rotating Fischer

structures changes its absolute configuration?
(a) An even number of switches (c) (d)
(b) An odd number of switches
(c) Rotating the Fischer projection by 180o in the plane
of the paper
(d) Exchange ligands across the horizontal as well as 20. How many open chain structural isomers of compound
those across the vertical bond with molecular formula C6H12 show geometrical isomerism ?
(a) 2 (b) 3
17. Which of the following operations on the Fischer for- (c) 4 (d) 5
21. Which one of the following compound will show

mula does not changes its absolute con- geometrical isomerism ?
figuration? (a) (b)

(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 (c) (d)
26. Which of the following molecules have (2R, 3-Z) con-
figuration?
22.
(a)
How many geometrical isomers of this bromonium ion
are possible?
(a) 0 (b) 2
(c) 3 (d) 4
(b)
23.
This compound can be named as

(a) 3-chloro-6-methyl-(3E, 5Z)-octadiene (c)
(b) 3-chloro-6-methyl-(3Z, 5E)-octadiene
(c) 3-chloro-6-methyl-(3Z, 5Z)-octadiene
(d) 3-chloro-6-methyl-(3E, 5E)-octadiene
24.
(d)
This compound can be named as

(a) only trans-3-methyl-2-pentene 27. Count the number of stereocentres in the molecule be-
(b) only 3-methyl-(2Z)-pentene low
(c) trans-3-methyl-2-pentene as well as 3-methyl-(2Z)-
pentene
(d) trans-3-methyl-2-pentene as well as 3-methyl-(2E)-
pentene
25. The most stable conformer of meso-1,2-dibromo-1,2-

dichloro ethane is
(a) three (b) five

(c) six (d) seven
(a) (b) 28. How many optically active stereoisomers are possible for
butane–2, 3–diol?
(a) 1 (b) 2
(c) 3 (d) 4
29. The optically active tartaric acid is named as D-(+)-tartaric

acid because it has a positive
(a) optical rotation and is derived from D–glucose
(b) pH in organic solvent
(c) optical rotation and is derived from D-(+)-glyceraldehyde
(c) (d) (d) optical rotation when substituted by deuterium
30. Which of the following can not show optical activity ?
35. Isomers which can be interconverted through rotation

(a)
around a single bond are
(a) conformers (b) diastereomers
(c) enantiomers (d) positional isomers
36. Number of stereoisomers of the compound 2–chloro–4–

methylhex–2–ene is
(a) 2 (b) 4
(c) 8 (d) 16
(b)
37. Which of the following are resolvable?
(c)
(a) (b)
(d) CH3CH2CH2CH2CHO
31. Which of the following compounds is optically active?

(a) 1-bromobutane
(b) 2-bromobutane
(c) 1-bromo-2-methylpropane (c) (d)
(d) 2-bromo-2-methylpropane
32. Which of the following amines have a stereogenic cen- 38. Which of the following on standing in dilute, aqueous
tre? basic solution will undergoes racemization?
(a) Ph–CHBr–CH2–CHO
(b) PhCHBr–CHCl–CHO
(a) (b) (c) Ph–CH2–CHBr–CHO
(d) Ph–CHClCHBr–CHO
Multiple Choice Questions
39. Only two isomeric monochloro derivatives are possible

for
(c) (d)
(a) n–Butane (b) 2, 4–Dimethylpentane
(c) Benzene (d) 2–Methylpropane
(a) a, b, c (b) c, d, e
(c) a, c, d (d) b, c, d 40. HCN and HNC are...... isomers :
(a) Functional (b) Tautomers
33. Following pair of molecules are related as (c) Chain (d) Position
41. Which can exhibit tautomerism here

and
(a) enantiomers (b) diastereomers
(c) identical (d) constitutional isomers
(a) (b)
34. Which of the following will have least hindered rotation
about carbon-carbon bond ?
(a) Ethane (b) Ethylene
(c) Acetylene (d) Hexachloroethane
(c) (d)
42. Keto–enol tautomerism is observed in

(c)
(a) (b)
(c)
(d)
43. CH3CH2NO2 will show ........... isomerism (d)

(a) Position (b) Functional
(c) Tautomerism (d) Geometrical
44. Which of the following molecules is identical with that

represented by
45. Which of the following compounds can show
geometrical isomerism as well as tautomerism here ?
(a)
(b) CH 3  CH  CH  CH 2  NO2
(c)  C2 H5 2 C  N  OH
(d) Ph  N  N  OH
46. Which of the following compound can exhibit

geometrical isomerism ?
(a) (b)
(a)
(c)
(d)
47. Which of these compound can exhibit geometrical

isomerism ?
(a) (b)
(b)
(c) (d) (d)
48. Which of the following can show geometrical isomerism ? 52. An organic molecule necessarily shows optical acitvity
if it
(a) contains asymmetric carbon atoms
(a) (b) (b) is non-superimposable on its mirror image
(c) is superimposed on its mirror image.
(d) is chiral
(c) (d) 53. Which of the following have asymmetric carbon atom?
(a) (b)
49. Which of the following do not show geometrical
isomerism ?
(a)
(b) (c) (d)
(c)
54. Which of the following will show optical isomerism as
well as geometrical isomerism?
(d)
(a)
50. Which is/are correct statements
about P and Q ? (b)

(a) P is cis and Q is trans
(b) P is Z and Q is E
(c) P is R and Q is S
(d) P and Q are same structure
(c)
51. Which of the following represent a pair enantiomers ?
(a)
(d)
55. Identify the compound, which has a stereocenter here.

(b)
(a) (b)
(c)
60. Select correct statements :
(a) both give

(c) (d)
colour with neutral FeCl3 solution.
(b) 2–pentanone and 3–pentanone are position as well
as metamers
(c) Product formed when benzaldehyde reacts with
56. Which of the following cyclopentane derivative is/are hydroxylamine shows geometric isomerism
optically active ? (d) 1, 2–dibromocyclohexane shows geometrical and
optical isomerism
Comprehension Based Questions

(a) (b)
Comprehension
A racemic mixture containing following enantiomers are
to be separated into pure enantiomers by reacting with
a pure enantiomer.
(c) (d) COOH COOH
H3C H H CH3
C2H5 C2H5
I II
57. Which dimethylcyclobutane is/are optically inactive ?
(a) trans–1, 2 (b) trans–1, 3
61. Which of the following amines can be used for the sepa-
(c) cis–1, 2 (d) cis–1, 3
ration of the above-mentioned racemic mixture?
58. Which of the following statements is true ? NH2 NH2
(a) Doubling the concentration of the solution doubles
the observed and specific rotation (a) H3C H (b) H CH3
(b) Doubling the concentration of the solution halves
C2H5 CH3
the observed and specific rotation
(c) Doubling the concentration of the solution doubles
the observed rotation without affecting the specific
NH2
rotation N
(d) Doubling the concentration of the solution and (c) (d) H CH3
doubling the length of the tube increases the
observed rotation by four times. NH2
59. Which out the following are non-resolvable? 62. What would be the stereometric relations between the
products formed when the above-mentioned racemic
mixture is allowed to react with desired amine of the
previous question in order for separation of racemic
(a) (b) mixture?
(a) The products would be identical
(b) The products would be a pair of enantiomer
(c) The products would be a pair of diastereomers
(d) The products would not be stereoisomers
Comprehension
A solution contain three stereoisomers of 2,3-dihydroxy
(c) (d) butanedioic acid. On fractional crystallization of this
solution, two fractions. Fraction–I and Fraction–II are
separated. Fraction-I on reaction with (+)-2-butanamine
gives a single salt while Fraction-II on reaction with the
same (+)-2-butanamine gives a mixture of two salts.
Answer the following three questions based on the
above information.
63. What can be accurately predicted about the molecules (c)

of fraction-I?
(a) Molecules of fraction-I are enantiomers
(b) Molecules of fraction-I are meso compound
(c) Molecules of fraction-I are in racemic form (d)
(d) Molecules of fraction-I has no chiral centre
64. What is the relationship between the molecules of frac- 70. The total number of stereoisomers possible for (A) is:
tion-I with the molecules of fraction-II (a) 8 (b) 7
(a) They are enantiomers (c) 6 (d) 4
(b) They are identical
(c) They are diastereomers 71. If the stereochemistry about the double bond in (A) is
(d) They are diastereomers as well as optically active cis, the total number of stereoisomers for (A) is:
(a) 2 (b) 3
65. What is the relationship between the two different salts (c) 4 (d) 5
obtained from fraction-II?
(a) They are structural isomers 72. If the stereochemistry about the double bond in (A) is
(b) They are enantiomers cis, the total number of enantiomers for (A) is
(c) They are diastereomers (a) None (b) 2
(d) They are conformers (c) 4 (d) 6
Comprehension Assertion and Reason Type Questions

An organic compound having only C, H atoms has a (a) Both Assertion and Reason are true and Reason is the
molecular wt. 86. By nature it is a liquid compound and correct explanation of ‘Assertion’
it is capable of showing chain, position isomerism. It
(b) Both Assertion and Reason are true and Reason is not
can also show free radical halogenation reaction also.
the correct explanation of ‘Assertion’
66. How many structural isomers of C6H14 are possible ? (c) Assertion is true but Reason is false
(a) 3 (b) 4 (d) Assertion is false but Reason is true
(c) 5 (d) 6
67. How many of it’s structural isomers is/are optically active 73. Assertion : Compound possessing same molecular
? formula but differing in their physical and chemical
(a) Zero (b) 1 properties are called isomers.
(c) 2 (d) 3 Reason : Rearrangement reactions produce isomers.
(a) A (b) B
68. Which of the following alkane on single mono (c) C (d) D
chlorination can give 3–mono substituted products ?
(a) 2–Methylpentane (b) n–Hexane 74. Assertion : Structural isomers have different physical
(c) 2, 2–Dimethylbutane and chemical properties.
(d) both (b) & (c) Reason : Structural isomers have different bonding pat-
tern.
Comprehension (a) A (b) B
An organic compound (A) (C10H20) on reductive ozo- (c) C (d) D
nolysis gives 2-methyl butanal. Based on this informa-
tion, answer the following questions. 75. Assertion : Cyclobutane is less stable than cyclopentane.
Reason : Presence of ‘bent bond’ causes loss of orbital
69. Compound (A) is overlap.
(a) A (b) B
(c) C (d) D
(a) 76. Assertion : Alkenes containing more than three carbons

exhibit chain isomerism.
3
Reason : All the carbon atoms in alkenes are sp –
hybridized.
(a) A (b) B
(b) (c) C (d) D
77. Assertion : 1,2-dichloro cyclopropane show geometrical
isomerism 85. Write structural formulae for the isomeric alcohols having
Reason : It has restricted rotation of atoms about a
the molecular formula C4H10O.
covalent bond
(a) A (b) B
(c) C (d) D 86. Calculate the total number of dichloro derivatives of
cyclobutane. Fill the answer in the box.
78. Assertion : Cyclobutane is less stable than cyclopentane.
Reason : Presence of ‘bent bond’ causes loss of orbital X = Total number of dichloro derivatives.
overlap. Y = Total number of optically active products.
(a) A (b) B Z = Total number of meso forms.
(c) C (d) D
87. How many different isomers (including stereo isomers) of
79. Assertion : Meso–tartaric acid is optically active. a monocarboxylic acid with molecular formulaC6H12O2, on
Reason : Optically active molecule is a molecule that decarboxylation with soda lime will produce the same n-
cannot be superimposed on its mirror image pentane?
(a) A (b) B
(c) C (d) D 88. Total number of isomers for C4H6Br2 containing cyclobutane
ring are (including stereoisomer) ?
80. Assertion : Enantiomers differ in their chemical action
with other enantiomer. 89. Write tautomeric forms of phenol.
Reason : A pair of enantiomers have different orienta-
tion of collision with another enantiomer forming differ- 90. Write the structure of all the possible isomers of
ent transition state. dichloroethene. Which of them will have zero
(a) A (b) B dipole moment?
(c) C (d) D
91. Find out the total number of stereocentre in the given
81. Assertion 1,3-dichloro propadiene rotate plane polar- compound.
ized light.
Reason The molecules of 1,3-dichloro propadiene are
dissymmetric
(a) A (b) B
(c) C (d) D
82. Assertion : Both cis-1,3-Dimethyl cyclobutane and

trans-1,3-dimethyl cyclobutane are optically inactive.
Reason : cis-1,3-dimethyl cyclobutane has the plane of 92. (a) (x) (Number of plane of symmetry)
symmetry, whereas trans form has the centre of symme-
try.
(a) A (b) B
(c) C (d) D
Integer Type Questions (b) (y) (Number of mesoisomer)
83. How many chirality centers are present in the following

molecule Sum of (x + y = ?)
93.
Number of stereoisomer are

84. Find out the total number of stereocentre in the given
compound. 94. How many chirality centers are present in the following
molecule
100. Match the structures in column I with the properties in
column II.
Column–I Column–II
(A) (p) Has plane of symmetry

95. Arrange in decreasing order of enolization of the
following compounds
(a)
(B) (q) Has axis of symmetry
(b)
(c)
(C) (r) Has centre of symmetry
(d)
Fill in the Blanks (D) (s) Rotate plane polarized light

96. .............. ring is most strained. (Cyclopropane, Cyclobutane,
Cyclopentane).
97. The IUPAC name of succinic acid is .................
98. Isomers which are .............. mirror images are known as 101. Match the molecule in column A with type of stereoi-
.............. (superimposable, non-superimposable, somerism shown by them in column B.
enantiomers, diastereomers, epimers) Column–I Column–II
(A) 2,3-dichlorobutane (p) Enantiomerism
(B) 2-methyl-3-pentenoic acid (q) Diastereomerism
Match the Following Questions
(C) 2-butanol (r) Meso form
(D) 1,3-dichloro propadiene (s) Conformational
99. Column I Column II
Compounds Characteristics 102. Match the terms in column A with properties in column
B.
(A) (p) S Column–A Column–B
(A) Enantiomers (p) Can be separated into
enantiomers
(B) Diastereomers (q) Have different actions on
(B) (q) Z enantiomer
(C) Racemic mixture(r) Have different action on
achiral compounds
(D) Meso form (s) Have permanent optical
(C) (r) E inactivity
103. Consider the following Fischer projections and match

the pair in column A with the relation in column B.
(D) (s) R
Column–I Column–II
(A) I + II (p) Enantiomers
(B) I + III (q) Diastereomers
(C) II + IV (r) Identical
(D) I + IV
EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTIONS

Objective Questions (Only one correct option)
1. Which of the following compounds will exhibit geometrical 8. Statement–1 : Molecules that are non-superimposable
isomerism ? (2000) on their mirror images are chiral. (2007)
(a) 1–phenyl–2–butene (b) 3–phenyl–1–butene Statement–2 : All chiral molecules have chiral centres.
(c) 2–phenyl–1–butene (d) 1, 1–diphenyl–1–propene (a) Statement–1 is True, Statement–2 is True; Statement–2
is a correct explanation for Statement–1.
2. Identify the pairs of enantiomers and diastereomers from (b) Statement–1 is True, Statement–2 is True; Statement–2 is
the following (2000) not a correct explanation for Statement–1.
(c) Statement–1 is True, Statement–2 is False.
3. The number of isomers for the compound with molecular (d) Statement–1 is False, Statement–2 is True.
formulaC2BrCFI is (2001)
(a) 3 (b) 4 9. The number of isomers of C6H14 is ( 2007)
(c) 5 (d) 6 (a) 4 (b) 5
(c) 6 (d) 7
4. Which of the following compounds exhibits, stereoisomerism ?
(2002) 10. The correct statement(s) about the compound given below
(a) 2–Methyl But–1–ene is (are) (2008)
(b) 3–Methyl But–1–yne
(c) 3–Methyl Butanoic Acid
(d) 2–Methyl Butanoic Acid
5. (a) the compound is optically active

(b) the compound possesses centre of symmetry
(c) the compound possesses plane of symmetry
(d) the compound possesses axis of symmetry
11. The correct statement(s) concerning the structures E, F

and G is (are) (2009)
C2 is rotated clockwise 120° about C2––C3 bond. The

resulting conformer is (2004)
(a) partially eclipsed (b) eclipsed
(c) gauche (d) staggered
(a) E, F and G are resonance structures
6. obs   i x i (b) E, F and E, G are tautomers
where i is the dipole moment of stable conformer and xi is (c) F and G are geometrical isomers
the mole fraction of that conformer. (d) F and G are diastereomers
(a) Write stable conformer for Z – CH2 – CH2 – Z in
Newman’s projection. 12. Give the total number of cyclic structural as well as stereo
If solution = 1.0D and mole fraction of anti form = 0.82, isomers possible for a compound with the molecular
find gauche formula C5H10. (2009)
(b) Write most stable meso conformer of (CHDY)2
13. The correct statement (s) about the compound
If (i) Y = CH3 about C2–C3 rotation and
H3C(HO) HC–CH=CH–CH(OH)CH3 (X) is (are)
(ii) Y = OH about Cl-C2 rotation. (2005) (2009)
(a) The total number of stereoisomers possible for X is 6.
7. The number of stereoisomers obtained by bromination of (b) The total number of diastereomers possible for X is 3.
trans-2-butene is (2007) (c) If the stereochemistry about the double bond in X is
(a) 1 (b) 2 trans, the number of enantiomers possible for X is 4.
(c) 3 (d) 4 (d) If the stereochemistry about the double bond in X is
cis, the number of enantiomers possible for X is 2.
19. The Fischer projection of D-erythrose is shown
14. The correct order of acidity for the following compounds below.
is (2013)
(a) I > II > III > IV (b) III > I > II > IV D-Erythrose and its isomers are listed and P, Q, R, and
(c) III > IV > II > I (d) I > III > IV > II S in Column-I. Choose the correct relationship of P, Q,
R and S with D-erythrose from Column-II.
15. The IUPAC name(s) of the following compound is (are)
(2017)
(a) 4-chlorotoluene
(b) 4-methylchlorobenzene
(c) 1-chloro-4-methylbenzene
(d) 1-methyl-4-chlorobenzene
16. (a) Draw Newman’s projection for the less stable

staggered form of butane.
(b) Relatively less stability of the staggered form is due
to (2019/Shift-1)
(i) Torsional strain
(ii) van der Waals’ strain
(iii) Combination of the above two
(2020/Shift-1)
17. Total number of isomers considering both structural
(a) P  2, Q  3, R  2, S  2
and stereoisomers, of cyclic ethers with the
molecular formula C4H8O is__________ (b) P  3, Q  1, R  1, S  2
(2019/Shift-2) (c) P  2, Q  1, R  1, S  3
(d) P  2, Q  3, R  3, S  1
18. Newman projections P, Q, R and S are shown below : 20. With respect to the compounds I-V, choose the
correct statement(s).
Which one of the following options represents

identical molecules ? (2020/Shift-1)
(a) P and Q (b) Q and S (a) The acidity of compound I is due to delocalization
(c) Q and R (d) R and S in the conjugate base.
(b) The conjugate base of compound IV is aromatic.
(c) Compound II becomes more acidic, when it has a –
NO2 substituent.
(d) The acidity of compounds follows the order
I > IV > V > II > III. (2020/Shift-1)
21. Consider the following four compounds I, II, III, and IV.
Choose the correct statement(s). (2020/Shift-2)

(a) The order of basicity is II > I > III > IV.
(b) The magnitude of pK b difference between I and II
is more than that between III and IV.
(c) Resonance effect is more in III than in IV.
(d) Steric effect makes compound IV more basic than
III.
Note:
Please share your valuable feedback by

scanning the QR code.
Teacher’s Note:
Have you ever wondered what causes the flavour of oranges &
lemons to be different even though both are citrus fruits? The
answer is Limonene. You might have also enjoyed the fragrance
that fills the air after the first rains & the taste of beetroot. Do
you know that a single molecule Geosmin is responsible for both
of them. But why does the same molecule impart different flavours
or fragrance? The answer is Optical Isomers !! This chapter will
open your eyes to one of the features of organic molecule which
can be well characterised as the fingerprint of an organic molecule.
Organic Chemistry is incomplete without Isomerism !!
"Samajh ayega to mazaa ayega,
Mazaa ayega to samajh ayega".
Vamsi sir is Graduate from IIT Bombay, his passion is

to Re-Imagine Teaching & Learning. he has been a
pioneer in creating a system to produce Top Ranks in
JEE and Olympiads. He has personally taught and
mentored AIR 1,6,7 (JEE ADVANCED), and thousands of
more students who have successfully cleared these
competitive exams in the last few years.
01
02
REAGENTS AND MECHANISM AND ALKYL
HALIDES
Chapter 02 67
REAGENTS AND MECHANISM AND

ALKYL HALIDES
1. INTRODUCTION Example - 2
The alkyl haldies or haloalkanes are a group of chemical
compounds, derived from alkanes containing one or more
halogens. They are used commonly as flame retardants, `
fire extinguishers, refrigerants, propellants, solvents and
pharamaceuticals. The alkyl halides are classified broadly
2.3 Elimination Reaction
into three categories based on type of carbon atom to which
This reaction involves the loss of atoms or groups of at-
the halogen atom is attached.
oms to form an unsaturated compound.
Example - 3
3. NUCLEOPHILIC SUBSTITUTIONS REACTIONS
Nucleophile is a reaccting species which attacks at posi-

tively charged carbon
Example - 4
X may be F, Cl, Br or I.
2. REACTION IN ORGANIC CHEMISTRY

These are various types of reactions possible in organic
compounds depending on reaction conditions and
attacking reagent. Reactions in organic chemistry are The replacement of halogen atom (leaving group) by the
classified into three categories : attacking nucleophile is called nucleophilic substitution
reaction at sp3 carbon. This reaction was studied in great
2.1 Addition Reaction detail and two extreme mechanisms have been outlined to
This reaction involves addition of groups to a  bond. explain the course of the reaction.
3.1 Substitution Nucleophilic Bimolecular - SN2
Example - 1
Example - 5
2.2 Substitution Reaction

This reaction involves the replacement of an atom or a
group of atoms by another atom or group of atoms.
SCAN CODE
Reagents and Mechanism and
Alkyl Halides
68
Note :- Key Features of SN2 Mechanism 4. ELIMINATION REACTIONS

1. Single step reaction. Example - 7
2. Rate = k [RX] [Nu]
3. No intermediate is formed. Reaction goes through a
transition state.
4. Rearrangement is not observed.
5. Inversion of configuration is observed (WALDEN The removal of halogen from the carbon to which it is
inversion). attached along with the removal of hydrogen from adjacent
6. Order of reactivity of alkyl halides : carbon is called , -elimination or simply elimination. Three
CH3X > 1° > 2° > 3° mechanisms have been outlined for elimination reactions.
This can be attributed to the steric hinderance to back 4.1 Elimination Bimolecular - E2
side attack of nucleophile. Example - 8
7. Favoured by polar aprotic solvents.
3.2 Substitution Nucleophilic Unimolecular - SN1

Example - 6
Step 1 :
Note:- Key Features of E2 Mechanism

1. Single step reaction.
2. Rate = k [RX] [Base]
3. No intermediate is formed. Reaction goes through a
transition state.
4. Rearrangement is not observed.
Step 2 : 5. Observed in presence of strong bases.
6. Order of reactivity of alkyl halides : 3° > 2° > 1°
This can be attributed to the stability of alkene formed.
7. Favoured by aprotic solvents.
4.2 Elimination Unimolecular - E1
Example - 9
Note: - Key Features of SN1 Mechanism Step 1 :
1. Two step reaction. First step is the formation (and

rearrangement) of carbocation while second step is the
attack of nucleophile on the carbocation.
2. Rate = k [RX]
Step 2 :
3. Carbocation is formed.
4. Rearrangement is commonly observed.
5. Racemic mixture is observed.
6. Order of reactivity of alkyl halides :
3° > 2° > 2° > 1° CH3X
This can be attributed to the stability of the carbocation
that is formed.
7. Favoured by polar protic solvents.
SCAN CODE
Alkyl Halides
69
Note: - Key Features of E1 Mechanism 5.1 Nucleophilicity vs Basicity

(a) Nucleophilicity & basicity will be parallel if the comparing
1. Two step reaction. First step is the formation of carbocation
nucleophile have same attacking atom e.g.
while second step is the loss of proton by a base.
2. Rate = k [RX]
4. Rearrangement is commonly observed.
(b) Negatively charged nucleophiles are stronger than neutral
5. Observed in presence of weak bases. nucleophiles. e.g.
6. Order of reactivity of alkyl halides :
3° > 2° > 1°
This can be attributed to the stability of carbocation as (c) Electrons on larger atoms are less tightly bound by the
well as the stability of alkene formed. nucles and are more polarisable and more readily available
to carbon & will be better nucleophile. But they will be
7. Favoured by protic solvents. weaker base as their bond with smaller H-atoms will be
4.3 Elimination Unimolecular via Conjugate Base - E1cB weaker & their conjugate acids will be more reactive. If the
attacking atoms are of same size, the stronger bases are
Example - 10 better nucleophile. (In a period basicity of anions
Step 1 : decreases) e.g.
Acidic Strength :
CH4 < NH3 < H2O < HF
Basic Strength and Nucleophilicity :
 
CH 3  NH 2   OH  F 
Step 2 :
(d) If the attacking atoms are different in size, the
nucleophilicity depends on the solvents. However, in
gaseous phase nucleophilicity parallels basicity.
(e) Nucleophilicity is inversly proportional to stability of
O
anion. || is a weaker nucleophile as it is
R  C O 
Note: - Key Features of E1cB Mechanism resonance stabilized.
1. Two step reaction. First step is the formation of (f) Steric factor limits nucleophilicity
carbocation and second step is the loss of leaving group.
2. Rate = k [RX]
4. Occurs when poor leaving group is present.
5. SUBSTITUTION AND ELIMINATION

Any species that acts as a base can also act as a
nucleophile. To understand how elimination and
substitution compete with each other, we compare the
nucleophilic behaviour with the basic behaviour. (g) A strong base can be made a good leaving agent e.g.
Oxygen containing group like OH can be made a weak
base in acidic medium by protonation & become a better

leaving agent  OH 2 .
SCAN CODE
Alkyl Halides
70
(h) Protic solvent : These solvents have a hydrogen atom Now the naked anions are highly reactive as a nucleophile
attached to an atom of a strongly electronegative element and now nucleophilicity follows the basicity e.g.
(e.g. oxygen). Molecules of protic solvent can, therefore
form hyfrogen bonds to nucleophiles as :
5.2 Saytzeff vs. Hofmann Rule

When alkene is formed by elimination of alkyl halides, the
orientation of the double bond formed is governed by two
rules.
5.2.1 Saytzeff’s Rule/Zaitsev Rule
This rule suggests the formation of more stable alkene and
A small nucleophile which is having high charge density therefore more substituted double bond. Reactions
than the large nucleophile is strongly solvated and this following this rule are said to be thermodynamically
solvation hinders the direct approach to the nucleophilic controlled.
centre. Hence the smaller nucleophile doesn’t act as a good 5.2.2 Hofmann Rule
nucleophile as the larger one. Hence in protic solvent
This rule suggests the formation of less stable alkene and
nucleophilicity is reverse of basicity.
therefore less substituted double bond. In such cases, the
more acidic b-hydrogen is abstracted to produce alkene.
Such reactions are said to be kinetically controlled.
Hoffmann product is formed of the Base is Bulky.
5.3 Effect of Temperature
(i) Aprotic solvents : These are the polar solvents that don’t
have H atom, capable of forming H-bonds e.g. High temperature favours elimination while low temperature
favours substitution reaction.
6. STEREOCHEMISTRY
6.1 Regioselectivity
It is the preference of one direction of chemical bond
making or breaking over all other possible directions.
Example - 11
These solvents dissolve ionic compounds and solvate the

cations.
6.2 Stereoselectivity
Stereoselective reactions give one predominant product
because the reaction pathway has a choice. Either the
pathway of lower activation energy (linetic control) is
preferred or the more stable product (thermodynamic
control).
SCAN CODE
Alkyl Halides
71
Example - 12 1. Alkanes
2 Cl
RH  RCl  HCl
This method gives a mixture of mono, di & trihalides.
2. Alkenes
6.3 Stereospecificity
Stereospecific reactions lead to the production of a
single isomer as a direct result of the mechanism of the
reaction and the stereochemistry of the starting material.
There is no choice. The reaction gives a different
diastereomer of the product from each stereoisomer of
the starting material.
Example - 13
3. Alkynes
6.4 Chemoselectivity
When there are two or more functional groups in a molecule,
a given reagent may react preferntially with one rather than
the other. Such reactions are called chemoselective.
7. ALKYLHALIDES
7.1 Preparation of Alkyl Halides
4. Alkyl Halides (Halogen Exchange reaction)
(i) Finkelstein Reaction
acetone
R  Br  NaI   R  I  NaBr
acetone
R  Cl  NaI   R  I  NaCl
(ii) Swartz Reaction
RI AgI
DMSO
R  Br  AgF 
Polar
 R  F  AgBr
aprotic
R  Cl AgCl
SCAN CODE
Alkyl Halides
72
5. Alcohol 2. Reaction with Ammonia

C2 H5 OH
R  X  NH3  
 R  NH 2  LiX
1 Amine
Note:-
If alkyl halide is in excess, then 1° and 1° amines and even
quaternary salts are also formed.
6. Carbonyl Compound
7.2 Reactions of Alkyl Halide
This reaction is called Hofmann ammonolysis of alkyl

halides.
3. Reaction with KCN
R  X  KCN 
 R  CN  KX
Alkyl nitrile
4. Reaction with AgCN
 
R  X  AgCN 
 R  N  C
Alkyl iso nitrile
5. Reaction with NaNO2
R  X  NaNO 2 
 R  O  N  O  NaX
6. Reaction with AgNO2

1. Coupling Reaction
(a) Wurtz Reaction RX  AgNO 2 
 R  NO 2  AgX
Et 2 O
2RX  2Na   R  R  2Nax 7. Reaction with LiAlH4
(b) Grignard Reagent
R  X  LiAlH 4 
 R  H (Reduction)
R  X  R  MgX 
 R  R  MgX 2
8. Williamson’s Synthesis
(c) Corey-House Synthesis
SN 2
R  X  R  O  Na   R  O  R   NaX
R  X  2Li 
 R  Li  LiX
9. Aq.KOH & Alc.KOH
2R  Li  CuI 
 R 2 CuLi  LiI
aq.KOH
R  X  R  OH
R 2 CuLi  R   X 
 R  R   Cu  LiX
alc KOH
R  X  
 Alkene
SCAN CODE
Alkyl Halides
73
10. Reactions of RMgX (Grignard reagent) (c) Diazotization
(d) Schiemann Reaction
8. ARYLHALIDES/HALOARENES
8.1 Preparation of Aryl Halide/Haloarenes
8.2 Reactions of Aryl Halide/Haloarenes
(a) Halogenation of Arenes
(a) Electrophilic Aromatic Substitution Reaction : Halogens

are weakly deactivating and ortho/para directing.
(b) Formation of Aryl Grignard Reagent :
Example - 14
(b) Sandmeyer Reaction

Reactivity order : Ar  I > Ar  Br > Ar  Cl > Ar  F
(c) SNAr  Aromatic Nucleophilic Substitution Reaction
SCAN CODE
Alkyl Halides
74
(b) Zinc Dust : (Dehalogenation)
Zn
XCH 2 CH 2 X 
Alcohol
 CH 2 == CH 2  ZnX2
Zn
CH3CHX 2 
Alcohol
 CH3  CH == CH  CH3
(c) Action of aq. KOH : (Alkaline Hydrolysis)

(d) Benzyne Mechanism explaination (Elimination Addition
Mechanism) Strong bases such as Na, K and amide react (i) Vicinal Dihalides
readily with aryl halides.
9. REACTIONS OF SPECIAL ALKYL HALIDES

9.1 Di-Halides
(ii) Gem Dihalides
9.1.1 Preparation
(a) Alkenes and Alkynes Halogenation of Alkenes & Alkynes
CH 2  CH 2  X 2  CH 2 X  CH 2 X Vicinal Dihalide
CH 2  CH  2HX  CH 3 CH 2 X Geminal Dihalide
(b) PCl5 with Diols & Carbonyl Compounds Note: -

The above reaction is used to distinguish bewteen gem
trand vicinal dihalides.
9.2 Tri-Halides & Tetra-Halides
CHCl3 CHBr3
9.1.2 Properties
Chloroform Bromoform
(a) Alcoholic KOH : (Dehydrohalogenation)
(liquid) (liquid)
Alcoholic
XCH 2 CH 2 X 
KOH
 CH  CH
CHCl3 CHBr3
Alcoholic
CH3CHX 2 
KOH
 CH  CH Iodoform Carbon Tetrachlodide
(yellow solid) (liquid)
SCAN CODE
Alkyl Halides
75
9.2.1 Chloroform : CHCl3 (ii) Carbylamine Reaction

(A) Preparation RNH2 + CHCl3 + 3KOH  RNC + 3H2O + 3KCl
(i) Ethyl Alcohol : (using NaOH/Cl2 or CaOCl2) C6 H 5 NH 2  CHCl3  3KOH  C6 H 5 NC  3H 2 O  3KCl
NaOH  Cl 2  NaOCl  HCl; NaoCl  [O] Isocyanides (carbylamines) have a very disagreable smell,
so the above reaction is used as a test of chlororom and
Cl2 Cl2 test of 1° (aliphatic and aromatic) amines.
C2 H5 OH 
[O]
CH3 CHO  CCl3 CHO 3HCl
Chloral (iii) Hydrolysis
Ca(OH)2
CCl3 CHO  Ca(OH)2 

 2CHCl3  Ca(HCOO) 2
Slaked Lime Chloroform
NaOH
Hydrolysis
CH3CHO  3Cl2 
 CCl3CHO  
(iv) Formation of Acetylene
NaOH
CCl3 CH(OH)2   CHCl3  HCOONa  H 2 O
Chloralhydrate
2CHCl3  6Ag 
 CH  CH  6AgCl
Acetylene
Note:-
(v) Formation of Chloropicrin
Pure form of chloroform is prepared from chloral by treating
it with NaOH. CHCl3  HNO3 
 CCl3 NO2
Chloropicrin
(an insecticide)
(ii) Methyl Ketones
(vi) Formation of Chloretone
9.2.2 Iodoform: CHI3

(iii) Carbon Tetrachloride (A) Preparation :
Fe  H 2 O
CCl 4  2[H] 
HCl
 CHCl3  HCl
(iv) Chlorination of Methane at 370C

370 C
CH 4  3Cl2  
Diffused Sunlight
 CHCl3  3HCl
(B) Reactions
(i) Oxidation
Chloroform in presence of light and air (O2) forms a highly
posionous gas, Phosgene. Note:-
light
This reaction is known as Iodoform reaction or Iodoform
2CHCl3  O 2   2COCl2  2HCl test. Since the iodoform is a yellow colored solid, so the
Phosgene
iodoform reaction is used to test ethyl alcohol,
Note:- acetaldehyde, sec. alcohols of R(CH3)CHOH (methyl alkyl
carbinol) and methyl ketones (RCOCH3), because all these
1% Ethonal is added and then chloroform is stored in brown form iodoform. The side product of the iodoform reaction,
bottles, filled upto brim to stop the above decomposition. sodium carboxylate is acidified to produce carboxylic acid
(RCOOH).
SCAN CODE
Alkyl Halides
76
9.2.3 Carbon Tetrachloride : CCl4 (B) Reaction

(A) Preparation : (i) CH 2  CHCl 2  alc.KOH 
 CH  CH  HCl
Acetylene
hv
(i) CH 4  4Cl 2  CCl 4  4HCl
diffused
Halogen atom is vinyl chloride is quite stable and does not
excess
respond to nucleophilic substitution reactions easily. It is
AlCl
due to resonance stabilisation of vinyl chloride.
(ii) CS2  3Cl 2 
Fe/I 2
 CCl 4  S2 Cl 2
S2Cl2 is separated by fractional distillation. It is then
treated with more CS2 to given CCl4 washed with NaOH
and distilled to obtain pure CCl4. 9.2.5 Allyl Chloride : H2C = CHCH2Cl
2S2 Cl2  CS2 
 CCl 4  6S
(A) Preparation
400 C
(iii) CH 3 CH 2 CH 3  Cl2   CCl4  HCl  C2 Cl6 500  600 C
70-100 atm (i) H 2 C  CHCH3  Cl2   CH 2  CHCH 2 Cl
Propene
Note:-
(ii) H 2C  CHCH 2OH PCl5  H 2C  CHCH 2Cl  POCl3  HCl
CCl4 is a colourless and poisonuous liquid which is Allyl Alcohol
insoluble in H2O. It is a good solvent for grease and (B) Reaction

oils. CCl4 is used in fire extingusher for electric fires as Pyrene. (i) Addition Reactions
It is also insecticide for hookworms.
CCl4
CH 2  CH  CH 2 Cl  Cl2   CH 2 ClCHClCH 2 Cl
(B) Reactions :
(i) Oxidation CH 2  CH  CH 2 Br  HBr 
 CH3 CHBrCH 2 Br
1, 2-Dibromopropane
500 C
CCl4  H 2 O   COCl2  2HCl The addition follows Markonikov’s Rule. However in
Steam presence of peroxides reaction is formed.
(ii) Nucleophilic Substitution Reactions
(ii) Reduction
Since in allyl chloride, there is no resonance (unlike in vinyl
Fe/ H2 O chloride), nucleophilic substitution reactions take place
CCl4  2[H]  CHCl3  HCl with ease.
KOH(aq)
(iii) Hydrolysis CH 2  CH  CH 2 Cl   CH 2  CHCH 2 OH  KCl
NH3
CH 2  CH  CH 2 Cl   CH 2  CH  CH 2 NH 2  HCl
KCN
CH 2  CHCH 2 Cl   CH 2  CH  CH 2 CN  KCl
dry
CH 2  CHCH2 Cl  Mg 
ether
 CH2  CHCH 2 MgCl
Grignard Reagent
(iv) Action of HF 9.2.6 Benzyl Chloride : C6H5CH2Cl : PhCH2Cl

SbF6 (A) Preparation
CCl4  4HF   CCl2 F2  2HCl
Freon
9.2.4 Vinyl Chloride : CH2 = CHCl

Vinyl grooup CH2 = CH
(A) Preparation
(i) CH  CH  HCl 
 CH 2  CHCl
KOH(alc.)
(ii) CH 2 ClCH 2 Cl 
Vicinal Dihalides
 CH 2  CHCl  KCl  H 2 O
600  C
(iii) CH 2  CH 2  Cl 2   CH 2  CHCl  HCl
SCAN CODE
Alkyl Halides
77
(B) Reactions 10.2 Reactions

The main reactions are like those of Alkyl Halides (since (A) Grignard reagent as a base reacts with compounds
there is no resonance in benzyl chloride and intermediate containing active H to give alkanes.
benzyl carbonium ion is stable supporting S N 1
substitution). Nucleophillic substitution reactions occur R  MgI  HOH 
 RH  Mg(OH)I
with ease unlike in case of aryl halides (due to resonance
in aryl halides). R  MgI  R O  H 
 RH  Mg(OR )I
(i)
R  MgI  R  NH  H 
 RH  Mg(NHR )I
(B) Grignard reagent acts as a strong nucleophile and shows
nucleophillic additions to give various products. Alkyl
group being electron rich (carbonian) acts as nucleophile
in Grignard Reagent.
(ii)
(iii)
Example - 15
(iv) Wurtz Reaction
Example - 16
(v) Oxidation
10. CHEMISTRY OF GRIGNARD REAGENT : R-Mg-X

10.1 Preparation
reflux in
RX  Mg 
ether
R  Mg  X
Alkyl Magnesium Halide Example - 17
Note: -
In Grignard reagent, we can have phenyl or alkenyl or
alkynyl or aromatic group instead of R. All the reactions
will remain same.
SCAN CODE
Alkyl Halides
78
Note:- (E) Cyanides

H 2 O/ H 
HCHO  RMgX 
1 alcohol Example - 21

H 2 O/ H
R CHO  RMgX   2 alcohol

H 2 O/ H
R COR  RMgX   3 alcohol
(C) Acid Chloride
Example - 18
Example - 22
Ketones (acetone) formed further reacts with Grignard (F) CO2

reagent to form 3° alcohols (tert. butyl alcohol). However,
with 1 : 1 mole ration of acid halide and Grignard Reagent,
one can prepare ketones.
(D) Esters
Example - 19
(G) Oxygen
The aldehydes react further with CH 3MgI to give 3°

alcohol, if present in excess. But 1 : 1 mole ration of reactants
will certainly give aldehydes.
Example - 20
(H) Ethylene Oxide (Oxiranes)
(I) Alkynes
The ketones react further with CH3MgI to give 3° alcohol, CH 3 C  C  H  CH 3 MgI 
 CH 3 C  C  MgI  CH 4
if present in excess. But 1 : 1 mole ration of reactants will
certainly give ketones. CH 3 C  C  MgI  CH 3 I 
 CH 3 C  C  CH 3  MgI 2
SCAN CODE
Alkyl Halides
79
(J) Alkyl Halides (K) Inorganic Halides
R  MgI  CH 3 CH 2 Br 
 CH 3 CH 2 R  Mg(Br)I
CH3 MgBr  CH 2  CHCH 2 Br 

 CH 2 CH 2 R  MgBr2
Alkyl Bromide
SCAN CODE
Alkyl Halides
REAGENTS AND MECHANISM AND ALKYL HALIDES 80
SOLVED EXAMPLES
Example-1 CH3
|
For the compounds
CH 3  C  CH3 
1 product
|
CH3Cl, CH3Br, CH3I and CH3F, the correct order of CH3
increasing C – halogen bond length is:
(a) CH3F < CH3Cl < CH3Br < CH3I
(b) CH3F < CH3Br < CH3Cl < CH3I Example-4
(c) CH3F < CH3I < CH3Br < CH3Cl Of the four isomeric hexanes, the isomer which can give two
monochlorinated compounds, is
(d) CH3Cl < CH3Br < CH3F < CH3I
(a) 2-methylpentane (b) 2, 2-dimethylbutane
Ans. (a)
(c) 2, 3-dimethylbutane (d) n-hexane
Sol. B.L  size of atom Ans. (c)
CH 3 F  CH 3Cl  CH 3 Br  CH 3 I
Example-2
Write the structure of all the possible isomers of
dichloroethene. Which of them will have zero dipole
moment ?
Ans. (c)
Sol. Ci isomer & trans isomer. Trans isomer has zero dipole
Example-3
On mixing a certain alkane with chlorine and irradiating it
with ultraviolet light, it forms only one monochloroalkane.
This alkane could be
(a) propane (b) pentane
(c) isopentane (d) neopentane
Ans. (d)
UV
Sol. Cn H 2n+2 + Cl2  2 monochloroalkanc
Example-5
2-methyl butane on reacting with bromine in the presence of
sunlight gives mainly
(a) 1-bromo-3-methylbutane (b) 2-bromo-3-methylbutane
(c) 2-bromo-2-methylbutane (d) 1-bromo-2-methylbutane
Ans. (c)
H CH3 H CH3
| | | |
HN
Sol. H3C  C|  C|  CH3  Br2  CH3  C|  C|  CH3  HBr
H H H Br
Example-6 (a) CH3CHO and CH3Br
The reaction conditions leading to the best yield of C2H5Cl (b) BrCH2CHO and CH3OH
are
(c)
UV light
(a) C2H6 (excess) + Cl2  
(d)
Dark Ans. (d)
(b) C2H6 + Cl2 (excess) 
room temp.
Sol.
UV light
(c) C2H6 + Cl2 (excess)  
UV light
(d) C2H6 + Cl2  
Ans. (a)
Sol. During chlorination of alkane, if excess of alkane is treated
with Cl2  g  in presence of light or heat chance of mono- Example-9
chlorination predominate.
Which of the following reactions will yield 2,
UV light
C2 H 6  excess   Cl2   CH 3CH 2 Cl  HCl 2-dibromopropane ?
(a)
Example-7 (b)
Reaction of one molecule of HBr with one molecule of 1, (c)
3-butadiene at 40°C gives predominantly (d)
(a) 1-bromo-2-butene under kinetically controlled conditions Ans. (a)
(b) 3-bromobutene under thermodynamically controlled Sol.
conditions
(c) 1-bromo-2-butene under thermodynamically controlled
conditions
(d) 3-bromobutene under kinetically controlled conditions
Ans. (c)
Sol.
Example-10
In the presence of peroxide, HCl and HI do not give
anti-Markownikoff’s addition to alkenes because:
(a) HCl is oxidizing and the HI is reducing
(b) All the steps are exothermic in HCl and HI
(c) Both HCl and HI are strong acids
(d) One of the steps is endothermic in HCl and HI
Ans. (d)
Sol. Because one of the step is endothermic in HCl and HI ,
Example-8
so furthur reaction do not occur.
HBr reacts with under anhydrous
conditions at room temperature to give Example-11
Write down the structures of the stereoisomers formed when
cis-2-butene is reacted with bromine.

Ans. (0)
Sol.
Sol.
Anti add’n of Br2 will take place.
Example-12 Example-15
The compound which reacts fastest with Lucas reagent at
room temperature is
(a) butan-2-ol (b) butan-1-ol The decreasing order of the rate of the above reaction with
–
nucleophile (Nu ) A and D is
(c) 2-methyl propan-1-ol – –
[Nu = (A) PhO–, (B) AcO–, (C) HO , (D) CH3O ]
(d) 2-methyl propan-2-ol
(a) D > C > A > B (b) D > C > B > A
Ans. (d)
(c) A > B > C > D (d) B > D > C > A
Sol. With lucas reagent 30 alcohol react faster Ans. (a)
Sol. More stable carbanion less will be nucleophile A and B is
stabilize by resonance D have highest -ve charge
concentrate on oxygen B form equivalent resonating
Example-13
structure is most stable among all
HBr reacts fastest with
(a) 2-methyl propan-2-ol (b) propan-1-ol
Example-16
(c) propan-2-ol (d) 2-methyl propan-1-ol
The major product formed when 1,1, 1 trichloro–propane
Ans. (a)
is treated with aqueous potassium hydroxide is :
Sol. HBr react fastest which for stable carbon
(a) 2–Propanol (b) Propyne
CH3 CH3
| | (c) Propionic acid (d)1–propanol
H
H 3 C  C  CH 3  CH 3  C  CH 3 Ans. (c)
| 
OH
Sol.
3 -alcohol form 3 carbocation Cl OH
CH 3 CH 2 C Cl Ag .KOH
 CH 3 CH 2 C OH
Cl OH
Example-14
 H 2O
Predict the structure of the product in the following reaction
CH3  CH 2  COOH
Example-17
The organic chloro compound, which shows complete
stereochemical inversion during an SN2 reaction is
(a) (C2H5)2CHCl (b) (CH3)3CCl
(c) (CH3)2CHCl (d) CH3Cl
Ans. (d)
Sol. Less hindranced undergo more SN 2 substitution
Example-18 Which one of the following undergoes complete inversion
The decreasing order of nucleophilicity among the of configuration ?
nucleophiles (a) C6H5CHC6H5Br (b) C6H5CH2Br
(A) (B) (c) C6H5CH2CH3Br (d) C6H5CCH3C6H5Br
Ans. (b)
Sol. In compound B , bromine attached to benzylic bromide
(C) give SN 2 mechanism, so inversion occure.
(D) Example-22
Draw the stereochemical structures of the products in the
following reactions
(a) (C), (B), (A), (D) (b) (B), (C), (A), (D)
(c) (D), (C), (B), (A) (d) (A), (B), (C), (D)
Ans. (b)
Sol. More concentrated  Vs charge more will be nucleophilicity
Ans. ()
in A, C, D charge is delocalized by resonance  b  comes
Sol.
first and most stablised by resonance is  d  comes last.
Example-19
Tertiary alkyl halides are practically inert to substitution by
SN2 mechanism because of
(a) steric hindrance (b) inductive effect Example-23
(c) instability (d) insolubility Following reaction
Ans. (a) (CH3)3CBr + H2O  (CH3)3COH + HBr is an example of
Sol. 30 alkyl halide do not undergo SN 2 mechanism due to (a) elimination reaction (b) free radical substitution
steric hindrance. (c) nucleophilic substitution
(d) electrophilic substitution
Example-20 Ans. (c)
Which of the following is the correct order of decreasing Sol. It is simply nucleophilic substitution Reaction
SN2 reactivity ?
(a) RCH2X > R3C X > R2CH X
Example-24
(b) R CH2X > R2CHX > R3C X
SN1 reaction is feasible in
(c) R3C X > R2CH X > RCH2 X
(d) R2CH X > R3C X > RCH2 X
(X = a halogen) (a)
Ans. (b)
Sol. SN 2 reactivity (b)
0 0
1 alkyl halide > 2 alkyl halide > 3 alkyl halide.
(c)
Example-21
In a nucleophilic substitution reaction:
DMF
R  Br  Cl  
 R  Cl  Br  , (d)
Ans. (a) Sol.
H H H H H
Sol. 30 carbocattern is more stable than primary carbocation. | | | | |
H 3 C  C  C  CH 3  H 3 C  C  C  CH 3  CH 3  C  C  CH 2
| | major | |
H Br H H
minor
Example-25
Example-28
n-propyl bromide on treatment with ethanolic potassium
hydroxide produces
(a) propane (b) propene
(c) propyne (d) propanol
Ans. (b)
The alkene formed as a major product in the above
elimination reaction is Sol. An alkyl halide containing at least one β - H, on treatment
with ethanoic KOH, undergoes dehydrohalogenation,
(a) (b) CH 2 CH2 giving alkene.
Me
Ethanol
Me Me CH 3  CH 2  CH 2  Br  KOH   CH 3  CH  CH 2
(c) (d)
Example-29
Ans. (b) 1-chlorobutane on reaction with alcoholic potash gives
Sol.
(a) but-1-ene (b) 1-butanol
(c) but-2-ene (d) 2-butanol
Ans. (a)
C2 H 5OH
Sol. CH 3  CH 2  CH 2  CH 2  Cl  KOH  
CH 3CH 2  CH  CH 2
1 butene
Example-26
Example-30
Trans-2-phenyl-1-bromocyclopentane on reaction with
alcoholic KOH produces Chlorination of toluene in the presence of light and heat
followed by treatment with aqueous NaOH gives
(a) 4-phenylcyclopentene (b) 2-phenylcyclopentene
(a) o-cresol (b) p-cresol
(c) 1-phenylcyclopentene (d) 3-phenylcyclopentene
(c) 2, 4-dihydroxy toluene
Ans. (d)
(d) benzoic acid
Ans. (d)
Sol.
Sol.
Anti - elimination
Example-27
Elimination of bromine from 2-bromobutane results in the Example-31
formation of
Identify the major product in the following reaction
(a) predominantly 2-butyne (b) predominantly 1-butene
(c) predominantly 2-butene
(d) equimolar mixture of 1 and 2-butene
Ans. (c)
Example-35
Alkyl halides react with dialkyl copper reagents to give
(a) alkenyl halides (b) alkanes
(c) alkyl copper halides (d) alkenes
Ans. (b)
C 6 H 5  C H  CH 2  CH 3
Sol. | Sol. R ' 2 C u L i+ R ' X  R -R '+ C u R + L iX
Br
Example-32 Example-36
Each of the following reactions gives two products. Write How will you prepare m-bromoiodobenzene from benzene
the structures of the products (in not more than 5-7 steps) ?
Sol. m-bromoiodobenzene can be prepared from benzene in the
Alc.KOH, heat
(i) C6H5CH2CHClC6H5   following way-

(ii) (CH3)2CH––OCH3  
HI excess 1. Treating benzene with nitrating mixture which gives
heat  nitrobenzene-
Sol. C6 H 6 + HNO3 H 2SO 4 ----------> C6 H 5 NO2
2. Bromination of nitrobenzene,giving
(i) m-bromonitrobenzene-
C6 H 5 NO2 + Br2 Fe ---------> 3  Br  C6 H 4 NO2
HI
(ii) (CH 3 ) 2 CH - OCH 3  (CH 3 ) 2 CH - I + H 2 O + CH 3 I
3. Reducing the above compound with Sn HCl-
Example-33 3- Br-C6 H 4 NO2 + Sn HCl ----------> 3-Br-C6 H 4 NH 2

The treatment of CH3MgX with produces 4. Treating 3- bromoaniline with NaNO2 HCl-
(a) (b) 3-Br-C6 H 4 NH 2 + NaNO2 HCl--------> 3-Br-C6 H 4 N 2 Cl
5. Finally treating the above diazonium compound with KI ,
(c) (d) yields m-bromoiodobenzene
Ans. (d) 3-Br-C6 H 4 N 2 Cl + KI---------> 3-Br-C6 H 4 I
+ +
Sol. CH 3 M gX  CH 3 C  C  H  CH 4  CH 3 C  C MgX
Example-37
Grignard reagent behave base Write down the reaction involved in the preparation of
following using the reagents indicated against in
Example-34 parenthesis.
(CH3)3CMg Cl on reaction with D2O produces “Ethyl benzene from benzene.”
(a) (CH3)3CD (b) (CH3)3COD [C2H5OH, PCl5, anhyd. AlCl3]
(c) (CD)3CD (d) (CD)3COD Sol. (i) C2 H 5 OH  PCl5  C2 H 2 Cl
Ans. (a)
(ii)
Sol.
CH3 CH3
|   |
 D2 O
CH 3  C  Mg Cl 
 CH 3  C  D
| |
CH3 CH3
Example-38 acetone gives a product which does not show optical

activity. Explain briefly.
Arrange the following in order of their
Sol. Formation of a racemic mixture.
(i) Increasing basicity
– –
H2O, OH , CH3OH, CH3O
Example-42
(ii) Increasing reactivity in nucleophilic substitution
reactions Complete the following, giving the structures of the principal
organic products
CH3F, CH3I, CH3Br, CH3Cl
Ans. Acidity order :
 
CH 3OH  H 2 O  CH 3 O  O H
 
O H  CH 3 O  H 2 O  CH 3OH
Basicity order Sol.
 ii  CH3 F < CH3Cl < CH3 Br < CH3 I
Example-43
Example-39
Conversion of benzene diazonium chloride to chloro
Write the structure of the major organic product expected benzene is an example of which of the following reactions?
from each of the following reactions
(a) Claisen (b) Friedel-craft
(c) Sandmeyer (d) Wurtz
Ans. (c)
(i)
N 2 Cl
Cl
(ii)
Sol. CuCl


Sol.
This is sandmeyer reaction

(i)
Example-44
Chlorobenzene can be prepared by reacting aniline with
(a) hydrochloric acid
(b) cuprous chloride
(ii)
(c) chlorine in presence of anhydrous aluminium chloride
(d) nitrous acid followed by heating with cuprous chloride
Example-40 Ans. (d)
Aryl halides are less reactive than alkyl halides towards Sol.
nucleophilic reagents. Give reason.
Sol. Because of sp2 hybridized carbon the bond between carbon
and halogen is stronger. Also in conjugated systems back-
bonding by halogens lead to formation of partial double
bond character. Example-45
The major organic compound formed by the reaction of
Example-41 1, 1, 1– trichloroethane with silver powder is :
Optically active 2-iodobutane on treatment with NaI in (a) Ethene (b) 2-Butyne
(c) 2-Butene (d) Acetylene
Ans. (b)
Sol.
Example-46
The compound formed on heating chlorobenzene with
chloral in the presence of concentrated sulphuric acid is
(a) gammexane (b) DDT
(c) freon (d) hexachloroethane
Ans. (b)
Sol.
[More stable product]
Example-47
Chloroform is stored in dark coloured bottles. Explain in not
more than two sentences.
Sol. Chloroform reacts with O 2 .
Example-48
Show by chemical equations only, how would you prepare
the following from the indicated starting materials. Specify
the reagents in each step of the synthesis.
(i) Chloroform from carbon disulphide.
(ii) Hexachloroethane (C2Cl6) from calcium carbide.
AlCl3
CS2  3Cl2 
 CCl 4  S2 Cl2
Sol. (i) | Fe / H 2 O Re duction
 CHCl3  HCl
(ii) Hydrolysis of calcium carbide will produce acetylene.

Reduce acetylene to ethane followed by chlorination (excess
Cl 2 ) will produce Hexachloroethane.

Θ Θ Θ Θ
Reagents 7. F,Cl,Br, I Among these nucleophiles, which of the
1. Which of the following species is an electrophile ?
following orders is correct for their nucleophilicity
(a) H (b) H
order in water ?
(c) both (a) and (b) (d) none of these Θ Θ Θ Θ Θ Θ Θ Θ
(a) F>Cl >Br> I (b) I >Br >Cl>F
2. Which of the following species is a nucleophile ? Θ Θ Θ Θ
(a) H2O (b) H 3 O  (c) I >Br >F>Cl (d) none of these
(c) both (a) and (b) (d) none of these
8. For the following :
(1) I– (2) Cl– (3) Br–
3. Which of the following species is a nucleophile ? the increasing order of nucleophilicity in polar protic
(a) C H 2 O  (b) CH3OH solvent would be
(c) both (a) and (b) (d) none of these (a) I–< Br–< Cl– (b) Cl–< Br–< I–
4. Among these nucleophiles, which of the following (c) I–< Cl–< Br– (d) Br–< Cl–< I–
orders is correct for their nucleophilicity order in gas
phase ? Substitution
9. The less reactivity of chlorine atom in CH 2 =CH-Cl
CH 3 , NH 2 , OH  ,F - is due to
(a) CH 3 >NH 2 >OH  >F - (a) Inductive effect (b) Resonancestabilization
(b) F   OH   NH 2  CH 3 (c) Electromeric effect (d) Electronegativity
(c) OH  >NH 2 >F - >CH 3 10. R-X+NaOH  ROH+NaX

(d) none of these The above reaction is classified as
(a) Nucleophilic substitution
5.
Θ Θ Θ Θ (b) Electrophilic substitution
C H 3 , N H 2 , O H, F
(c) Reduction
Among these nucleophiles, which of the following (d) Oxidation
orders is correct for their nucleophilicity in acetone ?
Θ Θ
(a) C H 3  N H 2  O H> F
Θ Θ 11. Isopropyl chloride undergoes hydrolysis by :
(a) SN1 mechanism
(b) F   OH   NH2  CH3 (b) SN2 mechanism
Θ Θ Θ Θ (c) SN1 and SN2 mechanism
(c) O H> N H 2  F  C H 3 (d) Neither SN1 nor SN2 mechanism
(d) none of these
12. Which one of the following is most reactive towards
Θ  Θ Θ nucleophilic substitution ?
6. F, Cl , Br, I
(a) H 2 C=CH-Cl (b) C6 H 5Cl
Among these nucleophiles, which of the following
orders is correct for their nucleophilicity order in (c) CH 3 -CH=CH-Cl (d) ClCH 2 -CH=CH 2
DMF ?
Θ  Θ Θ Θ Θ Θ Θ 13. Which of the following two reactions would be
(a) F> Cl >Br > I (b) I >Br > Cl >F faster?
Θ Θ Θ Θ Θ Θ
(c) I >Br >F>Cl (d) None of these (a) CH 3 -I+ O H  CH 3 -OH+ I
Θ Θ
(b) CH 3 -Cl+ OH  CH 3 -OH+ Cl
(c) both have similar rates
(d) rates cannot be predicted
Θ  19. Arrange the following halides in decreasing order of

14. H 3 C-S Na +CH 3 CH 2 -X  reactivity in SN1 reaction
The reaction is fastest when X is:
(a) – OH (b) – F 20. Rate of SN1 reaction is:
O O
(P) (Q) (R) (S)
(c) (d)
 O  C  C F3  O  C  CH 3 (a) S > Q > R > P (b) S > R > P > Q
(c) P > Q > R > S (d) S > R > Q > P
15. Among the following, the one which reacts most readily 21. The rate of SN1 reaction is fastest with:
with ethanol is
(a) p-nitrobenzyl bromide
CH2
(b) p-chlorobenzyl bromide
(c) p-methoxybenzyl bromide (a)
Br
(d) p-methylbenzyl bromide
16. In SN1 reaction, the racemization takes place. It is due to

(a) conversion of configuration CH
(b) retention of configuration (b)

Br
(c) inversion of configuration
(d) both (b) & (c)
17. Arrange the following halides in the decreasing order CH NO2
of SN1 reactivity (c)

(I) CH3CH2CH2Cl (II)CH2=CHCH(Cl)CH3 Br
(III) CH3CH2CH(Cl)CH3
(a) I > II > III (b) II > III > I
(c) II > I > III (d) III > II > I (d) CH2 Br
18. The increasing order of reactivity of the following

bromides in SN1 reaction is 22. Arrange the following in decreasing order of reactivity
towards SN1 reaction (Q 22 to 26)
(P) C H 3 -C l (Q)
(R) (S)
(a) S > R > Q > P (b) S > Q > R > P

(c) R > S > Q > P (d) P > Q > R > S
23. (P) (Q)
(R) (S)
(a) P > Q > R > S (b) Q > R > S > P

(a) III > I > II > IV (b) III > II > I > IV
(c) Q > P > R > S (d) Q > R > P > S
(c) II > III > I > IV (d) II > I > III > IV
26. (P) (Q)
24. (P) (Q)
(R) (S)
(a) P > Q > R > S (b) S > P > Q > R

(c) R > Q > P > S (d) R > P > Q > S
27.
(R) (S)
This reaction would follow which of the following

pathways predominantly?
(a) SN1/E1 (b) SN2/E2
(c) SN1/E2 (d)SN2/E1
(a) S > R > Q > P (b) R > S > Q > P
(c) Q > R > S > P (d) P > Q > R > S 28. Which of the following is the incorrect statement
regarding the following four alkyl halides?
(I) (II)
25. (P) (Q)

(III) (IV)
(a) I is most reactive for a SN2 reaction

(b) IV is most reactive for E1 reaction
(c) II is more reactive than III in SN1 reaction
(d) IV is most reactive for E2 reaction
29. Which of the following is the example of SN2 reaction
(a) CH 3 Br+OH -  CH 3 OH+Br -
(R) (S) (b)
Θ Θ
CH 3  CH(Br)-CH 3 +O H  CH 3CH(OH)-CH 3 + Br
(c) C H 3 C H 2 O H  -HO
2
 C H 2 =CH 2
(a) S > P > Q > R (b) R > Q > P > S
(c) Q > R > P > S (d) S > Q > P > R
(d)
CH3 CH3
(a) (b)
H3C CH3 + -
OH H3C CH3 + Br -
Br OH
(c) (d)
30. When the concentration of alkyl halide is tripled and
Θ
concentration of OH is reduced to half, the rate of
34. SN1 competes with E1 and SN2 competes with E2. This is
SN2 reaction increased by:
because
(a) 3 times (b) 1.5 times
(a) both SN1 and E1 have same rate-determining-step.
(c) 2 times (d) 6 times
Therefore E1 competes with SN1.
(b) a base is a nucleophile and a nucleophile is a base,
31. (P) (Q) Therefore, SN2 competes with E2.
(R) H 3 C-Br (S) H3 C=CH-Br (c) both a and b
(d) none of these
(a) S > P > Q > R (b) Q > S > R > P
(c) Q > R > P > S (d) R > Q > P > S -
35. C H 3 -C H 2 -C H 2 -C H 2 -B r+ C H 3 -C H 2 - O  D
MF

pathway predominantly?
(a) SN1 (b) SN2
(c) E1 (d) E2
32. (P) (Q)

36.
(a) SN1 (b) SN2
(c) E1 (d) E2
37. Arrange the following in decreasing order of SN2 reaction

(From question 37 to 39)
(P) CH3Cl (Q) CH3CH2Cl
(R) (S) Cl
(R) CH3CH2CH2Cl (S)

CH 3  CH  CH 3
(a) P > Q > S > R (b) P > Q > R > S
Arrange the following in the deceasing order of their (c) S > R > Q > P (d) S >Q> R > P
rate of Nucleophilic substitution.
(a) Q > R > P > S (b) R > Q > S > P
(c) P > Q > R > S (d) S > P > R > Q
38. (P) (Q)
33. Predict the major product of the reaction
(R) (S)
(a) P > Q > R > S (b) R > P > Q > S

(c) Q > R > P > S (d) R > Q > P > S
(a) (b)
39. (P) (Q)
(c) (d)
(R) (S)
(a) P > R > S > Q (b) P > Q > R > S 42.

(c) P > R > Q > S (d) R > Q > S > P
40. What alkyl halide would give the following alkene as the The major alkene obtained when this alkyl halide is
only product in an elimination reaction subjected to E1 reaction will be
(a)
(b)
(a) (b)
(c)
(c) (d) Both (a) and (b)
(d) All in equal proportions
41. Major product of the following reaction is:
43.
The major product obtained when this substrate is

subjected to E1 reaction will
(c)
(a) (b)
(d)
(c) (d) none of these
47. n-Propyl bromide on treatment with ethanolic

potassium hydroxide produces
44. Find the major product of the following reaction (a) Propane (b) Propene
(c) Propyne (d) Propanol
48. .
In the above reaction, maximum Saytzeff product will be

obtained where X is:
(a) I (b) Cl
(a) (b) (c) Br (d) F
49. In the above reaction Hoffman product is major when

base is:
(a) (b)
(c) (d)
Elimination (c) (d)

45. 2-bromopentane is heated with potassium ethoxide in
ethanol. The major product obtained is
(a) Pent-1-ene (b) cis pent-2-ene
(c) trans pent-2-ene (d) 2-ethoxypentane 50. Which of the following will undergo fastest elimina-
tion with alcoholic KOH?
46. The major product formed in the following reaction is
(a) (b)
(c) (d)
(a)
(b)
51. Find the major product of the reaction:
(d)
(a) (b)
54. Major product :
(c) (d) Both (a) and (b)
(a) (b)
(c) (d)
52. Product :
55. An halide C5H11Br on treatment with alc. KOH give 2-

pentene only. The halide will be:
(a)
(a) (b)
(b)
(c)
(c) (d) No reaction
(d)
53. Major product :
56.
(a) The major product obtained when this alkyl halide is

subjected to E2 – reaction will be
(a)
(b)
(c)
58.
(b)

subjected to E2 reaction will be
(a) (b)
(c)
(d) All three products in equal proportions

(c) (d) none of these
57.
The major product obtained when this alkyl halide is 59.


(a)
(a)
(b)
(b)
(c) (c)
(d) none of these
(d) all in equal proportion

(c) (d) all of these

60.
The major product obtained when this alkyl halide is

subjected to E2 reaction under the treatment of potassium
tert-butoxide will be 63.
The major product obtained when this alkyl halide is

(a)
(a)
(b)
(c) both (a) and (b)

(d) none of these
(b)
61.
Which of the following products will be major if this

substrate is subjected to E2 reaction?
(c)
(a)
(d) all three in equal proportions
Substitution vs Elimination
64.
(b)
(c) both in equal proportion

(d) not predictable +

62.
(a) SN1 (b) SN2
(c) E1 (d) E2
The products obtained when this substrate is subjected
to E2 reaction will be
65.
(a) (b)
(a) SN1 (b) SN2
(c) SN1/E1 (d) SN2/E2 70. Major product :
(a) (b)
66.
(c) (d)
(a) SN1 (b) SN2
(c) E1 (d) E2
67. If tert-butyl bromide and NaNH2 reacts, the product

formed is 71.
(a) tert-butylamine
(b) tert-butylammonium bromide
(c) a mixture of butyl amines
(d) iso butylenes Identify the major product Y:
68. Choose the correct major product of the reaction:
(a) (b)
(c) (d)
(a) (b)
(c) (d) 72. Major product :
69. The major product obtained on treatment of

CH3CH2CH(F)CH3 with CH3O–/ CH3OH is
(a) CH3CH2CH(OCH3) CH3
(b) (a) (b)
(c)
(d)
Preparation of alkyl halides
78. The following reaction is known as
(c) (d)
(a) Kharasch effect
(b) Darzen’s process
(c) Williamson’s synthesis
(d) Hunsdiecker synthesis reaction
73. What is the major product of the reaction sequence?
79. Which of the following reagents could be used to convert
cyclohexanol to chlorocyclohexane ?
(a) Cl2, light (b) SOCl2
(c) PBr3 (d) none of these
80. Decreasing order of reactivity of HX in the reaction

(a) (b) ROH + HX  RX + H2O
(a) HI > HBr > HCl > HF
(b) HBr > HCl > HI > HF
(c) HCl > HBr > HI > HF
(d) HF > HBr > HCl > HI
(c) (d)
81. Silver acetate + Br2 The main product of this
reaction is
Physical and General Properties (a) CH3 — Br (b) CH3COI
(c) CH3COOH (d) None of these
74. Which of the following is a primary halide
(a) Isopropyl iodide (b) Secondary butyl iodide 82. Preparation of alkyl halides in laboratory is least preferred by
(c) Tertiary butyl bromide (d) Neo hexyl chloride (a) Treatment of alcohols
(b) Addition of hydrogen halides to alkenes
(c) Halide exchange
75.
(d) Direct halogenation of alkanes
83. C3H8 + Cl2 C3H7Cl + HCl is an example of which of

the following types of reactions
(a) Substitution (b) Elimination
Among these compounds, which one has shortest C—Cl (c) Addition (d) Rearrangement
bond ?
(a) I (b) II
84. obtained by chlorination of n-
(c) III (d) IV
76. Correct order of B.P. for the alkyl halide is

butane will be :
(a) C2H5Cl > C2H5Br > C2H5I
(a) meso form (b) racemic mixture
(b) C2H5I > C2H5Br > C2H5Cl
(c) d-form (d) l-form
(c) C2H5I > C2H5Cl > C2H5Br
(d) C2H5Br > C2H5I > C2H5Cl
85. Which of the following organic compounds will give a mixture
of 1-chlorobutane and 2-chlorobutane on hydrochlorination
Isomerism in alkyl halide
(HCl)
77. The two optical isomers given below, namely (a)
CH3 CH3
H Cl H Cl
Cl H H Cl
C2H5 C2H5 (b)
(a) enantiomers (c)
(b) geometrical isomers (d)
(c) structural isomers
(d) diastereomers
86. What will be the product in the following reaction
(b) CH3 CH3
Br Br
Br Br
(c) CH3 CH3

(a) (b)
(d) BrCH2 CH2Br

(c) (d)
90. In the following reaction find the correct product :
87. Vinyl chloride reacts with HCl to form

(a) 1, 1- dichloro ethane
(b) 1, 2- dichloro ethane
(c) Tetrachloro ethylene
(d) Mixture of 1, 2 and 1, 1 – dichloro ethane
88. Analyse the following reaction and identify the nature of A

and B (a) (b)
HBr
B  HBr
peroxide
  A
(c) (d)
Reactions of Alkyl Halides : Elimination
91. When CH3CH2CHCl2 is treated with NaNH2 the product

formed is
(a) (b)
(c) (d)
Reactions of Alkyl Halides : Nucleophilic Substitution
92. Ethyl bromide reacts with silver nitrite to form

(a) Nitroethane
(b) Nitroethane and ethyl nitrite
(c) Ethyl nitrite
(d) Ethane
93. Ethylene dichloride and ethylidene chloride are isomeric

compounds. The false statement about these isomers is
CH2 CH2 + HBr
Peroxide
(A)
that they
89.
(a) React with alcoholic potash and give the same product
(b) Are position isomers
(A) is : (c) Contain the same percentage of chlorine
(d) Are both hydrolysed to the same product
(a) CH3 CH2Br
Br
94. Bottles containing C6H5I and C6H5CH2I lost their original
labels. They were labelled A and B for testing. A and B were
separately taken in test tubes and boiled with NaOH solution.
The end solution in each tube was made acidic with dilute
HNO3 and then some AgNO3 solution was added. Substance I II
B give a yellow precipitate. Which one of the following
statements is true for this experiment
(a) A was C6H5I
(b) A was C6H5CH2I
(c) B was C6H5I III IV
(d) Addition of HNO3 was unnecessary
95. What is the major product of the reaction ?
V
(a) I (b) II
(c) III (d) IV and V
(a)
98. Iodine from iodoethane can be substituted by cyanide
group in a number of ways. Which of the following is true
statement ?
(b) (a) With either KCN or AgCN, EtCN is formed as major
product.
(b) With either KCN or AgCN, EtNC is formed as major
product.
(c) (c) With AgCN, EtCN and with KCN, EtNC is formed.
(d) With AgCN, EtNC while with KCN, EtCN is formed as
major product.
(d) 99. What is the product of the following reaction ?
96. Which of the following reactions is a good way to prepare

methyl tert–butyl ether ?
(a) CH3O–Na+ + (CH3)3 CBr 

(b) (CH3)3CO– K+ + CH3I 


NaOH
(c) (CH3)3COH + CH3OH  (a)

(d) CH3MgBr + (CH3)3COCl 

97. The product B of the following sequence, would be

(b)
CH I
3  
2 Ag O
heat
 OH   B2 (c) Both (a) and (b)
(d) Neither (a) nor (b)
.100.
To make this ether which of the following reactions will be

most suitable ?
(a) 104.
(b)
P should be
(c)
(a)
(d) both (b) and (c)
Aq.KCN
101. CH3 – CH2 – CH2 – I 
EtOH
 P (b)
 Major 
P should be (c) both of these in equal proportions
(a) CH3 – CH2 – CH2 – CN (d) none of these
(b) CH3 – CH = CH2
(c) both (a) and (b) in equal proportions Reactions of Alkyl Halides : Metals
(d) none of these 105. An alkyl bromide (X) reacts with Na to form 4,
5-diethyloctane. Compound X is
(a) CH3(CH2)3 Br
102. CH 3  CH 2  NH 2  CH 3  I 
 P (b) CH3(CH2)5 Br
 Excess   Major  (c) CH3(CH2)3CH.Br.CH3
P should be (d) CH3(CH2)2CH.Br.CH2CH3
(a) CH3 – CH2 – NH – CH3
106. Which of the following cannot be obtained as the only
product in the Wurtz’s coupling reaction of halides with
(b) sodium metal in ether solution ?
(c)
(d) CH2 = CH2 (a) (b)
KCN
103. 
H O/ EtOH
 P
2  Major  (c) (d)
107. Na
CH3 – CH2 – CH2 – Br + CH3 – CH2 – Br  P
ether
(a) P is :
(a) P is mixture of three alkanes (n–hexane, n–butane and
n–pentane); none is formed in good yield
(b) P is a mixture of only two alkanes (n–hexane and n–
butane); both are formed in good yield.
(c) both (a) and (b) depending upon other conditions
(b) (d) none of these
(c) both (a) and (b) in equal proportions 108. Corey-House synthesis is a much more convenient method
(d) None of these for making alkanes for which of the following reasons ?
(a) Two different alkyl halides can be use. From one alkyl
halide, R2CuLi is prepared and then this is reacted
with another alkyl halide.
(b) The reagent R2CuLi can be prepared from 1°, 2° or 3°
alkyl halide as well as from halobenzenes
(c) both (a) and (b) (a)
(d) none of these
109. Which of the following combinations of reactants is better (b)

for making propane ?
(a) (CH 3 )2 CuLi  CH 3CH 2 Br 
 CH 3CH 2 CH3
(c)
(b) Et 2 CuLi  CH 3  Br 
 CH 3  CH 2  CH 3
(c) both of these
(d) none of these (d)
110. Which of the following combinations of reactants is better

3CH3MgBr
for making neopentane ? 114.  C2H5O2 CO 
H O
 A. A is :
3
(a) (C2H5O)2CHOH (b) (CH3)3COH
(a)
(c) (d) (CH3)2CHOH
115.
(b)
(c) both (a) and (b)

(d) none of these
Reactions of Alkyl Halides : Grignard Reagent

D is :
1. Mg / Ether
111. A (C6H13Br) 
2. CH OH  n–hexane. (a) (b)
3
4, 5–diethyloctane
Deduce the structure of ‘A’ :
(a) (b)
(c) (d)
(c) (d)
112. The addition of the Grignard reagent, CH3MgBr to

acetaldehyde is a nucleophilic addition to the carbonyl 116. 2CH3MgBr
  A. The
group. The nucleophile in this reaction is product A formed can
(a) CH3CHO (b) CH3 (a) give iodoform test
(b) further react with CH3MgBr/H3O to give t-butyl
(c) Br (d) CH3 alcohols
(c) be obtained by the ozonolysis of 2, 3 dimethyl–2–
3 H O butene
113. Ester A  C4H8 O2   CH3MgBr  C4H10 O
 2 parts   Alcohol B 
(d) all are correct
Alcohol B reacts fastest with Lucas reagent. Hence A and 117. Alkyl halides react with Mg in dry ether to form
B are : (a) Magnesium halide (b) Grignard’s reagent
(c) Alkene (d) Alkyne
Preparation of Aryl Halides
118. When phenyl magnesium bromide reacts with t-butanol,
the product would be 123.
(a) Benzene (b) Phenol
(c) t-butyl benzene (d) t-butyl phenyl ether
119. Which of the following compounds is not suitable solvent

for Grignard reagent ?
In the above process product A is
(a) Fluorobenzene (b) Benzene
(c) 1, 4-difluorobenzene (d) 1, 3-difluorobenzene
(a) (b)
124. C6H5Cl prepared by aniline with
(a) HCl
(b) Cu2Cl2
(c) (d) (c) Cl2 in presence of anhydrous AlCl3
(d) HNO2 and then heated with Cu2Cl2
Reactions of Aryl Halides

125. The following transformation proceeds through
PhMgBr  excess 
120.  (X); Product (X) is :
H O 3
(a) (b)
(c) (d)
(a) benzyne intermediate
(b) oxirane
(c) electrophilic - addition
121. In the given reaction (d) nucleophilic aromatic substitution
3 H CMgBr

 Product
H / H2 O
Find the product of reaction :
(a) (b)
126.
(c) (d)
This reaction follows
(a) S 1 pathway
N
1. CH3MgBr
122. 
2. NH4Cl
P (b) SN 2 pathway
(c) addition-elimination pathway
(d) none of these
P should be
(a) 127. In addition-elimination pathway of nucleophilic aromatic
substitutions, which of the following compounds is most
reactive ?
(b)
(c) both (a) and (b) (a) (b)

(d) none of these
131. Which of the following has the fastest rate of the reaction
with NaOC2H5 ?
(a) p–fluoronitrobenzene (b) p–bromonitrobenzene
(c) p–chloronitrobenzene (d) p–iodonitrobenzene
(c) (d)
132. Which of the following reaction is called Wurtz-Fittig
reaction ?
(a)
128. In addition-elimination pathway of nucleophilic aromatic
substitutions, which of the following compounds is most
reactive ?
(a) (b)
(b)
(c)
(c) (d)
129. In addition elimination pathway of nucleophilic aromatic (d) both (b) and (c)
substitutions, a–NO2 groups is
(a) o, p–directing and activating Polyhalogen Compounds
(b) o, p–directing and deactivating
(c) m–directing and activating 133. Iodoform can be used as
(d) m–directing and deactivating (a) Anaesthetic (b) Antiseptic
(c) Analgesic (d) Antifebrin
134. Which of the following is an anaesthetic

1. HO /  (a) C 2 H 4 (b) CHCl 3
130. 
  P
2. H  Major 
(c) CH 3 Cl (d) C 2 H 5 OH
135. A sample of chloroform being used as anaesthetic is tested

by
Based on the above reaction, the major product would be (a) Fehling solution
(b) Ammonical Cu2Cl2
(c) AgNO3 solution
(d) AgNO3 solution after boiling with alcoholic KOH
solution
(a) (b) 136. Chloroform for anesthetic purposes is tested for its purity
with the reagent
(a) Silver nitrate
(b) Lead nitrate
(c) both in equal proportions (d) none of these (c) Ammoniacal Cu2Cl2
(d) Lead nitrate
137. Chloropicrin is obtained by the reaction of
(a) Chlorine on picric acid (b) Nitric acid on chloroform
(c) Steam on carbon tetrachloride
(d) Nitric acid on chlorobenzene
(a) (b)
138. An important insecticide is obtained by the action of
chloral on chlorobenzene. It is
(a) BHC (b) Gammexene
(c) DDT (d) Lindane
139. DDT is prepared by reacting chlorobenzene with

(a) CCl4 (b) CCl3 –– CHO
(c) CHCl3 (d) Ethane
(c) (d)
140. Statement “Ozone in atmosphere is decreased by chloro-
fluoro-carbon (Cl 2 F2 C )
(a) Is true
(b) Is false
146. Consider the following sequence of reaction
(c) Only in presence of CO 2
(d) Only in absence of CO2 3CH CH MgBr
2 3 PBr
  A  B
HO 3
141. The formula of freon-12 is :
The product B is :
(a) CClF3 (b) CH2Cl2
(c) CCl2F2 (d) CH2F2
142. Haloforms are trihalogen derivatives of

(a) Ethane (b) Methane (a) (b)
(c) Propane (d) Benzene
143. CCl4 cannot give precipitate with AgNO3 due to

(a) Formation of complex with AgNO3 (c) (d)
(b) Evolution of Cl2 gas
(c) Chloride ion is not formed
(d) AgNO3 does not give silver ion 147. What is the major product of the reaction sequence ?
Conversions/Roadmaps
144. In the following sequence of reactions
(a) (b)
The product (C) is
(a) Propan – 2 – ol (b) Propan – l – ol
(c) Propyne (d) Propene
(c) (d)
148. Consider the following reactions,

NBS KCN
145. 
(2Mole)
 A  B; Product B
1Mole 
Br / FeBr
2 3  P 
2 H ,Ni
 Q
is :
NaNO 2  HCl CuCl
     R  S
0 5 C
The end product ‘S’ is :
158. How many of the following can give ppt. of
AgCl with both aq. AgNO3 and alc. AgNO3.
(a) (b)
159. How many of the following will give positive iodoform

test?
Numerics
149. In CH 3CH 2Br, % of Br is
150. How many structural isomers of C3H6ClBr are possible and

how many of them are optically active respectively ? 160. How many of the following reactions are
correct?
151. 2, 6 - Dimethylheptane on monochlorination
produces……. derivatives (i) CH3CH = CH2 + HCl  CH3CHClCH3
(ii) CH3CH = CH2 + HBr  CH3CH2CH2Br
152. Number of stereoisomers of the compound, 2-chloro-4- Peroxide
methylhex-2-ene is (iii) CH3CH = CH2 + HBr 
CH3CH2CH2Br
153. The number of enantiomers of the compound
Peroxide
(iv) CH3CH = CH2 + HI  CH3CHICH3
CH3CHBrCHBrCOOH is
154. How many isomers are possible with trisubstituted

benzene with all the three groups same ? 161. How many of the statement(s) is/are correct about
photochemical chlorination of the above compound?
155. Number of –bonds present in B.H.C. (Benzene
hexachloride) are (i) The major product will be chiral carbon atom
having optically inactive compound.
156. The fittig reaction involves x number of aryl halide (ii) The intermediate free radical of the major product
molecules x is is resonance stabilized.
157. How many of the following statements are correct? (iii) The intermediate free radical is tertiary.
(i) The C–Cl bond in chlorobenzene is shorter (iv) The intermediate free radical is planer, and
than in chloroethane. stabilized by only hyperconjugation.
(ii) The C–Cl bond in chlorobenzene has some
double bond character.
(iii) It is difficult to replace chlorine from
chlorobenzene than from benzoyl chloride.
(iv) Chlorobenzene on further chlorination gives
m-dichlorobenzene.
162. How many of the following reaction product

formation takes place by Hoffmann’s rule?

1. Elimination of bromine from 2-bromobutane results in
the formation of (2005)
(a) predominantly 2-butyne (a) (b)
(b) predominantly 1-butene
(c) predominantly 2-butene
(d) equimolar mixture of 1 and 2-butene
(c) (d)
2. CH 3 Br+Nu -  CH 3 -Nu+Br -
The decreasing order of the rate of the above reaction
with nucleophile (Nu-) A and D is: 6. The reaction of propene with HOCl
   
Nu   A PhO ,  B AcO ,  C  HO ,  D CH3O (2006) (Cl2 + H2O) proceeds through the intermediate : (2016)
(a) CH3  CH  CH2  Cl
3. The organic chloro compound, which shows complete
(b) CH3  CH(OH)  CH2
stereochemical inversion during an SN2 reaction is
(c) CH3  CHCl  CH2
(2008)
(a) (C2H5)2CHCl (b) (CH3)3CCl (d) CH3  CH  CH2  OH
(c) (CH3)2CHCl (d) CH3Cl
7. The gas evolved on heating CH3MgBr in methanol is :
Online 2016 SET (1)
4. 2-chloro-2-methylpentane on reaction with sodium (a) HBr (b) Methane
methoxide in methanol yields: (2016) (c) Ethane (d) Propane
8. Bromination of cyclohexene under conditions given below

yields : Online 2016 SET (2)
(a)
(b)
(c)
(a) (b)
(a) (a) and (c) (b) (c) only

(c) (a) and (b) (d) All of these
5. The product of the reaction given below is :

(2016) (c) (d)
9. Which one of the following reagents is not suitable for

the elimination reaction ? Online 2016 SET (2)
(a) NaOH /H2O (b) NaOEt /EtOH

(c) NaOH /H2O  EtOH 14. The increasing order of reactivity of the following halides
(d) NaI for the SN1 reaction is (2017)
(I) CH3CH(Cl)CH2CH3 (II) CH3CH2CH2Cl
10. Fluorination of an aromatic ring is easily accomplished by
(III) p-H3CO–C6H4 – CH2Cl
treating a diazonium salt with HBF4 . Which of the
following conditions is correct about this reaction ? (a) (III) < (II) < (I) (b) (II) < (I) < (III)
Online 2016 SET (2) (c) (I) < (III) < (II) (d) (II) < (III) < (I)
(a) Only heat (b) NaNO2 / Cu
15. The major product of the following reaction is : (2018)
(c) Cu2O / H2O (d) NaF/Cu
11. Which of the following compounds will not undergo

Friedel Craft’s reaction with benzene ?
Online 2017 SET (1)
(a) (b)
12. The major product of the following reaction is :
(c) (d)
Online 2017 SET (1)

(a) CH2 = CHCH2CH = CHCH3
16. Which of the following will most readily given the
(b) CH2 = CHCH = CHCH2CH3 dehydrohalogenation product. Online 2018 SET (1)
(c) CH3CH = C = CHCH2CH3
(d) CH3CH = CH – CH = CHCH3
(a) (b)
13. The major product of the following reaction is
Online 2017 SET (2)
(c) (d)
17. The total number of optically active compounds formed

in the following reaction is : Online 2018 SET (2)
(1) Two (2) Four

(3) Six (4) Zero
Online 2019 SET (2)
(a) (b)
(c) (d)
(2019-01-09/Shift-1)
(A)
(B)
(C)
(2019-04-10/Shift-1)
20. Heating of 2-chloro-1-phenylbutane with EtOK/EtOH

gives X as the major product. Reaction of X with
Hg(OAc)2 / H 2 O followed by NaBH 4 gives Y as the (D)
major product. Y is: (2019-04-09/Shift-2)
22. The major product of the following reaction is : 24. The major product obtained from E2 – elimination of 3-
(2019-01-12/Shift-2) bromo-2-fluoropentane is : (2020-09-02/Shift-2)
25. Consider the reaction sequence given below :
Which of the following statements is true :

(2020-09-02/Shift-2)
(a) Changing the concentration of base will have no
effect on reaction (1).
(b) Doubling the concentration of base will double the
23. Which of the following compounds will show retention
rate of both the reactions.
in configuration on nucleophilic substitution by OH–
(c) Changing the base from OH– to –OR will have no
ion ? (2020-09-02/Shift-1)
(d) Changing the concentration of base will have no
(a) (b)
26. The mechanism of SN1 reaction is given as :
(c) (d)
A student writes general characteristics based on the

given mechanism as :
(A) The reaction is favoured by weak nucleophiles.
30. Consider the following reactions:
(B) R would be easily formed if the substituents
are bulky.
(C) The reaction is accompanied by racemization.
(D) The reaction is favoured by non-polar solvents.
Which observations are correct ?
(2020-09-03/Shift-1)
(a) (A) and (B) (b) (A), (B) and (C)
(c) (A) and (C) (d) (B) and (D)
27. The decreasing order of reactivity of the following

compounds towards nucleophilic substitution (SN2) is :
Which of these reaction(s) will not produce Saytzeff

product? (2020-01-7/Shift-1)
(a) b and d (b) d only

(c) a, c and d (d) c only
31. For the following reactions,

(2020-09-03/Shift-2)
(a) (III) > (II) > (IV) > (I) (b) (IV) > (II) > (III) > (I)
(c) (II) > (III) > (IV) > (I) (d) (II) > (III) > (I) > (IV)
28. Among the following compounds, which one has the

shortest C – Cl bond? (2020-09-04/Shift-2)
(a) (b) H3C  Cl
ks and ke, are, respectively, the rate constants for

ks
substitution and elimination, and 
ke , the
(c) (d) correct option is ______. (2020-01-07/Shift-2)
29. The increasing order of the boiling points of the major (a)  A   B and ke  A   ke  B 
products A, B and C of the following reaction will be:
(b) B   A and ke  A   ke  B 
(1) (c)  A  B and ke  B   k e  A 
(d)  B   A and ke  B   ke  A
(2)
(3)
(2020-09-06/Shift-2)
(a) 1 < 2 < 3 (b) 3 < 1 < 2
(c) 1 < 3 < 2 (d) 2 <3< 1
32. The decreasing order of reactivity towards

dehydrohalogenation (E1) reaction of the following
compounds is:
(2020-01-08/Shift-1)
(a) B > A > D > C (b) B >D>C>A
(c) B >D>A> C (d) D>B>C>A
33. Which of the following reactions will not produce a

racemic product? (2020-01-09/Shift-2)

Single choice questions and elimination dominates.
1. Which of the following statements is correct about 5. Which of the following bases would give the best yield
retention/invertion of configuration during the course for the substitution product when reacted with 2-
of a reaction? chloropropane ?
– –
(a) Configuration is retained if reagent attacks from the (a) CH3COO (b) OH
same side of leaving group. – –
(c) NH2 (d) CH3CH2O
(b) Configuration is inverted if reagent attacks from the 6. Debromination of mesodibromobutane will give the
backside of leaving group.
product as :
(c) No change in configuration is possible if no bonds
(a) n-butane (b) 2-butyne
of the asymmetric centre are cleaved during the
course of reaction. (c) cis-2-butene (d) Trans-2-butene
(d) all of these 7. What is the product of the reaction of the following
compound with alcoholic potassium hydroxide ?
2. The compound most reactive towards SN1 reaction is Br
(a) Me3C––CH2Cl (b) MeOCH2Cl CH3
(a) 1-methylcyclohexane only

(c) PhCH2CH2Cl (d) (b) 1-Methylcyclohexene only
(c) 3-methylcyclohexene (major product),
3. C6H6Cl6, on treatment with alcoholic KOH, yields 1-methylcyclohexene (minor product)
(d) 3-methylcyclohexene only
(a) C6H6 (b) C6H3Cl3
(c) (C6H6) OH (d) C6H6Cl4 8. Which of the following undergoes E2 elimination in the
presence of a strong base to yield one product ?
(a) 3-bromo-2-methylpentane
4. What is true about the following reaction? (b) 1-bromo-1-methylcyclohexane
(c) 1-bromo-3, 3-dimethylbutane
(d) 3-bromo-3-methylpentane
9. What is the major product of the following reaction?
(a) Only substitution product is formed.

(b) Only elimination product is formed.
(a) (b)
(c) Both substitution and elimination products are formed
and substitution dominates.
(d) Both substitution and elimination products are formed
(c) (d)
12.
10. In the following reaction, the predominant substitution

and elimination products are
pathway predominantly ?
(a) SN1 (b) SN2
(c) E1 (d) E2
13. CH3CD2CHBrCH2CD3 on reaction with alc. KOH gives
(a) CH3CD2CH CHCD3

(a)
(b) CH3CD C CHCD
(c) CD3CD2CH CHCH3
(d) CH3CD CHCH2CD3
(b)
14. Choose the answer that incorrectly shows the major
product of the reaction.
(a)
(c)
(b)
(d)
11. Choose the major product of the reaction. (c)
(d)
(a) (b)
15. Among the following the most reactive towards

(c) (d)
alcoholic KOH is
(a) CH2 = CHBr (b) CH3COCH2CH2Br
(c) CH3CH2Br (d) CH3CH2CH2Br

16. Which of the following represents the correct order of 21. When but –3-en -2- ol reacts with aq. HBr, the product
densities ? formed is
(a) CCl4 > CHCl3 > CH2Cl2 > CH3Cl > H2O (a) 3 - bromobut - 1- ene
(b) CCl4 > CHCl3 > CH2Cl2 > H2O > CH3Cl (b) 1 - bromobut - 2- ene
(c) H2O > CH3Cl > CH2Cl2 > CHCl3 > CCl4 (c) A mixture of both a and b
(d) CCl4 > CHCl3 > H2O > CH2Cl2 > CH3Cl (d) 2 - bromobut - 2 - ene
Cl  H O
2 2  Major product :
17. Which of the following are arranged in the decreasing 22. 
order of dipole moment ?
(a) CH3Cl, CH3Br, CH3F
(b) CH3Cl, CH3F, CH3Br
(a)
(c) CH3Br, CH3Cl, CH3F
(d) CH3Br, CH3F, CH3Cl
(b)
18. The conversion of 2, 3-dibromobutane to 2-butene with
Zn and alcohol is
(a) -Elimination
(b) Redox reaction (c)
(c) Both -elimination and redox reaction
(d) -Elimination
(d)
19. The number of possible enantiomeric pairs that can be
produced during monochlorination of 2-methyl butane
is :
(a) 3 (b) 4 Cl
2 
23. 
(c) 2 (d) 1 CCl4
Stereochemistry of the product are :

Br2  H2O
20. 
 Product : (a) diastereomers (b) meso
(c) racemic mixture (d) pure enantiomers
24. An organic compound C3H7Br(A) with alcoholic KOH

forms C3H6 which decolorises Br2 in CCl4 but does not
(a) (b)
gives a white precipitate with ammonical AgNO3. (A) on
reaction with KCN forms a product which on reduction
with Na/C2H5OH produces n-butyl amine. Hence, the
compound (A) is
(a) n-propyl bromide
(b) isopropyl bromide
(c) (d) (c) 1, 1–dibromopropane
(d) none of these
25. A compound ‘A’ has molecular formula C5H9Cl. It does not 28. Consider the following reaction
react with bromine in CCl4. On treatment with strong base, it
produces single compound ‘B’ (C5H8) and reacts with Br2
(aq). Ozonolysis of ‘B’ produces a compound C5H8O2.
Which of the following is structure of A ?
X and Y are respectively

(a) (b)
(a) both nitroethane
(b) both ethyl nitrite (EtONO
(c) X = EtONO and Y = EtNO2
(d) X = EtNO2 and Y = EtONO
(c) (d) 29. Alkyl halides react with dialkyl copper reagents to give
(a) Alkenes
(b) Alkyl copper halides
26. Choose the correct statement(s) about the following (c) Alkanes
reaction. (d) Alkenyl halides
3CH OH


30. What would be the product formed when 1-Bromo-3-
I. The major product of the reaction is butyl-methyl chloro cyclobutane reacts with two equivalents of metallic
ether. sodium in ether
II. The major product of the reaction is 1-butene. Cl
III. The major product is formed by SN 2 reaction (a) (b)
mechanism. Br
IV. The major product is followed by E2 reaction
mechanism. (c) (d)
(a) I + III (b) II + IV
(c) I + IV (d) IV 31. Which of the following alkyl halides is not suitable for
Corey-House synthesis of alkanes ?
27. The major substitution product of the following reaction
is (a) CH3I (b)
(c) (d)
KSH


32.
(a) (b)
(a) (CH3)2CHCOCH3
(b)
(c) (d)
(c) (CH3)2CHCOCH(CH3)2
(d) Cl COOH
(a) (b)
 i  CH3MgBr  2 mol  conc. H2SO4
33. CH3CN   A  
 ii  H3O
B, A and B are COOH COOH
COOH COOH
(c) (d)
(a)
Br
(b) CH3CH 2OH,CH 2 =CH 2
(c)  CH3 2 CHOH,CH3CH=CH2 PhMgBr  excess 
37. 
  Product :
H3 O
(d)  C H 3 3 C -O H ,  C H 3 2 C =C H 2
34. End product of the following sequence of reaction is

(a) (b)
NBS Mg /ether 3 CH CN
  
 
 
H3O
(c) (d)
38.
(a) (b)
(a) (b)
(c) (d)
(c) (d)
35. Which of these do not form Grignard reagent
(a) CH3F (b) CH3Cl
(c) CH3Br (d) CH3I 39. Replacement of Cl of chlorobenzene to give phenol
requires drastic conditions but chlorine of 2, 4-
dinitrochlorobenzene is readily replaced because
36. Identify (Z) in the following reaction (a) NO2 make ring electron rich at ortho and para
Cl (b) NO2 withdraws e– from meta position
(c) denotes e– at meta position
+ Mg THF CO2 H (d) NO2 withdraws e– from ortho/para positions
(X) (Y) (Z)
1 mole
Br
40. Which chloroderivative of nitrobenzenes among the 43. Which of the following is (are) true regarding
following would undergo hydrolysis, most readily with intermediate in the addition-elimination mechanism of
aqueous NaOH ? the reaction below ?
O2N NO2 NO2
(a) Cl (b) O2N Cl NaOCH

3  intermediate 
 
O2N NO2
O2N O2N
I. The intermediate is aromatic.
(c) O2N Cl (d) Cl II. The intermediate is resonance stabilized anion.
III. Electron withdrawing group on the benzene ring
stabilize the intermediate
O2N O2N Cl (a) I only (b) II only
(c) I and III (d) II and III
41. Propyl benzene reacts with bromine in presence of light 44. Which is the major product of the reaction of 2, 4–
or heat to give dinitrochlorobenzene with methylamine ?
(a)
(a) (b)
(b)
(c) (c) (d)
45. Arrange the following in increasing order of reactivity in

aromatic nucleophilic substitution reaction.
(d)
42. The reaction of 4-bromobenzyl chloride with NaCN in

ethanol leads to (I) (II)
(a) 4-bromo-2-cyanobenzyl chloride
(b) 4-cyanobenzyl cyanide
(c) 4-cyanobenzyl chloride
(d) 4-bromobenzyl cyanide
(III) (IV)
(a) I < IV < III < II (b) IV < III < I < II
(c) I < IV < II < III (d) IV < I < II < III
(a) (b)
46. The use of the product obtained as a result of reaction
between acetone and chloroform is
(a) Hypnotic (b) Antiseptic
(c) Germicidal (d) Anaesthetic (c) (d)
47. Which plastic is obtained from CHCl 3 as follows

HF 800 o C Polymerisa tion 52. SOCl2   Mg, 
CHCl 3 
 X   Y     
 Plastic 
Pyridine Et O

SbF 3 2
(a) Bakelite (b) Teflon Product of reaction is :

(c) Polythene (d) Perspex
(a)
48. CCl4 is a well known fire extinguisher. However after using
it to extinguish fire, the room should be well ventilated.
This is because :
(a) it is inflammable at higher temperatures (b)
(b) it is toxic
(c) it produces phosgene by reaction with water vapours
at higher temperatures
(d) it is corrosive (c)
49. When CHCl3 is boiled with NaOH, It gives

(a) Formic acid (b) Trihydroxy methane
(c) Acetylene (d) Sodium formate
(d)
50. Which of the following is missing reagent in the following

reaction sequence ?
2 Br / hv Mg
53. A  B 
Et O  2
(a) (CH3)3CO–K+ , Br2 (b) (CH3)3CO–K+, HBr Conc.H SO

2 4 3 2 O / Zn  H O
D 

E 
(c) (CH3)3CO–K+, Br2/H2O
(d) H2SO4, Br2 Find out the structure of ‘A’ :
(a) (b)
51.
Which of the following is the structure of A ? (c) (d)

54. Which of the following sequence of reagent is best suited
Cl CH3 H Cl
for the reaction shown below ?
58.
H3 C H H3C H
(I) (II)
Choose the correct statements about molecule I and II.

(a) (i) CH3MgBr, H3O+ (ii) H+/ (iii) HBr/H2O2
(a) I and II are diastereomers.
(b) (i) CH3MgBr, H3O+ (ii) H+/ (iii) HBr
(b) I and II are constitutional isomers.
(c) (i) CH3MgBr, H3O+ (ii) HBr
(d) (i) HBr/ROOR (ii) CH3MgBr, H3O+ (c) Reactivity for SN1 path : II > I.
(d) Reactivity to SN2 path : II > I.
55. The major product of the following reaction is 59. Which of the following phrases are correctly linked
with SN1 reaction ?
Na / Ether 2 Br ,hv
Alc.KOH
     (a) Rate is affected by polarity of solvent
(b) Rearrangement is possible
(a) (b) (c) The strength of the nucleophile is important in

determining rate
(d) The reactivity series is tertiary > secondary > primary
60. Consider the following statements and pick up the
(c) (d) correct statements:
(a) will react more

Multiple choice questions
56. Which of the following statements correctly readily than for SN1
describes(s) E1 reactions of alkyl halides (RX) ?
(a) Rearrangements are sometimes seen
reaction
(b) Rate = k [base] [RX]
(c) Rate = k [RX]
(d) The reactions occur in two or more distinct steps
(b) will react more readily than for

57. Which of the following can give E1 cb reaction?
(a) (b) SN1 reaction
(c) (d)
(c) will react more readily than for
SN1 reaction
(d) SN1 reaction occurs in polar protic solvent
61. Which of the following compounds will give SN1 (a)
reaction?
(a)
(b)
(b)
(c)
(c)
(d)
62. Which of the following are SN2 reactions ? (d)
(a)
(b)
alc. KOH  E2
65. Reactant  HCl

(c)
Which of the following molecule(s) is/are suitable

(d)
reactant ?
Ph Ph
63. Which of the following compounds will not give SN2
reaction? H3 C H H3 C Cl
(a) (b)
H Cl H H
CH2Ph CH2Ph
(a) (b)
Ph Ph
H CH3 H CH3
(c) (d)
(c) (d) Cl H H Cl
CH2Ph CH2Ph
64. In the given reaction the products formed can be
66.
Here the product can be ?

69.
(a) (b)
Mark out the possible product.
(a)
(c) (d) (b)
(c)
67. In which product formation takes place according to
Hofmann’s rule?
(d)
(a)
(b)
70. Which of the following pair is correctly matched with
major products ?
Reaction Product
(c) (a) RX + AgCN RNC
(b) RX + KCN RCN
(d)
(c) RX + KNO2
(d) RX + AgNO2
68. Which of the following reactions involve free radical as
intermediate ?
71. Which of the following alkanes cannot be synthesized
by the Wurtz reaction in good yield ?
Cl  FeCl
2 3
(a) 
(a) (b)
(b) Br / hv
2 (c) (d)

(c) NBS

72. In the given reaction,
(d) 2Br /CCl

4
H / H O
2  3° Alcohol
 (X) + R MgX (excess) 
(X) may be :
(a) Cl will be substituted because it is a better leaving
group.
(a) (b) (b) F will be substituted because nitro from para position
facilitate this.
(c) after substitution of one halogen, substitution of the
second halogen would become further more difficult.
(c) (d)
(d) first chlorine and then fluorine would be substituted
subsequently.
73. Which of the following combinations give
77. Consider the following chlorofluorobenzene undergoing
nucleophilic aromatic (SNAr) substitution reaction with
KCN
KCN

Heat 
(a) PhMgBr and
The correct statement(s) is/are :

(b) CH3MgBr and (a) substitution by a chlorine at ‘1’ will promote
substitution of fluorine by CN–.
(b) substitution by a nitro group at ‘2’ will promote
substitution of fluorine by CN–.
(c) CH3MgBr and
(c) substitution by a cyano group at ‘1’ will promote
substitution of chloro by CN–.
(d) substitution by a methoxy group at either ‘1’ or ‘2’
(d) CH3CH2MgBr and will discourage the reaction as a whole.
ether
R – X + Mg  R –MgX  CH3OH
74.  n-butane
What can be R in the above reaction sequence ?
(a) n–propyl (b) n–butyl 78.
(c) sec–butyl (d) Isopropyl
75. Which of the following compounds give alcohol on

reaction with RMgX ?
(a) O2 (b)
(a) Product C is
(c) R – O – H (d)
76. Consider the following SNAr treaction
(b) Product D is
Heat
+ CH3 ONa  
The correct statement is (are)

(c) Product E is
(c) (d)
(d) Product F is
81. Which one of the following will give racemised product

in C2H5OH?
79. p–nitrofluorobenzene is more reactive than its meta isomer

in SNAr reaction with CH3ONa because
(a) nitro group from para position is in resonance with (a) (b)
lone pair of fluorine.
(b) nitro group from para position stabilizes the benzene
carbanion intermediate.
(c) nitro group from para position exert greater
electronwithdrawing inductive effect than from meta
position
(d) nitro group from para position gives less steric (c) (d)
hindrance than from meta position to the attack of
nucleophile.
Comprehension based questions 82. Which one of the following will give SN2 reaction?
Comprehension
Aliphatic nucleophilic substitution is mainly of two type
S N 1 and S N2. S N2 reaction proceed with strong (a) (b)
nucleophile in polar aprotic solvent 3º halides do not
give SN2 reaction. Inverted products are obtained in
this reaction and mechanism of reaction occurs through
the formation of transition state.
S N1 reaction proceed through the formation of
carbocation in polar aprotic solvent. Solvent itself acts (c) (d)
as nucleophile in this reaction. Racemization takes place
in SN1 reaction.
80. Which of the following compounds will give SN1 83. Transition state with maximum double-bond character
reaction? will be formed when methoxide reacts with
(a) 2-iodohexane to form 2-hexene
(b) 2-iodohexane to form 1-hexene
(a) (b) (c) 2-fluorohexane to form 2-hexene
(d) 2-fluorohexane to form 1-hexene
84. Transition state with least double-bond character will
be formed when methoxide reacts with
(b)
(a) 2-iodohexane to form 2-hexene
(b) 2-iodohexane to form 1-hexene
(c) 2-fluorohexane to form 2-hexene
(c)
(d) 2-fluorohexane to form 1-hexene
(d) None of these

85. Isopropyl bromide on heating with a concentrated
solution of alcoholic (ethanolic) KOH predominantly 89. Which of the following will not produce Hofmann’s
gives alkene as major product on reaction with strong base?
(a) Propene (b) Propan-2-ol
(c) Propan-1-ol (d) Isopropyl ethyl ether
(a) (b)
86. 2-Bromopropane is separately heated with aq.
CH3CO2Na or with CH3CH2ONa/CH3CH2OH, the major
product obtained in each case respectively are
(a) Propene, isopropyl ethyl ether
(b) Isopropyl acetate, propene
(c) (d)
(c) Isopropyl acetate, isopropyl ethyl ether
(d) Propene in both the cases
Comprehension
87. 2-Bromopentane is heated with potassium ethoxide in The following E2 is carried out with different halogen
ethanol. The major product obtained is substituent
(a) 2-Ethoxypentane (b) Pentene-1
(c) cis-Pentene-2 (d) trans-Pentene-2
Comprehension
Type of elimination reaction in which least substituted
alkene is major product known as Hofmann’s elimiation.
Such reaction occur in following conditions : Four different reaction flasks, containing equimolar
concentration of sodium methoxide in methanol
(X) when base is bulky
solvent, were charged with equal moles of one of the
(Y) when leaving group is very poor such as fluoride, four halide in each flask and allowed to react under
ammonium group etc. identical experimental conditions as shown above.
After a week, the percentage yield of two alkenes in
(Z) when alkyl halide contain one or more double bonds. each flask were measured and listed below
88. What is the major product of the following reaction? Flask No. Leaving Conj. % Yield % Yield
group Acid pKa of 2-hexene of 1-hexene
–
1. I –10 81 19
–
2. Br –9 72 28
–
3. Cl –7 67 33
–
4. F 3.2 30 70
(a) From the percentage yield of two products observed
with different leaving group, it was concluded that
both,ease of leaving group and steric hindrance to the
–
approach of base CH3O to –H control the orientation
of elimination reaction.
90. Based on the above observation, which flask will have
the largest amount of 1-hexene?
(a) 1 (b) 2
93.
1 xRMgX
 3° alcohol. Value of
(c) 3 (d) 4  2 NH4Cl
x is :
(a) 2 (b) 3
(c) 4 (d) 5
91.
94.
(a)
1 x PhMgBr


 2 H ,
(b)
Value of x is :
(a) 2 (b) 3
(c) 4 (d) 5
(c)
Comprehension
Addition of X2 on alkene is electrophilic addition reaction.
Reaction proceed through the formation of 3-membered
cyclic halonium ion. Nucleophile X– attacks from backside
(d) of cyclic halonium ion hence total reaction is anti addition
reaction. If this reaction proceed in polar solvent then
solvent itself acts as nucleophile.
Comprehension
Grignard reagent is usually prepared by
Et O
2  RMgX
R  X  Mg 
Grignard reagent Mechanism :
Et O
2  ArMgX
Ar  X  Mg 
Grignard reagent
Grignard reagent acts as a strong base. Grignard reagent
carry out nucleophilic attact k in absence of acidic
hydrogen. Grignard reagent form complex with its ether
solvent. Complex formation with molecule of ether is an
important factor in the formation and stability of Grignard
reagent.
92. What is the correct order of reactivity of halides with

magnesium ?
(a) R – Cl > R – Br > R – I
(b) R – Br > R – Cl > R – I
(c) R – I > R – Br > R – Cl
(d) R – I = R – Br = R – Cl
95. Which of the following statements is incorrect ? Assertion–reason type questions
(a) Symmertical trans alkene gives 2 products on reaction (a) Both Assertion and Reason are true and Reason is the
with Br2/CCl4 correct explanation of ‘Assertion’
(b) Symmetrical cis alkene gives 2 products on reaction
wit Br2/CCl4 (b) Both Assertion and Reason are true and Reason is not
(c) Trans alkenes give erythro product
(d) Cis alkenes gives threo product (c) Assertion is true but Reason is false
(d) Assertion is false but Reason is true
98. (A) Assertion : Benzyl bromide when kept in acetone -

Cl2 1Mole 
96. (C)   water, produces benzyl alcohol.
CCl4
Reason : The reaction follows SN2 mechanism.
(a) A (b) B
(c) C (d) D
99. (A) Assertion : Rate of reaction is dependent only on the

(a) (b) concentration of nucleophile in SN1 reactions.
Reason : Polar solvent favours SN1 reaction.
(a) A (b) B
(c) C (d) D
(c) (d) 100. (A) Assertion : In SN1 mechanism, the product with
inversion of configuration is obtained in higher amount
compared to the product with the retention of
configuration.
Reason : Front side attack of nucleophile is hindered due
Cl2 ,CH3OH to the presence of leaving group in the vicinity.
97. (C) 
 Major product :
(a) A (b) B
(c) C (d) D
o o
101. (A) Assertion : 1 allylic halides are more reactive than 1
(a) (b)
RX in SN1 reaction.
Reason : Allylic carbocation intermediate is stabilised
by resonance.
(a) A (b) B
(c) (d) (c) C (d) D
+ 2+
102. Assertion : Heavy metal ions Ag or Pb decrease SN1 108. Assertion : E1cb reaction is favoured by stabilisation
reactivity. of carbanion and poor leaving group.
Reason : The reaction is kinetically of the second order
Reason : They aid ionisation of RX. and unimolecular.
(a) A (b) B (a) A (b) B
(c) C (d) D (c) C (d) D
109. Assertion : Ph–CO–CH2CH2OCH3 has greater reactivity

103. Assertion : Rate of ethanolysis of 1 halide
o for E1CB than for E2 reaction.
Reason : A poor leaving group and acidic —H favour
( O ) by SN1 mechanism is fast. E1CB mechanism.
Br Me
(a) A (b) B
Reason : Carbocation is stabilised by resonance.
(c) C (d) D
(a) A (b) B
(c) C (d) D 110. Assertion : The carbon halogen bond in an aryl halide is
shorter than the carbon halogen bond in an alkyl halide.
3
Reason : A bond formed of an sp orbital should be shorter
2
104. Assertion : SN2 reaction of CH3––Br is faster in DMSO than the corresponding bond involving an sp orbital.
than in H2O. (a) A (b) B
Reason : DMSO has greater capability to solvate (c) C (d) D
nucleophile.
(a) A (b) B 111. Assertion : Alkyl iodide can be prepared by treating alkyl
chloride/bromide with NaI in acetone.
(c) C (d) D
Reason : NaCl/NaBr are soluble in acetone while NaI is
not.
105. Assertion : Treatment of (+)-2-chlorobutane with (a) A (b) B
aqueous NaCN gives laevo rotatory product. (c) C (d) D
Reason : S N 2 reaction leads to inversion of
configuration at the -carbon. 112. Assertion : Chlorination of allylic hydrogen is difficult
than vinylic hydrogen.
(a) A (b) B
Reason : Allyl radical is stabilised by resonance.
(c) C (d) D (a) A (b) B
(c) D (d) D
106. Assertion : Tertiary haloalkanes are more reactive than
primary haloalkanes towards elimination reactions. Acetone
113. Assertion : CH3 – CH2 – Cl + NaI  
Reason : The + I-effect of the alkyl groups weakens the CH3 – CH2 – I + NaCl 
C–X bond.
Reason : Acetone is polar Aprotic solvent and solubility
(a) A (b) B order of sodium halides decreases dramatically in order
(c) C (d) D NaI > NaBr > NaCl. The last being virtually insoluble in
this solvent and a 1° and 2° chloro alkane in acetone is
completely driven to the side of Iodoalkane by the
107. Assertion : 2-Bromobutane on reaction with sodium precipitation reaction.
exthoxide in ethanol gives 1-butene as a major product.
(a) A (b) B
Reason : 1-Butene is more stable than 2-butene.
(c) C (d) D
(a) A (b) B
(c) C (d) D
114. Assertion : Treatment of chloroethane with a saturated
solution of AgCN gives ethyl isocyanide as the major Matrix–match type questions
product. 120. Match the column (I) and (II)
Reason : Cyanide (CN– ) is an ambident nucleophile.
(a) A (b) B Column (I) Column (II)
(c) C (d) D Reaction Type of Reaction
115. Assertion : Wurtz’s coupling reaction of alkyl halide is

not suitable for an alkane containing an odd number of
carbons in the parent chain.
Reason : Wurtz’s coupling reaction involves heating of (A) (p) SN1
alkyl halides with sodium metal in ethereal solution.
(a) A (b) B
(c) C (d) D
116. Assertion : The presence of nitro group facilitates

nucleophilic substitution reaction in aryl halides.
Reason : The intermediate carbanion is stabilized due to (B) (q) SN2
the presence of the nitro-group.
(a) A (b) B
(c) C (d) D
117. Assertion : p-nitrochlorobenzene is more reactive than

m-nitrochlorobenzene towards aromatic nucleophilic
substitution reaction.
(C) (r) E1
Reason : Nitro group from para and meta positions has
opposite effect in aromatic nucleophilic substitution
reaction.
(a) A (b) B
(c) C (d) D
(D) (s) E2
118. Assertion : A dichlorobenzen is slightly more reactive
than chlorobenzene towards an aromatic nucleophilic
substitution reaction.
Reason : Chlorine has electron withdrawing effect on
aromatic ring. 121. Column I Column II
(a) A (b) B
(A) CH3CH = CH2 
HBr , RCOOR
 (p) Side chain substitution
(c) C (d) D
(B) CH3CH = CH2 
HBr
 (q) Anti-Markovnikov’s
119. Assertion : Chloral reacts with phenyl chloride to form addition
DDT. NBS , h
(C) C6 H5CH3   (r) Aromatic Substitution
Reason : It is an electrophilic substitution reaction
Br2 / FeBr3
(a) A (b) B (D) C6 H5CH3   (s) Markovnikov’s addition
(c) C (d) D
122. Match the column : 124. Column I Column II
Column-I Column-II (A) Sandmeyer reaction (p) C 6 H 5 COOAg, Br 2 /CCl 4 ,
Wurtz reaction Number of heat
dimerization (B) Balz-Schiemann reaction (q) CH3CH2CH2Br, KI,
product acetone, heat
(C) Hunsdiecker reaction (r) C6H5N2Cl, HBF4, heat
Na
(A) CH 3  Cl  (p) 5
dyether (D) Finkelstein reaction (s) C6H5N2Cl, CuCl/HCl, heat
Na
(B) CH3  Cl  CH3  CH 2  Cl  (q) 6
dryether

125. Match the column
(C) CH3 – Cl + CH3 – CH2 – Cl (r) 3 Column - I Column - II
Na
+ CH3 – CH2 – CH2 – Cl 
dryether

(A) (p) Nucleophilic
(D) H2C = CH – CH = CH – CH2 – Cl (s) 1
Na AlCl
+ CH3 – CH2 – Cl 
dryether
 3
 Ph  CH 2  Cl  substitution
123. Match the Column

Column-I Column-II (B) (q) Electrophilic
(Reactant) (Reactant)
(A) PhMgBr + substitution
(C) KOH  aq. (r) Cation


(A) 1° alcohol (p)
intermediate
(B) PhMgBr +
(D) 2 Br , hv (s) Free radical

(B) 2° alcohol (q)

substitution
(C) PhMgBr + 126. Column I Column II

(A) Anti-elimination (p) E1
(C) 3° alcohol (r) (B) Must have acidic -hydrogen (q) Ei
(C) No effect of solvent (r) E2
(D) carbocation (s) E1 CB
(D)PhMgBr +
127. Column (I) Column (II)

(D) (s)
Match the missing reagent A, B, C, D (A) (p) Elimination

Integer type questions
129. How many substrates will show rearrangement during
(B) (q) Rearrangement SN1 reaction
(C) (r) Unimolecular
130. If 1-chloro-4-methylcyclohexane is treated with

(D) (s) Bimolecular KOH(aq.), both substitution (SN2) and elimination (E2)
reactions occur simultaneously in comparable amount.
In total, how many substitution plus elimination
products would result ?
131. 1, 3-dichlorocyclopentane exists in three stereo-isomeric

forms, of which only two are chiral. If one mole of its
128. Column (I) Column (II) achiral stereoisomer is treated with exactly one mole of
NaOH in aqueous medium and, only mono substitution
(SN2) and mono-elimination (E2) occurs producing
(A) (p) Saytzeff’s product chlorocyclopentanoland chlorocyclopentane, how
many different products are expected?
132. Find out numbers of possible E 1 products from

following reaction.
(B) (q) Carbocation
(C) (r) E2 elimination

133. How many of the following reactions, leads to the
formation of diastereomers.
(D) (s) Hofmann product HCl

(a)  
CCl4
HBr
(b)  
CCl4
HBr
(c)  
CCl4
HCl
(d)  
CCl4
HCl
(e)  
CCl4
HCl
(f)  
CCl4
134. If an etheral solution containing 2–chloropentane and

chloroethane is heated with sodium, how many different
alkanes would result through Wurtz’s reaction ?
(1) 'X'RMgX
135. 
NH Cl
 3° Alcohol. Find
4
out value of ‘X’.
136. Total number of RMgX are consumed in the following

reaction

Objective Questions
1. Which of the following has the highest nucleophilicity ? 6. How would you synthesize 4-methoxyphenol from
bormobenzene in NOT more than five steps ? State clearly
(2000) the reagents used in each step and show the structures of
– – the intermediate compounds in your synthetic scheme.
(a) F (b) OH
(2001)
(c) CH3– (d) NH2–
7. An SN2 reaction of an asymmetric carbon of a compound
2. The order of reactivities of the following alkyl halides always gives (2001)
for a SN2 reaction is (2000) (a) an enantiomer of the substrate
(b) a product with opposite optical rotation
(a) RF > RCl > RBr > RI (c) a mixture of diastereomers
(b) RF > RBr > RCl > RI (d) a single stereoisomer
(c) RCl > RBr > RF > RI
(d) RI > RBr > RCl > RF 8. Cyclobutylbromide on treatment with magnesium in dry ether
forms an organometallic compound (A). The organometallic
reacts with ethanal to give an alcohol (B) after mild
3. An SN2 reaction at an asymmetric carbon of a compound acidification. Prolonged treatment of alcohol (B) with an
equivalent amount of HBr gives 1-bromo-1-
always gives (2001)
methylcyclopentane (C). Write the structures of (A), (B)
(a) an enantiomer of the substrate and explain how (C) is obtained from (B). (2001)
(b) a product with opposite optical rotation
9. Identify the set of reagents/reaction conditions X and Y in
(c) a mixture of diastereomers the following set of transformations (2002)
(d) a single stereoisomer
4. Which of the following has the highest nucleophilicity ?

(2000)
– – (a) X = dilute aqueous NaOH, 20°C, Y = HBr/acetic acid,
(a) F (b) OH
20°C
(c) CH3 (d) NH 2 (b) X = concentrated alcoholic NaOH, 80°C, Y = HBr/acetic
acid, 20°C
5. What would be the major product in each of the following (c) X = dilute aqueous NaOH, 20°C, Y = Br2/CHCl3, 0°C
reactions ? (2000) (d) X = concentrated alcoholic NaOH, 80°C, Y = Br2/CHCl3,
0°C
(i) 10. How many structures of F is possible ? (2003)
(ii)
(a) 2 (b) 5
(c) 6 (d) 3
15. When phenyl magnesium bromide reacts with t-butanol,
11. (2003) the product would be (2005)
(a) benzene (b) phenol
(c) t-butyl benzene (d) t-butyl phenyl ether
16. The major product of the following reaction is (2008)

(a) C6H5OC2H5 (b) C2H5OC2H5
(c) C6H5OC6H5 (d) C6H5I
12. Among the following, the molecule with the highest dipole
moment is (2003)
(a) CH3Cl (b) CH2Cl2
(c) CHCl2 (d) CCl4
(a) (b)
13. (2004)
Identify A to D . (c) (d)
14. The following compound on hydrolysis in aqueous acetone

will give (2005)
17. The correct statements for the following addition reactions

is (are) (2017)
(K)
(L)
(M)
(a) (M and O) and (N and P) are two pairs of enantiomers

(a) mixture of (K) and (L)
(b) Bromination proceeds through trans-addition in both
(b) mixture of (K) and (M)
the reactions
(c) only (M)
(c) O and P are identical molecules
(d) only (K) (d) (M and O) and (N and P) two pairs of diastereomers
18. List-I contains reactions and List-II contains major products.
(2018)
List-I List - II
(P)  1.
(Q) 2.
(R) 3.
(S) 4.
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
Note:
REAGENTS AND MECHANISM AND

ALKYL HALIDES
03
02
Chapter 03 139
1. Introduction
The compounds in which hydroxyl group (—OH) is attached to a
saturated carbon atom are called as Alcohols. The compounds in
which a hydroxyl group is attached to an unsaturated carbon
atom of a double bond are called as Enols. The saturated carbon
may be that of an alkyl, alkenyl, alkynyl, cycloalkyl or benzyl
group. However, if a hydroxyl group is attached to a benzene ring,
the compounds are called as Phenols.
The alcohols are further classified as : Monohydric (containing Bond angle is slightly less due to
one —OH group), Dihydric (containing two —OH groups) and
LP-LP repulsion.
Triliydric (containing three —OH groups).
Alcohols find usage in industry as well as day to day life. For
example, ordinary spirit used for polishing wooden furniture is
chiefly ethanol. Sugar, cotton, paper are all made up of compounds
containing —OH groups. Phenols are used in several important
polymers such as Bakelite and in several drugs such as Aspirin.
Ethers are commonly used as solvents and anaesthetics.
Lone pair of oxygen is delocalised on ring due to whi ch C —

2. CLASSFICATION
O bond length is less.
Bond angle in methoxymethane is more than tetrahedral angle

due to repulsive interaction between the two bulky (R) groups.
The C—O bond length is same as in alcohols.
3. STRUCTURES OF FUNCTIONAL GROUPS
4. PHYSICAL PROPERTIES
In alcohols, the oxygen of the —OH group is attached to carbon
by a sigma (o) bond formed by the overlap of a sp’ hybridised
orbital of carbon with a sp’ hybridised orbital of oxygen. The
following figure depicts structural aspects of methanol, phenol
and methoxymethane.
SCAN CODE
Alcohols, Phenols and Ethers
ALCOHOLS, PHENOLS AND ETHERS 140
4.1 Boiling Point Lower ethers are water soluble but solubility is less than alcohol
due to less H-bonding with water and low polarity.
The boiling points of alcohols and phenols increase with
increase in the number of carbon atoms (increase in van der Refer to Table 1, 2, 3 and 4 for reference to physical properties of
Waals forces). In alcohols, the boiling point decreases with alcohols, phenols and ethers.
increase in branching (decrease in Van der Waals forces due to
decrease in surface area).
The –OH group in alcohols and phenols contains a hydrogen, 5. PREPARATION OFALCOHOLS
bonded to an electronegative oxygen atom. Therefore, it is
capable of forming intermolecular hydrogen bond, strength of
which is even greater than amine.
It is due to the presence of strong intermolecular hydrogen 5.1 Alkane

bonding that alcohols and phenols have higher boiling points Controlled Oxidation
corresponding to other classes of compounds, namely,
hydrocarbons, ethers and haloalkanes/haloarenes, amines of CH 4 +  O  
Cu tube
 CH 3OH
100 atm
comparable molecular masses. 200°C
Their boiling points are lower than carboxylic acid which have 5.2 Alkane
even more strong H-bond. For isomeric alcohols boiling points
decreases with increase in branching due to decrease in van
Markovnikov addition with carbocation rearrangements
der Waals forces with decrease in size. The order of boiling
point is 1° alcohol > 2° alcohol > 3° alcohol.
In ethers, boiling point is very less, and comparable to those of
alkane of comparable molecular mass due to less dipole moment
and absence of H-bonding.
4.2 Solubility 5.2.2 Oxymercuration-Demercuration
The solubility of alcohols and phenols in water is due to Markovnikov addition without carbocation rearrangements
theirability to form hydrogen bonds with water molecules. The
solubility decreases with increase in the size of hydrophobic Example-1
group (R). Higher alcohol are insoluble. Branching increases
solubility, due to decrease in surface area of non-polar
hydrocarbon pan.
n-butylalcohol<isobuiylalcoho1<sec butylaloiho1< tert-
buiylaloiho1
5.2.3 Hydroboration-Oxidation
SCAN CODE
Anti-Markovnikov addition
Example-2
5.2.4 SYN Hydroxylation

Reagents : Cold dil. KMnO4/NaOH or OsO4/HCO
Example-3
5.3.3 Grignard Reagent/Organolithium Reagent

Nucleophilic addition to the carbonyl group
5.2.5 ANTI Hydroxylation

Reagents : Peroxy Acids followed by Acidic Hydrolysis
Example-4
(a) Addition to Formaldehyde- 1° Alcohol
Example-7
5.3 Alkyl Halide

5.3.1 Second-order Substitution
Primary (and some Secondary) Halides
Example-5
KOH
 CH 3 2 CHCH 2CH 2  Br 
H O
2
  CH3 2 CHCH 2  OH
5.3.2 First order Substitution

Tertiary (and some Secondary) Halides
Example-6
SCAN CODE
(b) Addition to Aldehyde- 2° Alcohol 5.4 Carbonyl Compounds
Example-8 5.4.1 Catalytic Hydrogenation
This method is usually not as selective or as effective as the

use of hydride reagents
5.4.2 Reduction with Metal Hydrides

1.Reduction of an aldehyde gives a primary alcohol
Example-12
(c) Addition to Aldehyde- 3° Alcohol

Example-9
2. Reduction of a ketone gives a secondary alcohol
Example-13
(d) Addition to an Acid Halide or Ester - 3° Alcohol

Example-10
3. Reduction of an acid or ester gives a primary alcohol
Example-14
Note:
Bouveault-Blanc Reduction: A chemical reaction in which Es-
(e) Addition to Ethylene Oxide - 1° Alcohol (with ter is reduced to primary alcohol using Absolute alcohol &
two carbon atoms added)
Example-11
SCAN CODE
6.3 Esterification
6. REACTIONS OF ALCOHOL
Esterification is catalyzed by an acid or base
6.4 Tosylation
Tosylation is used to convert poor leaving group OH into good
leaving group OTs.
Example-15
6.1 Dehydration
Example-16
6.5 Oxidiation
(a) Primary Alcohols
6.2 Substitution
SCAN CODE
7. PHENOL
Common Phenols and Aromatic Ethers
(b) Secondary Alchols
Secondary alcohol in the presence of any oxidising agent

is oxidised to ketone.
(c) Tertiary Alchols
8. PREPARATION OF PHENOLS
MnO2 is an oxidising agent which oxidises only allylic, ben-

zylic & propargylic alcohols.
SCAN CODE
8.1 Dow’s Process 8.5 Benzene
This is industrial method for preparation of phenol. It oc- Example-20
curs through Benzyne Mechanism
Example-17
8.6 Grinard Reagent

Example-21
8.2 Cumene process

Example-18
9. REACTIONS OF PHENOLS
9.1 Formations of Ethers
(a) Williamson Synthesis
(b) Nucleophillic Aromatic substitution

Example-22
8.3 Hydrolysis of Diazonium salts
8.4 Distillation of phenolic Acids with Sodalime

Example-19 9.2 Formations of Esters
Example-23
SCAN CODE
Example-27
Example-24
9.4.3 Electrophillic Substitution

(a) Halogenation
Example-28
9.3 Fries Rearrangement
Example-25
Example-29
9.4 Reaction of Benzene Ring

9.4.1 Hydrogenation
Example-26
9.4.2 Oxidation to Quinones
SCAN CODE
(b) Nitrosation This is achieved using Fires rearrangement.
Example-30 (g) Kolbe’s Synthesis
Example-33
Example-31
(h) Riemer-Tiemann Synthesis of Phenolic Aldehydes
Example-34
(d) Diazonium Salt Coupling - Azophenols
This reactions involves formation of carbene, CCL2.

G is an electron releasing groups such as –OH, OR, –NR2,–
NHR, – NH2. (i) Formation of Aspirin
(e) Ring Alkylation Example-35
Example-32
RX and AlCl3 give poor yields because AlCl3 co-ordinates

with lone pair of oxygen.
(f) Ring Acylation
SCAN CODE
This reactions follows Markovnikov orientation.

10.3 Bimolecular Dehydrations of Alcohols
This reactions is an industrial method for synthesis of ethers.
11 REACTION OF ETHERS
11.1 Cleavage by HBr and HI
(j) Formation of Oil of Wintergreen
Example-36
Example-37
11.2 Autoxidation
10. ETHERS
10.1 Williamson Ethers Synthesis
12. PREPARATION OF EPOXIDES
10.2 Alkoxymercuration-Demercuration 12.1 Peroxy Acid Epoxidation
SCAN CODE
Example-39
(c) Hydrohalic Acids (X= CI, Br, I)
12.1 Base-promoted cyclization of halohydrins
13.2 Base-catalyzed Opening

(a) with Alkoxides
Example-38
The alkoxy group bonds to the less highly substituted

carbon
Example-40
13. REACTION OF EXPOXIDES

13.1 Acid-catalyzed Opening
(a) In water
(b) With organometallics
Anti stereochemistry is followed.

(b) In alcohols Example-41
The alkoxy group bonds to the more highly substituted

carbon.
SCAN CODE
15.1 Analysis of alcohols-Characterization
(a) Alcohols dissolve in cold concentrated sulfuric acid.
This property they share with alkenes, amines, practically
all compounds containing oxygen, and easily sulfonated
compounds. (Alcohols, like other oxygen-containing com-
pounds, form oxonium salts which dissolve in the highly
polar sulfuric acid.)
(b) Alcohols are not oxidized by cold dilute, neutral per-
manganate (although primary and secondary alcohols are
oxidized by permanganate under more vigorous conditons.)
However, as we have seen, alcohols often contain impuri-
ties that are oxidized under these conditions, and so the
permanganate test must be interpreted with caution.
(c) Alcohols do not decolorize bromine in carbon tetra-
chloride. This property serves to distinguish them from
alkenes and alkynes.
Alcohols are further distinguished from alkenes and
alkynes and from nearly every other kind of compound by
their oxidation by chromic anhydride (CrO3) in aqueous
sulfuric acids. Within two seconds, the clear orange solu-
tion tums blue-green and becomes opaque.
14. ACIDIC STENGTH ROH + HCrO 4  Opaque, blue green

1°or 2° Clear
(i) Alcohols are weaker acids than thiols even though Tertiary alcohols do not give this test. Aldehydes do, but
oxygen is more electronegative than sulphur. Conjugate are easily differentiated in other ways.
base of alcohol
(d) Reactions of alcohols with sodium metal with the evo-
i.e. RO– is more basic than RS– as in RO– negative charge lution of hydrogen gas is of some use in characterization.
is placed on smaller oxygen atom so it will have more A wet compound of any kind, of course, will do the same
charge density. But in thing, until the water is used up.
RS– negative charge is dispersed on bigger sulphur so it (e) The presence of the -OH group in a molecule is often
is a poor base and its conjugate acid will be more indicated by the formation of an ester upon treatment with
acidic.Order of acidic strength of some of some of the an acid chloride or anhydride. Some esters are sweet-
chemical are given as: smelling; others are solids and sharp melting points, and
can be derivatives in identifications. If the molecular for-
RSO3HCO > RCOOH > Phenol H2O > ROH mulas of starting material and product are determined, it
is possible to calculate how many -OH groups are present.
HC = CH > NH3 > CH2 = CH2 > CH3 – CH3
(f) Whether an alcohol is primary, secondary or tertiary is
(ii) All alcohols (except CH3OH) are weaker acids than shown by the Lucas test, which is based upon the differ-
H2O due to +I effect of alkyl group. CH3OH is slightly ence in reactivity of the three classes toward hydrogen
stronger than H2O. Phenols are stronger than alcohol halides. Alcohols (of not more than six carbons) are soluble
due to electron withdrawing benzene ring & resonance in the Lucas reagent, a mixmre of concentrated hydro-
stabilized phenoxide ion. Alkoxide ions, the conjugate base chloric acid and zinc chloride. The corresponding alkyl
of alcohol have no resonance so they are less stable and chlorides are insoluble. Formation of a chloride from an
more basic. Phenol is weaker than carboxylic acid which alcohol is indicated by the cloudiness that appears when
the chloride separates from the solution. Hence, the time
have strong electron withdrawing carbonyl group and
required for cloudiness to appear is a measure of the re-
more stable resonating structures. activity of the alcohol.
15. TESTS FOR ALCOHOLS, PHENOLS & A tertiary alcohol reacts immediately with the Lucas re-
ETHERS
SCAN CODE
agent, and a secondary alcohol reacts within five min- As would be expected from the equations, a compound of
utes. Aprimary alcohol does not react appreciably at room structure also gives a positive test.
temperature. Benzyl alcohol and allyl alcohol react as rap-
idly as teritary alcohols with the Lucas reagent. Allyl chlo-
ride, however, is soluble in the reagent.
(g) Whether or not an alcohol contains one particular struc-
tural unit is shown by the iodoform test. The alcohol is In certain special cases this reaction is used not as a test,
treated with iodine and sodium hydroxide (sodium but to synthesize the carboxylic acid, RCOOH. Here, hy-
hypoiodite, NaOI). An pobromite or the cheaper hypochlorite would probably be
alcohol of the structure yields a yellow precipitate of io- used.
doform (CHI3m.p. 119°).
15.2 Analysis of Glycols, Periodic Acid Oxidation
Upon treatment with periodic acid, HIO4, compounds con-
taining two or more –OH or C=O groups attached to adja-
cent carbon atoms undergo oxidation with cleavage of
carbon-carbon bonds.
15.3 Miscellaneous Tests
(a) Ceric Ammonium Nitrate Test - Alcohols give red

colour with this reagent.
Ce(NH 4 ) 2 (NO 3 ) 6 +RCH 2 OH  Ce(NH 4 ) 2 (NO 3 ) 5 +

RCOOH + HNO3
(b) Potassium Dichromate Test - Alcohol turn orange

dichromate to green. Tertiary Alcohol do not give this first.
(c) Ester Test - Alcohol gives fruity smell of Ester with

carboxylic acid.
The reaction involves oxidation, halogenation and cleav-
(d) Methanol Forms oil of winter green with salicylic acid.
age
SCAN CODE
15.4 Victor Meyer’s Test H 2O
Diazonium Salt + Alcohol +Br2   No Reaction
15.5.2 Alcohol and Ethers

(a) Alcohols react with Na to give H2 but not ethers
(b) Alcohols give fumes of HCl with PCl5 but not ethers
15.5.2 Sodium Bicarbonate Test
Phenol, ROH and H2O do not displace CO2 from carbonate
& bicarbonates but RCOOH & RSO3H gives brisk efferves-
cence of CO2 which proves that RCOOH & RSO3H are stron-
ger acids H2CO3 but phenol is weaker acid than H CO .
Nitrophenols also giveeffervescence of CO2 with Na2CO3.
Trinitrophenol (Picric Acid) is highly acidic due to strong
electron withdrawing effect of threegroups its acidic strength
is comparable to that of carboxylic acids.Its anion is highly
resonance stabilised.
15.5 Differentiations Tests

15.5.1 Alcohol and phenols
1. Litmus Test : Phenol turns blue litmus red but not
alcohols
Neutral FeCL3
2. FeCL 3 : Phenol   Blue–Violet
3. Coupling reactions:
Weakly basic
Phenol+DiazoniumSalt 
medium
Yellow or
Orange Dye
Weakly basic
DiazoniumSalt + Alcohol 
medium
No
Reaction
4. Bromine Water Test:
15.5.4 FeCl3 Test

Phenol gives characteristic purple colour with FeCl3 but
alcohols do not react with FeCl3 Carboxylic acids also form
buff coloured precipitate with FeCl3. Only acetic acid forms
red coloured precipitate with FeCl3, so it can be used as a
test for acetate salts.
SCAN CODE
Table 1 : Physical Properties of Selected Alcohols

IUPAC Name Common Name Formula MP(°C) BP(°C) Density
methanol methyl alcohol CH 3OH –97 65 0.79
ethanol ethyl alcohol CHCH2OH –114 78 0.79
1-propanol n-propyl alcohol CHCH2CH 2OH –126 97 0.80
2-propanol isopropyl alcohol (CH3)2CHOH –89 82 0.79
1-butanol n-butyl alcohol CH3(CH2) 3OH –90 118 0.81
2-butanol sec-butyl alcohol CH, CH(OH)CH2CH3 –114 100 0.81
2-methyl-1-propanol isobutyl alcohol (CH3)2CHCH2OH –108 108 0.80
2-methyl-2-propanol t-butyl alcohol (CH3) COH 25 83 0.79
1-pentanol n-pentyl alcohol CH, (CH2)4OH –79 138 0.82
3-methyl-1-butanol isopentyl alcohol (CH3) 2CHCH2CH2OH –117 132 0.81
2,2- dimethyl neopentyl alchol (CH3) 3CCH2OH 52 113 0.81
–1–propanol
cyclopentanol cyclopentyl alcohol cyclo-C5H9OH –19 141 0.95
1-hexanol n-hexanol CH3(CH2)s H 52 156 0.82
cyclohexanol cyclohexyl alcohol cyclo-C6H, OH 25 162 0.96
1-heptanol n-heptyl alcohol CHP(CH 2)6OH –34 176 0.82
1-octanol n-octyl alcohol CH3(CH2) 7OH –16 194 0.83
1-nonanol n-nonyl alcohol CH3(CH2)gOH –6 214 0.83
I-decanol n-decyl alcohol CH (CH 2)9OH 6 233 0.83
2-propen-1-ol allyl alcohol H C = CH—CH2OH –129 97 0.86
phenylmethanol benzyl alcohol Ph—CH 2OH –15 205 1.05
diphenylmethanol diphenylcarbinol Ph2CHOH 69 298
triphenylmethahnol triphenylcarbinol Ph3COH 162 380 1.20
1, 2-ethanediol ethylene glycol HOCH2CH 2OH –13 198 1.12
1, 2-propanediol propylene glycol CH3CH(OH)CH2OH –59 188 1.04
1, 2, 3-propanetriol glycerol HOCH2CH(OH)CH2OH 18 290 126
SCAN CODE
Table 3: Comparison of the Boiling Points of Ethers, Alkanes and Alcohols of Similar
Molecular Weights
SCAN CODE
Table 4: Solubility ofAlcohols in Water (at 25°C)

Alcohol Solubility in Water
methyl miscible
ethyl miscible
n-propyl miscible
t-buty1 miscible
isobutyl 10.0%
n-butyl 9.1%
n-pentyl 2.7%
cyclohexyl 3.6%
n-hexyl 0.6%
phenol 9.3%
hexane-1, 6-diol miscible
Table 5: Acid-Dissociation Constants of Representative Alcohols
Alcohol Structure K, pK
methanol CHP–OH 63.2 ^ l0*’ 15.5
6
ethanol CH3CH2– OH 1.3 ^ 10 ‘ 15.9
2-chloroethanol Cl–CH2CH2–OH 5.0 ^ 10*” 14.3
isopropyl alcohol (CH3)2CH–OH 3.2^ 10*” 16.5
t-butyl alcohol (CH3)3C–OH 1.0^ 10 18.0
cyclohexanol COH –OH 1.0 ^ 10 18.0
0
phenol C6H5 – OH 1.0 ^ l0 *’ 10.0
Comparison with other Acids
water H2O 61.8 ^ 10*’ 15.7
acetic acid CH3COOH 1.6 x 10° 4.8
hydrochloric acid HCl 1.6 ^ 10’2 –2.2
SCAN CODE
SOLVED EXAMPLES
Example – 1 is the intermolecular associations of a large number of

Hydrogen bonding is maximum in molecules due to hydrogen bonding as -OH group is highly
(a) ethanol (b) diethyl ether polarized.
(c) ethyl chloride (d) triethyl amine
Ans. (a)
Sol. Ethanol is capable in forming intermolecular H-bonds:
hydrogen bonding
Example – 2 No such hydrogen bonding is present in ethers.

Acid catalyzed hydration of alkenes except ethene leads to
the formation of Example – 4
(a) mixture of secondary and tertiary alcohols In the hydroboration-oxidation reaction of propene with
(b) mixture of primary and secondary alcohols diborane, H2O2 and NaOH, the organic compound formed
(c) secondary or tertiary alcohol is:
(d) primary alcohol (a) CH3CH2OH (b) CH3CHOHCH3
Ans. (c) (c) CH3CH2CH2OH (d) (CH3)3COH
Sol. Water adds to more reactive alkenes in the presence of acids Ans. (c)
to yield alcohols. Hydroboration
Sol. CH 3  CH  CH 2   CH 3  CH 2  CH 2
oxidation
|
CH3
 | OH
H2O H
H3C  C  CH2    H3C3  C OH 3 alcohol
 
| | Example – 5
CH3 CH3
Phenyl magnesium bromide reacts with methanol to give

H2O H 
C  H3C3  CH  CH2  
 C  H3C3  C H  CH3 2 alcohol
|

OH (a) a mixture of anisol and Mg(OH)Br
(b) a mixture of benzene and Mg(OMe)Br
Example – 3
(c) a mixture of toluene and Mg(OH)Br
An ether is more volatile than an alcohol having the same
molecular formula. This is due to (d) a mixture of phenol and Mg(Me)Br
(a) dipolar character of ethers Ans. (b)
(b) alcohols having resonance structures Sol. CH3OH  C6H5MgBr  C6H6  Mg  OCH3  Br
(c) intermolecular hydrogen bonding in ethers
(d) intermolecular hydrogen bonding in alcohols
Ans. (d) Example – 6
Sol. The reason for the lesser volatility of alcohols than ethers In the following sequence of reactions,
| | + | | | |

H
 C  C   
 H2 O
  C|  C|   
  C|  C 
| | 
the compound ‘D’ is H OH H  OH H
2
(a) butanal
(b) n-butyl alcohol
(c) n-propyl alcohol protonated carbonium
alcohol
(d) propanal alcohol ion
Ans. (c)
 | |

H

  C  C
Sol.
alkene
Example – 9
Among the following compounds which can be dehydrated
very easily ?
(a) CH3CH2CH2CH2CH2OH
(b)
Example – 7 (c) (d)

Consider the following reaction
C2H5OH + H2SO4  Product
Ans. (c)
Among the following, which one cannot be formed as a
product under any conditions ? Sol The ease of dehydration of alcohols is tertiary  secondary
(a) Ethyl hydrogen sulphate  primary according to the order of stability of the
(b) Ethylene carbocations.
(c) Acetylene
(d) Diethyl ether CH3
|
CH3
|
H
Ans. (c) CH3  CH2  C  CH2  CH3  CH3  CH2  C  CH2  CH3
| 
Sol. Conceptual OH
The more stable carbocation is generated thus more easily

Example – 8 it will be dehydrated.
During dehydration of alcohols to alkenes by heating with
concentrated H2SO4 the initiation step is Example – 10
(a) protonation of alcohol molecule The main product of the following reaction is
(b) formation of carbocation Conc. H2SO4
C6H5CH2CH(OH)CH(CH3)2  ?
(c) elimination of water
(d) formation of an ester
Ans. (a) (a)
Sol Dehydration of alcohol to alkene in presence of
concentrated H 2SO4 involves following steps:
(b)
Ans. (d)
(c) Sol. OH>O- +H +  has maximum electronegativity diffrence 
Example – 15
(d) Among the following compounds, the strongest acid is
Ans. (a) (a) (b) C6H6

Sol. Double bond conjugated with benzene ring is most stable. (c) C2H6 (d) CH3OH
Trans porduct is more stable than cis. Ans. (d)
Sol. Alcohols behave as acid due to the polar bond of O-H
Example – 11
The best reagent to convert pent-3-en-2-ol into pent-3-en- Example – 16
2-one is
From amongst the following alcohols the one that would
(a) MnO2 react fastest with conc HCl and anhydrous ZnCl2, is
(b) chromic anhydride in glacial acetic acid
(c) acidic dichromate (a) 2-butanol (b) 2-methylpropan-2-ol
(d) acidic permanganate (c) 2-methylpropanol (d) 1-butanol
Ans. (b) Ans. (b)
Sol. Pyridinium chlorochromate oxidises an alcoholic group
Sol. The reagent,conc. HCl and anhydrous ZnCl2 is Lucas
selectively in the presence of carbon-carbon double bond.
Example – 12 reagent, which is used to distinguish between 10 , 20 and 30
alcohols.
A liquid was mixed with ethanol and a drop of concentrated
H2SO4 was added. A compound with a fruity smell was 30 alcohol + Lucas reagent  Immediate turbidity.
formed. The liquid was
(a) CH3OH (b) HCHO 20 alcohol  Lucas reagent  Turbidity after 5 mins.
(c) CH3COCH3 (d) CH3COOH 10 alcohol  Lucas reagent  No reaction.
Ans. (d)
Thus, the required alcohol is propan -2-ol, i.e.,
Sol. Fruity smell is due to ester formation which is formed
between ethanol and acid. CH3
|
Example – 13 H 3 C  C  CH 3
|
The most suitable reagent for the conversion of OH
R  CH2  OH  R  CHO is : (30 alcohol)
(a) K 2Cr2O7 (b) CrO3 Example – 17

(c) PCC (Pyridinium Chlorochromate) In the Victor-Meyer’s test, the colour given by 1o, 2o and
3o alcohols are respectively:
(d) KMnO4 (a) Red, blue, violet
Ans. (d) (b) Colourless, red, blue
PCC
Sol. R  CH 2  OH   R  CHO (c) Red, colourless, blue
(d) Red, blue, colourless
It is mild oxidising agent.
Ans. (d)
Example – 14
In CH3CH2OH, the bond that undergoes heterolytic cleavage
most readily is
(a) C—C (b) C—O Sol.
(c) C—H (d) O—H
Example – 18
Which one of the following statements is not correct?
(a) Alcohols are weaker acids than water
(b) Carbon- oxygen bond length in methanol, CH3OH is
shorter than that of C–O bond length in phenol.
Sol.
(c) Acid strength of alcohols decreases in the following
order RCH2OH > R2CHOH> R3COH
(d) The bond angle in methanol is 108.90

Example – 21
Ans. (b) The structure of the compound that gives a tribromo
derivative on treatment with bromine water is
Sol. CH 3 - OH
(a) (b)
In phenol C - O bond aquire some double bond character

(c) (d)
due to resonance so B.L of CH 3 OH > C6 H 5 OH
Example – 19
Phenol, when first reacts with concentrated sulphuric acid Ans. (a)
and then concentrated nitric acid, gives
(a) o–nitrophenol (b) p–nitrophenol
(c) Nitrobenzene (d) 2, 4,6–trinitrophenol
Ans. (d)
Sol.
Sol.
OH OH
NO2
NO2
H2 SO4

HNO3
 Example – 22
Phenol is heated with a solution of mixture of KBr and
KBrO3. The major product obtained in the above reaction is
NO2 (a) 2-bromophenol (b) 3-bromophenol
Example -20 (c) 4-bromophenol (d) 2, 4, 6-tribromophenol
Ans. (d)
Phthalic acid reacts with resorcinol in the presence of
concentrated H2SO4 to give; Sol. KBr( aq ) +KBrO3( aq )  Br2( aq )
(a) Phenolphthalein (b) Fluorescein
This bromine reacts with phenol gives 2, 4, 6 
(c) Alizarin (d) Coumarin tribromophenol
Ans. (b)
(c) (d)
Ans. (d)
Sol.
Example – 23
Phenol, when it first reacts with concentrated sulphuric acid
and then with concentrated nitric acid, gives
(a) 2, 4, 6-trinitrobenzene (b) o-nitrophenol
(c) p-nitrophenol (d) nitrobenzene
Ans. (b) Example – 25

Sol. (None of the option is correct.) In the following compounds
The order of acidity is

(a) III > IV > I > II (b) I > IV > III > II
Example – 24
(c) II > I > III > IV (d) IV > III > I > II
Sodium phenoxide when heated with CO2 under pressure at
125ºC yields a product which on acetylation produces C. Ans. (d)
Sol. order is based on-R and -R effect (which stabilize the
phenoxide ion)
Example – 26
125º H 
CO2 
5 Atm  B 
Ac O  C 2 Which of the following reagents may be used to distinguish
between phenol and benzoic acid ?
(a) Aqueous NaOH (b) Tollen’s reagent
The major product C would be : (c) Molisch reagent (d) Neutral FeCl3
Ans. (d)
Sol. reagents may be used to distinguish between phenol and
benzoic acid phenol in presence of neutral FeCl3 gives
(a) (b) aviolet red colour complex. this test is not shown by benzoic
acid. Aqueous NaOH Tollen’s reagent Molisch reagent are
the wrong answer
Example – 27
Allyl phenyl ether can be prepared by heating:
(a) C6H5Br + CH2 = CH – CH2 – ONa
(b) CH2 = CH – CH2 – Br + C6H5ONa
(c) C6H5 – CH = CH – Br + CH3 – ONa
(d) CH2 = CH – Br + C6H5 – CH2 – ONa
Ans. (b) (A) If both Assertion and reason are true and reason is
the correct explanation of the assertion.
Sol. CH 2  CH  CH 2  Br  C6 H 5ONa 
(B) If both assertion and reason are true but reason is not
the correct explanation of the assertion.
CH 2  CH  CH 2  O  C 6 H 5 (C) If assertion is true but reason is false.
Example – 28 (D) If both assertion and reason are false.
Williamson synthesis of ether is an example of :
(a) Electrophilic addition Example – 33
(b) Nucleophilic addition Assertion : Solubility of n-alcohol in water decreases with
(c) Electrophilic substitution increase in molecular weight.
(d)Nucelophilic substituion Reason : The reactive proportion of the hydrocarbon
Ans. (d) part in alcohols increases with increasing
molecular weight which permits enhanced
Sol. Williamson synthesis is nucleophilic substitution reaction. hydrogen bonding with water.
Example – 29 (a) A (b) B
Diethyl ether on heating with conc. HI gives two moles of (c) C (d) D
(a) ethanol (b) iodoform Ans. (c)
(c) ethyl iodide (d) methyl iodide Sol. R-OH  Hydrophilic
Ans. (c)
Hydrophobic
Sol. CH 3 -CH 2 -O-CH 2 -CH 3 +HI  2C 2 H5 l Increasing molecular weight increases hydrocarbon (R)
proportion that lowers the solubility in water.
Example – 30
Example – 34
A ................. diol has two hydroxyl groups on .................
carbon atoms. Assertion : p-nitrophenol is a stronger acid than
Ans. (Vicinal; same) o-nitrophenol.
Sol. Vicinal; same Reason : Intramolecular hydrogen bonding make the
o-isomer weaker than the p-isomer.
(a) A (b) B
Example – 31 (c) C (d) D
Ethanol vapour is passed over heated copper and the
product is treated with aqueous NaOH. the final product is
Ans. (a)
.....................
Sol. Conceptual
Ans. (aldol)
Sol. Example – 35
O Match the Column
||
Cu NaOH
C 2 H5 OH  CH 3 CHO  CH 3 - CH-CH 2 -CHO
Δ H2 O
Match the following choosing one item from column ‘X’ and
aidol the appropriate item from column Y.
Example – 32 X Y
Aliphatic ethers are purified by shaking with a solution of (A) Williamson’s synthesis (P) tert-alcohol
ferrous salt to remove ............... which are formed on (B) Neutral FeCl3 test (Q) Ether
prolonged standing in contact with water. (C) Lucas test (R) Phenol
Ans. (Peroxides) Ans. (A-q, B-r, C-p)
Sol. Peroxides: H 2 O2 +Fe2+  H 2 O+Fe3+ Sol. Williamson Ether synthesis: an SN 2 reaction
Assertion R
alkoxide primary or ether

nucleophile methyl alkyl hadile
Example – 36
Write the structures of the products :
HI (excess)
(CH3)2 CH—OCH3 
heat
HI
Sol.
 CH3 3 CH-O-CH3   CH3 - CH -CH 3 +CH 3 I
|
I
Example – 37
2, 2-dimethyloxirane can be cleaved by acid (H+). Write
mechanism.
Sol.
True/False
Example – 38
The yield of a ketone when a secondary alcohol is oxidised
is more than the yield of aldehyde when a primary alcohol is
oxidised.
Ans. (T)
Sol. Aldehydes (from primary alchols) may further be
oxidized easily to acids as compared to ketones (from
secondary alchols).

Properties of Alcohols
1. Glycerine has 8. The product of the following reaction is

(a) One primary and two secondary –OH groups
(b) One secondary and two primary –OH groups
(c) Three primary –OH groups
(a) 2-pentanol (b) pentane
(d) Three secondary –OH groups
(c) pentan-2-one (d) 1-pentanol
2. The structural formula of cyclohexanol is
9. Oxymercuration-demercuration reaction of 1-methylcyclohexene
gives
(a) (b) (a) trans-2-methyl cyclohexanol
(b) cis-2-methylcyclohexanol
(c) 1-methylcyclohexanol
(d) mixture of cis- and trans-2-methylcyclohexanol
(c) (d)
Reactions of Alcohols
10. 2-phenylethanol may be prepared by the reaction of

3. Which of the following is not characteristic of alcohols phenylmagnesium bromide with
(a) They are lighter than water (a) HCHO (b) CH3COCH3
(b) Their boiling points rise fairly uniformly with increasing
molecular weight
(c) Lower members are insoluble in water and organic (c) (d) CH3CHO
solvents but solubility regularly increases with
molecular weight
(d) Lower members have pleasant smell and burning taste, 11. Alcohols react with Grignard reagent to form
while higher members are odourless and tasteless (a) Alkanes (b) Alkenes
(c) Alkynes (d) All of these
Preparation of Alcohols
12. The alcohol that produces turbidity immediately with
4. Chlorination of toluene in the presence of light and heat ZnCl 2 + conc. HCl at room temperature
followed by treatment with aqueous NaOH gives (a) 1-hydroxybutane
(a) o-cresol (b) p-cresol (b) 2-hydroxybutane
(c) 2, 4-dihydroxy toluene (d) Benzyl alcohol (c) 2-hydroxy-2-methylpropane
(d) 1-hydroxy-2-methylpropane
5. Which of the following reagents convert the propene to
1-propanol 13. Lucas test is used for
(a) H2O, H2SO4 (b) Aqueous KOH (a) Alcohols (b) Amines
(c) MgSO4, NaBH4/H2O (d) B2H6, H2O2, OH– (c) Diethyl ether (d) Glacial acetic acid
6. Ethylene reacts with Baeyer’s reagent to give 14. Lucas reagent is

(a) Ethane (b) Ethyl alcohol (a) Conc. HCl and anhydrous ZnCl2
(c) Ethylene glycol (d) None of these (b) Conc. HNO3 and hydrous ZnCl2
(c) Conc. HCl and hydrous ZnCl2
7. Propan-1-ol can be prepared from propene by alcohol (d) Conc. HNO3 and anhydrous ZnCl2
(a) H2O/H2SO4
(b) Hg(OAc)2/H2O followed by NaBH4
(c) B2H6 followed by H2O2
(d) CH3CO2H/H2SO4
15. During dehydration of alcohols to alkenes by heating with
conc. H2SO4 the initiation step is 23. Which of the following will not react with NaOH
(a) Protonation of alcohol molecule
(b) Formation of carbocation
(c) Elimination of water
(d) Formation of an ester (a)
16. Ethylene may be obtained by dehydration of which of the

following with concentrated H2SO4 at 160–170°C
(b) C2H5OH
(a) C2H5OH (b) CH3OH
(c) CH3CONH2
(c) CH3CH2CH2OH (d) (CH3)2CHCH2OH
(d) CH(CN)3
17. Ethyl alcohol is heated with conc. H2SO4. The product formed is
24. Compound ‘A’ reacts with PCl5 to give ‘B’ which on treatment
with KCN followed by hydrolysis gave propanoic acid as
the product. What is ‘A’
(a) (b) C2H6
(a) Ethane (b) Propane
(c) C2H4 (d) C2H2 (c) Ethyl chloride (d) Ethyl alcohol
18. Which will dehydrate most easily 25. HBr reacts fastest with
(a) 3-methyl-2-butanol (b) Ethyl alcohol (a) 2-Methylpropan-1-ol (b) 2-Methylpropan-2-ol
(c) 2-methyl propane-2-ol (d) 2-methyl butan-2-ol (c) Propan-2-ol (d) Propan-1-ol
19. In the following series of chemical reactions, identify Z 26. For the reaction,
C 2 H 5OH  HX ZnCl
2  C 2 H 5 X  H 2O
the order of reactivity is
(a) (b) (a) HBr > HI > HCl (b) HI > HCl > HBr
(c) HI > HBr > HCl (d) HCl > HBr > HI
27. Methanol is industrially prepared by

(c) (d) (a) Oxidation of CH4 by steam at 900°C
(b) Reduction of HCHO using LiAlH4
(c) Reaction HCHO with a solution of NaOH
20. What is Z in the following sequence of reactions ? (d) Reduction of CO using H2 and ZnO–Cr2O3
PCl 
Z 5  X Alc
. KOH i Conc. H 2SO 4
 Y     Z 28. Victor Meyer’s test is not given by
ii  H 2O ; boil
(a) (CH3)3COH (b) C2H5OH
(c) (CH3)2CHOOH (d) CH3CH2CH2OH
(a) CH3CH2CH2OH (b) CH3CHOHCH3
(c) (CH3CH2)2CHOH (d) CH3CH = CH2
29. An organic compound ‘A’ reacts with methyl magnesium
iodide, to form an addition product which on hydrolysis
21. An organic compound A reacts with sodium metal and forms forms the compound ‘B’. Compound ‘B’ gives blue colour
B. On heating with conc. H2SO4, A gives diethyl ether. A salt in Victor Meyer’s test. The compounds ‘A’ and ‘B’ are
and B are respectively respectively
(a) C2H5OH and C2H5ONa (a) acetaldehyde and isopropyl alcohol
(b) C3H7OH and C3H7ONa (b) acetone and isopropyl alcohol
(c) CH3OH and CH3ONa (c) acetaldehyde and tertiary butyl alcohol
(d) C4H9OH and C4H9ONa (d) acetaldehyde and ethyl alcohol
22. Conc. H2SO4 reacts with C2H5OH at 170°C to form 30. Isopropyl alcohol heated at 300°C with copper catalyst to
(a) CH3COCH3 (b) CH3COOH form
(c) CH3CHO (d) C2H4 (a) Acetone (b) Dimethyl ether
(c) Acetaldehyde (d) Ethane
31. Which of the following vapours passed over heated copper
to form acetone
(a) (c) (d)
(b)
36. Ether is obtained from ethyl alcohol

(a) in presence of H2SO4 at 413 K
(b) in presence of H2SO4 at 474 K
(c)
(c) in presence of H2SO4 at 383 K
(d) in presence of H2SO4 at 273 K
(d)
37. The compound which does not react with sodium is
32. The compound which gives the most stable carbonium ion (a) C2H5OH (b)
on dehydration is (c) CH3COOH (d)
(a)
38. Product C in the following reaction, will be
(a) ethane (b) ethyl methyl ether

(b) (c) ethyl iodide (d) propane
Reactions of Ether
(c)
39. In the following reaction ‘A’ is
(d)
33. The best method to prepare cyclohexene from cyclohexanol (a) C2H5CH2CHO (b) C2H5CH2CH2OH
is by using (c) C2H5CH2OH (d) C2H5CHO
(a) Conc. HCl + ZnCl2 (b) Conc. H3PO4
(c) HBr (d) Conc. HCl 40. Which of the following product is formed, when ether is
exposed to air
Ether Preparation and Properties (a) Oxide (b) Alkanes
(c) Alkenes (d) Peroxide of diethyl ether
34. An ether is more volatile than an alcohol having the same
molecular formula. This is due to 41. The reaction of with RMgX leads to the
(a) Dipolar character of ethers
(b) Alcohols have resonating structures formation of
(c) Inter-molecular hydrogen bonding in ethers (a) RCHOHR (b) RCHOHCH3
(d) Inter-molecular hydrogen bonding in alcohols (c) R2CHCH2OH (d) RCH2CH2OH
35. What is the major product of the following reaction ? 42. Diethyl ether absorbs oxygen to form
(a) Red coloured sweet smelling compound
(b) Acetic acid
(c) Ether suboxide
(d) Ether peroxide
43. An organic compound of molecular formula C4H10O does

(a) (b)
not react with sodium. With excess of HI, it gives only one
type of alkyl halide. The compound is
(a) 1-butanol (b) ethoxyethane
(c) 1-methoxypropane (d) 2-methoxypropane
44. Diethyl ether is heated with one mole of HI, which is formed 49. The ether that undergoes electrophilic substitution reactions is
(a) Ethyl alcohol and ethyl iodide (a) CH3OC2H5 (b) C6H5OCH3
(b) Ethyl iodide only (c) CH3OCH3 (d) C2H5OC2H5
(c) Ethyl alcohol only
(d) Ethyl iodide and ethane Phenol Preparation and properties
50. Ortho-nitrophenol is steam volatile whereas para-nitrophenol

is not. This is due to
45. The ether
(a) Intramolecular hydrogen bonding present in ortho-
nitrophenol
when treated with HI produces (b) Intermolecular hydrogen bonding
(c) Intramolecular hydrogen bonding present in para-
(a) (b) nitrophenol
(d) None of these
51. Phenol is less acidic than

(a) Acetic acid (b) p-nitrophenol
(c) (d)
(c) Both (a) and (b) (d) None of these
52. Phenol is less acidic than

46. The products formed in the following reaction (a) Ethanol (b) Methanol
are (c) o-nitrophenol (d) p-methylphenol
(a)
53. The increasing order of acidity among phenol, p-methylphenol,
(b)
m-nitrophenol and p-nitrophenol is
(c) (a) m-nitrophenol, p-nitrophenol, phenol, p-methylphenol
(d) C6H6 and CH3OI (b) p-methylphenol, m-nitrophenol, phenol, p-nitrophenol
(c) p-methylphenol, phenol, m-nitrophenol, p-nitrophenol
47. On boiling with concentrated hydrobromic acid, phenyl ethyl (d) Phenol, p-methylphenol, p-nitrophenol, m-nitrophenol
ether will yield
(a) Phenol and ethyl bromide 54. Increasing order of acid strength among p-methoxyphenol,
(b) Bromobenzene and ethanol p-methylphenol and p-nitrophenol is
(c) Phenol and ethane (a) p-Nitrophenol, p-Methoxyphenol, p-Methylphenol
(d) Bromobenzene and ethane (b) p-Methylphenol, p-Methoxyphenol, p-Nitrophenol
(c) p-Nitrophenol, p-Methylphenol, p-Methoxyphenol
48. Which of the following reaction is correctly represented (d) p-Methoxyphenol, p-Methylphenol, p-Nitrophenol
55. The correct acidic order of the following is

(a)
(b)
(c)
(a) I > II > III (b) III > I > II
(c) II > III > I (d) I > III > II
(d)
56. Picric acid is 61. The compound ‘A’ when treated with methyl alcohol and few
(a) Trinitrotoluene (b) Trinitroaniline drops of H2SO4 gave smell of winter green. The compound
(c) A volatile liquid (d) 2, 4, 6-Trinitrophenol ‘A’ is
(a) oxalic acid (b) tartaric acid
Reactions of Phenols (c) salicylic acid (d) succinic acid
57. Kolbe-Schmidt reaction is used for
(a) Salicylic acid (b) Salicylaldehyde 62. With excess bromine, phenol reacts to form
(c) Phenol (d) Hydrocarbon
58. Benzenediazonium chloride on reaction with phenol in

weakly basic medium gives (a) (b)
(a) Diphenyl ether (b) p-hydroxyazobenzene
(c) Chlorobenzene (d) Benzene
59.
(c) (d) Mixture of (a) and (b)

(a)
(b) 63. Which of the following is a Riemer-Tiemann reaction

NaOH
(a) C 6 H 5 OH  CCl 4   Salicyclic acid
(c) (b) C 6 H 5 OH  Zn 
 C 6 H 6
(c) C 6 H 5 OH  NaOH 
 C 6 H 5 ONa
(d) None of these
(d)
64. In presence of NaOH, phenol react with CHCl3 to form
o-hydroxy benzaldehyde. This reaction is called
(a) Riemer-Tiemann’s reaction
60. The reaction of (b) Sandmeyer’s reaction
(c) Hoffmann’s degradation reaction
with HBr gives (d) Gattermann’s aldehyde synthesis
65. Which of the following reagents will produce salicyldehyde

(a) on reaction with phenol
(a) CHCl3/NaOH (b) CCl4/NaOH
(c) CH2Cl2/NaOH (d) CH3Cl/NaOH
(b)
66. In Friedal-Crafts acylation, besides AlCl3, the other reactants are
(c)
(a) (b)
(d)
(vii) NBS / 
(viii) SeO2 / 
(c) (d)
73. A compound with molecular formula C8H18O4 does not
Numerics give litmus test and does not give colour with 2,4–
DNP. If the compounds reacts with excess MeCOCl, it
67. Isopropyl alcohol on treatment with excess of conc. gives a compound whose. vapour density is 131.
H2SO4 gives ‘X’ which on treatment with HBr gives Compound A contains how many hydroxy groups?
‘Y’. When ‘Y’ is dissolved in ether and treated with
sodium gives ‘Z’. Calculate the molecular weight of
‘Z’. 74. How many of the following compound (s)
give(s) a yellow precipitate on hypoiodite
68. Number of products formed during dehydration of the
following compounds are: oxidation?
2-butanol, 1-acetyl cyclopentane, ethanol and
ethanal
75. How many of the following option(s) is/are correct

match?
69. Find the number of products in following reaction: (a) CH3OH – Wood alcohol
  HBr excess (b) C2H5OH – Grain alcohol
Ph  O  C2 H 5  OH 

(c)
70. What are the number of compounds having a benzene

nucleus can have the molecular formula C7H8O? (d)
71. The number of ether metamers represented by

molecular formula C4H10O, number of OH group
present in original substance is.
76. How many of the following test are used to

72. How many of the following reagents can be used to
distinguish 1o, 2o and 3o alcohol?
bring out given transformation?
(a) Lucas test
CH 3  CH 2  CH 2  OH  CH 3  CH 2  CHO
 (b) Victor Mayer test
(i) H / KMnO4 / 
(ii) TsCl/DM SO + NaHCO 3 (c) KMnO4
(iii) PCC (Pyridinium chloro chromate)
(d) Ceric ammonium nitrate test
(iv) Bendict solution
(v) Red hot Cu Tube
(vi) H  / K 2Cr2O7 / 
77. How many of the following statement(s) is/are
correct?
(a) o-phenolsulphonic acid can be converted into p-
phenolsulphonic acid in the presence of H2SO4 if
temperature is increased.
(b) Phenol is more acidic than benzyl alcohol
(c) Phenoxide ion activates the ring less in

comparison to phenol
(d) Bromination of phenol in aqueous medium

produces 2-bromophenol and 4-bromophenol.
78. ‘X’ is a smallest optically active alkanol. On

dehydration it can form Y number of alkenes
(including stereoisomers). On reaction with Lucas
reagent it forms z number of alkyl halides (including
stereoisomers). On reaction with CrO3/H+ it forms a
compound having W number of oxygen atoms. Value
of (X + Y + Z) will be
1. The reaction of with HBr
gives (2015)
(a)
(b) (a) (b)
(c)
(d)
(c) (d)
2. Phenol, when first reacts with concentrated sulphuric acid
and then concentrated nitric acid, gives
Online 2016 SET (1)
(a) o–nitrophenol (b) p–nitrophenol
6. Phenol on treatment with CO2 in the presence of NaOH
(c) Nitrobenzene (d) 2, 4,6–trinitrophenol
followed by acidification produces compound X as the
major product. X on treatment with (CH3CO)2O in the
3. The correct statement about the synthesis of erythritol
presence of catalytic amount of H2SO4 produces.
(C(CH2OH)4 used in the preparation of PETN is :
Online 2016 SET (2) (2018)
(a) The synthesis requires four aldol condensations
between methanol and ethanol.
(b) The synthesis requires two aldol condensations and
two Cannizzaro reactions.
(c) The synthesis requires three aldol condensations
and one Cannizzaro reaction.
(d) Alpha hydrogens of ethanol and methanol are
involved in this reaction.
4. The increasing order of the boiling points for the following

compounds is : Online 2017 SET( 2)
(a) (III) < (IV) < (II) < (I) (b) (IV) < (III) < (I) < (II)
(c) (II) < (III) < (IV) < (I) (d) (III) < (II) < (I) < (IV) 7. The major product of the following reaction is :
Online 2018 SET (1)
5. The major product formed in the following

reaction is: (2017)
(a) (b)
(a) (b)
(c) (d)
8. Which of the following compounds will most readily be

dehydrated to give alkene under acidic condition ?
(Online 2018 SET (3)
(a) 1-Pentanol (c) (d)
(b) 4-Hydroxypentan-2-one
(c) 3-Hydroxypentan-2-one
(d) 2-Hydroxycyclopentanone
11. The organic compound that gives following qualitative
analysis is:
9. An organic compound ‘X’ showing the following solubility Test Inference
profile is:
(a) Dil. HCl Insoluble
(b) NaOH solution Soluble
(c) Br2/water Decolourization
(2019-04-09/Shift-1)
(a) (b)
(2019-04-08/Shift-1)
(a) Oleic acid (b) o – Toluidine
(c) Benzamide (d) m – Cresol (c) (d)
10. The major product of the following reaction
12. The major product of the following reaction is:
(2019-04-08/Shift-1)
(2019-04-09/Shift-2)
(a) (b)
(a)
(c) (d)
(b) 14. What will be the major product when m-cresol is reacted
with propargyl bromide (HC  C  CH 2 Br) in presence of
K 2 CO3 in acetone (2019-04-12/Shift-2)
(a) (b)
(c)
(c) (d)
15. The products formed in the reaction of cumene with O 2

(d) followed by treatment with dil. HCl are:
(2019-01-09/Shift-2)
(a)
13. The major product of the following reaction is:
(b)
(2019-04-10/Shift-1)
18. The major product of the following reactions is:
(c)
(2019-01-11/Shift-1)
(d)
16. The increasing order of pKa values of the following

compounds is
(a) (b)
(2019-01-10/Shift-1)
(a) C < B < A < D (b) B < C < D < A
(c) D < A < C < B (d) B < C < A< D
(c) (d)
19. Which of the following compounds reacts with

ethylmagnesium bromide and also decolourizes bromine
water solution: (2019-01-11/Shift-2)
(2019-01-10/Shift-2)
(a)
(a) (b)
(b)
(c) (d)
(c)
(d)
20. (2020-09-02/Shift-2)
(a) (b)
(2019-01-12/Shift-1)
(a) CH 3CH 2 COCH 3  PhMgX
(b) PhCOCH 2 CH 3  CH 3 MgX
(c) PhCOCH3  CH 3CH 2 MgX
(d) HCHO  PhCH(CH 3 )CH 2 MgX
21. The major product of the following reaction is : (c) (d)
23. Two compounds A and B with same molecular formula

(C3H6O) undergo Grignard’s reaction with
methylmagnesium bromide to give products C and D.
Products C and D show following chemical tests.
(2019-01-12/Shift-2)
(a) (b)
C and D respectively are : (2020-09-02/Shift-2)

(a)
(c) (d)
(b)
(c)
(c)
(d)
26. The major product [B] in the following reactions is:
(d)
(2020-09-04/Shift-2)
(a) CH3  CH2  CH  CH  CH3
(b)
(c)
24. Consider the following reaction :
(d) CH2  CH2
The product ‘P’ gives positive ceric ammonium nitrate

test. This is because of the presence of which of
these – OH group (s) ? (2020-09-03/Shift-2)
(a) (b) only (b) (b) and (d)
(c) (c) and (d) (d) (d) only
(2020-09-05/Shift-2)
25. When neopentyl alcohol is heated with an acid, it
slowly converted into an 85: 15 mixture of alkenes A
and B, respectively. What are these alkenes?
(2020-09-04/Shift-1)
(a) (b)
(a)
(b) (c) (d)

28. The increasing order of boiling points of the

following is : (a)
(b)
(2020-09-05/Shift-2)
(c)
(a) I < III < IV < II
(b) III < I < II < IV
(c) I < IV < III < II
(d) III < I < II < IV (d)
29. A solution of phenol in chloroform when treated with

aqueous NaOH gives compound P as a major product.
32. Major product in the following reaction is:
The mass percentage of carbon in P is .......... (to the
nearest integer)
(Atomic mass : C = 12; H = 1 ; O = 16)
(2020-09-06/Shift-2)
(2020-01-08/Shift-1)
30. 1-methyl ethylene oxide when treated with an excess
of HBr produces: (2020-01-07/Shift-1)
(a)
(a) (b)
(b)
(c) (d)
31. In the following reaction sequence, structures of A

and B, respectively will be:
(c)
(2020-01-07/Shift-2)
(d)
33. Arrange the following compounds in increasing order

of C—OH bond length: methanol, phenol, p-
ethoxyphenol (2020-01-08/Shift-1) (c)
(a) Phenol < methanol < p-ethoxyphenol
(b) methanol < p-ethoxyphenol< phenol
(c) Phenol < p-ethoxyphenol< methanol
(d) methanol < phenol < p-ethoxyphenol
34. Find The major product [B] of the following sequence (d)
of reactions is: (2020-01-08/Shift-2)
(a)
(b)
(c)
(d)
35. Among the following compounds A and B with

molecular formula C9H18O3, A is having higher boiling
point than B. The possible structures of A and B are:
(2020-01-08/Shift-2)
(a)
(b)
Single Choice Questions

(b)
1. Total number of isomeric alcohols with formula C4H10O
is
(a) 2 (b) 1 (c)
(c) 3 (d) 4
2. When CH3MgI is made to react with acetone and the

addition product is hydrolysed, we get: (d)
(a) primary alcohol (b) secondary alcohol
(c) tertiary alcohol (d) an aldehyde
3. To prepare propan-2-ol from methyl magnesium iodide, LiAlH4

the chemical reagent required is: 8. CH3COOH  (A),
(a) CH3CHO (b) HCHO H3 O 
(A)  CH 3 COOH  (B)  H 2 O
(c) CH3COCH3 (d) CO2
In the above reaction ‘A’ and ‘B’ respectively are:
(a) CH3COOC2H5, C2H5OH (b) CH3CHO, C2H5OH
4. Which of the following will produce a primary alcohol
by reacting with CH3MgI ? (c) C2H5OH, CH3CHO (d) C2H5OH, CH3COOC2H5
(a) Ethylene oxide (b) Ethyl acetate
o
(c) Methyl cyanide (d) Acetone 9. 300 C
The product of reaction CH3CH2OH  ? is:
Cu
5. The major product formed in the following reaction is: (a) C2H6 (b) CH3COCH3
Aq. KOH
(c) CH3COOH (d) CH3CHO
CH3CH(Cl)CH2CH2OH 
(a) CH3CH=CHCH2OH (b) CH2=CHCH2CH2OH 10. The compound (B) formed in the following sequence
(c) of reactions,
5 PCl Alc.KOH
CH 3CH 2 CH 2 OH  (A)  (B) is :
(d) (a) propene (b) propyne
(c) propane (d) propanal
11. Identify (Z) in the series,

6. , (A) is: Conc. H SO
C3 H 7 OH 2 4 2
(X) 
Br
Excess of
(Y)  (Z)
o Alc. KOH
170 C
(a) (b)
(a) CH3CHO (b) CH3CH2OH
(c) H2C=CH2 (d) CH2OH–CH2OH
(c) CH 3  C  CH (d)
7. Which of the following reactions will not yield alcohol
as the major product ?
(a)
12. A compound ‘X’ undergoes reduction with LiAlH4 to
yield ‘Y’. When vapours of ‘Y’ are passed over freshly
reduced copper at 300oC, ‘X’ is formed. What is ‘Y’?
(a) CH3COCH3 (b) CH3CHO
(c) CH3CH2OH (d) CH3–O–CH3
13. The order of reactivity of the following alcohols 21. Which of the following is strongly acidic?
towards conc. HCl is: (a) Phenol (b) m-Nitrophenol
(c) m-Bromophenol (d) m-Cresol
22. Phenol is less acidic than:

(I) (II) (a) p-nitrophenol (b) ethanol
(c) cresol (d) benzyl alcohol
Zinc Conc. HNO3 Zn

23. Phenol 
distillation
(A) 
Conc. H 2SO4
(B) 
NaOH
(C)
at 60o C
In the above reaction, compounds (A), (B) and (C) are:

(III) (IV) (a) benzene, nitrobenzene and aniline
(a) I > II > III > IV (b) I > III > II > IV (b) benzene, dinitrobenzene and m-nitroaniline
(c) IV > III > II > I (d) IV > III > I > II (c) toulene, m-nitrobenzene and m-toluidine
(d) benzene, nitrobenzene and hydrazobenzene
14. HBr reacts fastest with
(a) 2-methyl propan-2-ol (b) propan-1-ol 24. Salol is prepared from:
(c) propan-2-ol (d) 2-methyl propan-1-ol (a) salicylic acid and methyl alcohol
(b) salicylic acid and phenol
15. The compound formed by reaction of ethylene glycol (c) both (a) and (b)
and periodic acid (HIO4) is: (d) none of the above
(a) carbon dioxide (b) formic acid
(c) formaldehyde (d) glyoxal
16. Heating together sodium ethoxide and ethyl chloride

will give: K 2S2 O8
25. 
Heat
?
(a) ether (b) ethyl alcohol
(c) acetaldehyde (d) acetic acid
The product formed in the reaction is:
17. Methyl phenyl ether can be obtained by reacting: (a) benzoquinone (b) diphenyl ether
(a) phenolate ions and methyl iodide (c) benzene sulphuric acid (d) hydroquinone
(b) methoxide ion and bromobenzene
(c) methanol and phenol 26. Phenol on standing in air develops a red colour due to
(d) bromobenzene and methyl bromide formation of:
(a) cyclohexane (b) resorcinol
(i) O 2 (c) phenoquinone (d) quinol
18. Cumene 
(ii) H O, H 
(X) and (Y) :
2
(X) and (Y) respectively are: 27. Phenol when condensed with phthalic anhydride in
(a) toulene, propene (b) toulene, propylchloride presence of conc. H2SO4, yields:
(c) phenol, acetone (d) phenol, acetaldehyde (a) methyl orange (b) phenolphthalein
(c) phenol red (d) salicylic acid
19. Benzene diazonium chloride on reaction with phenol in
weakly basic medium gives 28. Phenols react with ferric chloride sodium to give:
(a) diphenyl ether (b) p-hydroxy azobenzene (a) blue colouration (b) purple colouration
(c) chlorobenzene (d) benzene (c) green colouration (d) all of these
20. Phenol is more acidic than alcohol because: 29. Phenol is heated with CCl4 and alk. KOH to form salicylic
(a) phenol is more soluble in polar solvents acid. The reaction is known as:
(b) alcohol does not lose hydrogen atom (a) Friedel-Crafts reaction
(c) phenoxide ion is stabilised by resonance (b) Rosenmund reaction
(d) phenoxide ion does not exhibit resonance (c) Reimer-Tiemann reaction
(d) Perkin’s reaction
30. Sodium phenoxide when heated with CO 2 under
pressure at 125oC gives:
(a) sodium benzoate (b) salol (ii)
(c) sodium salicylate (d) salicylaldehyde
Subjective questions
39. An organic liquid ‘A’ containing C, H and O with boiling
point 78ºC, possessing a rather pleasant odour, on heating
31. State the conditions under which the following preparations with concentrated sulphuric acid gives a gaseous product
are carried out. Give necessary equations which need not ‘B’ with the empirical formula, CH2. ‘B’ decolourises bromine
be balanced. water as well as alkaline permanganate solution and takes
(i) Ethanol from acetylene up one mole of H2 (per mole of B) in presence of finely
(ii) Lead tetrathyl from sodium-lead alloy divided nickel at high temperature. Identify the substances
(iii) Methyl chloride from aluminium carbide A and B.
32. An alcohol A, when heated with conc. H2SO4 gives an alkene 40. 3, 3-dimethylbutan-2-ol losses a molecule of water in the
B. When B is bubbled through bromine water and the presence of concentrated sulphuric acid to give
product obtained is dehydrohalogenated with excess of tetramethylethylene as a major product. Suggest a suitable
sodamide, a new compound C is obtained. The compound mecahnism.
C gives D when treated with warm dilute H2SO4 in presence
of HgSO4. D can also be obtained either by oxidising A with 41. Give reasons for the following in one or two sentences.
KMnO4 or from acetic acid through its calcium salt. Identify “Acid catalysed dehydration of t-butanol is faster than that
A, B, C and D. of n-butanol.”
33. Write down the main product of the following reaction : 42. Which of the following is the correct method for synthesizing
methyl-t-butyl ether and why ?
(i) (CH3)3CBr + NaOMe
(ii) CH3Br + NaO-t-Bu
34. How may be the following transformation be carried out (in
not more than six steps) ?
“Ethyl alcohol to vinyl acetate.” 43. A compound ‘X’ containing C, H and O is unreactive towards
sodium. It does not add with bromine. It also does not react
with Schiff’s reagent. On refluxing with an excess of HI, ‘X’
35. Compound X (molecular formula, C5H8O) does not react yields only one organic product ‘Y’. ‘Y’ on hydrolysis yields
appreciably with Lucas reagent at room temperature but a new compound ‘Z’ which can be converted into ‘Y’ by
gives a precipitate with ammoniacal silver nitrate. With reaction with red phosphorus and iodine. The compound
excess of MeMgBr, 0.42 g of X gives 224 mL of CH4 at STP. ‘Z’ on oxidation with potassium permanganate gives a
Treatment of X with H2 in presence of Pt catalyst followed carboxylic acid. The equivalent weight of acid is 60. What
by boiling with excess HI, gives n-pentane. Suggest are the compounds ‘X’, ‘Y’ and ‘Z’ ? Write chemical
structure for X and write the equation involved. equations leading to the conversion of ‘X’ to ‘Y’.
36. A compound D(C8H10O) upon treatment with alkaline 

44. 2, 2-dimethyloxirane can be cleaved by acid (H ). Write
solution of iodine gives a yellow precipitate. The filtrate on mechanism.
acidification gives a white solid E (C7H6O2). Write the
structures of D, E and explain the formation of E.
45. A compound of molecular formula C7H8O is insoluble in
water and dilute sodium bicarbonate but dissolves in dilute
37. An optically active alcohol A (C6H10O) absorbs two moles aqueous sodium hydroxide and gives a characteristic colour
of hydrogen per mole of A upon catalytic hydrogenation with aqueous FeCl3. On treatment with bromine water, it
and gives a product B. The compound B is resistant to readily gives a precipitate of C7H5OBr3. Write down the
oxidation by CrO3 and does not show any optical activity. structure of the compound.
Deduce the structure of A and B.
46. Indicate steps which would convert :
38. Explain briefly the formation of products giving the (i) phenol to acetophenone
structures of the intermediates.
(ii) acetic acid to tert-butyl alcohol
(a) (i)
Multiple Choice Questions
51. Diethyl ether can be distinguished from n-butanol by:
47. When phenol is reacted with CHCl3 and NaOH followed
(a) aqueous FeCl3
by acidification, salicylaldehyde is obtained. Which of
(b) reaction with Na metal
the following species are involved in the above
(c) tollens reagent
mentioned reaction as intermediates ?
(d) reaction with CrO3 in dil H2SO4
52. What is the function of diethyl ether in the preparation

of Grignard reagent?
(a) (b) (a) To act as a catalyst
(b) To act as a solvent
(c) To provide lone pair of electrons for coordination
(d) To act as an acid
(c) (d)
53. The ether when
treated with HI produces:

48. Which of the following alcohol(s) can be prepared by
the action of Grignard reagents with aldehydes?
(a) Primary alcohols (a) (b)
(b) Secondary alcohols
(c) Tertiary alcohols
(d) Both primary and tertiary alcohols (c) (d)
49. Alcohol
54. When phenol is treated with CHCl3 and NaOH followed
by acidification, salicylaldehyde is obtained. Which of
which is/are true about alcohol and R? the following species are involved in the above
mentioned reaction as intermediates ?
Alcohol Reagent(R)
(a) BH3/THF, H2O2/OH–
(a) (b)
(b) Hg(OAc)2/NaBH4–H2O
(c)
(c) (d)
(d) None of the above

55. Salicylic acid is prepared from phenol by:
50. Which of the following reactions will yield propan-2- (a) Reimer-Tiemann reaction
ol?
(b) Kolbe’s electrolytic reaction

H
(a) H 2 C = CH  CH3  HOH  (c) Kolbe’s reaction
(d) none of the above
3 CH MgBr
(b) CH3  CHO 
HOH
(i) C H MgI
2 5
(c) CH 2 O 
(ii) HOH

NeutralKMnO4
(d) H 2 C  CH  CH 3  
Comprehension based questions
Comprehension
Secondary and tertiary alcohols always gives E1 reac-
tion in dehydration. Primary, alcohols whose -carbon
o o
is 3 or 4 also give E1 reaction. However, the primary
o o
alcohols whose -carbon is 1 or 2 give E2 reaction.
Dehydrating agents like conc. H2SO4, Al2O3, anhydrous
ZnCl2 are used.
The reactivity of alcohols for elimination reaction lies
in following sequence:
Tertiary alcohol > secondary alcohol > primary alcohol
Electron attracting groups present in alcohols increase
the reactivity for dehydration. Greater is the –I effect of
the group present in alcohol, more will be its reactivity.
Both E1 and E2 mechanism give the product according
to Saytzeff’s rule, i.e., major product is the most substi-
tuted alkene
Answer the following questions: (a) A > B > C > D (b) D > C > B > A
(c) C > B > D > A (d) B > C > A > D
56. Which among the following alcohols will be the most
reactive for dehydration?
(a) 58. In the reaction, the
product(s) obtained will be:

(b)
(a)
(c)
(b)
(d)
(c)
57. Arrange the reactivity of given four alcohols in (d) this alcohol cannot be dehydrated
decreasing order of dehydration.
59. Which among the following sequences of reactivity Assertion–Reason type questions
for dehydration is incorrect?
(a) Both Assertion and Reason are true and Reason is the
correct explanation of ‘Assertion’
(a) < < (b) Both Assertion and Reason are true and Reason is not
(c) Assertion is true but Reason is false
(d) Assertion is false but Reason is true
(b) CH3CH2CH2CH2OH < CH 3 – C H – CH 2 – CH3 <

 64. Assertion: Alcohols can be dried over anhydrous CaCl2.
Reason: Anhydrous CaCl2 absorbs moisture of aqueous
ethyl alcohol
(a) A (b) B
(c) < < (c) C (d) D
65. Assertion: HIO4, decomposes, 1,2-glycols but not 1,3-

or higher glycols.
Reason: Only 1,2-glycols from cyclic esters which
(d) < < subsequently undergo cleavage to form carbonyl
compounds.
(a) A (b) B
Comprehension (c) C (d) D
By a proper choice of reagents, both symmetrical and
unsymmetrical ethers can be prepared by Williamson 66. Assertion: Grignard reagent reacts with aldehydes and
synthesis which involves the reaction between an alkyl ketones to form alcohol.
halide and an alkoxide ion. The reverse process Reason: Alcohols have acidic hydrogen.
involving the cleavage of ethers to give back the (a) A (b) B
original alkyl halide and the alcohol can be carried out (c) C (d) D
by heating the ether with HI at 373 K.
67. Assertion : A rate of hydrolysis of methyl chloride to
60. Which of the following reagents when heated will give methanol is higher in DMF than in water.
a good yield of an ether Reason : Hydrolysis of methyl chloride follows second
(a) Isopropyl bromide and sodium isopropoxide order kinetics.
(b) Isopropyl bromide and sodium ethoxide (a) A (b) B
(c) Bromobenzene and sodium phenoxide (c) C (d) D
(d) Sodium tert-butoxide and ethyl bromide
68. Assertion : Resorcinol turns FeCl3 solution purple.
61. Which of the following ethers can be prepared by Reason : Resorcinol have phenolic group.
Willamson synthesis ? (a) A (b) B
(a) Benzyl methyl ether (b) Methyl vinyl ether (c) C (d) D
(c) Divinyl ether (d) Diphenyl ether
69. Assertion : Phenol undergo Kolbe reaction, ethanol
62. Allyl phenyl ether can be prepared by heating does not.
(a) C6H5Br + CH2 = CH—CH2ONa Reason : Phenoxide ion is more basic than ethoxide
ion.
(b) CH2 = CHCH2 Br + C6H5ONa (a) A (b) B
(c) C6H5CH = CHBr + CH3ONa (c) C (d) D
(d) CH2 = CHBr + C6H5CH2ONa
70. Assertion: Phenol is more reactive than benzene
63. Benzyl ethyl ether reacts with HI to form towards electrophilic substitution.
(a) p-Iodotoluene and ethyl alcohol Reason: In the case of phenol, the intermediate
(b) Benzyl alcohol and ethyl iodide carbocation is more resonance stabilized.
(c) Benzyl iodide and ethyl alcohol (a) A (b) B
(d) Iodobenzene and ethyl alcohol (c) C (d) D
71. Assertion: o-Phenol sulphonic acid on heating at 100oC
changes to p-phenol sulphonic acid
Reason: Sulphonation of phenol is a reversible process.
(a) A (b) B
(c) C (d) D
72. Assertion: Friedal-Crafts reaction between benzene and

acetic anhydride in presence of anhydrous AlCl3 yields
acetophenone and not polysubstitution product.
Reason: Acetophenone formed poisons the catalyst,
preventing further reaction.
(a) A (b) B
(c) C (d) D
Matrix–match type questions
73. (X) Match the following :

Column-I Column-II
(Compound) (Possible reaction)
(A) (P) Reaction with NaOH
(B) (Q) Reaction with NaHCO3
(C) CH3COOH (R) Reaction with PCl5

(D) C2H5OH (S) Reaction with NH3

Objective Questions I [Only one correct option]
(c)
1. Which one of the following will most readily be dehydrated
in acidic condition ? (2000)
(d) CH3CH2OH + NCONHNH2
(a) (b)
6.
(c) (d)
How many structures of F is possible ? (2003)

(a) 2 (b) 5
2. Cyclobutylbromide on treatment with magnesium in dry ether (c) 6 (d) 3
forms an organometallic compound (A). The organometallic
reacts with ethanal to give an alcohol (B) after mild 7. An organic compound ‘P’ having the molecular formula
acidification. Prolonged treatment of alcohol (B) with an C5H10O when treated with dil H2SO4 gives two compounds,
equivalent amount of HBr gives 1-bromo-1- Q & R both gives positive iodoform test. The reaction of
methylcyclopentane (C). Write the structures of (A), (B) C5H10O with dil H2SO4 gives reaction 1015 times faster than
and explain how (C) is obtained from (B). (2001) ethylene. Identify organic compound of Q and R. Give the
reason for the extra stability of P. (2004)
3. 1-propanol and 2-propanol can be best distinguished by
(2001)
(a) oxidation with alkaline KMnO4 followed by reaction with
Fehling solution
(b) oxidation with acidic dichromate followed by reaction
with Fehling solution 8.
(c) oxidation by heating with copper followed by reaction
with Fehling solution
(d) oxidation with concentrated H2SO4 followed by reaction
with Fehling solution
4. The compound that will react most readily with NaOH to

form methanol is (2001)
(a) (b) CH3OCH3 Identify X and Y. (2005)
(c) (d) (CH3)3CI 9. When phenyl magnesium bromide reacts with tert. butanol,
which of the following is formed ? (2005)
(a) Tert. butyl methyl ether
5. Compound ‘A’ (molecular formula C3H8O) is treated with (b) Benzene
acidified potassium dichromate to form a product ‘B’ (c) Tert. butyl benzene
(molecular formula C3H6O) ‘B’ forms a shining silver mirror (d) Phenol
on warming with ammoniacal silver nitrate. ‘B’ when treated
with an aqueous solution of H2NCONHNH2 and sodium
acetate gives a product ‘C’. Identify the structure of ‘C’. 10. The best method to prepare cyclohexene from cyclohexanol
(2002) is by using (2005)
(a) CH3CH2CH NNHCONH2 (a) conc. HCl + ZnCl2 (b) conc. H3PO4
(c) HBr (d) conc. HCl
(b)
11. (I) 1, 2-dihydroxy benzene (2006)
(II) 1, 3-dihydroxy benzene
(III) 1, 4-dihydroxy benzene
(IV) Hydroxy benzene
The increasing order of boiling points of above mentioned (c) (d)
alcohols is
(a) I < II < III < IV (b) I < II < IV < III
(c) IV < I < II < III (d) IV < II < I < III
12. CH3NH2 + CHCl3 + KOH  Nitrogen containing compound Comprehension

+ KCl + H2O. Nitrogen containing compound is
A tertiary alcohol H upon acid catalysed dehydration gives
(2006) a product I. Ozonolysis of I leads to compounds J and K.
(a) (b) Compound J upon reaction with KOH gives benzyl alcohol
and a compound L, where K on reaction with KOH gives
(c) (d) only M.
Comprehension
Reimer-Tiemann reaction introduces an aldehyde group, on
to the aromatic ring of phenol, ortho to the hydroxyl group.
This reaction involves electrophilic aromatic substitution.
This is a general method for the synthesis of substituted
(2008)
salicylaldehydes as depicted below :
16. Compound H is formed by the reaction of
(2007)
(a)
(b)
13. Which one of the following reagents is used in the above

reaction ? (c)
(a) aq. NaOH + CH3Cl
(b) aq. NaOH + CH2Cl2
(c) aq. NaOH + CHCl3
(d) aq. NaOH + CCl4 (d)
14. The electrophile in this reaction is

(a) : CHCl (b) CHCl2 17. The structure of compound I is
(c) : CCl2 (d) • CCl3
15. The structure of the intermediate I is (a) (b)
(a) (b) (c) (d)

18. The structures of compounds J, K and L respectively, are

(a) PhCOCH3, PhCH2COCH3 and PhCH2COO–K+
(b) PhCHO, PhCH2CHO and PhCH2COO–K+
(c) PhCOCH3, PhCH2CHO and CH3COO–K+
(d) PhCHO, PhCOCH3 and PhCOO–K+
Assertion Reason
(A) If both ASSERTION and REASON are true and

reason is the correct explanation of the assertion.
(B) If both ASSERTION and REASON are true but reason
is not the correct explanation of the assertion.
(C) If ASSERTION is true but REASON is false.
(D) If both ASSERTION and REASON are false.
(E) If ASSERTION is false but REASON is true.
19. Assertion : Bromobenzene, upon reaction with Br2/Fe gives

1, 4-dibromobenzene as the major product.
Reason : In bromobenzene, the inductive effect of the
bromo group is more dominant than the
mesomeric effect in directing the incoming
electrophile. (2008)
(a) A (b) B The correct option is (2018)

(c) C (d) D (a) P - 1; Q - 2,3; R - 1, 4; S - 2, 4
(e) E (b) P - 1, 5; Q - 3,4; R - 4, 5; S - 3
(c) P - 1,5; Q - 3,4; R - 5; S - 2, 4
20. The acidic hydrolysis of ether (X) shown below is fastest (d) P - 1, 5; Q - 2, 3; R - 1,5; S - 2, 3
when (2014)
Multiple Answer Questions
22. Among the following reactions(s) which gives(give)

tert-butyl benzene as the major product is(are) (2016)
(a) (b)
(a) one phenyl group is replaced by a methyl group.

(c) (d)
(b) one phenyl group is replaced by a para-methoxphenyl
group.
(c) two phenyl groups are replaced by two
para-methoxyphenyl groups. 23. The correct combination of names for isomeric alcohols with
(d) no structural change is made of X. molecular formula C4H10O is/are (2014)
(a) tert-butanol and 2-methylpropan-2-ol
21. The desired product X can be prepared by reacting the major (b) tert-butanol and 1, 1-dimethylethan-1-o1
product of the reaction in List-I with one or more appropriate (c) n-butanol and butan1-ol
reagents in List-II (d) isobutyl alcohol and 2-methylpropan 1-ol
(given, order of migratory aptitude : ary1 > alkyl > hydrogen)
24. The number of resonance structures for N is (2015) 26. An organic compound (C8 H10 O 2 ) rotates plane-
polarized light. It produces pinkcolor with neutral
FeCl3 solution. What is the total number of all the
possible isomers for this compound?
(2020/Shift-2)
25. Choose the correct option(s) for the following set of

reactions
(2019/Shift-1)
(a)
(b)
(c)
(d)
Note:

ANSWER KEY 190
Answer Key
CHAPTER -1 GENERAL ORGANIC CHEMISTRY-2
EXERCISE - 1 : EXERCISE - 2 :
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS
DIRECTION TO USE - DIRECTION TO USE -

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.
1. (a) 2. (a) 3. (b) 4. (c) 5. (b) 1. (d) 2. (d) 3. (c) 4. (a) 5. (c)
6. (d) 7. (b) 8. (c) 9. (c) 10. (b) 6. (b) 7. (d) 8. (a) 9. (a) 10. (b)
11. (d) 12. (b) 13. (b) 14. (c) 15. (c) 11. (c) 12. (b) 13. (d) 14. (c) 15. (c)
16. (c) 17. (c) 18. (d) 19. (b) 20. (d)
16. (b) 17. (d) 18. (c) 19. (b) 20. (c)
21. (c) 22. (d) 23. (d) 24. (b) 25. (d)
26. (c) 27. (b) 28. (b) 29. (c) 30. (b) 21. (a, b)
31. (d) 32. (a) 33. (c) 34. (a) 35. (b)
36. (c) 37. (d) 38. (b) 39. (d) 40. (d)
41. (d) 42. (d) 43. (d) 44. (d) 45. (d)
46. (b) 47. (a) 48. (b) 49. (a) 50. (b)
51. (a) 52. (b) 53. (c) 54. (d) 55. (d)
56. (c) 57. (c) 58. (c) 59. (b) 60. (d)
61. (c) 62. (c) 63. (b) 64. (c) 65. (b)
66. (b) 67. (c) 68. (b) 69. (a) 70. (c)
71. (a) 72. (c) 73. (a) 74. (c) 75. (c)
76. (c) 77. (b) 78. (a) 79. (b) 80. (c)
81. (c) 82. (b) 83. (a) 84. (c)
ANSWER KEY 191
EXERCISE - 3 :
ADVANCED OBJECTIVE QUESTIONS
DIRECTION TO USE -
Scan the QR code and check detailed solutions.
1. (a) 2. (d) 3. (c) 4. (d) 96. (Cyclopropane)

5. (c) 6. (d) 7. (d) 8. (b) 97. (Butanedioic acid)
9. (a) 10. (a) 11. (a) 12. (a) 98. (non-superimposable, enantiomers)
13. (b) 14. (a) 15. (a) 16. (b) 99. (A-,q B-r, C-s, D-p)
17. (c) 18. (c) 19. (b) 20. (c) 100. (A-p, r; B-q,s; C-p,q,r; D-p)
21. (b) 22. (b) 23. (b) 24. (c) 101. (A-p,q,r,s; B-p,q,s; C-p,s; D-p)
25. (c) 26. (c) 27. (c) 28. (b) 102. (A-q; B-q,r; C-p,q D-s)
29. (c) 30. (d) 31. (b) 32. (a) 103. (A-r; B-p; C-q; D-q)
33. (b) 34. (a) 35. (a) 36. (b)
37. (d) 38. (c) 39. (a,d) 40. (a,b)
41. (c,d) 42. (b,d) 43. (b,c) 44. (a,d)
45. (a,b,d) 46. (a,c,d) 47. (b,c,d) 48. (a,b,d)
49. (c, d) 50. (a,b) 51. (a,b) 52. (b,d)
53. (c,d) 54. (a,c,d) 55. (a,b,d) 56. (a,b,d)
57. (c,d) 58. (c,d) 59. (a,c) 60. (a,b,c,d)
61. (a) 62. (c) 63. (b) 64. (c)
65. (c) 66. (c) 67. (a) 68. (d)
69. (a) 70. (c) 71. (b) 72. (b)
73. (b) 74. (a) 75. (a) 76. (c)
77. (b) 78. (a) 79. (d) 80. (a)
81. (a) 82. (a) 83. (0008) 84. (0003)
85. (5) 86. (0621) 87. (0004) 88. (0006)
89. (Text) 90. (Text) 91. (0003) 92. (0004)
93. (0064) 94. (0008) 95. (2341)
ANSWER KEY 192
EXERCISE - 4 :
PREVIOUS YEAR JEE ADVANCED QUESTIONS
DIRECTION TO USE -
1. (a) 2. (Text) 3. (d) 4. (d)

5. (c) 6. (Text) 7. (a) 8. (c)
9. (b) 10. (a,d) 11. (b,c,d) 12. (Text)
13. (a,d) 14. (a) 15. (a,c) 16. (Text)
17. (10.00) 18. (c) 19. (c) 20. (a,b,c)
21. (c,d)
ANSWER KEY 193
Answer Key
CHAPTER -2 REAGENTS AND MECHANISM AND ALKYL HALIDES
EXERCISE - 1 :
BASIC OBJECTIVE QUESTIONS
DIRECTION TO USE -
1. (a) 2. (a) 3. (c) 4. (a) 81. (a) 82. (d) 83. (a) 84. (b)
5. (a) 6. (a) 7. (b) 8. (b) 85. (d) 86. (a) 87. (a) 88. (c)
9. (b) 10. (a) 11. (c) 12. (d) 89. (d) 90. (c) 91. (b) 92. (a)
13. (a) 14. (c) 15. (c) 16. (d) 93. (d) 94. (a) 95. (c) 96. (b)
17. (b) 18. (d) 19. (a) 20. (a) 97. (a) 98. (d) 99. (d) 100. (d)
21. (a) 22. (a) 23. (d) 24. (d) 101. (a) 102. (c) 103. (b) 104.(a)
25. (b) 26. (c) 27. (a) 28. (c) 105. (d) 106. (a,d) 107. (a) 108. (c)
29. (a) 30. (b) 31. (c) 32. (d) 109. (c) 110. (b) 111. (c) 112. (d)
33. (c) 34. (c) 35. (b) 36. (b) 113. (a) 114. (b) 115. (a) 116. (d)
37. (b) 38. (d) 39. (c) 40. (b) 117. (b) 118. (a) 119. (c) 120. (c)
41. (b) 42. (a) 43. (b) 44. (d) 121. (c) 122. (b) 123. (a) 124. (d)
45. (c) 46. (c) 47. (b) 48. (a) 125. (d) 126. (c) 127. (a) 128. (c)
49. (c) 50. (a) 51. (b) 52. (d) 129. (a) 130. (b) 131. (a) 132. (b)
53. (b) 54. (b) 55. (c) 56. (a) 133. (b) 134. (b) 135. (c,d) 136. (a)
57. (a) 58. (a) 59. (b) 60. (b) 137. (b) 138. (c) 139. (b) 140. (a)
61. (b) 62. (a) 63. (b) 64. (d) 141. (c) 142. (b) 143. (c) 144. (a)
65. (d) 66. (d) 67. (d) 68. (a) 145. (b) 146. (c) 147. (a) 148. (b)
69. (b) 70. (a) 71. (b) 72. (d) 149. (73) 150. (5,3) 151. (6) 152. (4)
73. (a) 74. (d) 75. (a) 76. (b) 153. (3) 154. (3) 155. (zero) 156. (2.00)
77. (d) 78. (b) 79. (b) 80. (a) 157. (3.00) 158. (3.00) 159. (3.00) 160. (3.00)
161. (2.00) 162. (4.00)
ANSWER KEY 194
PREVIOUS YEAR JEE MAIN QUESTIONS ADVANCED OBJECTIVE QUESTIONS
DIRECTION TO USE -
DIRECTION TO USE - Scan the QR code and check detailed solutions.
Scan the QR code and check detailed solutions. 1. (d) 2. (b) 3. (b) 4. (d)
5. (a) 6. (d) 7. (d) 8. (c)
1. (c) 2. (D>C>A>B) 3. (d) 4. (b) 9. (a) 10. (c) 11. (b) 12. (d)
5. (a) 6. (a) 7. (b) 8. (b) 13. (a) 14. (a) 15. (b) 16. (b)
9. (d) 10. (a) 11. (b) 12. (d) 17. (b) 18. (c) 19. (c) 20. (b)
13. (b) 14. (b) 15. (d) 16. (d) 21. (c) 22. (a) 23. (c) 24. (a)
17. (b) 18. (b) 19. (a) 20. (a) 25. (b) 26. (a) 27. (d) 28. (c)
21. (a) 22. (b) 23. (a) 24. (a) 29. (c) 30. (d) 31. (d) 32. (b)
25. (a) 26. (b) 27. (c) 28. (d) 33. (d) 34. (b) 35. (a) 36. (a)
29. (d) 30. (d) 31. (c) 32. (d) 37. (a) 38. (d) 39. (d) 40. (b)
33. (b) 41. (b) 42. (d) 43. (d) 44. (c)
45. (b) 46. (a) 47. (b) 48. (c)
49. (d) 50. (a) 51. (d) 52. (d)
53. (c) 54. (a) 55. (b) 56. (a,c,d)
57. (a,b) 58. (b,c,d) 59. (a,b,d) 60. (a,c,d)
61. (c,d) 62. (a,c) 63. (a,b,c,d) 64. (a,b,c)
65. (a,b,c) 66. (b,c,d) 67. (a,c,d) 68. (a,c,d)
69. (a,b) 70. (a,b) 71. (a,b,d) 72. (a,b,c)
73. (a,b,d) 74. (b) 75. (a,b,d) 76. (b,c)
77. (b,c,d) 78. (a,b,c,d) 79. (b,d) 80. (a)
81. (c) 82. (b) 83. (a) 84. (c)
85. (a) 86. (b) 87. (d) 88. (a)
89. (d) 90. (d) 91. (a) 92. (c)
93. (b) 94. (b) 95. (a) 96. (b)
97. (d) 98. (c) 99. (d) 100. (a)
101. (a) 102. (d) 103. (a) 104.(c)
105. (d) 106. (b) 107. (e) 108. (b)
109. (a) 110. (c) 111. (c) 112. (d)
113. (a) 114. (b) 115. (b) 116. (a)
117. (c) 118. (a) 119. (a)
120.(A-q; B-s; C-p; D-r)
121. (A-q, B-s, C-p, D-r) 122. (A-s, B-r, C-q, D-r)
123.(A-s, B-r, C-q, D-s) 124. (A-s, B-r, C-p, D -q)
125.(A-q,r : B-q,r : C-p;D-s)
126. (A-r, s; B-S; C-q; D-P)
127. (A-p,q,r; B-p,r; C-p,s; D-p,r)
128. (A-r, s; B-r, s; C-p, r; D-p, q) 129. (0006)
130. (0004) 131. (0004) 132. (0004)
133. ((4)- b d e f) 134. (0003) 135. (003)
136. (008)
ANSWER KEY 195

EXERCISE - 4 :
PREVIOUS YEAR JEE ADVANCED QUESTIONS
DIRECTION TO USE -
1. (c) 2. (d) 3. (d) 4. (c)

5. (Text) 6. (Text) 7. (d) 8. (Text)
9. (b) 10. (d) 11. (b) 12. (a)
13. (Text) 14. (a) 15. (a) 16. (a)
17. (b,d) 18. (b)
ANSWER KEY 196
Answer Key
CHAPTER -3 ALCOHOLS, PHENOLS AND ETHERS
BASIC OBJECTIVE QUESTIONS PREVIOUS YEAR JEE MAIN QUESTIONS

1. (b) 2.(a) 3.(c) 4.(d) 5.(d) 1. (b) 2. (d) 3. (c) 4. (a) 5. (a)
6. (c) 7.(c) 8.(d) 9.(c) 10.(c) 6. (b) 7. (b) 8. (b) 9. (d) 10. (d)
11. (a) 12.(c) 13.(a) 14.(a) 15.(a) 11. (b) 12. (c) 13. (c) 14. (c) 15. (c)
16.(a) 17.(c) 18.(c) 19.(d) 20.(b) 16. (d) 17. (b) 18. (a) 19. (b,c) 20. (a)
21. (a) 22.(d) 23.(b) 24.(d) 25.(b) 21. (b) 22. (c) 23. (b) 24. (a) 25. (c)
26. (c) 27. (c) 28. (c) 29. (68.85%)
26. (c) 27.(d) 28.(a) 29.(a) 30.(a)
30. (c) 31. (a) 32. (c) 33. (c) 34. (c)
31. (b) 32.(b) 33.(b) 34.(d) 35. (d)
35. (b)
36. (a) 37.(b) 38.(b) 39.(b) 40.(d)
41. (d) 42.(d) 43.(b) 44.(a) 45.(a,d)
46. (b) 47.(a) 48.(a) 49.(b) 50.(a)
51. (c) 52.(c) 53.(c) 54.(d) 55.(b)
56. (d) 57.(a) 58.(b) 59.(a) 60.(b)
61. (c) 62.(c) 63.(a) 64.(a) 65.(a)
66. (b) 67. (86.00) 68. (4.00) 69. (2.00)
70. (5.00) 71. (4.00) 72. (4.00) 73. (2.00) 74. (4.00)
75. (4.00) 76. (3.00) 77. (2.00) 78. (6.00)
ANSWER KEY 197
CHAPTER -3 ALCOHOLS, PHENOLS AND ETHERS
ADVANCED OBJECTIVE QUESTIONS PREVIOUS YEAR JEE ADVANCED QUESTIONS

1.(d) 2.(d) 3.(a) 4.(a) 1. (a) 2. (Text) 3. (c) 4. (a)

5.(d) 6.(b) 7.(a) 8.(d) 5. (a) 6. (d) 7. (Text) 8. (Text)
9. (b) 10. (b) 11. (c) 12. (d)
9.(d) 10.(a) 11.(c) 12.(c)
13. (c) 14. (c) 15. (b) 16. (b)
13.(c) 14.(a) 15.(c) 16.(a) 17. (a) 18. (d) 19. (b) 20. (c)
17.(a) 18.(c) 19.(b) 20.(c) 21. (d) 22. (b,c,d) 23. (a,c,d) 24. (9)
25. (a,c) 26. (006.00)
21.(b) 22.(a) 23.(d) 24.(b)
25.(d) 26.(c) 27.(b) 28.(d)
29.(c) 30.(c) 31.(Text) 32.(Text)
33.(Text) 34.(Text) 35.(Text) 36.(Text)
37.(Text) 38.(Text)
39.(A is ethanol B is an alkene) 40.(Text)
41.(Text) 42.(Text) 43.(Text) 44.(Text)
45.(Text) 46.(Text) 47.(a,d) 48.(a,b)
49.(a,b,c) 50. (a,b) 51. (b,d) 52. (b,c)
53. (a,d) 54. (a,d) 55. (a,c) 56. (a)
57. (c) 58. (a,b) 59. (c) 60. (d)
61. (a) 62. (b) 63. (c) 64. (d)
65. (a) 66. (b) 67. (c) 68. (a)
69. (c) 70. (a) 71. (b) 72. (c)
73. (A–P, R, S; B–P, Q, R, S; C–P, Q, R, S; D–P, R, S)
ANSWER KEY 198
Note

JEE - MODULE 2 - CHEM - Organic Chemistry 1

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

JEE - MODULE 2 - CHEM - Organic Chemistry 1

Uploaded by

Copyright:

Available Formats

Published by

Vedantu Innovations Private Limited

Key Points on ‘How to obtain optimal benefits from ‘Tatva’ ?

I wish you all the best.

Anand Prakash Sir has been a pioneer in producing

Suraj Bhan Singh

GENERAL ORGANIC CHEMISTRY-2

Exercise - 1 : Basic Objective Questions........................................................................................... 39

Exercise - 2 : Previous Year JEE MAIN Questions ............................................................................ 47

REAGENTS AND MECHANISM AND ALKYL HALIDES

Solved Examples ............................................................................................................................... 80

Exercise - 1 : Basic Objective Questions........................................................................................... 88

Exercise - 2 : Previous Year JEE MAIN Questions ............................................................................ 108

Exercise - 3 : Advanced Objective Questions ................................................................................. 114

Exercise - 4 : Previous Year JEE Advanced Questions .................................................................... 134

Answer Key ........................................................................................................................................ 193

Theory ...................................................................................................................................................... 138

Exercise - 1 : Basic Objective Questions.................................................................................................. 163

Exercise - 2 : Previous Year JEE MAIN Questions ................................................................................... 170

Answer Key .............................................................................................................................................. 196

GENERAL ORGANIC CHEMISTRY-2

1. Introduction General Organic Chemistry is the detailed study of the

Hybridisation is a process in which two or more atomic

Wohler successfully synthesized an organic compound

2.2 Dienes (a) Isolated Diene

Table : Hybridization of Common Molecules.

(b) Conjugated Diene

(A) Characterstics of Inductive Effect (b) Applications of Inductive Effect

 Effect on Acidic/Basic Strength

 Nature of Inductive Effect

(a) Compare the acidic strength of :

Order of acidic strength : II > III > IV > I

Series of +I and –I groups in order of their strength

 Basicity of Amines Example

To determine the basic strength of amines in aqueous

(A) Conjugated Systems

(3) Pi alternate Negative Charge (C) Criteria for Major/Minor Contributors

Example Resonance forms can be compared using the following

(B) Rules for Validity of Lewis Structures

(ENZ > ENY)

(a) Electron-Releasing and Electron-Withdrawing Groups

Groups which release or withdraw electrons by resonance

 Electron-Withdrawing Groups (–R or –M effect)

EWG increases the acidic strength and decreases the basic

Arrange the following in the order of decreasing acidic

Order of acidic strength

(2) Effect on Reactivity of Carboxylic Acid Derivatives

A typical nucleophilic reaction is represented as :

The order of acidic strength is : II > V > I > III > IV

The stronger is the bond between C and Z, the difficult it

Reactivity order of carboxylic acid derivatives towards

Now, greater the number of -H, greater the number of

3.3 HYPERCONJUGATION Methyl > 1° > 2° > 3°

Which alkene is more stable ?

-Carbon is the carbon attached to a functional group such

(b) Mechanism of Electron Donation in Hyperconjugation

I is more stable than II.

Resonance/Mesomeric Effect is a - interaction and acts

2. STERIC INHIBITION OF RESONANCE (SIR)

Mark the order of basic strength :

3.4 ELECTROMERIC EFFECT

Electromeric effect is observed only in the presence of a