Volume-02 Functional Group Organic Chemistry-I

BCHCT-133
Indira Gandhi National

Open University
CHEMICAL ENERGETICS,
School of Sciences EQUILIBRIA AND
FUNCTIONAL ORGANIC
CHEMISTRY-I
FUNCTIONAL GROUP ORGANIC Vol. 2

CHEMISTRY-I
BCHCT-133
Indira Gandhi National Open University EQUILIBRIA AND
School of Sciences
FUNCTIONAL ORGANIC
CHEMISTRY-I
VOL.
2
FUNCTIONAL GROUP ORGANIC
CHEMISTRY-I
BLOCK 3
AROMATIC HYDROCARBONS AND
HALOGEN DERIVATIVES 5
BLOCK 4
OXYGEN CONTAINING ORGANIC
COMPOUNDS 115
Course Design Committee
Dr. Rakesh Kumar School of Sciences,

Dept. of Chemistry, IGNOU
University of Delhi,
Delhi Prof. Vijayshri, Director
Prof. Sunita Malhotra
Dr. Vijay Sarda (Retd.) Prof. Bharat Inder Fozdar
Dept. of Chemistry, Prof. Javed A. Farooqi
Zakir Husain College Prof. Sanjiv Kumar
University of Delhi, Prof. Lalita S. Kumar
Delhi Prof. Kamalika Banerjee
Dr. Toqueer Ahmad

Dept. of Chemistry,
Jamia Millia Islamia,
New Delhi
Dr. C. K. Seth
Dept. of Chemistry,
Hindu College
University of Delhi,
Delhi
Block Preparation Team

Prof. Bharat Inder Fozdar (Units 13-19) Prof. J.M. Khurana (Editor)
School of Sciences, IGNOU Department of Chemistry, DU, Delhi
Prof. Javed A. Farooqi (Units 10-12)
School of Sciences, IGNOU
Course Coordinators: Prof. Bharat Inder Fozdar and Prof. Sanjiv Kumar
Production
Mr. Rajiv Girdhar Mr. Sunil Kumar Mr. Hemant Kumar
AR(P), MPDD, IGNOU AR(P), SOS, IGNOU SO(P), MPDD, IGNOU
Acknowledgements:
 Sh. Sarabjeet Singh for word processing and CRC preparation.
 The utilisation of some content of Units 6-14 of Organic Chemistry (CHE 05) course is
gratefully acknowledged.
December, 2019
Indira Gandhi National Open University, 2019
ISBN: 978-93-89668-67-4
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BCHCT-133
Indira Gandhi National EQUILIBRIA AND
Open University
School of Sciences FUNCTIONAL ORGANIC
CHEMISTRY I
Block
3
AROMATIC HYDROCARBONS AND HALOGEN
DERIVATIVES
UNIT 10
Preparation of Aromatic Compounds 5
UNIT 11
Reactions of Aromatic Hydrocarbons-I 23
UNIT 12
Reactions of Aromatic Hydrocarbons-II 40
UNIT 13
Alkyl Halides 55
UNIT 14
Aryl Halides 94
AROMATIC HYDROCARBONS AND HALOGEN
DERIVATIVES
In the first course of first semester, we introduced you to the basic concepts of organic
chemistry. In that course you learnt about the aliphatic hydrocarbon compounds mainly. A
brief description about aromaticity in terms of experimental and theoretical criteria was also
dealt in the last unit of that course.
This block contains five units. In Unit 10, 11 and 12 deal with the aromatic hydrocarbons. In
these units you will study the preparations and properties of benzene. We shall see the
characteristic reactions of aromatic hydrocarbons involve electrophilic substitution reactions,
in which the resonance-stabillised ring system is preserved. In the Unit 12, we shall also take
up the effect of substituents on the reactivity and the orientation in the benzene ring.
Unit 13 and Unit 14 deal with the chemistry of the halogen derivatives. In Unit 11, our main
focus is on the chemistry of alkyl halides. Some important reactions of alkyl halides such as
nucleophilic substitutions (SN1 and SN2) and elimination reactions (E1 and E2) will be dealt in
detail. In Unit 14 we shall take up the unique chemistry of aryl halides. This unit ends with the
description on the relative reactivity and relative strength of CꟷX bond in different type of
halogen derivatives.
Expected Learning Outcomes

After studying this block, you should able to:
 describe the preparations of benzene;
 discuss the important reactions of benzene;
 explain the effect of substituents on the reactivity and orientation in benzene ring;
 classify and draw structures of simple halogen derivatives;
 outline the methods of preparation of aliphatic and aromatic halogen derivatives;
 describe reactions of aliphatic and aromatic halogen derivatives;
 explain the mechanism of nucleophilic substitution and elimination reactions of alkyl

halides; and
 explain the mechanism of nucleophilic substitution reactions of aryl halides.

Unit 10 Preparation of Aromatic Hydrocarbons
UNIT 10
PREPARATION OF
AROMATIC
HYDROCARBONS
Structure
10.1 Introduction 10.7 Carcinogenic Nature of
Benzene
10.8 Preparation of Benzene and
10.2 Aromatic Hydrocarbons - An
Alkylbenzenes
Introduction
Preparation of benzene
Huckel’s Rule
Preparation of Alkylbenzenes
10.3 Occurrence
10.9 Summary
10.4 Structure of Benzene
10.10 Terminal Questions
10.5 Physical Properties of
Benzene 10.11 Answers
10.6 Uses of Benzene and its
Derivatives
10.1 INTRODUCTION
Aromatic compounds are the backbone of organic chemistry. Many of the
drugs contain aromatic compounds. So it is very important to understand the
chemistry of aromatic compounds. Benzene is a basic aromatic hydrocarbon
with general formula C6H6, having conjugated double bonds. Lots of
household items like paints, varnish, detergents etc. contain aromatic
compounds.
This is the first Unit of this block. In this unit first we will give you a brief
introduction of aromatic compounds. Then we will discuss the isolation and
occurrence of benzene. We will recall Huckel’s rule for aromaticity. We will
also learn the physical properties of benzene. In the last section of this unit,
we will discuss different methods for the preparation of benzene and alkyl
benzenes.
5
Block 3 Aromatic Hydrocarbons and Halogen Derivatives
In the next two units we will familiarise you with the reactions of benzene and
alkylbenzenes.

After studying this unit you should be able to:
 explain the basic concept of aromatic hydrocarbons;
 explain Huckel’s rule;
 describe the structure of benzene;
 describe the physical properties of benzene;
 describe the carcinogenic nature of benzene; and
 Outline the methods of preparation of benzene and alkylbenzene.
10.2 AROMATIC HYDROCARBONS – AN

INTRODUCTION
You have already studied the basics of aromatic compounds in Unit 19 of 1st
semester course. The word "benzene" derives from "gum benzoin" (benzoin
resin), an aromatic resin. In the earlier stages, the organic compounds were
arbitrarily classified as aliphatic or aromatic. The meaning of word “aliphatic”
means fatty. The aliphatic compounds were so named because the fatty acids
were one of the first members of this class. In addition to the aliphatic
compounds, there was a large number of another type of compounds, which
were also obtained from natural sources, e.g., resins, balsams, aromatic oils,
etc. The structures of these compounds were as unknown but they had one
thing in common, a pleasant odour. Thus, these compounds were arbitrarily
classified as aromatic compounds (Greek: aroma ‘fragrant smell’). There was
a time when chemists used to smell the compound and sometimes even taste it
to identify chemicals. Just because of this wrong practice, a famous Swedish
Scientist Carl Scheele died while tasting a chemical substance in his laboratory.
Another chemist “Robert Bunsen” used to tast poisonous arsenic and this made
his tongue black.
In present scenario, word aromatic is used for benzene and its derivatives.
Remember it does not mean that all the aromatic compounds contain benzene
ring. There are number of aromatic compounds which do not contain benzene
ring. These types of compounds are classified as non-benzenoid aromatic
compounds. So we can say that aromatic compounds are of two types:
i) benzenoid compounds; and
ii) non-benzenoid compounds.
Before we proceed further, let us recall some important facts of aromatic

compounds, which will help you to understand this unit. Benzene is a basic
aromatic hydrocarbon with the chemical formula C6H6. Aromatic hydrocarbons
6
are compounds having alternate single and double bonds between the two
carbon atoms of the ring.
A hydrocarbon can be an aromatic compound if it follows the Huckel’s rule.

Details of this rule you have studied in Unit 19 of the 1st Semester Course. Let
us recall Huckel’s rule.
10.2.1 Huckle’s Rule

According to Hϋckel’s Rule, a compound can be aromatic if it contains the
following distinct properties:
 The compound is a cyclic structure.
 The compound must contain (4n + 2)  electrons, where n is any number

i.e. 1,2,3,4…….. This means that only the rings with 2, 6, 10, 14,……
electrons may be aromatic.
 The compound must be coplanar.
Some examples of the compounds following Huckel’s rule are given below:
Cyclobutadiene
No. of -electrons = 4
4n + 2-electrons are required for aromacity. Cyclobutadiene has

4 -electrons, hence cyclobutadiene is not aromatic as it does not follows
Huckel’s rule.
Benzene
No. of -electrons = 6
Benzene is a typical example of an aromatic compound. Here, the Huckel’s

rule is followed as it has 6 electrons which are required for a compound to be
aromatic. All the carbon atoms of benzene ring are sp2 hybridised and it is a
planar molecule. It is an excellent example of an aromatic system.
Cycloheptatrienyl cation and cycloheptatriene
1,3,5-cycloheptatrienyl 1,3,5-cycloheptatriene
cation
In the above two compounds both have 6 elections but 1, 3, 5-

cycloheptatrienyl cation is aromatic and 1,3,5-cycloheptatriene is not. You 7
can ask why it is so. Cycloheptatriene has three double bonds i.e. 6 electrons
but because of the presence of one sp3 carbon atom it is not coplanar and
hence not aromatic compound. In case of cycloheptatrienyl cation generation
of the cation removes the hindrance and the delocalised 6 electrons
(Huckel’s rule) make the cation planar and aromatic.
From the above example, it is clear that a flat planar geometry is required for
proper overlap resulting in delocalisation of -electrons which is a necessary
condition for a compound to be aromatic.
SAQ 1
1, 3, 5-cycloheptatrienyl cation is aromatic and 1,3,5-cycloheptatriene is not.
Explain.
10.3 OCCURANCE
First time in 1825, Michael Faraday isolated benzene from whale oil giving it
the name bicarburet of hydrogen. In 1833, a famous scientist Eilhard
Mitscherlich obtained benzene by distilling benzoic acid and lime. He gave the
compound the name benzin.
The biggest consumer
Benzene is produced naturally by volcanoes. In the year 1845, Holman
country of benzene was
China, followed by the isolated benzene and its derivatives from coal tar. Later on benzene became
USA. Benzene very important compound in organic chemistry as a large number of the
production is currently medicines are aromatic in nature, e.g., aspirin, paracetamol, diclofinac sodium,
expanding in the Middle etc.
East and in Africa,
whereas production Benzene is a natural constituent of crude oil and is one of the
capacities in Western elementary petrochemicals. Benzene is a byproduct of the incomplete
Europe and North
combustion of many materials. In earlier days benzene was obtained as a by-
America are stagnating.
product of coke for the steel industry. After 1950s, the demand of benzene
increased tremendously especially for the growing polymer industries, Today,
major amount of benzene comes from the petrochemical industries, and only a
small fraction is obtained from coal.
SAQ 2
Fill in the following blanks
i) In 1825, Michael Faraday isolated benzene from -----------.
ii) Benzin was isolated from ----------- and lime.
iii) In 1845, Holman isolated benzene and its derivatives from ------------.
iv) -------------- is a byproduct of the incomplete combustion of many

materials.
v) Today, major amount of benzene comes from ----------------.
8
10.4 STRUCTURE OF BENZENE

You have studied structure of benzene in Unit 19 of1st semester course. Here
we will just recall only important points which will help you to understand this
unit. We cannot write a single structure for benzene which would encompass
all its properties rather it is considered to be the resonance “hybrid” of the
following hypothetical structures I-V:
I II III IV V
These structures are called resonance structures or contributors or canonical

forms. The two “Kekule” forms, I and II, are of lower energy (more stable) than
the three “Dewar” forms, III to V. Structures I and II could be expected to
“contribute” more to the hybrid than either III, IV or V. Hence, the properties of
benzene would be expected to resemble more closely to either I or II than to
III, IV or V. Since I and II have the same energy, each would contribute to the
hybrid by the same amount. The symbol of resonance, double-headed arrow
(), does not indicate an equilibrium. The canonical structures I-V are
hypothetical and do not have any physical existence. Structures I and II can be
represented as structure VI. It shows that hydrogen atom is attached to each
angle of benzene ring.
I II VI
Orbital picture of benzene
Benzene is visualised as a symmetrical, flat, planar molecule having a regular

hexagonal shape. Each carbon atom is bonded to two other carbon atoms and
one hydrogen atom by sigma bonds using sp2 hybrid orbitals, Fig. 10.1 (a). All
the carbon-carbon bonds are of equal length of 139 pm, similarly all the
carbon-hydrogen bond are of 110 pm. You will notice that all the bond angles
of carbon-carbon and carbon-hydrogen atoms are equal i.e.120o.
H H + +
+ H H
H H
pm
139 pm
0
11
+ +
 
H H H  H H H
o + +
120
o 
120 
o
H -
120
 
H H H
H H
(a) (b) (c)
Fig. 10.1: a)  Skeleton of benzene; b)  Bond formation in benzene;

c)  Cloud in benzene, aromatic sexlet.
The third p orbital of each carbon atom lies perpendicular to the plane of the
molecule and has a lobe each, above and below the plane, as shown in Fig.
10.1 (b). These p orbitals have one electron each. The sideways overlap of 9
these p orbitals accounts for the π bonding in benzene. The six electrons
which form an electron cloud above and below the plane of the ring are called
aromatic sextet, Fig. 10.1 (c).
SAQ 3
Draw the orbital picture of benzene.
10.5 PHYSICAL PROPERTIES OF BENZENE

Aromatic Hydrocarbons are well known for their exceptional physical and
chemical properties. In this section we will learn about some important physical
properties of benzene.
Octane number is a Benzene is a colorless liquid at room temperature. It is highly flammable liquid
measure of quality of which gives sooty yellow flame on heating. Benzene has sweet smell, which is
gasoline: higher the
responsible for the aroma around petrol stations. As benzene has a
octane number, better
the fuel. high octane number, it is an important component of gasoline.
Like other hydrocarbons, benzene is also non-polar in nature. Benzene is

immiscible with water and miscible in organic solvents, such as acetone,
aldehydes, ethers, carbon tetrachloride, chloroform and hexane etc. Benzene
has been widely used as a solvent, but due to its carcinogenic nature it has
been banned in most of the countries. Benzene is used to prepare azeotrope
with water. Benzene is lighter than water and its density is 0.87g cm-3. Boiling
point of benzene is 358.5 K (80.5 oC) and melting point is 283.5 K (5.5 oC).
Benzene evaporates into the air very quickly. Its vapors are heavier than air
and may sink into low-lying areas.
10.6 USES OF BENZENE AND ITS DERIVATIVES

Because of the pleasant smell of benzene, in the 19th century benzene was
used as an after-shave lotion but due to its carcinogenic nature it was replaced
Azeotrope is
by methylbenzene, which has similar physical properties but it was not
a mixture of liquids that
has a constant boiling. carcinogenic. You will be surprised to know that lot of household items contain
The boiling point of an benzene. Some of them are:
azeotropic mixture may
be higher or lower than  Paint,
that of any of its  lacquer,
components.
 varnish removers,
 glues,
 furniture wax,
 detergents and
 thinners.
In several chemical industries, aromatic hydrocarbons have wide applications.
Benzene is used mainly as an intermediate to make other chemicals
like: ethylbenzene, cumene, cyclohexane, nitrobenzene, and alkylbenzenes.
10 More than half of the entire benzene production is used for the preparation of
ethylbenzene, a precursor to styrene, benzene is used to make plastics,

resins, synthetic fibers, rubber lubricants, dyes, detergents, drugs and
pesticides.
Due to carcinogenic nature of benzene, in most of the industries, it is being

replaced by toluene as a substitute for benzene as a fuel additive.
SAQ 4
Which of the following are true or false? Write “T” for true and “F” for false in
the boxes given below
i) Benzene is a colorless or light yellow liquid at room temperature.

ii) Benzene has a low octane number.
iii) Benzene is polar compound.
iv) Benzene is immiscible with acetone.
v) Benzene is used to prepare azeotrope with water.
vi) Benzene is lighter than water.
10.7 CARCINOGENIC NATURE OF BENZENE

As benzene is a carcinogen, most non-industrial applications have been
limited. Both International Agency for Research on Cancer (IARC) and IARC: The International
Agency for Research on
Environmental Protection Agency (EPA) declared benzene as “carcinogenic
Cancer is part of the
compound”. It causes Acute Myeloid Leukemia (AML).
World Health
Organization (WHO).
The major effect of benzene from long-term exposure is on the blood (Long-
One of its goals is to
term exposure means exposure of a year or more). Benzene causes harmful
identify causes of
effects on the bone marrow and can cause a decrease in red blood cells, cancer.
leading to anemia. Benzene oxidises in the body to produce an epoxide, which
itself is carcinogenic. The epoxide interacts with DNA to produce cancer.
EPA: Environmental
Direct exposure of the eyes, skin, or lungs to benzene can cause tissue injury Protection Agency is an
and irritation. Even death is possible if a person inhales very high levels of agency of the United
benzene. Inhalation of benzene may develop the following symptoms: States federal
government whose
 Vomiting, mission is to protect
 Irritation of the stomach, human and
environmental health.
 Sleepiness,
 Drowsiness, AML: (Acute Myeloid
Leukemia) is a cancer of
 Regular heartbeat.,
the blood and bone
 Headaches, marrow. This type of
 Tremors, cancer usually gets
worse quickly if it is not
 Unconsciousness.
treated.
Benzene can react with other air pollutants to form ground levels ozone which
can damage crops and other materials.
11
SAQ 5
What are the symptoms of benzene Inhalation?
10.8 PREPARATION OF BENZENE AND

ALKYLBENZENES
Benzene and alkylbenzenes can be prepared by numerous methods. In this
unit we will discuss only few of them.
10.8.1 Preparation of Benzene

Benzene can be prepared from aromatisation of aliphatic hydrocarbons, cyclic
polymerisation of ethyne, decarboxylation of sodium benzoate, reduction of
phenol, hydrolysis of sulphonic acids and reduction of benzenediazonium
salts.
Some important methods for preparation of benzene are summarised in

Table 10.2.
Table 10.2: Methods of preparation benzene
Sr. No. Reactions
1. Aromatisation of aliphatic hydrocarbons
i)
D
CH3(CH2)4CH3
catalyst
n-Hexane Benzene
ii) CH3
D
CH3(CH2)5CH3
catalyst
n-Heptane
Toluene
iii) CH3
D
CH3(CH2)6CH3 catalyst
n-Octane
CH3
Xylenes
2. Cyclic polymerisation of ethyne
Cu
3 HC CH o
300 C
Acetylene
Benzene
3. Decarboxylation of sodium benzoate

COONa
CaO
+ NaOH + Na 2CO 3
Sodium benzoate Benzene

12
4. Reduction of phenol
OH
Zn dust
+ Zn + ZnO
Distillation
Phenol Benzene
5. Reduction of Benzenediazonium Salts

+ .. -
N NCl
+ H3PO 2 + H2O + H3PO 3 + HCl + N 2

Hypophosphorus
Benzene diazonium acid Benzene
chloride
6. Hydrolysis of sulphonic acids:

SO3H
+ H2O + H2SO4
Sulphonic acid Benzene
7. Hydrodealkylation
CH3
773-873 K
Toluene Benzene
Let us study each method in detail.

i) Aromatization of aliphatic hydrocarbons or Hydroforming
This is a process of converting aliphatic hydrocarbon to aromatic
hydrocarbons. This is also known as hydroforming or catalytic reforming.
Alkane with six or more carbon atoms, when heated strongly (775 K) under
pressure in the presence of platinum catalyst, gives aromatic hydrocarbon.
This process involves cyclisation, isomerisation and dehydrogenation. In this
process, the product contains the same number of carbon atoms as the
aliphatic starting materials. Aromatization of gasoline increases their octane
number from 40 to 95 because unsaturated hydrocarbons are better fuels.
Cr2O3/Al2O3
CH3(CH2)4CH3 + 4H 2
775 K
n-Hexane
Benzene
CH3
Pt
CH3(CH2)5CH3
670 K
n-Heptane
Toluene
13
CH3 CH 2-CH 3
CH 3(CH 2)6CH 3 +
+ 4H2
n-Octane
Ethylbenzene
CH3
p-Xylene
Catalytic aromatisation in the presence of platinum is sometimes referred to as

platforming or hydroforming. This process also constitutes a valuable method
for commercial production of these hydrocarbons.
Since, benzene is obtained in much smaller amount than toluene can be

converted into benzene by heating with hydrogen under pressure in the
presence of a metal oxide catalyst. This process is called hydro-dealkylation.
CH3
catalyst
+ 4H2
Toluene Benzene
ii) Cyclic Polymerisation of Ethyne
Ethyne undergo two types of polymerisation reaction- i) linear and ii) cyclic.
Cyclic polymerization of ethyne results in the formation of aromatic
hydrocarbons. It is one of the important chemical reactions of alkynes. When
ethyne (acetylene) gas is passed through a red hot copper tube at 873 K, the
ethyne molecules then undergo cyclic polymerization to form benzene.
Cu
3 HC CH
873K
Benzene
Here copper acts as catalyst. Three molecules of ethyne are involved in this
reaction. This can be explained from following mechanism.
CH Red hot copper tube

HC CH or
873K
HC CH
CH
iii) Decarboxylation of sodium benzoate
Benzene can be prepared from aromatic acids. Decarboxylation of sodium

benzoate gives benzene. Reaction of sodium salt of the benzoic acid (sodium
benzoate) with sodium hydroxide in presence of calcium hydroxide (mixture
of sodium hydroxide and calcium hydroxide is known as soda lime) gives
benzene and sodium carbonate. This is a common method of preparation of
14 benzene in laboratory. For example:
COONa
CaO
+ NaOH + Na 2CO3
D
iv) Reduction of phenol
Benzene can be prepared by reduction of phenol. When phenol vapours are

passed over heated zinc dust, benzene is formed. This reaction takes place in
presence of strong reducing agents like zinc with strong heating.
OH
D ZnO
+ Zn +
v) Reduction of Benzenediazonium Salts
Benzene can be prepared from benzenediazonium salts by heating it.

Reduction of benzenediazonium chloride with hypophosphorus acid yields
benzene.
+ -
N NCl
+ H3PO 2 + H2O + H3PO 3 + HCl + N 2
Hypophosphorus
Benzenediazonium acid Benzene
chloride
vi) Hydrolysis of sulphonic acid
Benzene can be prepared by hydrolysis of sulphonic acids. In this reaction,

sulphonic acid is exposed to superheated steam leading to the formation of
benzene.
SO3H
+ H2O + H2SO4
vii) Hydrodealkylation of Toluene
Toluene can be converted into benzene by dealkylation. In this reaction

toluene and hydrogen is heated at a high temperature (773-873 k) and 40–60
atm pressure, in presence of a catalyst chromium, molybdenum,
or platinum oxide . Sometimes, much higher temperatures are used instead of
a catalyst (at the similar reaction condition). Under these conditions, toluene
undergoes dealkylation to benzene and methane. This reaction gives good
yield benzene i.e. about 95. Xylenes can also be converted into benzene with
similar efficiency.
15
CH3
773-873 K
Toluene Benzene
CH3
773-873 K
CH3
p-Xylene Benzene
SAQ 6
Predict the products of the following reactions:
D
Cu
i) CH3(CH2)4CH3 3 HC CH o
ii) 300 C
Hexane Acetylene
OH SO3H
Zn dust
iii) + Zn iv) + H 2O
Distillation
Phenol Sulphonic acid
10.8.2 Preparation of Alkylbenzenes

Alkylbenzenes are very important aromatic compounds. They can be
prepared from Friedel-Crafts alkylation, Wurtz-Fittig reaction, Grignard
reagent, Wolff-Kishner reduction and Clemmensen reduction. Some important
methods for preparation of alkylbenzenes are summarised in Table 10.3.
Table 10.3: Methods of preparation alkylbenzenes (Arenes)
Sr. No. Reactions
1. Friedel-Crafts Alkylation
  CH 2CH 3
 
CH 3CH 2Cl ....... AlCl 3
Benzene Ethylbenzene
2. Wurtz-Fittig reaction
Br CH2CH3
dry ether
+ 2Na + CH3CH2Br + 2NaBr
Bromoethane
Bromobenzene Ethylbenzene
16
3. From Grignard reagent

MgBr CH 2CH 3
dry ether
+ CH 3CH 2Br
Bromoethane
4. Wolff-Kishner reduction
O
CCH3 CH2CH3
KOH, H2O
+ NH 2-NH 2
(OH, CH2CH2)2O,
515K
Acetophenone Ethylbenzene
5. Clemmensen Reduction
H
C O CH3
Zn/Hg
25% HCl
Benzaldehyde Toluene
Now let us discuss each reaction in detail.
i) Friedel-Crafts Alkylation
Benzene on heating with a haloalkane in the presence of anhydrous aluminum

chloride gives its homologue, alkylbenzene. This reaction is known as
Friedel–Crafts reaction. Details of this reaction you will learn in Unit 11 of
this course.
R
AlCl3
+ RCl
Benzene Alkylbenzene
Benzene on heating with chloromethane gives methylbenzene (toluene) and

with chloroethane it gives ethylbenzene.
CH 3
AlCl3
+ CH 3Cl
Benzene Methyllbenzene
CH 2CH 3
AlCl3
+ CH 3CH 2Cl
Benzene Ethylbenzene
17
ii) Wurtz–Fittig reaction:
In year 1855, Charles-Adolphe Wurtz reported a reaction what is now known

as the Wurtz reaction. In Wurtz reaction, two molecules of alkyl halide are
treated with sodium in dry ether to give alkanes. Details of this reaction, you
have studied in Unit 15 of 1st semester course
2RX + 2Na RR + 2NaX
In the 1860s, another scientist Rudolph Fittig extended the Wurtz reaction by
coupling of an alkyl halide with an aryl halide. This modification of the Wurtz
reaction is considered a separate process and is named for both scientists i.e.
Wurtz–Fittig reaction.
Alkylbenzenes, also known as Arenes, can be obtained by the reaction aryl

halides and alkyl halide. In this reaction aryl halides and alkyl halides are
treated with sodium in presence of dry ether. The result is the joining of alkyl
and phenyl groups with the loss of halogens. The product is alkyl benzene
(Arenes). This reaction is called Wurtz–Fittig reaction
Br CH2CH3
dry ether
Bromoethane
Biphenyl: In isolated
systems, two or more
rings are joined to each The Wurtz-Fittig reaction can also take place with metals other than sodium,
other either directly or
like potassium, iron, copper, and lithium. In presence of lithium, it gives good
through carbon chain.
yield but under ultrasonic irradiation.
The reaction works best for forming asymmetrical products. Typically the
reaction is used for the alkylation of aryl halides. However, with the use of
ultrasound, the reaction can also be made useful for the production of biphenyl
CH 2 compounds
Like Wurtz reaction, Wurtz-Fittig reaction also gives some undesired side
products, which limits its applications.
iii) From Grignard Reagent:
Alkylbenzenes (Arenes) can also be prepared by the reaction of

arylmagnesium halide (Grignard reagent) and alkylhalide. For example
MgBr CH2CH3
dry ether
+ CH3CH2Br
Bromoethane
Phenylmagnesium bromide Ethylbenzene
iv) Wolff-Kishner Reduction
Aldehydes and ketones can be reduced to alkanes by treating them with

hydrazine, H2N – NH2, at a high temperature, in alkaline medium. This reaction
18
is known as Wolff-Kishner reduction. It is a useful synthetic method for

converting an aldehyde or a ketone to an alkane. For example,
O
CCH3 CH2CH3
KOH, H2O
+ NH 2-NH 2
(HOCH2CH2)O,
515K
Acetophenone Ethylbenzene
Wolff-Kishner reduction can be carried out at room temperature if a strong

base like potassium 2-methyl-2-propoxide is used in a polar solvent like
dimethyl sulphoxide
v) Clemmensen Reduction
Clemmensen Reduction is used to reduce alkylhalide and ketones this results

in the conversion of CO group to CH2 group. In other words aldehydes and
ketones can be converted to the corresponding alkanes under acidic
conditions by Clemmensen reduction. In this reaction, zinc amalgam (an
alloy of zinc and mercury) and concentrated HCl are used to reduce an
aldehyde or ketone.
H
C O CH3
Zn/Hg
25% HCl
Benzeldhehyde Methylbenzene
Wolff-Kishner or Clemmensen reduction is particularly useful for the synthesis

of compounds having alkyl groups attached to benzene ring. You may recall
that Friedel-Crafts alkylation can also be used for this purpose. But in Friedel-
Crafts alkylation, rearrangement of the alkyl groups is usually observed.
10.9 SUMMARY
 Benzene is a basic aromatic hydrocarbon with the chemical formula
C6H6. Aromatic Hydrocarbons are compounds having alternate  and 
bonds between the carbon atoms of the ring.
 A hydrocarbon can be an aromatic compound if it follows the Huckel’s Rule

and is a planar molecule. According to Huckel’s Rule, a compound must
contain (4n + 2)  electrons, (where n is any number i.e., 0,1,2,3,4……..)
and must be co- planer .
 Benzene is produced naturally by volcanoes. Coal tar is a good source

of benzene.
 Benzene is a colorless highly flammable liquid at room temperature.
 Benzene is non-polar solvent which is immiscible with water and miscible

in organic solvents. Benzene is lighter than water and its density is 0.87g
19
cm-3. Boiling point of benzene is 358.5 K (80.5 oC) and melting is 283.5 K
(5.5 oC)
 Lot of household items like paint, lacquer, varnish removers, glues,

furniture wax, detergents and thinners contain benzene.
 Benzene can be prepared by:

 Aromatization of aliphatic hydrocarbons or hydroforming
 Cyclic Polymerization of ethyne
 Decarboxylation of sodium benzoate
 Reduction of phenol
 Reduction of benzenediazonium Salts
 Hydrolysis of sulphonic acids
 Dealkylation of toluene
 Alkylbenzene can be prepared by:
 Friedel-Crafts alkylation
 Wurtz–Fittig reaction
 Grignard reagent
 Wolff-Kishner reduction
 Clemmensen reduction
10.10 TERMINAL QUESTIONS

1 What are the main points of Huckel’s rule?
2. How would you prepare benzene form ethyne? Give its mechanism
3. What is hydroforming ? Explain with the help of an example.
4 Give one example of the following name reactions
ii) Wurtz-Fitting reaction
iii) Clemmensen Reduction
iv) Wolff-Kishner reduction
10.11 ANSWERS
Self-Assessment Questions
1. Cycloheptatriene has three double bonds i.e. 6 electrons but because of
the presence of one sp3 carbon atom it is not coplanar and hence not
aromatic compound. In case of cycloheptatrienyl cation, generation of the
cation removes the hindrance and the delocalised 6 electrons (Huckel
rule) make the cation planar and aromatic.
20
2. i) whale oil
ii) benzoic acid
iii) coal tar.
iv) benzene
v) the petrochemical industries.
3. H H H + + H H
H
pm
139 pm
0
+ +
11
- -
H H H + + H H
120
o
- - H
o
120 -
o
120
H - H
H H H H
(a) (b) (c)
4. i) T , ii) F, iii) F, iv) F, v) T, vi) T
5. Vomiting, irritation of the stomach, sleepiness, drowsiness, irregular

heartbeat, headaches, tremors, unconsciousness.
6. i) D
CH3(CH2)4CH3
Hexane
Benzene
Cu
ii) 3 HC CH o
300 C
Acetylene
Benzene
OH
iii) Zn dust
+ Zn + ZnO
Distillation
Phenol Benzene
SO3H
iv)
+ H2O + H2SO4
Terminal Questions
1. The important points of Hϋckel’s rule are:
 The compound should be a cyclic structure.
 The compound must contain (4n + 2)  electrons, where n is any
number i.e. 0,1,2,3,4…….. This means that only the ring with 2,
6, 10, 14,…… electrons may be aromatic.
 The compound must be coplanar.
2. Cyclic polymerisation of ethyne results in the formation of aromatic
hydrocarbons. When ethyne (acetylene) gases is passed through a red hot
copper tube at 873 K, The ethyne molecules then undergo cyclic
polymerization to form benzene. 21
CH
Red copper tube
HC CH or
873K
HC CH
CH
3. This is a process of converting aliphatic hydrocarbon to aromatic

hydrocarbons. This is also known as hydroforming or catalytic
reforming. Alkane with six or more carbon atoms, when heated strongly
(775 K) under pressure in the presence of platinum catalyst, gives
aromatic hydrocarbon. This process involves cyclisation, isomerisation
and dehydrogenation. In this process the product contains the same
number of carbon atoms as the aliphatic starting materials.
Cr2O3/Al2O3
CH3(CH2)CH3 + 4H 2
775 K
Hexane
Benzene
CH3
Pt
CH3(CH2)5CH3
670 K
Heptane
Toluene
4.
  CH 2CH 3
 
ii) Wurtz-Fittig reaction
Br CH2CH3
dry ether
Bromoethane
iii) Clemmensen Reduction
H
C O CH3
Zn/Hg
25% HCl
Benzaldehyde Toluene
iv) Wolff-Kishner reduction
O
CCH 3 CH 2CH 3
dry ether
+ NH 2-NH 2
22 Acetophenone Ethylbenzene
Unit 11 Reactions of Aromatic Compounds-I
UNIT 11
REACTIONS OF
AROMATIC
COMPOUNDS-I
Structure
11.1 Introduction Friedel-Crafts Acylation
Expected Learning Outcomes Mechanism of Electrophilic

Substitution
11.2 Reactions of Aromatic
Compounds 11.4 Addition Reactions of
Benzene
11.3 Electrophilic Aromatic
Substitution Reactions Addition of Halogen to Benzene
Nitration Reduction
Halogenation 11.5 Summary

Sulphonation 11.6 Terminal Questions
Friedel-Crafts Alkylation 11.7 Answers
11.1 INTRODUCTION
In the previous Unit, we have discussed isolation, preparation of benzene and
alkylbenzene. Benzene is the most important aromatic compound. In this unit
we will study some important reactions of benzene.
Benzene is carcinogenic and injurious to health. Prolonged exposure to

benzene leads to bone-marrow depression. Therefore, benzene should used
as a solvent carefully, avoiding evaporation in the open or inhaling its vapours.
Keeping in view the importance of aromatic compounds, we shall study some

important electrophilic substitution reactions of benzene like nitration,
halogenation and sulphonation in this unit. It is important to understand the
pathway of any chemical reaction, so we will discuss the mechanism of these
electrophilic substitution reactions. In addition to this, we will discuss Freidel-
Crafts alkylation and Freidel-Crafts acylation of aromatic compounds. At the
end we will learn some addition reactions, like chlorination and reduction of
benzene. In the next unit, we will study reactions of alkylbenzene in detail.
23

After studying this unit, you should be able to:
 discuss the nitration, halogenations and sulphonation of benzene;
 discuss the Friedel-Crafts alkylation of benzene;
 explain the limitations of Friedel-Crafts alkylation reactions;
 discuss the Friedel-Crafts acylation of benzene;
 explain the mechanism of electrophilic substitution reactions of

benzene;
 describe the addition reactions of benzene; and
 discuss reduction of benzene.
11.2 REACTIONS OF AROMATIC COMPOUNDS

The characteristic reactions of aromatic compounds are electrophilic
substitution, in which the resonance-stabilised ring system is preserved. Why
is this so? You may answer by saying that this is due to the resonance
stabilisation of the benzene. But then the question arises, why then benzene
enters into reactions at all, why is it not inert? This dual behaviour, the
coexistence of stability and reactivity is due to the presence of the circulating 
electrons in the benzene ring which, on one hand, keep the carbon nuclei
within bonding distance and, on the other, offer a site of attack to positively
charged species i.e. electrophile.
Electrophilic substitution includes a wide variety of reactions, such as nitration,

halogenation, sulphonation, Friedel-Crafts alkylation and Freidel-Crafts
acylation reactions. Infect, electrophilic substitution reactions undergone by
nearly all aromatic rings. In addition to electrophilic substitution reactions,
benzene also undergoes few addition reactions. Some important reactions are
summarised in Table 11.1.
Table 11.1: Reactions of Benzene
1) Nitration
H2SO4
ArH + HNO 3 ArNO2 + H2O
2) Halogenation
Fe
ArH + X2 ArX + HX
3) Sulphonation
H2SO4
ArH + SO3 ArSO3H + H2O
4) Friedel-Crafts alkylation
AlCl3
ArH + RCl ArR + HCl
24
5) Friedel-Crafts acylation
AlCl3
ArH + RCOCl ArCOR + HCl
6) Addition of halogen to benzene
H Cl
Cl H
h H Cl
+ 3 Cl 2 Cl H
H Cl
Cl H
7) Reduction of benzene
Ni, 425-525 K
+ 3 H2
25 atm
Note: Ar = C6H5-
Let us study these reactions in detail.
11.3 ELECTROPHILIC AROMATIC

SUBSTITUTION REACTIONS
In this section, we will discuss some important electrophilic substitution
reactions of aromatic compounds, taking example of benzene. The
characteristic reactions of aromatic compounds are electrophilic substitution
reactions. In these reactions electrophile attacks the aromatic  electrons and
replaces one hydrogen atom of the aromatic ring. Benzene is a conjugated
system with six  elections, hence benzene acts as an electron donor in most
of the reactions.
11.3.1 Nitration
Replacement of a hydrogen atom of the aromatic compound in the ring by the
nitro-group is known as “Nitration”. The nitration of benzene gives
nitrobenzene. Nitration of benzene can be carried out by reaction of benzene
with a mixture of concentrated nitric and sulphuric acids.
NO 2
HNO3/ H2SO4
325 K
Benzene Nitrobenzene
The electrophile in this reaction is the nitronium ion, NO 2 . It is generated by

the reaction of H2SO4 with HNO3.
H
H2SO 4 + HONO 2 -
HONO 2 + HSO4
+
H
+
HONO 2 H2O + NO 2
+
Nitronium ion 25
Further evidence for the participation of the nitronium ion comes from the fact
that other species capable of producing nitronium ion, such as NO+2 BF4- ,
NO+2 NO3- and NO+2 ClO-4 and also nitrate benzenoid compounds.
Nitration of benzene is an important reaction because the nitro group can be

converted into other functional groups.
SAQ 1
Give the reaction for generation of NO 2 .
11.3.2 Halogenation
Normally benzene does not react with halogens. Halogens are not electrophilic
enough to attack on aromatic ring. However, benzene reacts with halogens in
the presence of Lewis acid as catalyst (FeBr3, FeCl3) to yield halogen
substituted products, i.e., aryl halides. In presence of a catalyst, halogens
become a powerful electrophile. The main function of the catalyst is to partially
or completely polarise the halogen-halogen bond and generate X+ e.g.
-  - 
  FeX 3  
X X3Fe .......X....... X - +
X = FeX 4 X
X
FeX 3
+ X2
Bromobenzene
X = Br2, Cl2
A typical reaction of aromatic halogenations is the bromination of benzene. As

a general rule, fluorine is too reactive and a poor yield of fluorobenzene is
obtained. Chlorine reacts smoothly and gives an excellent yield of
chlorobenzene. Iodine itself is unreactive; however, iodination of benzene is
carried out in the presence of oxidising agent such a hydrogen peroxide, H2O2,
or copper salt such as CuCl2. This oxidising agent oxidises molecular iodine to
an electrophile I+
++ + +
I2 + 2 Cu 2I + 2 Cu
I
+ +
+ I + H
Iodobenzene
Reactivity of halogens has the following order:
I2 < Br2 < Cl2
Halogenations can also be affected by other reagents, such as hypochlorous

or hypobromous acids in presence of strong acids.
26
+ +
H O Cl + H H2O Cl
Cl
+ -H2O
+ H2O Cl
Chlorobenzene
SAQ 2
Fill in the following blanks
i) Benzene reacts with halogen in presence of catalyst to produce ………...
ii) The main function of catalyst is to polarise the ………………bond.
11.3.3 Sulphonation
Benzene can be sulphonated by the reaction with fuming sulphuric acid
(H2SO4 + SO3) Benzene reacts with HSO+3 to give benzenesulphonic acid.
Aromatic compounds in which the sulphonic group (- SO3H) is directly
attached to the benzene ring are called aromatic sulphonic acids.
Replacement of hydrogen of benzene by the sulphonic group is called
sulphonation. This is another example of electrophilic substitution reaction.
Sulphonation is usually accomplished using sulphuric acid or fuming sulphuric
acid (H2SO4 + SO3) containing varying proportions of sulphur trioxide. This
mixture is called “oleum”.
SO 3H
313 K
+ H2SO 4 + SO3
Sulphonic acid
Here the reactive spice is neutral SO3, as is evident from its structure given
below:
O-
- -
O O O O O O O
+ 2+ 3+
S S S S
O O- O- O-
Unlike other electrophilic substitution reaction of benzene, sulphonation is a

highly reversible reaction and the direction depends on the reaction conditions.
Sulphonation is favoured in the presence of concentrated or fuming sulphuric
acid, however, desulphonation is favoured in hot, dilute aqueous acids.
Sulphonation is used in preparation of detergents and manufacture of dyes.
SAQ 3
Fill in the following blanks:
i) Sulphonation is an …………….. substitution reaction .
ii) Desulphonation is not possible in ……………… acid.
27
11.3.4 Friedel-Crafts Alkylation

In 1877 two scientists Freidel and Crafts discovered the alkylation of benzene
in presence of AlCl3. Introduction of alkyl group in an aromatic ring is called
Friedel-Craft alkylation. Complex substituted aromatic compounds are almost
always synthesised from the simpler, readily available aromatic compounds.
Since benzene is very common and easily available, chemists use it as
starting material and introduce the desired substituents. You have already
studied the introduction of halogen, nitrogen and sulphur-based functional
groups in the aromatic ring. Now you will study another important reaction, i.e.,
alkylation of aromatic ring.
Reaction of benzene with haloalkane in presence of aluminium halide gives

alkylbenzene and hydrogen halide. This reaction is known as Friedel-Craft
alkylation. Friedel-Craft alkylation can also take place in presence of any other
Lewis acid as catalyst. The reaction of 2-chloropropane with benzene in the
presence of AlCl3 to yield (1-methylethyl) benzene is a typical Friedel-Crafts
alkylation reaction.
CH(CH 3)2
AlCl3
+ (CH 3) 2CHCl + HCl
2-Chloropropane
(1-Methylethyl)
benzene
The electrophile in the Friedel-Crafts reaction is R+. This ion is formed when
an alkyl halide reacts with a Lewis acid. Lewis acids, such as AlCl3, FeCl3,
ZnCl2, AlBr3, BF3 etc. are used in Friedel-Crafts alkylations. In case of
alkylation with tertiary alkyl halides, the electrophilic species is a free
carbocation. However, in primary and secondary alkyl halides, it appears that
instead of free carbocations, the electrophilic species is an alkyl halide Lewis
acid complex with positively polarised carbon.
CH3 CH3
+ -
CH 3 C Cl + AlCl 3 CH 3 C + AlCl 4
CH3 CH3
tert-Alkyl halide
CH3
CH3 C CH3
+
+ CH 3 C CH3
CH3
 -
 
CH 3CH 2Cl + AlCl 3 CH 3CH 2Cl ....... AlCl 3
Alkyl halide Alkyl halide Lewis
acid complex
 - CH 2CH 3
 
28
The reactivity of haloalkane increases with polarity of CꟷX bond. The order is:
RI < RBr < RCl < RF
R= Alkyl group
Friedel-Crafts reaction is widely applicable in organic synthesis. However, it

has some limitations, which are given below:
Limitations of Friedel-Crafts Alkylation

i) The main difficulty with the Friedel-Crafts alkylation is that the
substitution of the first alkyl group activates the ring towards further
substitution.
R R R
R
AlCl3 R-X
+ RX +
AlCl3
The best way of avoiding this second reaction is to use an excess of

aromatic compound.
ii) Friedel-Crafts alkylation reactions are limited to alkyl halides, aryl halides
and alkenyl halides do not react. This is because aryl and alkenyl
carbocations are too unstable to form under Friedel-Crafts reaction
conditions.
Cl
AlCl3
+ No reaction
Aryl halide
AlCl3
+ CH 2 CHCl No reaction
Alkenyl halide
iii) If the aromatic compound has an electron withdrawing substituent, it

does not undergo Friedel-Crafts alkylation since the deactivated ring is
not reactive to attack by carbocations.
G
AlCl3
+ RX No reaction
G = electron-withdrawing group
iv) Aromatic amines fail to undergo alkylation, probably because amino

group forms a complex with Lewis acid. Since this complex has a
positive charge on nitrogen, it deactivates the aromatic ring for
electrophilic substitution.
29
+ -
NH2 NH 2AlCl 3
AlCl3 RX
No reaction
AlCl3
v) Sometimes during the alkylation, the attacking electrophile undergoes

rearrangement by 1, 2-shift of H or R. For example, the alkylation of
benzene with 1-chloropropane leads to a mixture of n-propylbenzene
and (1-methyl)ethyl benzene.
No rearrangement
CH 2CH 2CH 3
.. -AlCl4
+ CH 2 Cl
.. AlCl 3
CH 2 minor
CH 2
Rearrangement
H
 - -AlCl4 + -
CH 3CHCH 2 Cl AlCl 3 CH 3CHCH 3 + AlCl4
CH(CH 3)2
+
+ CH3CHCH 3
major
The mechanism is similar to alkylation with an alkyl halide and this reaction
proceeds through the more stable carbocation intermediate.
SAQ 4
Give the product(s) of the following reactions:
NO 2
AlCl3
a) + CH3 I
AlCl3
b) + CH3CH2CH2Cl +
AlCl3
c) + CH3CH2Cl
Cl
AlCl3
d) +
30
11.3.5 Friedel-Crafts Acylation
The RCOꟷ group or ArCOꟷ group is called an acyl group. Substitution of an

acyl group into an aromatic ring by the reaction with an acid chloride in the
presence of Lewis acid as catalyst is called Friedel-Crafts acylation. For
example, the reaction of benzene with ethanoyl chloride (acetyl chloride) gives
the ketone, phenylethanone (acetophenone).
O
O CCH 3
AlCl3
+ CH3CCl + HCl
Acetyl chloride Phenylethanone

(acid halide)
The Friedel-Craft acylation is very important reaction in organic chemistry. It

has many applications e.g. It is an excellent method for synthesis of aromatic
ketones.
The mechanism of Friedel-Crafts acylation, which we will explain in section

11.3.6, is similar to other electrophilic aromatic substitution reactions. The
electrophile in this reaction is the resonance stabilised carbocation, acylium
ion. This ion is formed when the acid chloride reacts with the Lewis acid,
AlCl3.
O
+ + -
:
RCCl + AlCl 3 R C O: R C O : + AlCl 4
Acylium ion
Carboxylic acid anhydrides can be used as alternative to acid chlorides for the
Friedel-Crafts acylation reaction.
O
O O CCH 3 O
AlCl3
+ CH3COCCH 3 + CH3COH
Acetic Ethanoic acid
anhydride Acetophenone
Friedel-Crafts acylation reaction is synthetically useful reaction. For example

the carbonyl group of the ketone produced by Friedel-Crafts acylation can be
reduced to >CH2 group by using zinc amalgam and hydrochloric acid. This
method of reduction is known as Clemmensen reduction which you have
studied in Unit-10 of this course. By the combination of Friedel-Crafts acylation
and Clemmensen reduction, an alkylbenzene may be prepared.
O
O CCH 2CH 3 CH 2CH 2CH 3

AlCl3
+ CH3CH 2CCl Zn/Hg
Propanoyl chloride HCl
Phenylethyl ketone Propylbenzene
Unlike Friedel-Crafts alkylation, Friedel-Crafts acylation reactions are not

accompanied by rearrangements within the acyl group. Moreover, there is no 31
polysubstitution as the aromatic ring is deactivated after the introduction of the

first acyl group. Acylation reactions are free from limitations of alkylation
reactions. Secondly, acylium ions do not undergo rearrangements.
11.3.6 Mechanism of Electrophilic Substitution

All the electrophilic substitution reactions take place by similar mechanism. It
is necessary to understand the principles of this mechanism. Thus, we will
discuss the general electrophilic substitution mechanism by using E+ for
electrophilies.
Before studying detailed mechanism, let us briefly recall what we have learnt
about electrophilic addition to alkenes. Electrophilic attack on C = C gives
carbocation intermediate which is then attacked by nucleophile to yield
addition product.
E E
+ Nu-
C C + E C C C C
+
Nu
An electrophilic aromatic substitution reaction begins in a similar way. The 

electrons of the ring attack on electrophile E+, forming a  bond with
electrophile. In this process, the positive charge of the electrophile is
transferred to the adjacent ring carbon atom which is called carbonation. This
is a slow step and is, therefore, the rate determining step.
Formation of CꟷE bond converts sp2 hybridised carbon to sp3 hybridised
carbon atom of the ring, which disturb the conjugation of benzene ring. Hence,
the resulting intermediate is not aromatic.
E
+
+ E H
+
This carbocation is stabilised by resonance as shown below:
+
E E E
H H H
+ +
These three resonance structures of the intermediate are often combined and
represented as follows:
E
+ H
In the case of alkenes, you have seen that nucleophile attacks the carbocation
to yield the addition product. Since, in the present case, the addition of the
nucleophile would destroy the aromatic stabilisation of the benzene ring, this
type of addition does not take place in aromatic carbocations. Instead,
nucleophile acts as base and abstracts a ring proton yielding substituted
32 aromatic product.
E E
-
H B + BH
+
X
E
H
H
B
This reaction is exothermic in nature because CꟷE bond is stronger than CꟷH
bond. The potential energy diagram (Fig.11.1) of electrophilic substitution
reaction of benzene also confirmed that this is an exothermic reaction.
Intermediate carbocation
E -
+ X
H
Energy
+ -
H + E X
E + HX
Reactants
Product
Reaction coordinate
Fig. 11.1: Potential energy diagram for an electrophilic substitution

reaction of benzene.
SAQ 5
Give the structure of the product expected from the reaction of each of the
following compounds with benzene in the presence of AlCl3.
O
a) (CH ) CHCCl
3 2
O
b) CCl
O O
c) C2H5COCC 2H5
33
11.4 ADDITION REACTIONS OF BENZENE

In addition to electrophilic substitution reactions, benzene also undergoes few
addition reactions, e.g. addition of halogens to benzene and addition of
hydrogen to benzene (reduction of benzene). Let us discuss these reactions in
little detail.
11.4.1 Addition of Halogen to Benzene

You have already studied in the first semester that addition of chlorine to an
alkene gives 1,2-dichloroalkane.
Cl
Cl2
RCH CHR ' RCHCHR '
Cl
In contrast to this, the addition of chlorine to benzene takes place with some
difficulty and produces several isomers of 1, 2, 3, 4, 5, 6-
hexachlorocyclohexanes. In the presence of sunlight, benzene gives an
addition product. For example, when treated with chlorine or bromine in the
presence of sunlight, benzene forms the benzenehexachloride
(C6H6Cl6, known as gammaxene) and benzenehexabromide (C6H6Br6)
respectively. These addition reactions proceed by the free radical mechanism.
hv
.
2 Cl
Cl 2
H H
. Cl2 Cl
.
+ Cl Cl Cl + Cl
hv
H
H Cl
H Cl H
2 Cl2
Cl H Cl
Cl hv Cl H
H H Cl
Cl H
1,2,3,4,5,6-Hexachlorocyclohexane
The 1,2,3,4,5,6-hexachlorocyclohexane, theoretically can exist in eight

stereoisomerism forms but only seven of these are known. One of the
isomers, is gammaxene, is a powerful insecticide. It is very stable and acts
more quickly than DDT. Remember all the isomers exist in chair form.
11.4.2 Reduction of benzene

Hydrogenation of benzene at higher temperature and under pressure yields
cyclohexane.
Ni, 425-525 K
+ 3H2
25 atm.
Benzene Cyclohexane
34
Although benzene is not reduced by metals and acid, or by sodium in ethanol,

it is reduced by sodium in liquid ammonia in the presence of ethanol (Birch
reduction) to give 1, 4-dihydrobenzene (cyclohexa-1, 4-diene). This reaction
has also been shown to have free radical mechanism.
H ..
.
e
+ Na + Na+
.
H
H .. H H
-
+ C2H5OH + C2H5O
. .
H H
H H H H
e +
+ Na + Na
. ..
H H
H H H H
e -
+ C2H5OH + C2H5O
..
H H H
Lithium in anhydrous ethylamine, however, reduces benzene to cyclohexene

and cyclohexane.
SAQ 6
Give the mechanism of conversion of benzene to cyclohexane.
11.5 SUMMARY
In this unit you have studied that:
 Unlike alkenes, benzene does not undergo addition reactions but it

undergoes electrophilic substitution reactions, e.g., nitration,
halogenation, sulphonation, Friedel-Crafts alkylation, Friedel-Crafts
acylation etc.
 Nitration of benzene gives nitrobenzene. Nitration of benzene can be

carried out by reaction of benzene with a mixture of concentrated nitric
and sulphuric acids.
 Benzene reacts with halogens in the presence of a catalyst (AlCl3, FeBr3,

FeCl3) to give aryl halides. Fluorine is too reactive and a poor yield of
35
fluorobenzene is obtained. Chlorine reacts smoothly and gives an

excellent yield of chlorobenzene. Iodine is unreactive; however,
iodination of benzene is carried out in the presence of oxidising agent
such as hydrogen peroxide.
 Benzene reacts with SO3 to give benzenesulphonic acid. Sulphonation

is usually accomplished using sulphuric acid or fuming sulphuric acid
(H2SO4 + SO3) containing varying proportions of sulphur trioxide.
Sulphonation is a highly reversible reaction.
 Reaction of aromatic compounds with alkyl halides in presence of

anhydrous AlCl3 as catalyst gives alkylated products. This reaction is
known as Friedel-Crafts alkylation. This Friedel-Crafts reaction is widely
applicable in organic synthesis, but it has some limitations e.g.The first
alkyl group activates the ring towards further substitution. Friedel-Crafts
alkylation reactions are limited to alkyl halides; aryl halides and alkenyl
halides do not react. Sometimes during the alkylation, the attacking
electrophile undergoes rearrangement by 1, 2-shift of H or R. Aromatic
amines fail to undergo alkylation. If the aromatic compound has an
electron withdrawing substituent, it does not undergo Friedel-Crafts
alkylation.
 Substitution of an acyl group into an aromatic ring by reaction with acid

chlorides in presence of Lewis acid as catalyst is called an aromatic
acylation reaction or Friedel-Crafts acylation.
 The addition of chlorine to benzene takes place with some difficulty. In

the presence of sunlight, benzene gives an addition product. Several
isomers are 1, 2, 3, 4, 5, 6-hexachlorocyclohexanes are obtained.

1. Arrange the following compounds in the expected order of the reactivity
towards Friedel-Crafts alkylation.
CH3CH2Br, CH3CH2Cl, CH3CH2I, CH3CH2F
2. How do you convert benzene to the following compounds?
a) Bromobenzene b) Benzenesulphonic acid
c) Cyclohexane d) Ethylbenzene
e) Hexachlorocyclohexane
3. Write the mechanism of sulphonation of benzene using SO3 as

electrophile.
11.7 ANSWERS
1. The electrophile in this reaction is the nitronium ion, NO+2. It is

36
generated by the reaction of H2SO4 with HNO3.

H
H2SO 4 + HONO 2 HONO 2 + HSO4

+
H
+
HONO 2 H2O + NO 2
+
Nitronium ion
2. i) aryl halide
ii) halogen-halogen
3. i) E3lectrophilic
ii) hot aqueous
4. a) No reaction.
CH 2CH 2CH 3 CH(CH 3)2

b)
+
Minor Major
CH 2CH 3
c)
d) No reaction.
O CCH(CH 3)2
5. a)
AlCl3
+ (CH 3)2CHCCl
O O
CCl C
b)
+
O O CC 2H5 O
c)
+ C2H5COCC 2H5 + C2H5COH
37
H ..
.
e
6). + Na + Na+
.
H
H .. H H
-
+ C2H5OH + C2H5O
. .
H H
H H H H
e +
+ Na + Na
. ..
H H
H H H H
e -
+ C2H5OH + C2H5O
..
H H H
Similarly, following same step we get cyclohexane.
Terminal Questions
1. Reactivity increases as follows:
CH3CH2I < CH3CH2Br < CH3CH2Cl < CH3CH2F
Br
FeBr3
+ Br2
2. a)
SO 3H
+ H2SO 4 + SO3
b)
Ni
+ 3 H2
c) 
C2H5
AlCl3
+ C2H5Cl + HCl
d)
38
Cl
Cl Cl
e) h
+ 3 Cl 2
Cl Cl
Cl
O
O S O-
3. O O
H
+ S
+ -
O SO3H
O
O O
- H OSO 3H
S O S OH
-
O O + OSO 3H
+
39
UNIT 12
REACTIONS OF
AROMATIC
COMPOUNDS - II
Structure
12.1 Introduction 12.3 Reactions of Side Chain
Expected Learning Outcomes Substitution in Side Chain
12.3 Effect of Substituents on Oxidation of Side-chain

Reactivity and Orientation
12.4 Summary
Effect of substituents on
reactivity
12.6 Answers
Effect of Substituents on
Orientation
12.1 INTRODUCTION
In the last unit, Unit 11, we have learnt some important reactions of aromatic
compounds. There are two main types of substitution reactions in aromatic
compounds i.e. i) substitution reactions at aromatic ring and ii) substitution
reactions at the side chain of aromatic ring. In that unit, we have also
discussed electrophilic substitution reactions on benzene ring. In this unit, we
will explain the effect of substituents on reactivity and orientation of aromatic
compounds. In the next section we will consider the meaning of ortho, para
and meta directing activators/deactivators. In addition to this, we will study the
substitution reactions of side chain of aromatic compounds. You will notice
that the substitution of side chain follows free radical mechanism while
substitution at ring carbon follows ionic mechanism. In the last section, we will
discuss the oxidation of side chain of aromatic compounds.

 explain the effect of substituents on reactivity;
40  explain the effect of substituents on orientation;

Unit 12 Reactions of Aromatic Compounds-II
 state the concept of ortho, para and meta directing

activator/deactivator;
 describe the substitution in the side chain of aromatic compounds; and
 explain the oxidation reactions of the side chain.
12.2 EFFECT OF SUBSTITUENTS ON

REACTIVITY AND ORIENTATION
Benzene forms only one monosubstituted product by the electrophilic
substitution. Let us see what happens when we carry out an electrophilic
substitution on a substituted benzene. Studies have shown that the
substituents effect the reactivity and the orientation in the benzene ring. Three
possible disubstituted products, viz., ortho, para and meta can result. These
three products are not formed at random; rather, a given substituent already
attached to the benzene ring usually directs the position of the second
substituent. There are two types of substituents – one is electron-donating
groups, such as –NR2, ꟷOH, ꟷOR, ꟷNHCOR, and alkyl groups and other is
electron-withdrawing groups which include halogens, ꟷCHO, ꟷCOR, ꟷCOOR,

ꟷCN, ꟷNO2, ꟷ NR3 etc..
Now we will study the effect of substituents on reactivity and orientation.
12.2.1 Effect of Substituents on Reactivity

To compare the rates of electrophilic substitution in benzene, methyl
substituted benzene (methylbenzene or toluene) and nitro substituted benzene
(nitrobenzene) are compared in a reaction, say nitration. It is found that
nitration of methylbenzene (toluene) is more facile than benzene whereas
nitration of nitrobenzene is more difficult than benzene. In other words,
benzene ring seems to be activated in methylbenzene and deactivated in
nitrobenzene. If we compare the reactivities of benzene, methylbenzene and
nitrobenzene towards nitration reaction, we find the following order:
methylbenzene > benzene > nitrobenzene
i.e., as compared to benzene, methylbenzene is more reactive while

nitrobenzene is less reactive. CH3 group is called an activating group, while
NO2 is a deactivating group for electrophilic substitution of aromatic
compounds. By and large, the meta directing groups are deactivating and the
ortho and para directing groups are activating, with the exception of halogens.
Let us see if we can explain this on the basis of the intermediate carbocation
formed.
H E H E H E
+ + +
CH3 NO 2
I II III
In the case of methylbenzene (II), the methyl group, which is an electron-

donating group, tends to neutralise the charge on the carbocation, this 41
dispersal of the charge stabilises the carbocation thus leading to faster

reaction than benzene.
In case of nitrobenzene (III), the NO2 group which is electron-withdrawing

group, tends to intensify the positive charge and destabilise the carbocation.
Due to this effect, the rate of the reaction is slower than in benzene. Reactivity
in electrophilic aromatic substitution depends therefore then, upon the
tendency of a substituent group to release or withdraw electrons. A group that
releases electrons activates the ring while a group that withdraws electrons
deactivates the ring. Hence, the order of reactivity of the above compounds
towards electrophilic substitution reaction is:
CH3 NO 2
> >
SAQ 1
Which compound would you expect to undergo aromatic nitration more readily,
C6H6 or C6H5CCl3 and why?
12.2.3 Effect of Substituents on Orientation

The second effect of a substituent is to direct the position of the incoming
substituent. Thus, for instance, nitration of phenol gives ortho- and para-
nitrophenols as major products.
OH OH OH OH
NO 2
HNO3/H2SO4
+ +
NO 2
o-Nitrophenol m-Nitrophenol
NO 2
Phenol
(45%-50%) (trace) p-Nitrophenol
(45%-50%)
Halogens are unusual in their effect on electrophilic aromatic substitution, we
will discuss it under the heading “ortho and para directing deactivators” of this
section . Nitration of chlorobenzenes yields ortho-chlorobenzene and para-
chlorobenzene as the major products.
Cl Cl Cl Cl
NO 2
HNO3/H2SO4
+ +
NO 2
NO 2
Chlorobenzene o-Nitrochlorobenzene m-Nitrochlorobenzene p-Nitrochlorobenzene
(35%) (1%) (64%)
On the other hand, nitration of nitrobenzene yields meta- dinitrobenzene as

the major product, i.e.,
42
NO 2 NO 2 NO 2 NO 2
NO 2
HNO 3/H2SO4
+ +
NO 2
o-Donitrobenzene
NO 2
Nitrobenzene m-Dinitrobenzene
(7%) (92%) p -Dinitrobenzene
(2%)
This shows that different substituents have different effect on the substitution
reaction. Thus substituents can be classified into three the following groups.
i.e.
 ortho and para-directing activators
 ortho and para-directing deactivators
 meta-directing deactivators
Table 12.1 gives a list of substituents with their directive influence and also
whether they activate or deactivate the ring.
Table 12.1: Lists some of the groups in each category
Ortho- and para- Ortho- and para- Meta-directing

directing activators directing deactivators deactivators
+
ꟷNH2 ꟷI  N (CH3)3
ꟷOH ꟷBr  NO2
ꟷOCH3 ꟷCl  CN
ꟷNHCOCH3 ꟷF COCH3
COOCH3
COOH
CHO
CH3
Before we try to account for the orientation in electrophilic substitution, we

should clarify our concept of activating and deactivating groups. Remember
activating groups activate all the positions of the ring. They are ortho and para
directors because they activate ortho and para position much more than they
do the meta position. Similarly, deactivating groups deactivate all positions in
the ring. They are meta directors because they deactivate the ortho and para
position more than they deactivate meta position. Thus, the effect of any
group, whether activating or deactivating, is strongest at the ortho and para
positions.
Ortho- and para-directing activators:
To understand the orientation effect of the substituents, we have to first write

all the possible resonance forms of the charged intermediates (carbocations)
for each of the three possible reaction courses.
Let us take the example of nitration of phenol. Reaction of NO+2 at the ortho,
meta and para positions of phenol gives the intermediate, carbocation with the
following resonance structures:
43
a) Ortho-Attack
OH +OH
OH OH OH
H H + H H
+ NO 2 NO 2
+ NO 2 NO 2 NO 2
+ +
I II III IV
b) Meta-Attack
OH OH OH OH
+ +
+ NO 2
H H H
NO 2 NO 2 + NO 2
V VI VII
c) Para-Attack
+
OH OH OH OH OH
+
+
+ NO 2
+
+
H NO 2 H NO 2 H NO 2 H NO 2
VIII IX X XI
In case of ortho and para attacks, structures IV and X respectively show that
the unshared electron pair of oxygen delocalizes the positive charge of the
carbocation and, hence, four resonance structures are possible. In the case of
meta attack, lone pairs of oxygen are not involved in the delocalisation of
positive charge. Hence, the carbocation that is formed has only three
resonance structures, therefore, ortho- and para- nitrophenols are the major
products.
Now take the example of electrophilic aromatic substitution on alkyl substituted

benzene ring. Let us inspect the possible resonance structures of carbocation
formed by the attack of the electrophile, NO+2 , on toluene.
a) Ortho-Attack
CH3 CH 3 CH3 CH3

H H H
+
+ NO 2
+ NO 2 NO 2 NO 2
+ +
I II III
b) Meta-Attack
CH3 CH3 CH3 CH 3
+ + +
+ NO 2
H H H
NO 2 NO 2 + NO 2
IV V VI
c)
44
Para-Attack
CH3 CH 3 CH3 CH 3
+
+
+ NO 2
+
+
H NO 2 H NO 2 H NO 2
VII VIII IX
As indicated above, in structures III and VIII, resulting from ortho and para
attacks respectively, the positive charge is located on the carbon atom to
which the methyl group is attached. Because that structure has tertiary
carbocation character, it is more stable than the others’ in which the positive
charge is at a secondary carbocation. On the other hand, meta attack
produces an intermediate in which none of the resonance structures benefits
from such tertiary carbocation stabilisation. Thus, electrophilic attack on a
carbon located ortho or para to methyl group leads to a cationic intermediate
that is more stable than the one derived by attack at the meta carbon.
Substitution at ortho- and para-position is, therefore, preferred to the
meta-substitution.
This can also be explained on the basis of inductive effect. The carbocations
III and VIII formed by the ortho- and para-attacks respectively are stabilised by
inductive effect of methyl group and are therefore, formed in major amount.
Let us understand this on the basis of potential energy diagram for nitration of
methylbenzene (Fig. 12.1). The carbocations formed from attack at ortho and
para positions of toluene are more stable than the carbocation formed from
meta position. However, all the three carbocations obtained from
methylbenzene are more stable than the carbocation obtained from benzene.
Fig. 12.1: Schematic potential energy diagram for AESR in benzene (----------) and
methylbenzene ( )
Meta-directing deactivators:
We can apply similar arguments to meta-directing groups. These groups are

all electronegative groups without an unshared electron pair on an atom
adjacent to the benzene ring. In all these cases, the benzene ring would be
deactivated. Let us take the example of nitration of nitrobenzene. The possible
resonance structures of the carbocation formed are as follows: 45
a) Ortho-Attack
   
O + O O + O O + O O + O
N N N N
+ H
H H
+ NO 2
+ NO 2 NO 2 NO 2
+ +
I II III
b) Meta-Attack
  
O + O O + O O + O O + O
N N N N
+ +
+ NO 2
H H H
NO 2 NO 2 + NO 2
IV V VI
c) Para-Attack
   
O + O O + O O O O + O
+
N N N N
+
+
+ NO 2
+
+
H NO 2 H NO 2 H NO 2
VII VIII IX
In
all the three cases, carbocations formed have three resonance structures. But
the structures III and VIII resulting from ortho and para attack, respectively, are
very unfavourable because the positive charge is placed directly on the carbon
carrying the electron withdrawing group. A severe electrostatic repulsive
interaction between the carbocation and the positive end of the NO2+ group
strongly disfavours these carbocations. However, the carbocations formed by
meta attack, have no such form with similar charges on adjacent atoms.
Therefore, its transition state is the most stable, and attack at meta-position is
preferred. Potential energy diagram of the reaction is shown in Fig. 12.2. The
carbocation obtained from meta attack is more stable than the ortho and para
attack.
Fig. 12.2: Schematic potential energy diagram for AESR in benzene (-----)
46
and nitrobenzene ( )
Ortho and para directing deactivators:

Halogens are unusual in their effect on electrophilic aromatic substitution. They are
deactivating yet ortho and para directing. For understanding the orientation, consider
the attack of electrophile at ortho, meta and para position of chlorobenzene.
a) Ortho-Attack
:
:
: Cl: : Cl: : Cl : +
: Cl Cl:
H H + H H
+ NO 2
+ NO 2 NO 2 NO 2 NO 2
+ +
I II III IV
b) Meta-Attack
:
:
:
: Cl : : Cl: : Cl: : Cl :
+ + +
+ NO2
H H H
NO2 NO2 + NO2
V VI VII
c) Para-Attack
:
+
:
:
: Cl :
:
:
: Cl : : Cl: : Cl: :Cl :
+
+
+ NO 2
+
+
NO 2 H NO 2 H NO 2 H NO 2 H
VIII IX X XI
In structures, III and IX, resulting from ortho and para attacks respectively,
there is a positive charge on carbon bearing the halogen atom. Through its
inductive effect, chlorine withdraws electrons, making this structure unstable.
But there is another factor that one should not forget. It is known that halogens
can share a lone pair of electrons and accommodate the positive charge, as
shown in structures IV and X, for ortho and para attacks, respectively. These
structures are comparatively stable. No such structure is possible when the
electrophiles attack on meta position. Structures IV (in ortho attack) and X (in
para attack) outweigh the instability rendered by structures III and IX.
Therefore, attack at ortho and para position is preferred. The potential energy
diagram of this reaction is shown in Fig. 12.3. The carbocation obtained from
ortho and para attack is more stable than the carbocation obtained from attack
at meta position.
Fig. 12.3: Schematic potential energy diagram for AESR in benzene (-----------)
and chlorobenzene ( ) 47
SAQ 2
Predict the major and minor products of the following reactions:
a) Nitration of bromobenzene c) Bromination of nitrobenzene
b) Nitration of nitrobenzene d) Chlorination of pheno
12.3 REACTIONS OF SIDE-CHAIN

12.3.1 Substitution in the Side Chain
Alkylbenzene clearly offers two position for attack by halogen: the ring and the
side chain.
.
Cl CH 3
CH3
and
+
Cl
We can control the position of attack by choosing the proper reaction

conditions. Halogenation of an alkane requires condition under which halogen
atoms are formed by homolyses of halogen molecules, that is, high
temperature or light. Halogenations of benzene, on the other hand, involve
transfer of positive halogen, which is promoted by Lewis acid catalyst like
ferric chloride.
heat or light
CH 4 + Cl2 CH 3Cl + HCl
Cl
FeCl3, cold
+ Cl 2 + HCl
The position of attack in methylbenzene (toluene) would be decided by the

nature of the attacking particle and by the condition employed. If the reaction
is carried out in the presence of light, substitution occurs almost exclusively in
the side chain. In the absence of light and in the presence of ferric chloride,
substitution occurs mostly in the ring, for example:
CH3 CH2 Cl
hv
+ Cl 2
CH3 CH3 CH3

FeCl3
+ Cl 2 +
Cl Cl
Chlorination of methylbenzene (toluene), in the presence of light, takes place

via free radical chain mechanism as shown below:
hv
Cl2 2 Cl
48
H
C
. H
C H
. H
H + Cl + HCl
Cl
C H C H
H H
+ Cl Cl + Cl
In alkylbenzenes, with side chains larger than methyl, it is expected that the
free radical substitution may take place on any of the side chain carbon atoms;
so we must consider the likelihood of obtaining a mixture of isomers. For
example, chlorination of ethylbenzene should give two isomeric products, 1-
chloro-1-phenylethane and 2-chloro-1-phenylethane in equal amounts. But 1-
chloro-1-phenylethane is the major (91%) product becouse of the stabilisation
of free radical intermediate.
Cl
CHCH 3 CHCH 3
Cl2
CH 2CH 3 sec-Radical (91%)

(more stable)
+ Cl
CH 2CH 2 CH 2CH 2Cl
Cl 2
pri-Radical (9%)
(less stable)
You can ask, why is it so? This is because the bond dissociation energy of
benzylic CꟷH bond, C6H5CH(CH3)H, (355 kJ mol1) is less than -phenyl ethyl
CꟷH bond, C6H5ꟷCH2CH2ꟷH (435 kJ mol1). That means, less energy is
required for the homolylic fission of benzylic CꟷH bond. In other words, benzyl
radical is more stable. The greater stability of benzyl radical is due to
delocalisation of the odd electron over the ring as shown below:
H
CHCH 3 CHCH 3 CHCH 3 CHC H3 CHCH 3
Since the benzylic radical formed is more stable, 1-chloro-1-phenylethane is

the major product.
SAQ 3
Write the mechanism of chlorination of methyl benzene.
12.3.2 Oxidation of Side-chain

Although benzene is quite unreactive towards the usual oxidising agents
(KMnO4, K2Cr2O7 etc.), the benzene ring renders an aliphatic side chain quite
susceptible to oxidation. The side chain, irrespective of its length is oxidised to 49
a carboxyl group (ꟷCOOH). Tertiary alkyl substituted aromatic compounds do

not undergo this reaction. For example, toluene, propylbenzene,
(1-methylethyl)benzene are oxidised to benzoic acid in high yields.
p-Methyltoluene on oxidation gives terephthalic (benzene-1,4-dicarboxylic)
acid but tertiary butylbenzene is not effected.
The number and the position of the carboxylic groups produced indicate the
number and position of alkyl chain(s) attached to the aromatic ring.
CH3
[O ]
Toluene
CH 2CH 2CH 3 COOH CH(CH 3)2
[O] [O]
Propylbenzene Benzoic acid (1-Methylethyl)benzene
C(CH 3)3
[O]
No reaction
tert Butylbenzene
Terephthalic acid is used for the production of polyester fibres in industries.

Remember for industrial purposes Terephthalic acid is prepared from
p-xylene by simple oxidation using air as the oxidant and Co(III) salt as a
catalyst .
CH 3 COOH
[O]
CH 3 HOOC
p-Methyl toluene
SAQ 4
Draw the structural formulas for the starting materials in the following reaction:
COOH COOH
KMnO4, H2O
a) C8H10 c) KMnO4, H2O
C8H10
COOH
KMnO4, H2O
COOH
b) C8H10
COOH
12.4 SUMMARY
 Alkylbenzenes offer two main areas for attack by halogenthe ring and
the side chain.
 In the presence of light, halogen goes to side chain while in the presence
of acid catalyst it goes to ring.
50
 Substituents affect the reactivity and the orientation in the benzene ring.
 A given substituent already attached to the benzene ring usually directs
the position of the second substituent.
 There are two types of substituents – one is electron donating group,

such as as ꟷNR2, ꟷOH, ꟷOR, ꟷNHCOR, and ꟷR and other is electron
withdrawing groups which include halogens, ꟷCHO, ꟷCOR, ꟷCOOR,

ꟷCN, ꟷNO2, ꟷ NR3 etc.
 Besides being different in their ‘directing’ tendencies,-CH3 and -NO2

groups differ in one more aspect and that is the rate of the reaction. Rate
of nitration of benzene, methylbenzene and nitrobenzene is as follows:
 Methylbenzene > benzene > nitrobenzene

 The second effect of a substituent is to direct the position of the
incoming substituent. Thus, nitration of phenol gives ortho and para-
nitrophenol as major products. On the other hand, nitration of
nitrobenzene yields meta dinitrobenzene as the major product,
 This shows that different substituents have different effect on substitution
reaction. Thus substituents can be classified into three groups. i.e.,
 ortho and para-directing activator
 meta-directing deactivator
 ortho and para-directing deactivator
 The side chain, irrespective of its length, is oxidised to a carboxyl group
(-COOH).
 Tertiary alkyl substituted aromatic compounds do not follow oxidation
reaction.

1) Write equation to show how the following conversion takes place.
a) Methylbenzene to m-bromobenzonic acid
b) benzene to p-nitrotoluene
c) benzene to m-nitrocetophenone
2) Write the chemical equation for the oxidation of the following compounds
with hot KMnO4.
a) n-Butylbenzenes
b) 1,1-Dimethylethyl benzene
c) 1,3,5-Trymethylbenzene
3) Write the resonance structures of cation formed from C6H5NH2 during:
a) ortho-bromination
51
53
b) meta-bromination
c) para-bromination
4) Compound A, B and C are the three isomeric dibromobenzenes. Identify

which is ortho, para and meta from the number of mononitration
products.
HNO3/H2SO4
a) Compound A two mononitration products
HNO3/H2SO4
b) Compound B three mononitration products
HNO3/H2SO4
c) Compound C one mononitration products
12.6 ANSWERS
1. While the CH3 group is electron releasing and activates the ring, the CCl3
group is strongly electron withdrawing because of the influence of the
electronegative chlorine atoms and hence, deactivates the ring. Therefore,
C6H5CCl3 undergoes substitution more slowly.
Br Br Br Br
NO 2
2. a) HNO3/H2SO4
+ +
NO 2
NO 2
(Major) (Minor) (Major)
NO 2 NO 2 NO 2 NO 2
NO 2
b) HNO3/H2SO4
+ +
NO 2
NO 2
(Minor) (Major)
(Minor)
NO 2 NO 2 NO 2 NO 2
Br
Br2
+ +
c) Br
Br
(Minor) (Major)
(Minor)
OH OH OH OH
Cl
Cl2
+ +
d) Cl
Cl
(Major) (Minor)
(Major)
52
54
3. See Sub-Sec. 12.3.1

CH 2CH 3 CH3
4. a)
c)
CH3
CH3
b)
CH3
Terminal Questions
CH3 COOH COOH
1. a)
KMnO4 Br2
 FeBr3
Br
(Minor)
CH3 CH3
b) AlCl3 HNO3/H2SO4
+ CH3Cl
NO 2
O O
CCH 3
c) O CCH 3
AlCl3
HNO3/H 2SO 4
+ CH 3CCl
NO 2
CH 2CH 2CH 2CH 3 COOH
2. a)
KMnO4

C(CH 3)3
b)
KMnO4
No reaction.

CH3 COOH
c) KMnO4

CH 3 CH3 HOOC COOH
3. a) Ortho-Attack
+
: NH2 : NH2 : NH 2 : NH2 NH 2
H H H
+ H
Br2 Br Br Br
Br
+ +
53
55
b) Meta-Attack
: NH2 : NH2 : NH2 : NH2
Br2 + +
H H H
Br Br + Br
c) Para-Attack
+
: NH2 : NH2 : NH2 : NH : NH2
+
Br2
+
+
Br H Br H Br H Br H
Br Br Br
4) a) Br Br Br
+
NO 2
NO 2
Only these two products are possible
from o-dibromobenzene
Br Br Br Br
b) NO 2
HNO3/H2SO4
+ +
Br Br Br NO 2 Br
NO 2
Three products are possible from m-dibromobenzene
Br Br
c) NO 2
HNO3/H2SO4
Br Br
Only one product is possible
from p-dibromobenzene
On the basis of above reactions, we can say that:

Compound A is a o-dibromobenzene
Compound B is a m-dibromobenzene
Compound C is a p-dibromobenzene.
54
52
Unit 13 Alkyl Halides
UNIT 13
ALKYL HALIDES
Structure
13.1 Introduction Chemical Properties of Alkyl
Halides
Uses of Alkyl Halides
13.2 Classification of Halogen
Derivatives 13.5 Lab Detection
13.3 Preparation of Alkyl Halides 13.6 Summary
13.4 Structure and Properties of 13.7 Terminal Questions
Halogen Derivatives
13.8 Answers
Structure of Halogen Derivatives
Physical Properties of Halogen

Derivatives
13.1 INTRODUCTION
In earlier units of this Block, we have described the preparations and reactions of
aromatic hydrocarbons. In this unit and in the next units, we will study halogen
derivatives of hydrocarbons. Replacement of one or more hydrogen atoms in a
hydrocarbon by halogen atom(s) [F, Cl, Br, or I] gives the halogen derivatives.
These compounds are important laboratory and industrial solvents and serve as
intermediates in the synthesis of other organic compounds. Many
chlorohydrocarbons have acquired importance as insecticides. Although there
are not many naturally occurring halogen derivatives, yet you might be familiar
with one such compound, thyroxine (T4)-a thyroid hormone.
Tyroxine (T4)
In this unit, we shall take up the chemistry of the alkyl halides in detail. We shall
begin with classification of halogen derivatives and go over to methods of the
preparation of alkyl halides. We shall also discuss the reactivity of these halogen
compounds and our main focus will be, on some important reactions such as
nucleophilic substitution (SN) and elimination (E) reactions. Finally, we shall take
up uses of halogen derivatives and the methods for their detection.

 classify the halogen derivatives;
55
 outline the methods of preparation of alkyl halides;
 list the physical properties of halogen derivatives;
 describe the reactions of alkyl halides, specially nucleophilic substitution

and elimination reactions in detail;
 list and describe the industrial uses of halogen derivatives; and
 describe the laboratory detection of halogen derivatives.
13.2 CLASSIFICATION OF HALOGEN DERIVATIVES

The halogen derivatives are conveniently divided into three classes depending
upon the nature of the hydrocarbon residue to which the halogen atom is
attached: (i) Alkyl halides (haloalkanes) (ii) Alkenyl halides (haloalkenes) (iii) Aryl
halides (haloarenes). Compounds in which the halogen atom is bonded to an alkyl
or a substituted alkyl-group are called alkyl halides. Compounds in which a
halogen atom is attached to a carbon atom which is attached to another carbon
atom by a double bond are called alkenyl (vinylic or vinyl) halides. Finally,
compounds in which one of the hydrogen of an aromatic ring is replaced by a
halogen atom are called aryl halides. A few examples are given below:
H3C X
In polyfunctional R X C C HC C Cl X
compounds, where H3C CH3
groups other than
halogen functional A haloalkane A haloalkene A Haloalkyne A haloarene
groups are present, one (an alkyl halide) (an alkenyl or (an aryl halide)
vinylic halide)
group is identified as the
principal functional group
Before going further in details of classification of alkyl halides, just to recall, in
and this principal
functional group is used IUPAC system of nomenclature, a halo- (i.e. fluro-, chloro-, bromo-, or iodo-) is
as a suffix in the name of prefixed and the carbon chain is so numbered so as to give the lowest number
the compound. The to the carbon to which the halogen is attached. When more than one of
priorities for selection of
halogen atoms are present, their names are arranged in alphabetical order.
principal functional group
are given below in the Common names are arrived at by writing the name of alkyl group followed by
order of decreasing the name of the halide.
precedence: carboxylic
acid, sulphonic acid, Alkyl halides are further classified on the basis of nature of carbon atom [i.e.
ester, acid anhydride, primary (1o), RCH2−X; secondary (2o), R2CH−X or tertiary (3), R3C−X] and on
acylhalide, amide, nitrile,
aldehyde, ketone, the basis of number of halogen atoms present in a molecule [i.e. mono-, di-,
alcohol, thiol, amine, tri- or tetra-). Now we will consider few examples of simple alkyl halides from
imine, alkyne, alkene, each class (name given in brackets are common names):
ethers, halides, nitro.
Notice the IUPAC name
of allyl chloride in main CH2 CH CH2 Cl CH2 Cl
CH3 CH3
text.
Bromomethane 3-Chloropropene Chloromethylbenzene
(Methyl bromide) (Allyl chloride) (Benzyl chloride)
Cl
Cl
Cl
1-Chloropropane 2-Chlropropane 1-Chlorobutane
(n-Propyl chloride) Isopropyl chloride) (n-Butyl chloride)
(1o) (2o) (1o)
56
Cl
Cl Cl
1-Chloro-2-methypropane 2-Chlorobutane 2-chloro-2-methylpropane

(Isobutyl chloride) (sec-Butyl chloride) (tert-Butyl chloride)
(1o) (2o) (3o)
Di-, tri-, and tetrachloromethanes are examples of di-, tri-, and tetra halogen
derivatives, respectively,
CH2Cl2 CHCl3 CCl4
Dichloromethane Trichloromethane Tetrachloromethane
(Methylene chloride) (Chloroform) (Carbon tetrachloride)
These halogen derivatives are excellent solvents for nonpolar and slightly
polar substances.
The dihalogen derivatives of alkyl halides can be subdivided into two types:
i) Geminaldihalides: In these both halogen atoms are attached to the

same carbon atom i.e., they are in geminal (gem-) position.
Geminaldihalides are also referred to as alkylidene halides.
Cl
C H
CH3CH2Cl2 CH3CBr2CH3
Cl
1,1-Dichloroethane 2,2-Dibromopropane Dichloromethylbenzene
(Ethylidene chloride) (Isopropylidenedibromide) (Bezyylidine chloride or
benzal chloride
ii) Vicinal dihalides: When two halogen atoms are attached to adjacent
carbon atoms, they are said to be in vicinal (vic-) position and such
compounds are also named as the dihalides.of the alkene from which
they may be prepared by addition of the halogen, e.g.
CH2BrCH2Br CH3CHClCH2Cl
1, 2-Dibromoethane1 2-Dichloropropane
(Ethylene dibromide) (Propylene dichloride)
We have discussed above classification of halogen derivatives. In the next

section, we shall be discussing the preparations of mono halogen derivatives
of alkyl halides and alkenyl halides. We will take up aryl halides separately in
next unit. Before that, try the following SAQ to test your understanding of the
classification of halogen derivatives.
SAQ 1
Classify each of the following alkyl halides as 1°, 2°, or 3°.Also write IUPAC
name of each compound.
Cl
a) b)
Br
Cl
c) d) Cl
57
13.3 PREPARATION OF ALKYL HALIDES

We have already looked at several methods of preparation of halogen
derivatives in earlier units of 1st semester course. In this section, we shall
briefly review these methods and also take up some other methods for the
preparation of halogen derivatives.
Alkyl halides can be prepared from alcohols, alkenes, alkanes, Grignard

reagents, carboxylic acids, other halides and by chloromethylation of benzene.
General reactions of these methods of preparation are summarised below in
Table 13.1.
Table 13.1: Preparation of alkyl halides
From Alcohols
HX or PX3
OH X
or SOCl2 or PCl5
From Alkenes
H
HX
HX= HCl, HBr, HI

X
From Alkanes
Light or peroxide
H + X2 X + HX
X2 = Cl2, Br2
From Grignard Reagents

RMgX + X 2 CH3 X + MgX 2
X2 = Cl2, Br2
From Carboxylic Acids

RCOOAg + Br 2 R Br + AgBr + CO 2
From Halide Exchange

R X + KI R I + KX
From Chloromethylation of Benzene
H + HCHO + HCl CH2 Cl + H2O
Let us study these methods of preparation in a brief manner.
i) From alcohols: The most widely used method for the preparation of alkyl
halides is from alcohols. The hydroxyl group of the alcohol (R—OH) can be
replaced by a halogen atom by using either a hydrogen halide (HX), a
phosphorus halide (PX3 or PCl5), or thionyl chloride (SOCl2). These reactions
58
will be discussed in more detail in the next unit. The net reaction is
represented by the equations,
R—OH + HX → R—X + H2O

R—OH + PCI3 → R—X + H3PO3
R—OH + PCI5 → R—Cl + POCl3 + HCl
R—OH + SOCl2 → R—Cl + SO2↑ + HCl
C6H5CH2 OH + SOCl2 CH3CH2 Cl
Phenylmethanol Chloromethylbenzene
(Benzyl alcohol) (Benzyl chloride)
ii) From alkenes: Hydrogen halides (HCl, HBr, HI) reacts with alkenes to form
alkyl halides. The mode of addition follows Markownikoff’s rule except for the
addition of hydrogen bromide in the presence of peroxide. The mechanisms
for both modes of additions were shown in Unit 17 of first semester course.
Examples:
CH3 CH CH2 + HCl CH3 CH CH2

1-Propene Cl H
2-Chloropropane
CH3 CH CH2 + HBr CH3 CH CH2

Br H
2-Bromopropane
Peroxide
CH3 CH CH2 + HBr CH3 CH CH2
Br H
1-Bromopropane
iii) From Alkanes: Direct halogenation of alkanes is of limited application

because in most cases mixture of mono and polyhalogenated compounds
is formed. You have learned in Unit 17 that chloromethane, however, can
be prepared directly by photochlorination or heating if a large excess of
methane is employed. Similarly tetrachloromethane (carbontetrachloride),
CCl4, can also be prepared from methane if a large excess of chlorine is
used.
Sun light/
CH4 + Cl2 CH3Cl
Excess of methane
Sun light/
CH4 + Cl2 CCl4
Excess of chlorine
Chloromethylbenzene can also be similarly prepared.

CH3 CH2 Cl
hn
+ Cl2 +
reflux HCl
Methylbenzene Chloromethylbenzene
(Toluene) (Benzyl chloride)
59
The above mentioned reactions are examples of free radical substitution

reactions. Alkenes having allylic carbon undergo similar type of reactions
Allylic carbon: A carbon at high temperature or in the presence of light rather usual electrophilic
adjacent to a carbon-
carbon double bond. addition reactions. Such reactions are called allylic substitution.
Selectivity in allylic high temp.

substitution is due to the CH2 CH CH3 + Br2 CH3 CH CH2Br
resonance stability of 1-Propene 3-Bromopropane
intermediate allylic
Allylic substitution
radical.
room temp.
CH2 CH CH3 + Br2 CH2 CH CH3
CH2Cl2
1-Propene Br Br
1,2-Bromopropane
Electrophilic addtion
This is because in the first reaction above, the formation of π-complex

which is an intermediate in halogen addition reaction, unfavourable in the
absence of polar solvent. Therefore, substitution is favoured over addition.
At high temperature concentration of halogen radicals is much higher than
at room temperature, which further accelerates substitution.
N-Bromosuccinimide (NBS) deserves a special mention because it is a

specific reagent for bromination at allylic and benzylic positions in
alkenes.
NBS
CH2 CH CH3 CH2 CH CH2Br
CH3 CH2Br
NBS
A mechanism has been proposed for such reactions, in which NBS acts
as a bromine reservoir maintaining a low concentration of molecular
bromine by reacting with HBr, which is initially formed in a side reaction:
RH + Br R + HBr
O O
N Br + HBr N H + Br2
O O
Bromine molecule dissociates into bromine atoms on heating or on

exposed to light. Radical bromine abstracts hydrogen from allylic position
and generates resonance stabilised allylicradical which then reacts with
molecular bromine to give the product.
CH2 CH CH3
CH2 CH CH3 + Br
+ HBr
CH2 CH CH2
60 CH2 CH CH3 + Br2 CH2 CH CH2Br + Br

The chain then continues with the production of HBr and bromine atoms.
A low concentration of bromine favours allylic bromination over addition to
the double bond.
iv) From Grignard reagents: Direct reaction of alkyl or aryl halides with
metallic magnesium in a dry solvent (ether) gives the Grignard reagent, a
valuable intermediate in synthetic organic chemistry. Grignard reagents
react with halogens to give alkyl halides.
RMgX+X2 R—X + MgX2

Grignard Alkyl
Reagent halide
v) From carboxylic adds: The dry silver salt of a carboxylic acid upon
refluxing with bromine in tetrachlomethane (carbon tetrachloride) affords
the corresponding alkyl bromide. This reaction is known as Hunsdiecker
reaction.
RCOOAg+Br2 R—Br + AgBr + CO2↑

Silver salt of
carboxylic acid
vi) From Halide exchange: This is a good procedure for preparing alkyl
Chlorofluorocarbons
iodides and alkyl fluorides.
(CFC) also called Freons
are inert nontoxic gases
acetone used as refrigerants in
R X + KI R IX + KX
air— conditioners and
refrigerators. Freon 12 is
Alkyl fluorides often are prepared by the reaction of metallic fluoride such the most commonly used
as AgF, Hg2F2, CoF2 or SbF3. The reaction is termed as Swarts reaction. refrigerant. Unfortunately
Freons catalyse the
2R—Cl + Hg2F2 2R—F + Hg2Cl2 decomposition of ozone
and thus can destroy the
Alkyl Mercurous Alkyl Mercurous protective layer that
Chloridefluoride fluoride chloride surrounds the earth. For
this reason most of
3CCl4 + SbF3 3CCl2F2 + 2SbCl3 countries in the world
have banned the use of
Tetra- Antimony Dichloro- Freons.
Chloromethane fluoride fluorometane(Freon12)
(a chlorofluorocarbon, CFC)
vii) From Chloromethylation of benzene: This method isused to prepare

benzylic halides.
Ar—H + CH2O + HCl Ar—CH2—Cl + H2O

Aromatic Methanal Benzylic halide
Hydrocarbon (Formaldehyde)
SAQ 2
Write equations showing the preparation of the following halides from the starting
materials indicated.
a) C6H5CHBrCH3 from C6H5CH2CH3 c) 1-bromopropane from propene
b) CH3CHBrCH3 from CH3CHOHCH3 d) 1,2-dibromopropane from propene
61
SAQ 3
Predict the monohalogenation product that might be formed in the following reactions.
Cl2, light
a)
Cl2, light
b)
Br2, light
c)
13.4 STRUCTURE AND PROPERTIES OF

HALOGEN DERIVATIVES
In the previous section, we have discussed the preparation of alkyl halides. Now we
will discuss to the structure and physical properties of halogen derivatives along
with chemical properties of allkyl halides.
13.4.1 Structure of Halogen Derivatives

In a halogen derivative, halogen atom is the functional group, and the C−X bond is
the site of chemical reactivity. As might be expected, the nature of the chemical
bond between the halogen and carbon decides the reactivity of halogen derivatives.
In the alkyl halide, the carbon-halogen sigma bond results through overlap of the
sp3 hybrid orbital with the p orbital of the halogen atom. The carbon halogen
sigma bond in alkenyl and aryl halides results from the overlap of sp2 hybrid orbital
of the carbon with a halogen p orbital.
sp3 carbon sp2 carbon sp2 carbon

H H Cl
H
H C C Cl C C Cl
Electronegativity on the H H H H
Pauling and Sanderson
scales
As you know, the bond formed by halogen with asp2 hybridised carbon is shorter
Element Pauling Sanderson and stronger than the bond formed with a sp3 hybridised carbon because of the
F 4.0 4.000
higher s character. This difference in the nature of the C−X bond is mainly
Cl 3.0 3.475 responsible for different behaviour of aryl and alkenyl halides as compared to
Bi 2.8 3.219 alkyl halides. To further explain the unique chemistry of aryl and alkenyl halides,
I 2.5 2.778
C 2.5 2.746 we shall study the reactions of chlorobenzene and chloroethene in next unit. Let
us first examine the nature of the C−X bond in alkyl halides.
You may recall that halogens are more electronegative than carbon and thus the
C−X bond of alkyl halide is polarised and the electron density along the C−X
bond increases in the direction of X. This effect places a partial negative charge
62 (δ−) on the halogen atom and a partial positive charge (δ+) on the carbon atom. The
resulting dipole moment is appreciable and governs a substantial part of the chemical
and physical properties of the halogen derivatives.
m
H
-
d+ d
H C Cl
H
The magnitude of dipole moment depends on the electronagativities of the bonded

atoms. For methyl halides, dipole moment is summarised in Table 13.2.
Table 13.2 : Dipole Moments of Methyl Halides The dipole moment (μ) is
a measure of the polarity
of the molecule. It is the
Compound Dipole moment µ, D (C m) product of charge (e) and
distance (d).
−30
CH3F 6.16  10 (1.85 D*)
μ=ed
−30
CH3Cl 6.23  10 (1.87 D)
−30
CH3Br 6.03  10 (1.81 D)
−30
CH3I 5.40  10 (1.62 D)
-30
*Where D is debye unit, 1 D = 3.33 x 10 C m (Coulomb/meter)
Another important factor on which the nature of C−X bond depends is its bond
strength. Bond enthalpies, which measure the bond strength, decrease as we go
down the group in the periodic table. This is because, the size of halogen atom
increases as we go down the group in the periodic table, fluorine atom is the
smallest and iodine atom, the largest. Consequently the carbon-halogen bond
length also increases from C−F to C−I and bond strength decreases from C−F to
C−I. Bond lengths and bond enthalpies of typical halides are given in
Table 13.3. These bond energy values show that C−I bond is the weakest bond
and C−F bond is the strongest bond. Therefore, the order of reactivity of
haloalkanes is iodoalkane > bromoalkane > chloroalkane > fluoroalkane. We will
further go in details of the relative reactivity of alkyl halides in subsequent
sections. We will also explain how the slight positive charge on the carbon
attached to halogen atom is mainly responsible for the nucleophilic substitution
(SN) reactions of halogen derivatives.
Table 13.3: Carbon-Halogen (C−X) Bond Length and BondEnthalpies
Bond Bond length/pm C-X Bond enthalpy/ kJ mol-1
C—F 139 452

C—Cl 178 351
C—Br 193 293
C—I 214 234
Thus we can summarise that both dipole moment and bond strength of C−X
govern a substantial part of the chemical and physical properties of the
63
13.4.2 Physical Properties of Halogen Derivatives

The alkyl halide has a higher boiling point than an alkane of comparable size
and shape. For example, the boiling points of ethane and bromomethane are
184 K and 277.5 K, respectively. Although both the molecules are
approximately of same size. The boiling point of bromethane is considerably
Van der Waals forces: A higher. This difference in boiling point is due to the dipole moment in
group of intermolecular bormomethane. The dipole-dipole interactions increase van der Waals forces
attractive forces among molecules; therefore, more energy is needed to overcome these forces
including dipole-dipole,
dipole-induced dipole, before boiling. The physical properties such as boiling points and densities of
and induced dipole- some alkyl halides, aryl halides and alkenyl halides are summarised in Table
induced dipole forces. 13.3. Common names of some of them are also given.
These forces are very
week in comparison to Table 13.3: Physical properties of halogen derivatives
electrostatic ionic forces
in ionic compounds. Density,
IUPAC Name Common Name Formula Bp,K kg dm
-3
at b293 K
Alkyl halides
Fluoromethane Methylfluoride CH3F 195 Gas
Chloromethane Methylchloride CH3Cl 249 Gas
Bromomethane Methybromide CH3Br 277.5 Gas
Iodomethane Methyliodide CH3I 315.8 2.28
Dichloromethane Methylene chloride CH2Cl2 313 1.34
Trichloromethane Chloroform CHCl3 334 1.49
Tetrachloromethane Carbontetrachloride CCl4, 350 1.60
Aryl halides
Fluorobenzene — C6H5F 358 1.024
Chlorobenzene — C6H5Cl 405 1.107
Bromobenzene — C6H5Br 429 1.495
lodobenzene — C6H5I 462 1.832
Alkenyl halides
Chloroethene Vinyl chloride CH2=CHCl 259 Gas
Note the increase in boiling point and density with the increase in the atomic
mass and atomic size of the halogens atom. The table emphasises also the
increase in the boiling point with the progressive replacement of the hydrogen
atoms with halogen atoms. These effects are related to the enhancement of van
der Waal's attraction with the increase in molecular volume. Compare, for
example, the boiling points of CH3Cl, CH2CI2, CHCI3, and CCl4. The density would
also increase in the same way.
The boiling points of higher alkyl halides increase with the increase in mass
and size. Boiling points of isomeric alkyl halides decrease with increase in
branching. For example, 2-chloro-2-methylpropane has the lowest boiling point
64 among the three isomers.
CH3
CH3
H3C Cl H3C
Cl CH3
Cl
CH3
Bp = 350.5 K Bp = 341.7 Bp = 324.5
In general, halogen compounds are insoluble in water but are readily soluble in
organic solvents and with the exception of some fluro and mono-chloro
compounds, they are more dense than water. Aryl halides are fairly pleasant
smelling liquids, but benzylic halides having the structure ArCH2X are irritating to
the eyes, skin and nasal passage. The toxicity varies. However, the
polychlorinated hydrocarbons such as CCI4 and CHCl2CHCl2 are quite toxic and
should be used with care.
SAQ 4
Arrange the following molecules in order of increasing boiling points. Give reason
for this trend.
CHCI3, CH2Cl2, CCI4, CH3CI
13.4.3 Chemical Properties of Alkyl Halides

Most important reactions of alkyl halides are nucleophilic substitution (SN) and
elimination (E). In this section we shall take up a fairly detailed description of
these reactions. We have already encountered the term nucleophilic reagent or
nucleophile and have learned that it is applied to an electron rich atom or group
such as,
- -
NH3 H2 O ROH HO HS
1) Substitution reactions: As explained earlier the C−X bond is polar bond, and
the carbon to which halogen group is attached carries a positive charge Nucleophilic substitution
refers to a reaction in
because of the higher electronegativity of halogens compared to carbon. which an electron-rich
-
The carbon atom is, therefore, susceptible to attack by a nucleophile. nucleophile, Nu: ,
replaces a leaving group,
-
X.
- Nucleophilic substitution -
Nu: + C X Nu C + X
Nucleophile Electrophilic carbon Leaving group

(Strong base) (weak base)
If we regard the reaction as a type of Lewis acid-base reaction, then we can

understand that it tends to occur because of the formation of the halide ion
which, as the conjugate base of a strong acid (HX), would be a weak base.
Accordingly, a weak base like the halide ion is said to be a good leaving
group. The order of reactivity of the alkyl halides increases from fluoro-
substituted to iodo-substituted compounds
RF < RCl < RBr < RI

65
The reason of this order is that the iodide ion, being the weakest base as the
conjugate base of the strongest acid, HI, is the best leaving group, the fluoride ion
being a stronger base is the poor leaving group.
Now let us summarise some nucleophilic substitution reactions of alkyl halides in

Table13.4.
Table 13.4: Some Nucleophilic Substitution Reactions
- -
Reaction : R X + Nu: X + R Nu
Nucleophile Products Class of compounds formed

- R OH An alcohol
OH (Hydroxide)
+
H 2O (Water) R OH2 An alcohol (after loss of proton)
-
OR (Alkoxode) R OH An ether
- R SH A thiol
SH (Thiolate)
- R SR A sulphide
SR (Alkanethiolate)
-
C CH (Alkynyl anion) RC CH An alkyne
-
C N (Cyanide) RC N A nitrile
- An alkyl iodode
I (Iodide ion) R I
+
NH3 (Ammonia) R NH3 An aalkylammonium ion
NR'3 (Amine) R NR' 3 An alkylammonium ion

- An alkyl azide
N3 (Azide) R N3
On the basis of the mechanism of substitution reactions, nucleophilic

substitution reaction can be divided into two types:
i) SN2 reactions (SN2 means 'substitution, nucleophilic bimolecular')
ii) SN1 reactions (SN1 means 'substitution, nucleophilic unimolecular’)
The terms bimolecular and unimolecular are related to the number of

molecules involved in the rate determining step in these reactions. Now, let us
consider these reactions in detail.
The SN2 reaction: The reaction of bromoethane with the hydroxide ion to
yield ethanol and bromide ion is a typical example of SN2 reaction.
CH3CH2ꟷBr + OH− CH3CH2ꟷOH + Br−
Bromoethane Ethanol
In general methyl or primary alkyl halides undergo SN2 reaction with any
relatively strong nucleophile: OH−, OR−, CN− etc. Secondary alkyl halides can
also undergo SN2 reactions, but, tertiary alkyl halides do not. The above
reaction has been found to follow second order kinetics which means that the
rate of the reaction is proportional to the concentrations of both the alkyl
halide and the hydroxide ion. Thus, for the above reaction,
66 Rate = k2[C2H5Br] [OH−]

Where k2 is the rate constant and [C2H5Br] and [OH−] represent the
concentrations in mole dm−3 of the alkyl halide and the hydroxide ion,
respectively.
Mechanism: On the basis of reaction kinetics and the stereochemistry of SN2

reactions, a one step, concerted mechanism is proposed.
- -
HO + CH3CH2 X CH3CH2 OH + Br
In an SN2 reaction, the
CH3 CH3 - CH3 other three bonds, (which
H H H
d- are not taking part in
- d-
HO C Br HO C Br HO C + Br
- substitution change) to
the central carbon
H H H progressively flatten put
and flip to the other side
Transition state with simultaneous of the carbon in a
bond breaking and bond forming
manner similar to the
Fig. 13.1: The mechanism for SN2 reaction. The dashed lines are depicting spokes of an umbrella
partially formed or broken bonds. inverting in a windstorm.
The flipping is called
inversion of
Note how the hydroxide ion attacks from the rear, away from the negatively
configuration, or Walden
charged field of the bromide ion. As the hydroxide ion begins to bond to the inversion, which you
carbon atom from the rear, the bromine begins to leave as the bromide ion from have already studied in
the front. Groups larger than hydrogen tend to block the approach of the Unit 3.
nucleophile, so methyl halides are more reactive than other primary halides.
Table 13.5 shows the effect of the structure of alkyl halides over the reaction rate.
In this table we have given average reaction rates (taking the reaction rate for
ethyl halides are one) of SN2 reaction of some alkyl halides.
Table 13.5: Effect of branching in the alkyl hallde on the rate of SN2 reaction
Alkyl halide Reaction rate

CH3−X 30
CH3CH2−X 1
(CH3)2CH−X 0.02
(CH3)3C−X 0
Therefore, among alkyl halides, order of relative rate is
CH3 > p-RX > sec-RX > tert-RX
This order of reactivity is interpreted to be due to steric hindrance, which

means obstruction of space. The more the number of alkyl groups around the
carbon holding the halogen, the more they hinder the nucleophile approaching
at backside of that carbon.
H
H
H H C
- H C
Nu: C Cl no S N2 reaction
H
H
H H
tert-Butyl bromide
67
Molecular orbital model provides a good description of the bonding

interactions that occur in the SN2 process. The filled nonbonding orbital of
nucleophile is attacking from the backside of the antibonding molecular orbital,
σ*, of the C−X bond, weakening the C−X bond as the new C−Nu, σ bond
becomes stronger. The back side interaction of nucleophile is the most
effective way to fill this nonbonding, σ* orbital, which result in breaking of the
C−X bond. Thus both valance bond and molecular orbital models predict that
the SN2 reaction proceeds through a transition state with the inversion of the
configuration.
-
Nu C X Nu C. X Nu C + X
H C
3
CH
Antibomding (s*) C-Cl orbital Transition state
In the transition state, the hybridisation of the central carbon atom changes
from sp3 to sp2. The geometry of the transition state is trigonal bipyramidal
with one bond partially forming and one bond partially breaking. Finally, sp3
hybridisation is reestablished in the product with inversion of configuration.
The potential energy diagram of SN2 reaction is given in Fig. 13.2, which
illustrates potential energy change during the formation of substituted product.
_
-
d- d
Nu C X
Potential energy
- C X
Nu:
-
Nu C X
Reaction
Reactioncoordinate
coordinate
Fig. 13.2: Potential energy diagramed for the SN2 reaction. Higher energy state
indicates transition state.
The SN1 reaction:
You can see from Table 13.5, that the tertiary alkyl halides do not undergo SN2
reaction. And yet when tertiary butyl bromide is treated even with a very weak
base, (such as H2O or CH3CH2OH) substitution takes place. Now, the question
arises, if tertiary alkyl halides cannot undergo SN2 reaction, how are the
68
substitution products formed? The answer is that tertiary alkyl halides undergo
substitution by a different mechanism, called the SN1 reaction (substitution,
nucleophilic, unimolecular). An example of such a reaction is the hydrolysis of
2-chloro-2-methylpropane with water. This reaction is found to be of first order
(SN1). That means the rate of the reaction is proportional to the concentration
of the one reacting species i.e. alkyl halide and independent of the
concentration of the nucleophile.
Rate = k1 [(CH3)3CCl]
In this equation, k1 represents the first order rate constant and [CH3)3CCl]
represents the concentration of the alkyl halide in mole dm-3.
Mechanism: On the basis of reaction kinetics and stereochemistry of SN1

reaction, a two steps mechanism has been proposed for this reaction. Nucleophiles such as
H2O or CH3CH2OH are
Step 1: Ionisation ofthe C−X bond forms a carbocation intermediate. This is also used as the
solvents. Substitution
the relatively slow, rate determining step. reactions of such
nucleophiles are
sometime called
CH3 solvolysis reactions (from
H3C solvent and by "breaking
slow - down" or "loosing").
C Cl + +
C Cl
In most stepwise
H3C H3C CH3 reactions, the slowest
CH3 step in the entire
2-Chloro-2-methylpropane Carbocation intermediate sequence is the rate-
(tert-Butyl chloride) determining step as a
reaction cannot proceed
faster than its slowest
Step 2: Carbocation (an electrophile) reacts with water (a nucleophile) to form step does.
an oxonium ion.
CH3 CH3
H
fast +
H O + O C
C k2
CH3
H H
H3C CH3 CH3
Nucleophile Electophile An oxonium ion
Proton transfer from the oxonium ion to water completes the reaction and
gives 2-methyl-2-propanol (tert-butyl alcohol)
CH3 CH3 H
H fast
+ +
H O O C CH3 O C + H O
CH3
H H H H
CH3 CH3
2-Methyl-2-propanol
(tert-Butyl alcohol)
From the above mechanism it is clear that the first step in this mechanism is
ionisation of the alkyl halide to a carbocation intermediate. This ionisation is a
simple heterolytic bond cleavage. In the second step, a nucleophile may
approach the central carbon atom from either side with equal probability
69
(unlike the SN2 reaction where the nucleophile approaches only from the
back). According to valance bond approach, the central carbon atom of
carbocation is sp2 hybridised and it has a trigonal planar geometry and,
therefore, the nucleophile may engage the empty p orbital from either side of
the molecule.
CH3
- + -
Nu C Nu
H3C CH3 empty p orbital
Thus, SN1 reaction of an optically active alkyl halide should give racemic
substitution products. The potential energy diagram of SN1 reaction is given in
Fig. 13.3. Step 1 has high energy of activation and is, therefore, the slow step.
As shown in this figure, an intermediate carbocation has lower energy than
transition states shown as I and II where bond breaking and bond making
actually occur.
d+ d-
C Cl Intermediate
(I) d+ d-
C OH 2
(II)
Potential energy
(CH 3) 3 C ++ H2O
(CH3)3CCl + H2O
(CH 3)3 COH + H 3O +
Reaction coordinate
Fig. 13.3: Potential energy diagram for hydrolysis of 2-chloro-2-methylpropane

by SN1 mechanism. You can see two transition states. The first (I) is
for formation of the carboction intermediate, the second (II) is for the
reaction of the carbocation with nucleophile (H2O) to give an oxonium
ion.
As in the case of SN2 reaction, the structure of the alkyl halides also affects the
rate of the reaction. We are giving the relative rates of reaction of some alkyl
bromides under typical SN1 conditions in Table 13.6.
70
Table 13.6: Relative reaction rates of hydrolysis of some alkyl bromides under
typical SN1 conditions
Alkyl bromide Relative rate

CH3−Br 1.00*
CH3CH2−Br 1.00*
(CH3)2CH−Br 11.6
6
(CH3)3C−Br 1.2  10
*The observed reactions on the methyl or other primary alkyl bromides probably occur
by SN2 route not SN1 so their relative rates are considered as one.
Therefore, among alkyl halides, the order of relative rates is
tert-RX>sec-RX >p-RX > CH3X
This order is reasonable, since the order of stability of the intermediate

carbocation formed in the slow rate determining step is also the same.
(CH3)3C+> (CH3)2CH+> CH3CH +2 >CH3+

Tertiary Secondary Primary
The SN1 reaction has also been found to be associated with rearrangements.
The intermediate carbocation can rearrange to a more stable carbocation. The
following is an example of one such rearrangement:
Step 1
CH3 CH3
slow + -
H3C C CH2 Br H3C C CH2 + Br
CH3 CH3
1-Bromo-2,2-dimethylpropane Primary carbocation
(Neopentyl bromide) (less stable)
Step 2
CH3 CH3
+ fast +
H3C C CH2 H3C C CH2 CH3
Among halide ions,
CH3 Tertiary carbocation iodide anion is having
(more stable) the largest size and is
least electronegative, its
Step 3 negative charge is
CH3 H CH3 delocalised over the
+ fast large volume of space,
H3C C CH2 CH3 + O H H3C C CH2 CH3 therefore, is the most
- H+ stable. Thus, HI is the
OH strongest acid of halogen
2-Methyl-2-butanol acids. On the other hand,
(tert-Amyl alcohol) fluoride anion is the
smallest ion, its charge is
the most concentrated,
You can notice in step 2, how the primary carbocation rearranges, through the and fluoride ion is the
shift of a —CH3 group, to produce the more stable tertiary carbocation. least stable. Therefore, it
is the weakest acid of the
After studying both the mechanisms, you can point out some of key halogen acids.
differences. First, SN2 reaction involves a single step and has no intermediate.
In contrast, SN1 reaction has two steps with the formation of intermediate
71
carbocation. SN2 follows second order kinetics whereas SN1 follows first order
kinetics. SN2 reaction of an optically active alkyl halide gives product with
inversion of the configuration, on the other hand,SN1 reaction of an optically
active alkyl halide gives generally racemic substitution products. In SN2
reaction, each replacement of hydrogen by an alkyl group decreases the rate
of reaction and opposite is observed in SN1 reaction. Nature of halide group
also influences the rate of reaction. We have seen in transition state of both
SN2 and SN1 reactions that the leaving group develops a partial negative
charge. Therefore, the ability of a leaving group is related to how stable it is as
anion. The most stable anions are the best leaving group and the weak
conjugate bases of strong acids. Thus on the basis of strength of acids we can
determine which anion is best leaving group. For example the order of relative
strength of halogen acids and relative stability of halide ions is shown below:
- - - -
I Br Cl F
HI > HBr > HCl > HF
Stability of anion; strength of acid
Among halogen acids, the order of strength increases from HF(weakest) to HI

(strongest). Thus, the best leaving group among halide is I- and poorest
leaving group is F-.
In fact, both SN2 and SN1 mechanisms can be viewed as the limits of a
mechanistic continuum. Beside the nature of alkyl halide there are many
factors such as nature of nucleophile, nature of leaving group, solvent system
used during reaction etc. which influence the preference of one mechanism
over the other. We are not going in detail of these factors at this stage but we
present a brief overview useful to predict the type of mechanism that
dominates under certain reaction conditions in Table 13.7.
Table 13.7: A summary of SN2 vs SN1 reactions
Alkyl Halide SN2 SN1

CH3−X SN2 reaction is favoured SN1 reaction does not occur because of the unstable
methyl cation
RCH2−X SN2 reaction is favoured SN1 reaction rarely occurs as the formation of
primary carbocation rarely takes place, exceptions
areallylic and benzylic carbocations. Allylic and
bebzylic halides follow both SN2 and SN1
mechanisms
R2CH−X SN2 reaction is favoured in SN1 reaction is favoured in protic solvents with poor
aprotic solvents with good nucleophiles and good leaving groups
nucleophile
R3−X SN2 reaction does not occur SN1 reaction is favoured because of the ease of
Reaction at because of steric factor. formation of tertiary carbocation
chiral centre Inversion of the configuration Racemisation is favoured
(optically active
centre)
Rearrangement No rearrangements in SN2 Rearrangements possible during SN1 reaction
reactions reaction
72
SAQ 5
The reaction of 2-bromo-2-methylpropane with azide ion in methanol is a
typical SN1 reaction. What happens to the rate of the reaction if concentration
of azide ion is doubled?
Some Typical Nucleophilic Substitution Reactions:
As mentioned above the mechanism of a particular nucleophilic substitution

reaction is based on the structure of alkyl halide, nature of nucleophile and
leaving group, and solvent. Now we will consider few reactions which support
this argument.
Substitution Reactions of Allylic and Benzylic Halides:
The behaviour of substituted alkyl halides such as allylic and benzylic halides
in SN1 and SN2 reactions deserves to be considered separately. Both these
halides are very reactive under both SN1 and SN2 conditions. They undergo
SN1 reaction at faster rate than tertiary alkyl halides. The reason for the
enhanced reactivity under SN1 conditions lies in the resonance stabilisation
of the carbocation intermediate and for SN2 reaction in the stabilisation of the
SN2 transition state due to charge delocalisation on π bond orbitals. To
illustrate this, further let us consider SN1 reaction of allyl chloride and benzyl
chloride with H2O.
SN1 + H2O
Cl OH
- +
Cl -H
2-Chloropropene Prop-2-ene-1-ol
(Allyl chloride) +
(Resonance structures
of allyl cation)
+
CH2 Cl H2C CH2 CH2 CH2 CH2 OH
SN1 +
+ H2O
- +
Cl -H
+
Chloromethyl benzene Phenylmethanol
(Benzyl chloride) (Benzyl alcohol)
Now, consider the SN2 reactions. Allylic halides and benzylic halides also
undergo SN2 reaction at a faster rate than primary alkyl halides or even methyl
halides. The reason for the greater SN2 reactivity of allylic and benzylic halides
is stability of the transition state. In the case of allylic and benzylic halides
partial overlap of the π bond orbitals helps in delocalisation of the negative
charge on the transition structure thus increasing the rate of the reaction (see
Fig. 13.4).
73
- OHd- -
HO
_ Cl-
Cl OH
2-Chloropropane
(Allyl chloride)
Cld-
SN2 transition state
Fig. 13.4: Stabilisation of SN2 transition state through overlap of the p-orbitlas of
π bond and p-orbital that formed on rehybridisation of carbon centre.
SAQ 6
Which member of each of the following pairs would undergo the faster SN2
reaction? Explain your answer.
Cl CH3
a) or Cl c) H3C Cl or (CH3)2CHCH2Cl
CH3
Cl
b) or CH3CH2CH2Cl
Cl d) CH3 CH CH Cl or
Hydrolysis of Alkyl Halides
Hydrolysis of alkyl halides can be achieved by simply water or aqueous

solution of NaOH and KOH. Methanol or ethanol is also added to the aqueous
solution to dissolve alkyl halide.
The reaction between a primary alkyl halide and water is very slow even if they
are heated. In this reaction, halogen atom is replaced by –OH through SN2
mechanism. For example, consider the reaction of typical primary alkyl
halide,1-bromoethane:
CH3CH2Br + H2O CH3CH2OH + HBr
With water, nucleophilic substitution is very slow because water is not a very
good nucleophile. But if we add hydroxide ion, the hydrolysis will be
faster than just water because the hydroxide ion is a more powerful
nucleophile. Although water and hydroxide ion are electron pair donors, the
hydroxide ion carries a full negative charge which enhances the nucleophilicity
of hydroxide ion compared to the electrically neutral water molecule.
Now consider the reaction of a tertiary alkyl halide with water, when it is
heated under reflux with water, the halogen is replaced by —OH to give an
alcohol. This reaction happens much faster than the corresponding one
involving a primary alkyl halide and it follows SN1 mechanism. For example:
(CH3)3Br + H2O (CH3)3COH + HBr
The rate of the overall reaction is governed entirely by how fast the alkyl
74 halide isionised. In this case addition of hydroxide ion doesn’t affect the
reaction rate. The water/OH- is not involved in the slow step of the reaction.
Thus, this reaction is generally carried out in water in place of aqueous
solution of NaOH or KOH. Secondary alkyl halides follow both SN2 and SN1
mechanism not as fast as we observed in case of tertiary alkyl halide. This
relative reactivity of alkyl halide may be used in identification of primary,
secondary and tertiary alkyl halides using alcoholic silver nitrate solution. The
tertiary halide produces a precipitate of silver halide almost instantly and the
secondary halide gives a slight precipitate after a few seconds. The precipitate
thickens up with time. The primary halide may take considerably longer to
produce a precipitate.However, aryl halides and alkenyl halides will not react
with alcoholic silver nitrate.
Reaction with Cyanide Ion:
Alkyl halide on treatment with a solution of sodium or potassium cyanide in

ethanol, gives a nitrile. The cyanide ion is a good nucleophile as there is a
formal negative charge and a lone pair on the carbon atom.
For example, using 1-bromobutane as a typical primary alkyl halide:
CH3CH2CH2CH2Br +:CN‒ CH3CH2CH2CH2CN + Br‒
In this reaction, bromine is simply replaced by a —CN groupby SN2

mechanism and gives pentanenitrile (Butyl cyanide). A small amount of
pentaneisonitrile is also formed in the above reaction. Secondary and tertiary
alkyl halides also behave similarly, although the mechanism will vary
depending on which type of alkyl halide you are using.
This reaction is very useful as it affords a method of adding one carbon atom
to a chain. The resultant nitrile can be either hydrolysed by heating with dilute
acid to a carboxylic acid:
CH3CH2CH2CH2CN + 2H2O + H+ CH3CH2CH2CH2COOH + NH4+
or it can be transformed into an amine by reaction with hydrogen at 423 K in

the presence of a nickel catalyst:
CH3CH2CH2CH2CN +2H2 CH3CH2CH2CH2CH2NH2
The reaction of AgCN with alkyl halides produces mainly isonitrile, RNC, in
contrast to similar reactions discussed above with alkali metal cyanide (NaCN
and KCN), which yield mostly nitriles. This is because of the presence of two
nucleophilic centres in cyanide ion. In fact cyanide ion has two resonating
structures as shown below:
- -
C N C N
I II
Therefore, it may react either by carbon or nitrogen centre. Such nucleophilic

species which have more than one site for reaction are called ambident
nucleophiles. Alkali metal cyanides such as NaCN and KCN,are ionic
compounds and dissociate as cyanide ion and metal ion. In cyanide ion,
carbon centre is a better nucleophile than nitrogen centre because it has full
75
negative charge besides having a lone pair; therefore, cyanide normally reacts
with alkyl halide through its carbon centre and giving nitrile as major product.
On the other hand, silver cyanide is predominantly covalent, therefore, silver
remain bonded to carbon of cyanide group and leaving the nitrogen end free to
be nucleophilic (whereas potassium or sodium ions is not so attached to
cyanide ion during reaction). Thus, only nitrogen centre is available for the
attack on electrophilic centre of alkyl halide. As a result, alkylisonitriles are
formed as main products. Silver cyanide also promotes an SN1 reaction, as the
silver interact with the halide ion, forming carbocation or enhancing
carbocation character of transition state. Now comparatively weak nitrogen
nucleophilic centre of cyanide ion can attack on such activated carbon centre
and forming alkylisonitrile as major product. Products formed during the
reaction of 1-bromopropane with potassium cyanide and silver cyanide are
shown below.
- +
C N K
CH3CH2CH2 C N
Butanenitrile
(n-Propyl cyanide)
CH3CH2CH2 Br + -
CH3CH2CH2 N C
1-Isocynoprpane
N C Ag (1-Propyl isocyanide)
Reaction with Nitrite Ions
Similar to cyanide ion, nitrite ion is also an ambident nucleophile with two
different nucleophhilic centres, i.e. one through oxygen results formation of
alkyl nitrite and other through nitrogen gives nitroalkanes.
-
O O
N N
-
O O
Resonance stabilised nitate ion
Alkyl halides react with alkali metal nitrites i.e. NaNO2 or KNO2 to give
corresponding alkyl nitrates as the major product along with nitroalkanes as
minor product. However, when alkyl halides are treated with silver nitrite
(AgNO2), nitroalkanes are formed as major product.
-
O O +
N K
CH3CH2 O N O
Ethyl nitrite
CH3CH2 I O
+
CH3CH2 N
-
O
O Nitroethane
N
O Ag
76
Alkali metal nitrites (NaNO2 and KNO2) are predominately ionic compounds;
therefore, nitrite ion attacks mainly trough better nucleophilic site i.e. negative
charged oxygen to electrophilic centre of alkyl halide to form alkyl nitrite. On
the other hand, silver nitrate is covalent in nature and remains bonded to
oxygen atom of nitrite group and leaving the nitrogen end free to be
nucleophilic. This nucleophilic nitrogen through its lone pair of electrons
attacks and as a result, nitro compounds are formed as major products.
Reaction with Metals
Alkyl halides react with certain metals to give compounds containing carbon-
metal bonds. Such compounds are known as organo-metallic compounds.
For example, the reaction of chloroethane with a sodium lead alloy under
pressure gives tetraethyllead.
2 C 2H5 Cl + 4 Na/Pb (C2H5)4Pb + 4 NaCl

Chloroethane Tetraethyllead
Tetramethyl and tetraethyl-lead are used as anti-knock additives to petrol.
An important class of organo-metallic compounds discovered by Victor

Grignard in 1900 is alkyl magnesium halides, RMgX, referred as Grignard
Reagents. These reagents are obtained by the reaction of alkyl halide with
magnesium metal in dry ether.
Mg in ether
R X RMgX
In the Grignard reagent, the carbon-magnesium bond is covalent but highly

polar, with carbon pulling electrons from electropositive magnesium and
making the carbon atom both nucleophilic and strongly basic; the magnesium
halogen bond is essentially ionic.
d-
+ -
R CH2 Mg X
Carbon is a nucleophilic centre
Grignard reagents, therefore, take part in nucleophilic addition reaction.

Grignard reagents are used to prepare a large variety of organic compounds.
Some of the important reactions are:
i) Preparation of alkanes: Alkanes are prepared by the reaction of

Grignard reagents with water, alcohols, ammonia, amines etc.:
RMgX + H2O → RH + Mg(0H)X

Water Alkane
RMgX + R'OH → RH + Mg(OR')X

Alcohol
RMgX + NH3 → RH + Mg(NH2)X

Ammonia
RMgX + R'NH2 → RH + Mg(NHR')X

Amlne
77
In these reactions Grignard reagents act as very strong bases and react
with any source of proton (acid) to give hydrocarbons. It is therefore,
necessary to avoid even traces of moisture while using a Grignard
reagent.
ii) Preparation of alcohols: Primary alcohols are obtained by the reaction

of methanal and Grignard reagent followed by treatment with dilute acid:
H3O+
HCHO + RMgX RCH2OMgX RCH2OH + Mg(OH)X
Methanal Primary alcohal
Secondary alcohols are obtained when a Grignard reagent is treated with

anyaldehyde (other than methanal) followed by decomposition of the
addition product with a dilute acid:
1 1
R H3O+ R
1
R CHO + RMgX CH OMgX CH OH + Mg(OH)X
R R
Aldehyde (Secondary alcohal)
Tertiary alcohols are obtained on treatment of a ketone with Grignard

reagent and subsequent addition of dilute acid:
1 1
1 R R
R
2 H3O+ 2
C O + RMgX R C OMgX R C OH + Mg(OH)X
2
R R
Ketone R
Tertiary alcohal
Alcohols are also obtained when epoxides are reacted with Grignard
reagent and the addition product is hydrolysed with dilute acid:
O H3O+
+ RMgX OMgX OH + Mg(OH)X
R R
iii) Preparation of Ketones: Ketone can be prepared by the reaction of an

alkyl nitrile with a Grignard reagent:
1 1
R H3O+ R
1
R C N + RMgX C NMgX C O + NH3
2
R R
Ketone
Grignard reagents also react readily with oxygen and carbon dioxide as
shown below. These side reactions can be prevented by forming the
Grignard reagent under an inert atmosphere such a nitrogen.
RMgX H3O+
RMgX + O2 RO2MgX 2ROMgX 2 ROH + 2 Mg(OH)X
H3O+
RMgX + CO2 RCOOMgX RCOOH + Mg(OH)X
78
Another side reaction that occurs during the formation of Grignard reagents is
the coupling reaction between two alkyl (or aryl) halides as shown below. This
side reaction can be minimized if the concentration of the halide is kept low by
the slow addition of an ether solution of the halide to a mixture of magnesium
and ether.
Ether
RX + RMgX RR + MgX 2
This reaction is similar to Wurtz reaction which you have studied earlier.
Using the reactions discussed above, attempt the following SAQ.
SAQ 7
How would you prepare primary, secondary and tertiary alcohols? Give one
reaction for each case.
SNi Reaction
So far we have discussed substitution reactions which involve two reactants, a

substrate (alkyl halide) and a nucleophile. In some substitution reactions, the
nucleophile is a part of the substrate. Such intramolecular substitutions are
more rapid than the corresponding intermolecular reactions. Consider
following reaction:
C 6 H5 C 6 H5 C 6H 5
SOCl2 
C OH C OSOCl C Cl + SO2
H3C H3C H3C
CO2H CO2H CO2H
This reaction is said to proceed by SNi mechanism meaning substitution

nucleophilicinternal (intramolecular), since both the nucleophile and the
leaving group are part of a single molecule. Stereochemistry of these reactions
shows retention of configuration at the chiral carbonatom i.e. nucleophile
attacks from the same face as the leaving group departure.
The first step is like that an SN1 reaction, i.e., formation of ion pair. In the
second step, a part of the leaving group attacks only from the front side
leading to retention of configuration.
C6 H5 -
C6 H5 O O C 6H 5

C O S O + S C Cl + SO2
C
H3C H3C
Cl Cl
CO2H H3C CO2H CO2H
Chlorine attacks carbocation
on same face of tight ion pair
If, however, an external chloride ion is available in the presence of an amine

like pyridine, a normal SN2 reaction occurs in the above case with inversion of
configuration.
79
C6H5 C6H5
- +
C O S O Cl + C O S N
H3C H3C
Cl O
CO2H CO2H
C6H5
N
Cl C SO 2 +
CH3 +
CO2H
Result is inversion
The SNi reaction mechanisms did not meet with wide acceptance, even though
in chemical literature this In gold system is still utilised to describe similar
types of substitution reactions.
Finally, neighbouring group participation can occur to produce the same result
as SNi - i.e. overall retention of configuration in product. For example, if the
molecule in question has a nucleophilic substituent that can reach
the electrophilic site, then that substituent may participate in the reaction as
well as the incoming nucleophile. If the electrophilic site is chiral, there will be
overall retention rather than inversion, as shown in the following example;
C - C
- Br- OH
HO CH Br + HO CH OH
O
H Ph
Ph Ph
It is worth noting that both steps of this reaction involve the SN2 mechanism,
with inversion, so the overall result (of double inversion) is retention.
Elimination Reactions
A side reaction that occurs during substitution reactions of alkyl halides is the
elimination of HX (dehydrohalogenation) to produce an alkene.
SN1/SN2
Substitution product
Alkyl halide
E1/E2 Alkene(s)
Under appropriate conditions such as the use of a strong base (OH- or OR-),
and high temperature, elimination can be the principle reaction and thus
become a method for the preparing alkenes. We have already introduced such
reaction in Unit 16 of first semester course.
Like the nucleophilic substitution reactions, elimination reactions of alkyl

halides can proceed by either a first or a second order mechanism. The first
order elimination reaction is symbolised as E1 and the second order
elimination reaction as E2.
80
E1 reaction: In the absence of a strong base tertiary alkyl halides, and to

some extent secondary alkyl halides, dehydrohalogenate via the E1
mechanism to give alkenes. The mechanism has two steps.
Step 1 (slow): Ionisation of the C─X bond gives stable carbocation:

CH3 CH3
slow, rate
determining +
H3C C Br H3C C + Br-
CH3 CH3
2-Bromo-2-methylpropane Carbocation intermediate
(tert-Butyl bromide)
Step 2: Proton transfer from carbocation intermediate to form alkene:

CH3 CH3
H
+ +
O + H CH2 C H3O + H2C C
CH3
H CH3
2-Methylpropene
The first step, as in SN1 reactions is ionisation of the alkyl halide. Since, this is
the slow i.e., rate determining step the E1 reaction follows first order kinetics.
Note that the base here attacks the hydrogen atom and not the carbon
carrying the positive charge.
E1 reactions of alkyl halides occur under the same conditions as SN1 reaction
(polar solvent, very weak base etc.) Therefore the E1 reaction is a strong
competitor of the SN1 reaction. The order of reactivity of different halide types
is the same in both reactions, that is tert > sec > p. The E1 reaction is
favoured by the higher temperature and is most common in tertiary halides.
E2 reaction: The most useful elimination reaction of alkyl halides is the E2

reaction (bimolecular elimination). The E2 reactions of alkyl halides are
favoured by the use of strong bases, such as OH− or OR− and high E2 elimination reaction is
an example of β-
temperature. Typically the E2 reaction is carried out by heating the alkyl halide elimination. In a β-
with KOH or NaOCH2CH3 in ethanol. elimination reaction two
groups are eliminated
from adjacent atoms. It is
Br by far the most common
- CH3CH2OH - type of elimination
CH3 CH CH3 + CH3CH2O CH3 CH CH2 + CH3CH2OH + Br reaction in organic
heat chemistry.
2-Bromopropane Ethoxide ion Propene
B:
H
A mechanism consistent with the rate-law is given below, in which the proton b a b -elimination
and the halide ion are removed simultaneously to give the alkene i.e. bond X
breaking and bond forming are concerted.
CH3
- -
CH3CH2O + H CH2 CH Br CH3CH2OH + H2C CH CH3 + Br
Stereochemical studies reveal that E2 elimination reactions are

stereoselective anti-eliminations. The anti-elimination involves all backside
electronic displacements.
81
Backside attack of the base on the C−X bond
B
..
B: Empty C-X s* orbital

Filled C-H s orbital
H
H ..
Cl
X
anti elimination Leaving group
Similar to SN2 reactions, there is an orbital-based reason for the anti-

elimination. This can be explained using molecular orbital approach. You can
see in above diagram that filled C−H σ bonding molecular orbital aligned with
the empty C−X σ* antibonding molecular orbital. As the strong base removes
the proton, the two electrons moves from C−H σ bonding orbital to empty C−X
σ* antibonding orbital and thereby breaking the C−X bond. This anti and
coplanar arrangement of the molecular orbitals leads to proper phasing to form
new π bond.
Substitution versus Elimination
We have said earlier that substitution and elimination are competitive

reactions; one reaction occurs at the expense of the other. Now, we consider
the important factors which determine the direction of the reaction.
i) The structure of the alkyl halide,
ii) The nature of the base, and
iii) Temperature.
We have summarized the effect of these variables in Table 13.8.
Table 13.8: Substitution versus Elimination
Alkyl Halide Weak base Moderate base Strong base
Primary S N2 SN2 SN2 with good

Alkyl halide nucleophile and E2
with poor nucleophile
and high temperature
Secondary SN1 or SN2; Some SN2; E2 at high E2

Alkyl halide E1 at high temperature
temperature
Tertiary SN1 and E1; E1 E2 E2

Alkyl halide predominates at
higher temperature
82
In general, branching in alkyl halides and higher temperature increases the

ratio of elimination to substitution.
To further understand effect of above factors, we will now consider some

specific examples and analyse the factors that determine the direction of the
reaction.
Example 1
CH3CH2O-Na+ O
Br
+
CH3CH2OH
91 % 9%
In above example alkyl halide is primary and therefore the major reaction is
SN1 and E1 is a minor reaction. Further, ethoxide ion is strong base as well as
a good nucleophile, therefore, SN2 reaction dominated over E2 reaction.
Example 2
CH3CH2O-Na+ O
Br
+
CH3CH2OH
40 % 60 %
Because of branching in primary alkyl halide (steric factor) in this case this will
give nearly equal amount of SN2 and E2 reactions. Similar reaction with
secondary alkyl halides will be dominated by E2 reaction.
Example 3
CH3CH2OH
O +
Br
~100 % little to none
Here, ethanol is a weak base i.e. weak nucleophile and alkyl halide is tertiary,
therefore SN2 and E2 reaction can easily be ruled out. It is expected that this
reaction will follow SN1 and E1. Generally, E1 only is a minor reaction.
The reaction of the same alkyl halide with strong base such as sodium ethoxide in
ethanol, follows E2 reaction predominantly.
CH3CH2O-Na+
O +
Br
CH3CH2OH
13 %
87 %
Example 4
CH3COO-Na+ O
Br
+
CH3CH2OH
O
major minor
83
This reaction alkyl halide is secondary and acetate ion is weak base.
Therefore, there will be little or no E2 reaction. This reaction predominantly
follows SN2 reaction. If same alkyl halide is treated with strong base such as
NaOC2H5 in ethanol, E2 would have been the dominated reaction.
CH3CO-Na+
Br
CH3CH2OH +
Elimination reaction in
quaternary ammonium major minor
+ -
hydroxides (R4N OH )
does ‘not follow Saytzeff In this above reaction, formation of more substituted alkene is dominated over
rule, but they undergo
elimination reactions and less substituted alkene. More substituted alkene is thermodynamically more
yield the Hofmann stable than the less substituted alkene. Hence, products of such reaction are
product, the alkene with governed by the relative stability of products. In β-elimination reactions, relative
fewer alkyl groups on the
stability of products provides a rationale for the Saytzeff rule of regiochemistry.
π-bonded carbons. Such
reactions are known as Now, let us discuss this rule.
Hofmann eliminations
and follow E2 Saytzeff rule: In the alkyl halides, where the halogen is not attached to the
mechanism. The terminal carbon atom, elimination is possible in two directions, giving two
formation of the less
isomeric alkenes. An illustrative example is the dehydrobromination of
substituted less stable
alkene can be attributed 2-bromobutane to give 1- and 2-butenes:
to steric hindrance in the
transition state stability CH3CO-Na+
(relative transition state
Br
energies) due to the CH3CH2OH +
group, e.g..butyl in the
example given below: 2-Bromobutane 2-Butene 1-Butene
(Preferred product)
+ -
N(CH3)3OH
398 K In the above reaction, the major product is 2-butene. This follows the rule

formulated in 1875 by Alexander Saytzeff. Saytzeff rule states that in a
+ dehydrohalogenation reaction of alkyl halides, the major product will be the
1-Pentene 94 % 2-Pentene (6%)
one that has the more alkyl groups attached to the resultant carbon-
carbon double bond. The rule parallels the order of thermodynamic stability
of the alkenes; that is, the alkene with more alkyl groups attached to the
carbon-carbon double bond is more stable.The order of stability of alkenes
may be represented as:
R2C=CR2 > R2C=CRH > RHC=CHR and R2C=CH2 > RCH=CH2
Because of the relative stability of the resultant alkenes, tertiary halides

undergo dehydrohalogenation more readily than secondary halides, which
dehydrohalogenate more readily than primary halides (as we have already
noticed earlier).
Exceptions to the Saytzeff rule are exemplified by the Hofmann rule. This rule
predicts that β-elimination will occur preferentially to gives the less substituted
alkene as major product. For example thermal decomposition of sec-
butyltrimethylammonium hydroxide gives 1-butene as the major product.
- +
HO N(CH 3)3
Heat
CH3CH2 CH CH3 H3 C CH CH CH3 + CH3CH2 CH CH2 + (CH3)3N + H2O
(5 %) (95 %)
84
If there are more than one β-hydrogen is anti to leaving group, then there will
be competition between Hofmann and Saytzeff elimination. Eliminations
involving halide ions or negative charged leaving groups generally follow
Saytzeff rule, unless a bulky base is used. On the other, if leaving group is
neutral in nature such as N(CH3)3 and S(CH3)2, the eliminations will follow
Hofmann rule. Bulkier bases such as (CH3)3COK also predominantly give
Hofmann product. The regioselectivity of β-elimination can be explained on the
bases of relative stability of transition state during elimination reaction.
SAQ 8
Predict whether each reaction proceeds predominantly by SN1 or SN2 or E1 or
E2.
Br
CH3CO-Na+ NaCN
b)
a) Cl DMF
CH3CH2OH
CH3
- +
CH3COO Na CH3OH
d) CH3 C CH3
c)
CH3CH2OH Br
Cl
SAQ 9
Write the equation for the formation of alkenes from the following starting
material. If you expect more than one product, indicate which alkene is the
major product.
CH3 - +
C2H5O Na
CH3CH2 C CH3
C2H5OH
Br
13.4.5 Uses of Alkyl Halides

Alkyl halides find a variety of uses and applications in our everyday lives. They
are used in labs as synthetic intermediate compounds and as
solvents. Dichloromethane (CH2Cl2, methylene dichloride), trichloromethane
(CHCl3, chloroform), tetrachloromethane CCl4, carbon tetrachloride) and
trichloroethylene (Cl2C=CHCl), for example, are used as solvents.
In agriculture, alkyl halide such as2,4-D applied as herbicides captan as

fungicides. The insecticide DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane)
is effectively used to control many diseases such as malaria, typhus, and
cholera. Most countries have banned the use of DDT. Since DDT accumulates
in fatty tissue of warm-blooded animals (and humans), it was suspected to be
carcinogenic. Latter, this assumption has been proven not to be correct.
85
Cl O
O
Cl O CH2 C OH N S CCl3
2,4-D Captan O
CCl3
Cl CH Cl
DDT
Until the mid-1980s, chlorofluorocarbons (CFCs) were produced in large

quantities. They are derivatives of methane and ethane. Freons such as
trichlorofluoromethane (freon-11), tetrafluoromethane (freon-14) and
trichlorotrifluoroethane (freon-113), for example, are relatively simple CFCs in
which all hydrogen atoms have been substituted by chlorine or fluorine atoms.
They are prepared by the action of hydrogen fluoride on tetrachloromethane
(carbon tetrachloride), trichloromethane and hexachloroethane. CFCs are
produced at a reasonable price and are stable, non-toxic, non-inflammable, and
non-corrosive. Therefore, CFCs were considered perfect materials for usage in
many practical applications, including propellants, coolants in refrigerators and
fire-extinguishing agents. Unfortunately, due to their high chemical stability,
CFCs have been identified as a severe environmental liability. They are a main
cause of ozonolysis in the stratosphere and are largely responsible for the ozone
hole. As a result, the production of CFCs is prohibited worldwide. However, due
to their high stability, the CFC concentration in the stratosphere will not
considerably decrease to a safe level until the year 2050. Now, CFCs are
replaced by third generation products such as hydrofluorocarbons (HFCs).They
do not harm the ozone layer as much but these products more expensive to
produce than CFCs.
Tetrafluoroethene (CF2=CF2) on polymerisation gives aplastic Teflon. It is

unaffected by chemical reagents, even by boiling aqua regia. It is widely used
as a liner in frying pans and on other utensils and tools to provide nonsticking
surfaces. Polychlorofluoroethenes are used as oils and greases.
Perfluoroheptane is used in the separation of uranium isotopes. Poly
(chloroethene) .or polyvinyl chloride (PVC) is a plastic material of commercial
importance.
At present, more than 15,000 halogenated organic compounds are produced for
industrial purposes. They are used as feedstock for the production of PVC,
industrial lubricants, pesticides, insecticides, herbicides, solvents and many
others. However, the fact that many of these compounds are either not at all or
only barely biodegradable has serious implications on health and environment.
Simple compound, carbon tetrachloride used as a fabric cleaner is known to
cause damage to liver. Similarly, chloroform a popular anesthetic has been
proven to be cancerous. Therefore, use and circulation of alkyl halides has
86
been restricted to some extent.
13.5 LAB DETECTION

The presence of halogen in an organic compound is readily detected by the
Beilstein test. In this test a small amount of the compound is placed on a small
loop of copper wire, and the loop heated in a flame. A green flame is evidence of
the presence of halogen. To ascertain which halogen is present, the covalently
bonded halogen has to be converted to the halide ion which can then be
identified by the usual methods of inorganic qualitative analysis. This is done by
two methods; through sodium fusion (treatment with hot molten sodium metal):
Heat + -
Na + RX Na X
Organic
compound
or through Schoniger oxidation by oxygen gas under alkaline condition
NaOH + -
RX + O2 Na X + H2O
Organic
compound
In alkyl halides, benzyl halides and allyl halides the presence of halogen can be
detected by warming the organic compound with alcoholic silver nitrate. The
silver halide formed can be analysed further.
NaOH
RX + AgNO 3 AgX (s) + RONO2
Organic
compound
However, aryl halides and alkenyl halides will not react with alcoholic silver
nitrate.
The reaction helps in distinguishing alkyl halides from aryl and alkenyl halides.
13.6 SUMMARY
In this unit, we have described the chemistry of alkyl halides. We are
summarising below what we have studied:
 Substitution of one or more hydrogen atoms in alkanes by a halogen atom(s)

gives rise to alkyl halides. Monohalogen derivatives of alkyl halide can be
further classified as primary, secondary and tertiary halides depending on
the alkyl group to which halogen is attached.
 Alkyl halides can be prepared from alcohols, from alkanes, from Grignard
reagents and through halogenation of hydrocarbons in the presence of light
or heat and catalysts.
 The halogen in alkyl halides can be replaced by various nucleophiles. These

reactions occur by two different pathways, SN1 and SN2. Benzyl and allyl
halides are more reactive than alkyl halides. Aryl and vinyl halides are least
reactive and theydo not follow SN2 and SN1 paths. The reactivity order of
halides is allyl > benzyl > alkyl > aryl or vinyl. 87
 Alkyl halides undergo elimination reaction (dehydrohalogenation) to give

alkenes. These reactions occur by the E1 or E2 pathway. If the halides are
such that the lossof a hydrogen on adjacent carbon (β-hydrogen) can
occur from either side, isomeric alkenes are formed. Usually, the most
stable i.e. more highly substituted alkene is formed as the major product
(Saytzeff rule).
 Alkyl halides react with magnesium to form alkyl magnesium halides,

called the Grignard reagents. They are very reactive compounds and take
part in many reactions to give alkanes, alcohols (primary, secondary and
tertiary), ketones and carboxylic acids, etc.
 The halogen derivatives are very useful in industry. The chloro

compounds are powerful insecticides and moth repellants. The
chlorofluoro compounds (Freons) are refrigerants, aerosol and
propellants. Polymerisation of vinyl chloride and tetrafluoroethylene gives
plastic in the name PVC and teflon, respectively.
 The halogen can be detected as halide ion.

1. Write IUPAC names of the following:
a) H3C Br
Cl
b) HO CH3
c) Cl Br
2. Write the possible isomers for molecular formula C4H9Cl. Give IUPAC
name for each isomer and also classify them as primary, secondary and
tertiary.
3. Write the products of the following reactions:

OH
a) + SOCl 2
CH3
b) + HBr
CH3
Peroxide
c) HBr
+
d) CH3COOAg + Br2
Heat
e) H2C CHCH 2CH 3 + Br 2
88
f) CH3Br + AgF
4. Among the following pairs of alkyl halides which would undergo SN2
reaction faster:
a) 3-Chloro-1-butene and 4-Chloro-1-butene
b) 1-Iodopropane and 1-Chloropropane
5. Write the equations for the following reactions:
a) CH3CH2CH2CH2Br + NaOH (aq) 
b) C6H5CH2Cl + H2O 
c) CH3CH2CH2Br + NaSH 
6. Complete the equations given below:
a) CH3CH2CH2Br + CH3CH2O-Na+ 
b) C6H5CH2Cl + AgNO3 
c) Chlorobenzene + AgNO3 
7. a) Reaction of 1-Bromopropanewith sodium cyanide
b) Reaction of 1-Bromopropane with silver cyanide
c) Reaction of 1-Bromopropane with sodium nitite
d) Reaction of 1-Bromopropane with silver nirite
8. Complete the equation for each of the following reactions and if more
than one product is formed, indicate which one is major.
a) + KOH
Br
CH3
b) Cl 
+ C2H5O-Na+
C2H5OH
9. Name a simple chemical test or reagent which will readily distinguish

between each of the following pair of compounds.
a) Cl and Cl
b) CH3 Cl and CH2Cl
Cl
c) and Cl
89
13.8 ANSWERS
Self Assessment Questions
1. a) Secondary alkyl halide, 2-chloro-4-Methylpantane; b) Secondary alkyl
halide, 3-Bromopentane; c) Primary alkyl, 1-Chloro-2,2-dimethylpentane;
b) tertiary alkyl halide, 2-Chloro-2,4-dimethylpentane.
hv
2. a) C6H5CH2CH3+ Br2 C6H5CHBrCH3 + HBr
PBr3
b) CH3CHOHCH3 CH3CH2BrCH3
HBr
c) CH3CH = CH2 CH3CH2CH2Br
Peroxide
CH2Cl2
d) CH3CH = CH2 + Br2
room temp.
Cl
Cl2, light
a)
CH3
Cl2, light
b) Cl
Br
Br2, light
c)
4. Increasing order of boiling point of following alkyl halides:
CH3Cl < CH2Cl2 < CHCl3 < CCl4
Since molecular mass and size of compounds is also increasing in the

same order.
5. The reaction of 2-bromo-2-methylpropane with azide ion follows SN1

reaction; therefore rate of reaction is proportional to concentration of alkyl
halide, so the increase concentration of azide ion does not have much
effect on the rate of the reaction.
6. a) and b) CH2 Cl
In both a) and b) cases (Chloromethyl)benzene (benzyl chloride)

undergoes SN2 reaction at faster rate than chlorocyclohexane and
chlorobenzene. The reason for greater SN2 reactivity of
(chloromethyl)benzene is the stability of transition state. Further, the low
reactivity of chlorobenzene is attributed to the stronger Ar—Cl bond.
90
c) (CH3)2CHCH2Cl d) CH2CHCH2CI
7. Primary alcohols are prepared by the reaction of Grignard reagents with

methanal and followed by hydrolysis
H H+/H2O H
HCHO + RMgX CH OMgX CH OH + Mg(OH)X
R R
Methanal (Primary alcohal)
Secondary alcohols are obtained when a Grignard reagent reacts with

aldehydes(other than methanal) followed by hydrolysis.
1 1
R H+/H2O R
1
R CHO + RMgX CH OMgX CH OH + Mg(OH)X
R R
Aldehyde (Secondary alcohal)
Tertiary alcohols are prepared by the action of a ketone with Grignard

reagent and subsequent addition of dilute acid.
1 1
1 R R
R +
2 H /H2O 2
C O + RMgX R C OMgX R C OH + Mg(OH)X
2
R R
Ketone R
Tertiary alcohal)
8. a) Major product wills2-methyl-2-butene. This reaction will proceed by

E2 elimination as reaction is carried out with tertiary halide in
presence of strong base (good nucleophile).
Br
CH3CO-Na+
b) Reaction of the primary alkyl halide with a moderate nucleophile such

as cyanide ion in presence of polar aprotic solvent will give major
substitution product by SN2 reaction.
NaCN
Cl DMF CN
c) Here alkyl halide is secondary and but nucleophile is a weak

base. Hence SN2 will dominate over E2.
CH3COO-Na+
+
CH3CH2OH
Cl OH
Major
d) Here alkyl halide is tertiary and nucleophile is a weak base so E2 and

SN2 can be ruled out. This reaction will give mixture of substitution
91
(SN1) and elimination (E1) products. It is difficult to predict the ratio of

substitution to elimination products for such reactions.
CH3 CH3 CH3
CH3OH
CH3 C CH3 CH3 C CH3 + CH3 C CH2
Br OCH3
9. Over all reaction can be written as:
Br
C2H5O-Na+
CH3CH2 CH3 CH3CH C CH3 + CH3CH2 C CH2
C2H5OH
CH3 CH3 CH3
(I) (II)
Two products are formed in this case, one (I) is three alkyl substituted
alkene and the other (II) is two alkyl substituted, therefore, according to
Saytzeff rule (I) alkene will be the major product.
Terminal Questions
1. a) 4-Bromo-2-butene; b) 3-Chloro-1-butanol; c) 1-bromo-3-chloropropane.
Cl
2. a) CH 3CH 2CH 3CH 2 Cl b) CH 3CH 2CHCH 3

Primary Secondary
1-Chlorobutane 2-Chlorobutane
CH3
c) CH 3 CH CH 2 Cl d) H3C C Cl
CH 3 CH3
Primary Tertairy
1-Chloro-2-methylpropane 2-Chloro-2-methylpropane
OH Cl
3. a) + SOCl 2 + SO 2 + HCl
CH3 CH3
b) + HBr Br
CH3 CH3
Peroxide
c) + HBr
Br
d) CH 3COOAg + Br 2 CH 3Br + AgBr + CO
2
Heat
e) H2C CHCH 2CH 3 + Br2 H2C CHCHCH 3 + HBr
Br
f) CH 3Br + AgF CH 3F + AgBr
92
4. a) 3-Chloro-1-butene will undergo SN2 reaction at faster rate as it is

an allyl alkyl halide.
b) 1-Iodopropane as iodine is better leaving group because of its larger

size. It will be released at a faster rate on the attack of a nucleophile.
5. a) CH3CH2CH2Br + NaOH(aq) CH3CH2CH2OH + NaBr
b) C6H5CH2Cl + H2O C6H5CH2OH + HCl
c) CH3CH2CH2Br + NaSH CH3CH2CH2SH + NaBr
6. a) CH3CH2CH2Br+Na+-OCH2CH3 CH3CH=CH2+CH3CH2OH+NaBr
b) C6H5CH2Cl + AgNO3 + H2O C6H5CH2OH + AgCl
c) Chlorobenzene + AgNO3+ H2O no reaction.
7. a) Butanenitrile
b) Propylisonitrile
c) 1-Nitropropane
d) Propylnitrite
8. a)
+ KOH + CH2
Br
Major (more
substituted)
CH3
CH3 CH2
Cl - + 
+ C2H5O Na +
C2H5OH
Major (more
substituted)
9. Following pairs can be distinguished by the action of alcoholic AgNO3

reagent with the halides.
a) With alcoholic AgNO3 chlrobenzenewill not react
b) Aryl halide (4-Chlorotoluene) also will not react with alcoholic AgNO3,
c) CH3CH2CH=CHCl also will not react with AgNO3.
93
UNIT 14
ARYL HALIDES
Structure
14.1 Introduction Electophilic Substitution
Reactions
Reactions due to C−X bond
14.2 Structure and Reactivity
14.5 Reactivity and Relative
14.3 Preparation of Aryl Halides
Strength of C−X Bonds in
14.4 Reaction of Aryl Halides Halogen Derivatives
Nucleophilic Substitution by 14.6 Summary
Addition-Elimination
Nucleophilic Substitution via
14.8 Answers
Benzene Intermediate
14.1 INTRODUCTION
In Unit 13, we have pointed out that there is a difference in the nature of C−X
bond of aryl halides and aryl halides. Because of this aryl halides differ from
the alkyl halides in their preparation and properties. In this Unit, we will study
the unique chemistry of aryl halides.
First, we shall take up the structure and reactivity of aryl halides, which is
followed by their preparations and properties. At the end of the unit we shall
compare the reactivity and relative strength of C−X bond in different type of

 explain why aryl halides are less reactive than alkyl halides,
 outline the methods of preparation of aryl halides,
 describe the reactions of aryl halides, and
 explain the difference in structure and reactivity of alkyl, alkenyl and aryl
halides towards nucleophilic substitution reactions.
94
Unit 14 Aryl Halides
14.2 STRUCTURE AND REACTIVITY

Before going into the details of the preparations and properties of aryl halides let
us take a look at the structure and reactivity of these compounds so that we can
understand why their reactions are different from alkyl halides.
Compounds in which one or more hydrogen atoms of an aromatic ring are

replaced by halogen atom(s) are called aryl halides. These compounds are also
known as haloarenes and have the general formula, Ar–X.
Just to recall, in IUPAC naming of halogens, the prefix – chloro, bromo, iodo etc.
is added before the name of arene. The relative position of halogen atoms are
indicated by numbers. The prefixes ortho (o), meta (m) and para (p) are also
used to indicate the relative positions of substituents.
Some representative examples are given below:

Br Cl Cl
CH3 Br
Bromobenzene 1-Chloro-4-methyl 1-Bromo-4-chloro-
benzene) benzene (p-bromo-
(p-chlorotoluene) chlorobenzene)
Cl CH3
Cl
NO 2
Cl
3-Nitrochlorobezene 2-4-dichloro-
(m-nitrochlorobenzene) methylbenzene
(2,4-Dichlortoluene)
Now, let us focus our attention on the structure and reactivity of aryl halides. It
has been discussed earlier that C−X bond in the aryl halide is shorter and
stronger because of the difference in hybridisation of carbon atom in C−X bond.
In alkyl halides, the carbon atom attached to halogen is sp3 hybridised while in
case of aryl halides, the carbon atom attached to halogen is sp2-hybridised.
X H
sp2 hybridized carbon
C
sp3 hybridized
R X
carbon
H
The sp2 hybridised carbon with a greater s-character is more electronegative and
can hold the electron pair of C−X bond more tightly than sp3-hybridised carbon in
alkyl halide with less s-character. Besides this factor, the unbounded p-orbital
having electron pairs of the halogen atom can overlap with the  system of the
aromatic ring. This will provide partial double bond character in C−X bond (C−Cl
bond length in alkyl halide is 177 pm while in aryl halide is 169 pm). The partial
95
double bond character of C−X bond can be explained by drawing resonating

structures for chlorobenzene. The electron pairs on chlorine atom are in
conjugation with π-electrons of the ring and the following resonating structures
are possible:
Cl + + +
Cl Cl Cl
- -
Because of these two factors, the C−X bond in aryl halides becomes shorter
and stronger in comparison to C−X bond of alkyl halides. Since it is difficult to
break a shorter and stronger bond, therefore, aryl halides undergo relatively few
reactions involving the carbon-halogen bond.
Aryl halides do not undergo substitution by either the SN1 or SN2 pathways that
X
are characteristic of nucleophilic substitution reactions in alkyl halides.
+
-X
Elimination reactions also do not occur in aryl halides. Under certain conditions,
they do undergo nucleophilic substitution reactions by different mechanism. The
Phenyl cation
reason for the lack of SN1 reactivity of aryl halide is the difficulty in generation of
Very difficult to generate
phenyl cation phenyl cation from a corresponding aryl halide. Phenyl cation, if so formed, as a
result of self-ionisation will not be stabilised by resonance. Further, the electron
rich aromatic ring reduces  + on carbon atom of C−X bond and also repel
approaching electron rich nucleohile for its back side attack (condition needed for
SN2 reaction).
The aromatic ring of aryl halides will react same way as in benzene and will
undergo elecrophilic substitution reactions. In these reactions, halogens
influence the reactivity and orientation. The halogens are relatively
electronegative and have an electron withdrawing inductive effect. Therefore,
they deactivate aromatic ring system. On the other hand through its resonance
effect halogens activate aromatic ring system. Thus, the inductive and resonance
effects of the halogen are counter to each other, but the former is stronger than
the latter. Thus the halogens weakly deactivate the ring, and are ortho-para
directing during electrophilic substitution reactions.
SAQ 1
How do you account for the fact that aryl halides are less reactive towards
nucleophilic substitution reactions under ordinary conditions?
SAQ 2
Give explanations for the lack SN1 and SN2 reactivity of aryl halides.
14.3 PREPARATION OF ARYL HALIDES

Aryl halide may be prepared by one of the methods given below in Table 14.1
96
Table 14.1: Preparation of Aryl halide
From Aromatic Hydrocarbons (Direct Halogenations Method)
Lewis acid
Ar H + X 2 Ar X + HX
X2=Cl2, Br2
Lewis acid = FeCl3, AlCl3, TI(OAc)3 etc.
From Aromatic Amines (Diazonium salt method)
HNO2/HX + CuX
Ar NH2 Ar N2 Ar X + N2
273 K
diazonium
salt
CuCl, CuBr
The main drawback of direct halogenations is to get single halogenated product.

Generally, with mono-halogenated products, mixture of ortho and para
dihalogenated products are also formed. Thus diazonium salt method is preferred
for the preparation of aryl halides.
Let us briefly consider these methods of preparation.
i) From Aromatic Hydrocarbons: As discussed in Unit 11, the aromatic

halogenation of aromatic hydrocarbon needs the assistance of a Lewis acid
as a catalyst. Generally ferric halides or aluminum halides are used as
catalysts (FeCl3, FeBr3, AlCl3 etc.).
Lewis acid
Ar H + X2 Ar X + HX
Dark, 310-320 K
Aromatic Aryl
hydrocation halide
In actual practice, iron filings in the presence of chlorine or bromine are

commonly used. The halogens react with iron filing to form corresponding
Lewis acid.
Cl
FeCl3
+ Cl2 + HCl
310-320 K
Chlorobenzene
Br
FeBr3
+ Br2 + HBr
310-320 K
Bromobenzene
If two moles of chlorine (per mole of benzene) are used, a mixture of ortho-
and para-dichlorobenzene is obtained in which the para compound
predominates for steric as well as electronic reasons.
97
Cl Cl
Cl
FeCl3
+ 2Cl2
Cl
1,2-Dichlorobenzene 1,4-Dichlorobenzene
(o-Dichlorobenzene) (p-Dichlorobenzene)
Fluorobenzene and iodobenzene are difficult to prepare by direct fluorination

and iodination. The reaction with fluorine is violent and cannot be controlled.
Reaction of iodination is reversible. This reaction is carried out in the
presence of oxidizing agents such as iodic acid or nitric acid which oxidises
HI formed in the reaction to iodine enabling the reaction to proceed in the
forward direction.
I
+ I2 + HI
Iodobenzene
5HI + HIO3 3H2O + 3I2

Iodic acid
ii) From Aromatic Amines: In this process the amine is first converted to the
diazonium salt (ArN2+X), which is then converted to aryl halide using the
solution of cuprous halide dissolved in the concentrated halogen acid. This
method is known as Sandmeyer reaction.
NaNO2HCl CuX/HX
+ -
Ar NH2 Ar N2Cl Ar X
cold
Aromatic amine Diazonium salt Aryl halide
Copper powder can also be used in place of cuprous halide. This modified
reaction is called Gattermann reaction.
Cl Br
+ - Cu, HCl or HBr

ArN 2Cl or
Replacement of the diazonium group by – I does not require the use of a

cuprous halide.
+ - KI
Ar N2X Ar I + N2 + KX
Chlorobenzene is prepared commercially by the Rasching process in which

a mixture of benzene vapour, air and hydrogen chloride is passed over
98 copper chloride.
CuCl2
C6H6 + HCl + 1/2O 2 C6H5Cl + H2O
Fluorobenzene cannot be prepared by either Sandmeyer reaction or

Gattermann reaction. For preparing fluorobenzene, benzene diazonium
chloride is treated with fluoroboric acid. This reaction produces diazomium
fluoroborate which, on heating, produce fluorobenzene. This reaction is called
Balz-Schiemann reaction.
+ - + -
N2Cl N2BF 4 F
D
+ HBF 4 + BF3 + N2
Fluorobenzene
SAQ 3
How the following conversions can be carried out?
a) Aniline to chlorobenzene
b) Benzene to Iodobenzene
c) Aniline to Fluorobenzene
14.4 REACTION OF ARYL HALIDES

As discussed earlier, the aryl halides are relatively unreactive towards nucleophilic
substitution reactions; they do not react under ordinary conditions with NaOH,
C2H5ONa, NaCN, NaSH, H2O, or NH3.
Cl
+ Nucleophile, e.g. No reaction

- - -
OH , OR , CN , NH 3
Chlorobenzene
Aryl halides may be forced to react with nucleophiles under drastic conditions such
as with very strong base (NaNH2) or with moderate base (NaOH) at high
temperature and pressure. For example, chlorobenzene when heated at 573 K
under high pressure with NaOH, it is converted to sodium phenoxide. Neutralisation
of this salt gives phenol.
- +
Cl O Na
238 atm
+ 2NaOH + NaCl + H 2O
573 K
We have already mentioned the possible explanations of the low reactivity of aryl
halides in earlier section. In above example, the chlorine atom in the C−Cl group is
more tightly bound in Ar‒Cl than in C−C−Cl because of the higher s character of
sp2 carbon of benzene ring. Another explanation was given that due to resonance,
99
the carbon-halogen bond in aryl halides acquires partial double-bond character and
hence the halogen atom is more strongly bound to carbon as compared to alkyl
halides in which no resonance of this type exists. We also mentioned that
electronegative halogen atom deactivates the benzene ring.
On the other hand, when a strong electron withdrawing group is present at ortho
and/or para to the halogen atom in an aryl halide, the replacement of halogen by
nucleophilic reagents is facilitated, e.g.
OH Cl NH 2
aq NaOH NH3/C2H5OH
473 K 473 K
NO 2 NO 2 NO 2
4-Nitrophenol 1-Chloro-4-nitrobenzene 4-Nitroaniline

(p-nitrophenol) (p-nitrochlorobenzene (p-nitroaniline)
The resonance forms for the starting material (p-nitrochlorobenzene) indicate a low
electron density at the halogen-bearing carbon. Similar forms can be written for the
o-nitrochlorobenzene.
Cl Cl Cl Cl
+ + + +
-
N N - N - N -
O - - -
O O O O O O O
Resonance structure of 1-chloro-4-nitobenzene (p-nitrochlorobenzene)
As shown above, the presence of nitro groups at ortho-position(s) and/or para-

position withdraws the electron density from the benzene ring and thus creates
intense positive charge on the carbon attached to chlorine. This facilitates the attack
of the nucleophile on carbon attached to chlorine.
Nucleophilic aromatic substitutions do not follow SN1 and SN2 pathways. They
occur by two different mechanisms: The addition elimination mechanism and the
benzyne intermediate mechanism, which involves the highly reactive elimination
reaction intermediate, benzyne.
Cl
strong base
+ NH 3
HCl
Chlorobenzene Benzyne
The aromatic ring to which halogen is attached can undergo typical electrophilic
aromatic substitution reactions, which we have already discussed in Units 11 and
100 12 . As you would recall, the halogen is deactivating and ortho, para directing. Now,
we will take up reactions of aryl halides in some more detail.
SAQ 4
Explain why the dipole moment of chlorobenzene is lower than that of
chlorocyclohexane?
SAQ 5
Write the resonating structures for 3-chloronitrobenzene. Compare these
structures with 4-chloronitobenzene and give reason why nitro group at 3
position is not effecting reactivity of 3-chloronitrobenzene for nucleophilic
substitution reactions?
14.4.1 Nucleophilic Substitution by Addition –

Elimination
Now consider again the example of 1-chloro-4-nitrobenzene. When this
compound is treated with aqueous sodium hydoxide (15 %), it is converted
into 4-nitrophenol (p-nitrophenol). Such reactions occur in two steps:
nucleophilic addition is followed by elimination. Step one is the slow and
therefore it is rate determining step.
Mechanism: Nucleophilic Aromatic Substitution by Addition-Elimination
Step 1: Bond formation between hydoxide ion (a nucleophile) and carbon of

C─ X bond (an electrophile)
- -
O O
+ - + Cl
N Cl + OH Slow, rate N
determining -
O O OH
A Meisenheimer complex
The intermediate complex is stabilized by a resonance interaction with nitro

group. Such intermediates are named Meisenheimer complexes after the
German Chemist who first characterised them. You can see how nitro group at
para position is participating in delocalisation of the negative charge in the
complex.
Step 2: Elimination of halide ion (leaving group) to regenerate aromatic ring

and formation of phenol.
-
O O
+ Cl Fast
N + -
- N OH + Cl
O -
OH O
14.4.2 Nucleophilic Substitution via Benzyne

Intermediate
Aryl halides not having any strong electron withdrawing group at ortho- and
101
para- positions undergo nucleophilic substitution reaction via benzene

intermediate.
Examples:
- +
O Na
Cl
H2O
+ 2 NaOH + NaCl + H2O
Pressure
Sodium phenoxide
CH3 CH3 CH3
NH3
+ NaNH 2 + + NaCl
(-33 oC)
NH2
Cl NH2
4-Methylaniline 3-Methylaniline
(p-toluidine) (m-toluidine)
In second example you may have noticed that nucleophilic ( NH-2 ) is not only
attacking at the carbon centre of CꟷX bond but also at a position adjacent to
it. To account for such experimental observation, it has been proposed that
elimination of HX occurs to form a benzyne intermediate which then
undergoes nucleophilic addition to the triple bond to give the products shown
above.
Mechanism: Nucleophilic aromatic substitution via Benzyne Intermediate
Step 1: Dehydrohalogenation of the benzene ring to form a benzyne

intermediate.
CH3 CH3
- NH3
+ NH 2 + NH3
(-33 oC)
H
Cl
Step 2: Amide ion (nucleophile) can attack both the carbon centres of triple
bond to form two carbanion intermediates.
CH3 CH3
-
+ NH 2
NH2
-
CH3 CH3
-
+ NH 2
-
NH2
102
Step 3: Cabanions so formed abstract protons from ammonia to give final

products.
CH3 CH3
+ H NH2
NH2 NH2
-
CH3 CH3
+ H NH2
-
NH2
NH2
14.4.3 Electophilic Substitution Reactions

Similar to benzene, the benzene ring of chlorobenzene undergoes
electrophilic aromatic substitution reaction. The most common electrophilic
substitution reactions in chlorobenzene are halogenations, nitration,
sulphonation and Friedel Crafts reaction. We have already discussed that
chloro group in chlorobenzene is weakly deactivating and ortho and para
directing. Because of this we need more drastic reaction conditions. Ortho and
para directing orientation of chloro group for electrophilic aromatic substitution
can be explained on the basis of the relative stability of carbocation
intermediates formed by attack of electrophile on chlorobenzene. A chlorine
ortho or para to the site of electrophilic attack can help to stabilise the
carbocation intermediate by delocalization of the positive charge through
resonance involving unshared electron pairs. Such stabilisation is not possible
in carbocation intermediate formed on metra attack.
Cl Cl Cl
E
+ + +
H E
H
H E
cation intermediate
on meta attack
+ +
Cl Cl
E
H E
cation intermediate cation intermediate
formed on ortho attack on para attack
103
Cl Cl
Cl
Cl2/FeCl3 +
Cl
Cl Cl
NO 2
HNO3/H2SO4
+
Cl
NO 2
Cl Cl
SO 3H
H2SO4
+
SO3H
Cl Cl
CH3Cl/AlCl3
CH3
CH3
These reactions follow the mechanics discussed for the electrophilic addition
reactions of benzene.
14.4.4 Reactions due to C−X Bond

Besides the substitution reactions, aryl halides undergo reaction with metals to
form organometallic compounds.
Bromo- and Iodobenzene: They react with magnesium metal to form Grignard
reagents. Chlorobenzene is relatively unreactive.
Br MgBr
Dry ether
+ Mg
-
Phenylmagnesium bromide
Aryl halides react with alkyl halide in the presence of sodium metal to yield
alkyl benzene. This reaction is known as Wutz- Fittig reaction. It is a
modification of the Wurtz reaction which you have studied earlier.
I + 2 Na + CH Br CH3
3
Aryl halides on heating with copper powder give diaryls. This reaction is
104
known as Ullmann reaction.
573 K
2 I + Cu - -
D
SAQ 6
How will you bring about the following conversions?
a) Iodobenzene to biphenyl.
b) Bromobenzene to phenylmagnesium bromide
c) Benzene to 1-bromo-4-nitrobenzene
14.5 REACTIVITY AND RELATIVE STRENGTH OF

C−X BONDS IN HALOGEN DERIVATIVES
Before taking up the reactivity and relative strength of C−X bond among
halogen derivatives let us also understand the nature of alkenyl and alkynyl
halides.
Alkenyl and alkynyl halides also similar to aryl halides and are less reactive
towards nucleophilic substitution reactions and do not undergo SN1 and SN2
reactions.
In general, similar to aryl halides, C−X bonds are shorter and stronger in
alkenyl and akynyl halides because i) in alkenyl halide, carbon attached to
halogen is sp2 hybridised and in alkynyl halide it is sp hybridised; ii) the C−Cl
bond acquires partial double bond character due to resonance. As a result, the
bond cleavage in alkenyl and alkynyl halide are difficult than alkyl halides and
therefore, they are also less reactive towards nucleophilic substitution
reaction. Both, alkenyl halides and alkynyl halides do not undergo SN1and SN2
reactions.
-
+
H2C CH Cl H2 C CH Cl
Resonating structures of chloroethene
Lack of SN1 and SN2 reactivity of alkenyl halides and alkynyl halides can also
be explained on the basis of the ease of formation of transition states.
Because of the high s character of double and triple bonded carbons, they are
stronger electron – attracting centres than saturated (sp3) carbon, that is the
reason alkyne and alkenes are stronger acids than alkanes. Therefore, it will
be much more difficult to generate carbocations such as CH2 = CH+ and
HC  C+ from the corresponding halides. Thus, this factor supports the lack of
SN1 reactivity of alkenyl and alkynyl halides. Further, p orbitals of carbon
double and triple bond block the back side attack of nucleophile as shown
below. This factor explains the lack of SN2 reactivity in alkenyl and alkynyl
halides.
105
-
Nu
X
H2C CH Cl
Under drastic conditions, substitution of the halogens occurs in alkenyl and

alkynyl halides. Such reactions follow different mechanism. In these cases, the
nucleophile first adds to the carbon centre of C–X bond, and in a subsequent
step the halogen leaves as halide ions. This is as “addition – elimination”
mechanism.
Step 1:
Addition
- Nu
-
C6H5 C C Cl + Nu C6H5 C C
Cl
Step 2:
Elimination
- Nu
-
C6H5 C C C6H5 C C Nu + Cl
Cl
From our discussion on the nature and reactivity of alkyl, aryl, alkenyl and
alkynyl halides, it can be concluded that the relative reactivity of halogen
derivatives can be predicted on the basis following factors:
(i) s character of hybridised carbon attached to halogen
(ii) Resonance effect
(iii) Stability of carbocation formed on self ionisation od C−X bond

(condition for SN1 reaction)
(iv) Feasibility of back side attack on C−X bond (condition for SN2
reaction)
The C−X bond of alkenyl, alkynyl and aryl halide is shorter compared to alkyl
halides because the carbon attached to halogen is either sp2 or sp hybridised.
Resonance effect also contributes in increasing bond strength of C−X in these
compounds. Lack of stability of carboction, if formed, on self ionisation and
lack of feasibility of backside attack of nucleophile on C−X bond explain that
these compounds are less likely to follow SN1 and SN2 mechanisms.
In the Table 14.1 below, we have listed bond length and bond strength of each
106 class of halogen derivatives.
Compound C−X bond length (pm) Bond Strength/kJ mol1
C2H5– Cl 177 340
CH2 = CH– Cl 169 435
HC≡ C– Cl 163 --
C6H5 – Cl 169 465
SAQ 7
Arrange following halides in order of expected increasing reactivity
towards sodium iodide.
Cl
Cl
Cl
14.6 SUMMARY
In this unit, we have described the chemistry of aryl halides. We are
summarizing below what we have studied:
 Aryl halides can be prepared from aromatic hydrocarbons by direct

halogenation and form amines by forming diazonium salt.
 Aryl halides are not as reactive as alkyl halides for nucleophilic

substitution reactions. They may react with moderate base such as NaOH
at high temperature and high pressure or with very strong base such as
NaNH2.
 Aryl halides are activated by presence of ortho and/or para strong electron
withdrawing groups.
Nucleophilic aromatic substitutions in ary halides do not follow SN1 and SN2
pathways. These reactions occur by two different mechanisms: The addition-
elimination mechanism and the benzyne intermediate mechanism.
The aromatic ring to which halogen is attached can undergo typical

electrophilic aromatic substitution reactions. Halogen group is deactivating and
ortho, para directing.
 Aryl halides react with magnesium to form aryl magnesium halides called
the Grignard reagents.

1. Complete the equation for each of the following reactions. Write only
major monohalogen substituted product in each case.
107
CH3
Fe
a) + Br2
Dark
CH3
Heat
b) + Br2
or light
CH2Br
c) + AgNO 3
Br
d) + AgNO 3
2. Which of the following compounds undergo SN2/SN1 reaction? Explain.
a) Benzyl chloride;
b) Chlorobenzene;
c) Chloroethene;
d) Chloroethyne.
3. Write the equation for each of the following reactions:
a) 2,4-dinitrochlorobenzene and sodium hydroxide
b) 2,4-dinitrochlorobenzene and sodium phenoxide
c) 2,4-dinitrochlorobenzene and ammonia
d) Chlorobenzene and sodium amide (sodamide).
4. In the following reaction only meta isomer is formed though this reaction
undergoes benzyne mechanism. Explain.
Br
OCH3
NaNH 2, liq. NH3
5. Although chlorine is an electron withdrawing group, yet it is ortho-, para-

directing in electrophilic aromatic substitution reactions. Why?
6. What happens when?
(i) Iodobenzene is heating with copper powder,
(ii) bromobenzene is heated with Mg,
(iii) chlorobenzene is subjected to hydrolysis,

108
(iv) Chlorobenzene is treated with alkyl halide in the presence of sodium

metal,
14.8 ANSWERS
1. The carbon-halogen bond in aryl halides is shorter and stronger than
CꟷX bond of alkyl halide because of the (i) carbon atom of CꟷX bond is
sp2 hybridized (having higher s character), (ii) resonance effect causes
partial double bond character in CꟷX bond. Therefore, it is difficult to
break during substitution reaction. Few more factors for low reactivity of
aryl halide are: poor bond polarity of CꟷX bond, unfavorable geometry for
back side attack of nucleophile due to benzene ring and difficulty in
generation of phenyl cation.
2. There are two main reason beside CꟷX bond strength: (i) formation of
phenyl cation in case of aryl halides is difficult (SN1 condition is not
fulfilled), (ii) Back side attack on CꟷX carbon by nucleophile is not
possible because of the electron rich aromatic ring (SN2 condition is not
fulfilled).
3. + -
NH2 N2 Cl Cl
NaNO2-HCl CuCl/HCl
a) Cold
HIO3
+ I2
b)
+ - +
NH2 N2 Cl N2 BF4
NaNO2-HCl HBF4
c) cold
F
D
+ BF3 + N2
4. There are two main factors which are responsible for the lower dipole
moment for the CꟷCl bond in chlorobenzene than the dipole moment of
the same bond in cyclohexyl chloride:
i) In chlorobenzene, the carbon attached to chlorine is sp2 hybridized,

on the other hand, in cyclohexyl chloride it is sp3 hybridized.
Because of the higher s character of sp2 carbon, it is more
109
electronegative than sp3 carbon and hence it has fewer tendencies

to release electron to chloride atom. This in turn will make the
dipole moment weaker when we compare with sp3 hybridized C−Cl
bond.
ii) Delocalisation of lone pairs of electrons of chlorine atom over the

benzene ring causes partial double bond character in C−X bond.
Thus, the C−X because of resonance effect is shorter than single
bond. The bond length has a direct impact on dipole moment
because dipole moment depends on charge and distance.
5. Resonance structures of 1-chloro-3-nitrobenzene:
Cl Cl Cl
+ +
- -
+ O + O + O
N N N
- - -
O O O
Cl
-
+ O
N
+
-
O
None of the resonating structure bear the +ve charge on carbon atom
attached to the −Cl group. But you can see presence of nitro group at 4
position withdraw the electron density from carbon attached to Chlorine
atom (See resonance structure III, Sec. 14.4). Further the transition state
formed by the attack of a nucleophile is stabilised by the nitro group
while in case of 3-chloronitrobenzene, none of the resonating structure
bear the negative charge on carbon bearing the NO2 group.
Nucleophilic attack on 1-chloro-3-nitobenzene
-
Nu Cl Cl Nu Cl Nu Cl Nu
Slow step - -
+ O + O + O + O
N N N N
-
- - - -
O O O O
Nu
-
Cl
Fast step + O
N
-
O
110
Nucleophilic attack on 1-chloro-4-nitobenzene

-
Nu Cl Cl Nu Cl Nu Cl Nu
- -
Slow step
-
+ + + +
– N N – N – N
–
O O O O O O O O
Nu
Cl Nu
-
Cl
This structure further
stabilised the
Fast step
intermediate
+
– N +
O O – N -
O O
513 K
6. a) I + Cu
D
Dry ether
b) Br + Mg MgBr
Br Br
Lewis acid HNO3/H2SO4

c) + Br2
NO 3
7. Cl
< Cl <
Cl
Terminal Questions
CH3 CH3
1. a) Fe
+ Br2
Dark
Br
CH3 CH2 Br
Heat
b) + Br2
or light
111
CH2Br CH2 OH
c) + AgNO 3
d) Br
+ AgNO 3 No reaction
2. Formation of carbocations and back side attacks of nucleophile in the

case of chlorobenzene, chloroethene and chloroethyne are not feasible,
therefore they will not go for SN1 and SN2 reactions. On the other hand in
benzyl chloride, benzene ring contributes in stabilisation of both
carocation and transition state of SN2 reaction formed during SN1 and SN2
reactions. So benzyl chloride will go for SN1/SN2 reaction.
Cl OH
NO 2 NO 2
3. a) + NaOH
NO 2 NO 2
Cl OC6H5
NO 2 NO 2
b) + NaOC 6H5
NO 2 NO 2
Cl NH2
NO 2 NO 2
c) + NH3
NO 2 NO 2
Cl NH2
d) + NaNH 2
4. Br
H2N OCH3
Liq.NH3
+ NaNH 2
Consider the mechanism of the reactions.

112
-
NH 2
-
Br NH 2 NH2 NH2
H OCH3 OCH3 OCH3
- Br
- OCH3 -
NH3
or (I)
- OCH3
- OCH3 H2N OCH3 H2N
NH 2
NH3
(II)
The carbanion (II) formed after amide addition to the intermediate

benzyne is stabilised by the electron-withdrawing effect of the methoxy,
therefore it is formed regio-selectively. Thus, in this reaction, only one
product, i.e. 3-methoxyaniline (m-anisidine) is formed.
5. In chlorobenzene, Inductive effect deactivates the benzene ring, but it is

ortho and para directing for electrophilec substitution reactions because
of the resonance effect. Carbocation formed after electrophilc attack is
more stabilised when it is attacked by an electrophile on ortho or para
position.
+
Cl Cl Cl
H H
+ +
+ E E E
+
Cl Cl Cl
+ +
+ E
H E H E
Above shown contribution of chlorine atom in resonance stabilisation is

not feasible for meta attack.
Cl Cl Cl
+ + +
+ E
E E
H H
6. i) biphenyl is formed
ii) phenylmagnesium bromide is formed

113
iii) at normal temperature there is no reaction but on heating at 573 K

and at pressure 238 atom with aqueous NaOH it forms phenol.
iv) alkylbenzene is formed.
114
BCHCT-133
Indira Gandhi National Open University EQUILIBRIA AND
School of Sciences
FUNCTIONAL ORGANIC
CHEMISTRY-I
Block
4
OXYGEN CONTAINING ORGANIC COMPOUNDS
UNIT 15
Alcohols 117
UNIT 16
Phenols 150
UNIT 17
Ethers 179
UNIT 18
Aldehydes and Ketones 205
UNIT 19
Aromatic Aldehydes and Ketones 251
OXYGEN CONTAINING ORGANIC COMPOUNDS
The important classes of organic compounds with functional groups containing oxygen are
alcohols, phenols, ethers, aliphatic aldehydes and ketones, aromatic aldehydes and ketones,
carboxylic acids and their derivatives. In this Block, we shall study the chemistry of five
classes of compounds, viz., (i) alcohols (ii) phenols (iii) ethers (iv) aliphatic aldehydes and
ketones, and (v) aromatic aldehydes and ketones . Another important class of oxygen
containing organic compounds is carboxylic acids and their derivatives. The chemistry of
these compounds will be taken up in third semester course.
This Block has five Units. Units 15 and 16 are on alcohols and phenols, respectively. An
alcohol has a −OH group bonded to an aliphatic carbon atom. In a phenol, a –OH group is
bonded to an aromatic carbon atom. In these Units, we shall discuss laboratory and industrial
preparations of alcohols and phenols. We shall also explain the behavior of alcohols and
phenols as weak acids and illustrate their chemical properties.
Unit 17 deals with the chemistry of ethers. In this unit, first we shall discuss different types of
ethers and their preparations. After that, we shall explain their physical and chemical
properties.
The chemistry of aliphatic and aromatic aldehydes and ketones is discussed in Unit 18 and
Unit 19, respectively In these units we will study the preparation and properties of these
compounds in detail.

After studying this block, you should be able to:
 classify and draw structures of simple alcohols, phenols, ethers, aliphatic and
aromatic aldehydes and ketones;
 outline the methods of preparation of the above classes of compounds;
 describe the physical properties, chemical reactions and laboratory detection of

compounds belonging to the above classes;
 explain the mechanism of nucleophilic substitution and elimination reactions of

alcohols, and
 describe the mechanism of nucleophilic addition to carbonyl group of aldehydes

and ketones.
116
Unit 15 Alcohols
UNIT 15
ALCOHOLS
Structure
15.1 Introduction 15.6 Chemical Properties
Expected Learning Outcomes Acidic and Basic Nature of
Alcohols
15.2 Classification of Alcohols
Reactions of the O−H Bond
15.3 Structure of Alcohols
Reactions of the C−O Bond
15.4 Preparation of Alcohols
15.7 Oxidation of Alcohols
General Methods of the
Preparation of Alcohols 15.9 Diols
Commercial Preparations of 15.10 Lab Detection
Alcohols
15.10 Summary
15.5 Physical Properties
15.12 Answers
15.1 INTRODUCTION
In the previous Unit, we described the aryl halides. In this Unit and in
subsequent Units, we will discuss oxygen-containing organic compounds.
Alcohols and phenols can be regarded as mono-alkyl and mono-aryl
substitution products of water, respectively. Similarly, ethers can also be
considered as derivative of water in which both the hydrogen atoms of the
water molecule have been replaced by alkyl or aryl groups or by both. We
shall study the chemistry of phenols and ethers in Unit 16 Unit 17,
respectively.
O H O H O H O R O R O Ar
H R Ar R
Ar Ar
W
a
t
e
r
Alcohol Phenol Ethers
In this unit, we shall take up chemistry of alcohols in detail. Alcohols may also
be defined as hydroxy (−OH) derivatives of hydrocarbons. Monohyric alcohols
have general formula CnH2n+1 OH. Alcohols provide us with a great number of
useful products, which include germicides, antifreeze agents, pharmaceuticals,
117
Block 4 Oxygen Containing Organic Compounds
explosives, solvents and plastics. Alcohols also play central role in synthetic
organic chemistry. They can be converted into many other types of
compounds, including alkenes, alkyl halides, ethers, aldehydes, ketones, and
carboxylic acids. These compounds can also be converted back to alcohols.
In this unit, first we will discuss the classification of alcohols, their structure
and then give an outline of the different methods available for the preparation
of alcohols. We will then review the physical properties of alcohols. Finally, we
will consider the chemical properties of alcohols and diols.

 classify alcohols;
 outline the preparation of alcohols;
 describe the commercial methods for manufacture of alcohols;
 define the physical properties of alcohols;
 explain acidic and basic nature of alcohols;
 describe the reactions of alcohols with active metals such as Li, Na,
and K;
 explain the nucleophilic substitution reactions and acid-catalysed

dehydration reactions of alcohols;
 describe various reagents used for oxidation of alcohols; and
 explain pinacol-pinacolone rearrangement .
15.2 CLASSIFICATION OF ALCOHOLS

Hydrocarbons in which an sp3 carbon carries a hydroxyl (−OH) group are
called alcohols. Depending on the number of hydroxyl groups present in the
molecule, alcohols are called monohydric (1 −OH group), dihydrics (2 −OH
groups), trihydric (3 –OH groups) or polyhydric (more than 3 −OH groups).
sp3 carbon CH2 CH2 CH2 CH CH2

CH3 CH2 OH OH OH OH OH OH
Ethanol 1,2-Ethanediol or 1,2,3-propanetriol or

(ethyl alcohol) ethane-1,2-diol propane-1,2,3-triol
(ethylene glycol) (glycerol, glycerine)
Monhydric alcohol Dihydric alcohol Trihydric alcohol
Monohydric alcohols, like the alkyl halides, may be subdivided into primary,
secondary and tertiary alcohols. Primary alcohols contain a -–CH2–OH group,
secondary alcohols contain the R2CH–OH group and tertiary alcohols contain the
R3C–OH group. For example, the molecular formula C4H9OH can represent the
following four monohydric alcohols:
118
Unit 15 Alcohols
OH
CH3CH2CH2CH2 OH CH3CH2CHCH3
1-Butanol 2-Butanol
(butyl alcohol) (sec-butyl alcohol)
Primary alcohol Secondary alcohol
CH3
CH3 CH3 C CH3
CH3 CH CH2 OH OH
2-Methyl-1-propanol 2-Methyl-2-propanol
(isobutyl alcohol) (tert-butyl alcohol)
Primary alcohol Tertiary alcohol
Unlike gem dihalides, gem diols are unstable as they undergo dehydration to
the corresponding more stable aldehyde or ketone.
OH O
-H2O
CH3 C OH C
H3C CH3
CH3
OH O
-H2O
CH3 C OH C
H3C H
H
Just to recall, in IUPAC naming of alcohols, the longest chain of carbon

containing the hydroxyl group is selected as the parent alkane and numbered
from the end closer to hydroxyl group. Finally -e of the parent alkane is replaced
with suffix -ol. For naming polyhydric alcohols, the -e of the alkane is retained
and suffix –diol (for two hydroxyl groups) , triol ( for three hydroxyl groups) and so
on is added, depending on the number of hydroxyl groups present in a molecule.
The common names for alcohols are derived by naming the alkyl group bonded
to hydroxyl group and then adding the word alcohol. Common names of several
low molecular weight alcohols are still widely used. Therefore, we have used
both the common names and the IUPAC names. The common names are
given in parentheses below the IUPAC names of the compounds.
In substituted alcohols, the number for the hydroxyl group is often placed
between the infix and suffix. For example, IUPAC name of tert-butyl alcohol
may be written as 2-methylpropan-2-ol or either 2-methyl-2-propanol, both
names are acceptable.
Alcohols with double or triple bonds are named using the -ol suffix on the
alkene or alkyne by replacing their -e. In such alcohols, numbering is done in
such a way so as to give the hydroxyl group the lowest possible number.
When the hydroxyl functional group is present together with a functional group
of higher nomenclature priority such as aldehyde, ketone, carboxylic acid
derivative or carboxylic acid group, then it must be cited and located by the
prefix hydroxy and with an appropriate number. For further illustration, some
examples are given below. 119
O
2 3
3 OH 2
1 OH
1
OH
2-Propen-1-ol 2-Hydroxypropanoic acid
(allyl alcohol) (lactic acid)
SAQ 1
Classify each alcohol as primary, secondary or tertiary. Also write IUPAC
names of each alcohol.
OH
OH b) c)
a)
CHO OH
OH
OH
d) e) f)
OH
15.3 STRUCTURE OF ALCOHOLS

The Hydroxyl functional group (–OH) of an alcohol is bonded to a sp3
hybridised carbon. The oxygen atom of an alcohol is also sp3 hybridised. The
two sp3 hybridised orbitals of oxygen form two σ bonds, one with hydrogen
atom and one with carbon atom. Each of the remaining two sp3 hybridised
orbitals of oxygen contain an unshared pair of electrons.
142 pm
d+ d+
H3C O H O
- + d- d+
d d
H 105.0o
H
108.5o
sp3 Water
Methanol
μ = 1.7 D μ = 1.8 D
The geometry around oxygen atom of an alcohol molecule is essentially the

same as that in water. The measured C−O−H bond angle in methanol is
108.5o, very close to the perfectly tetrahedral angle of 109.5o. Further, both
the C−O and the O−H bonds are polar covalent bonds due to the high
electronegativity of the oxygen atom. As shown above, in case of methanol
molecule, carbon and hydrogen bear partial positive charges and oxygen
bears a partial negative charge. The presence of these polar bonds makes
alcohols to be polar molecules. The dipole moment (μ) of methanol is very
similar to water. You will find, in alcohols their physical and chemical
properties are due to these structural aspects i.e. presence of lone pairs of
electrons on oxygen and polar bonds (C−O and O−H). We will take up
physical and chemical properties after a brief discussion on the preparation of
120 alcohols.
Unit 15 Alcohols
15.4 PREPARATION OF ALCOHOLS

In this section, we will first consider the general methods for the laboratory
preparation of alcohols and then take up the industrial preparation of a few
important members of this class of compounds.
15.4.1 General Methods of the Preparations of Alcohols

Alcohols can be prepared from alkenes, alkyl halides, esters, ethers,
aldehydes, ketones and from the Grignard reagents. The general reactions of
these methods of preparation are summarised below in Table 15.1.
Table 15.1: Preparation of Alcohols
i) From alkenes
+
C C + H3 O C C
H OH
BH3 H2O2
C C C C C C
NaOH
H BH2 H OH
ii) From alkyl halides

- -
R X + OH /H 2O ROH + X
iii) From esters
- +
RCOOR' + OH /H2O or H3O RCOOH + R'OH
iv) From ethers
H2SO4
R O R + H2O 2 ROH
v) From aldehydes and Ketones
2 [H]
C O C OH
H
vi) From Grignard reagent
1. dry ether
C O + RMgX C OH
2. H3O+
R
121
Let us study these methods of preparation in a brief manner.
i) From Alkenes: We have already described the acid catalysed hydration

of alkenes in Unit 17 of the first Semester chemistry course. In this
reaction, the direction of addition is governed by the Markownikoff’s rule.
The general reaction is,
+
C C + H3 O C C
H OH
This method is employed for the preparation of several alcohols:

+
H2C CH2 + H3O CH3 CH2 OH
Ethene Ethanol
OH
+
CH3 CH CH2 + H3O CH3 CH CH3
Propene 2-Propanol
(isopropanol)
If sulphuric acid is used as the acid catalyst, then the reaction proceeds
as follows:
H2C CH2 + HOSO2OH CH3 CH2 OSO2OH
Ethyl hyrogen sulphate
H2O
CH3 CH2 OSO2OH CH3 CH2 OH
Ethanol
OSO2OH OH
H2O
R CH CH2 R CH CH3 R CH CH3
Secondary alcohol
These reactions are useful for laboratory synthesis as well as industrial

preparation of alcohols.
Hydroboration-oxidation method is also important because it leads to

overall, effective anti-Markownikoff addition of water. We have already
described this method earlier in Unit 17 of the first Semester chemistry
course. In this method diborane, B2H6, is allowed to react with an alkene
in an inert solvent such as ether. Diborane is in ready equilibrium with
the Lewis acid borane, BH3, which adds to the alkene. Here, the electron
seeking (acidic) part of reagent is boron, and addition of BH3 proceeds
according to MarkowniKoffs rule to give an intermediate organoborane
compound. Oxidation of this intermediate with basic hydrogen peroxide
converts it to an alcohol.
CH3 CH3 CH3

H2O2
CH3 C CH2 + H BH2 CH3 C CH2 CH3 C CH2
NaOH
H BH2 H OH
Organoborane Primary alcohol
B 2H6
122
Unit 15 Alcohols
ii) From Alkyl Halides: Hydrolysis of alkyl halides with an aqueous

solution of an alkali is a common and convenient method for the
synthesis of alcohols, e.g.,
- -
R X + OH /H 2O ROH + X
Alkyl halide Alcohol
These reactions can proceed via SN1 or SN2 mechanism which we have
described in Unit 13. A useful application of this method is in the
synthesis of phenylmethanol (benzyl alcohol) from
(chloromethyl)benzene (benzyl chloride) which is itself obtained from
methylbenzene (toluene) as shown below:
Cl2/hn Aq. NaOH

CH3 CH2 Cl CH2 OH
Methylbenzene (Chloromethyl)benzene Phenylmethanol
iii) From Esters: Alcohols may be prepared by base or acid catalysed

hydrolysis of esters.
- +
RCOOR' + OH /H 2O or H3O RCOOH + R'OH
Ester Caboxylic Alcohol
acid
This method is used industrially as certain alcohols occur in nature as

esters.
iv) From Ethers: Alcohols are also obtained by heating ethers with dilute
sulphuric acid under pressure:
D
C 2H 5 O C2H 5 + H 2O 2 C 2H5 OH
Ethanol
This method is important industrially as the ethers are formed as by-

products in the preparation of some alcohols. We will discuss this
reaction further in detail in Unit 17.
v) From Aldehydes and Ketones: Alcohols are also obtained by the

reduction of aldehydes and ketones with sodium and ethanol or H2/Ni or
by metal hydrides, such as lithium aluminium hydride. Aldehydes give
primary alcohols while ketones secondary alcohols. We will discuss this
reaction further in detail in Unit 18.
O OH
2 [H]
R C H R C H
Aldehyde H
Primary alcohol
O OH
2 [H]
R C R R C R
Ketone H
Secomdary alcohol
123
vi) From Grignard Reagents: Primary, secondary and tertiary alcohols are
also prepared by the reaction of suitable carbonyl compound with the
Grignard reagent. You have already studied this method in Unit 13.
1. dry ether
C O + RMgX C OH
2. H+/H2O
R
SAQ 2
Write chemical equations, showing all necessary reagents, for the preparation
of i) 2-butanol and ii) 1-butanol by each of the following methods:
a) from an alkene
b) from an alkyl halide
c) by the Grignard reagent
d) by the reduction of ketone/aldehyde.
15.4.2 Commercial Preparations of Alcohols

Alcohols are of great commercial importance. In this Sub-sec. you will learn
how large quantities of these compounds are prepared from different abundant
natural sources.
i) By the catalytic hydration of alkenes using dilute acid solution: We

have already come across the conversion of alkenes to alcohols in
connection with the general methods for small scale preparation of
alcohols. The method has been extended to commercial preparations of
some alcohols, such as ethanol and 2-propanol. The reactions for the
preparation of ethanol and 2-propanol have been already shown.
Similarly, hydration of 2-methylpropene (isobutene) in aqueous acidic
medium gives tert-butanol.
CH3 CH3
+
CH3 C CH2 + H3O CH3 C OH
CH3
2-Methylpropene 2-Methyl-2-propanol
(tert-butanol)
In a recent modification ethene is hydrated directly by passing a mixture

of the alkene and steam over a solid acid catalyst (phosphoric acid or
silica at 573 K at a pressure of about 70 atmospheres:
573 K
H2C CH2 + H2O CH3CH2OH
70 atm.
Ethene Ethanol
ii) By heating a mixture of carbon monoxide and hydrogen under

pressure in the presence of a catalyst: This method is used for the
124 preparation of methanol.
Unit 15 Alcohols
Cu Catalyst
CO + 2H 2 CH3OH
533 K, 150 atm
Methanol
iii) By the oxidation of natural gas: A mixture of methanol, ethanol,

propanols and butanols is obtained.
Catalytic oxidation of methane gives methanol:
Cu
CH4 + 1/2 O 2 CH3OH
473 K
Methanol
iv) Fermentation of starch: This method has been the source of ethanol,
the constituent of alcoholic beverages responsible for their intoxicating
action, since times immemorial. Common sources of starch are wheat,
barley, potato, etc. These are mashed with hot water and heated with
malt (germinated barley) which contains the enzyme 'diastase'.
Enzymes are a
Enzymatic hydrolysis of starch at 323 K gives the sugar maltose: particularly important
group of proteins. They
Diastase are the catalysts which
(C6H10O5)n + n/2 H 2O n/2 C12H22O11
enable living organism to
bring about necessary
The product is cooled to 303 K and fermented with yeast, which contains reaction.
various enzymes. One of these, 'maltase', converts maltose to glucose
and the other 'zymase' decomposes glucose to ethanol:
Maltase
C12H22O 11 + H2O 2 C 6H12O6
Zymase
C6H12O6 CH3CH2OH + 2 CO2
Ethanol
Fermentation of molasses (a by-product of sugar industry) also gives

ethanol.
Inverase
C12H22O11 + H2O 2 C 6H12O6
Cane sugar
Zymase
C6H12O6 CH3CH2OH + 2 CO2
Ethanol
Ethanol may also be prepared from glucose directly. Grape juice, a rich
source of glucose, ferments to produce wine with a maximum alcoholic
content of approximately 12% by volume. The alcoholic content of
liquors is usually designated in terms of proof spirit, 100 proof indicating
an alcoholic content of about 50% by volume. The term "proof spirit"
supposedly has its origin in an early and rather crude analytical
procedure for determining the alcoholic content of whisky. Whisky of
high alcoholic content, when poured onto the gun powder would ignite
and burn with a flame sufficiently hot to ignite the powder also. This was
'proof' of spirit content. If the gunpowder failed to ignite, the presence of
too much water was indicated, as the powder would have become too
wet to burn. 125
Absolute ethanol: Regardless of the methods of manufacture, all aqueous

solutions of ethanol on fractional distillation yield a 'constant boiling mixture' of
95 percent ethanol and 5 per cent water which is known as rectified spirit. A
constant boiling mixture of two or more liquids, called an azeotrope, cannot be
separated by fractional distillation. In order to obtain absolute or 100% pure
ethanol, water has to be removed by methods other than fractionation. In the
laboratory, rectified spirit is refluxed over quick lime for about 6 hours, and
then allowed to stand overnight. On distillation, this gives 99.5 % or lime
distilled alcohol. The remaining water is removed by reaction with magnesium
metal, by which water is converted into insoluble Mg(OH)2.
In industry, calculated amount of benzene is added to the rectified spirit.

Distillation of the mixture yields three fractions:
At 338 K, a constant boiling mixture of ethanol, benzene and water (a

'ternaryazeotrope').
At 341 K, a constant boiling mixture of ethanol and benzene (a 'binary

azeotrope').
At 351 K, pure ethanol or absolute alcohol.
SAQ 3
How can the following conversion be carried out on the commercial scale?
a) Ethanol from ethene
b) Methanol from carbon monoxide
c) Ethanol from cane sugar.
15.5 PHYSICAL PROPERTIES

The physical properties of alcohols can be understood if we consider the fact
that alcohols are similar in structure to water. As mentioned earlier, the oxygen
in an alcohol molecule is in the sp3 hybridised state and has two unshared
pairs of valence electrons. Similar to H−O bonds in water molecules, the C−O
and O−H bonds of hydroxyl group of alcohols are polar bonds.
As might be expected, molecules of alcohol like water are strongly hydrogen

bonded. The formation of hydrogen bonds leads to the association of a large
number of alcohol molecules. These molecular associations have to be broken
up before boiling occurs. Hence, alcohols have the higher boiling points when
we compared to other molecules of the same size.
H O H O H O H O
R R R R
Hyrogen bonding in alcohol molecules
Table 15.2 compares the boiling points of some alcohols and chloro
126 compounds with the same carbon skeletons.
Unit 15 Alcohols
Table 15.2: Comparison of the boiling points of some alcohols and

chloroalkanes
Alcohol Bp/K Chloroalkane Bp/K
CH3−OH 337 CH3−Cl 249
CH3CH2−OH 351 CH3CH2−Cl 286
CH3CH2CH2−OH 370 CH3CH2CH2−Cl 319
Further, in a group of isomeric alcohols, the primary alcohol has the highest
boiling point and the tertiary, the lowest, with the secondary alcohols having an
intermediate value. In the straight chain compounds, the van der Waals
attractive forces are relatively large due to the large surface area. In the
branched chain structures, the molecule tends to become spherical and hence
with the decrease in surface area, the attractive forces are also reduced. The
physical properties of some alcohols are summarised in Table 15.3.
Table 15.3: Physical properties of some alcohols
IUPAC Common name Formula Bp/K Density/ Solubility in

Name kg dm
-3 water
Methanol Methyl alcohol CH3O−H 337 0.79 infinite
Ethanol Ethyl alcohol CH3CH2−OH 351 0.79 infinite
1-Propanol Propyl alcohol CH3CH2CH2−OH 370 0.80 infinite
2-Propanol Isopropyl alcohol (CH3)2CH−OH 355 0.79 infinite
3
1-Butanol Butyl alcohol CH3CH2CH2−OH 380 0.81 8.3 g/100 cm
The water solubility of lower alcohols can also be explained by their ability to
form hydrogen bonds with water molecules.
R O H O and H O H O
H H H R
Hyrogen bonding with water molecules
The solubility of alcohols in water decreases as the length of the hydrocarbon

chain of the alcohol molecule increases. As discussed in earlier units, the
hydrocarbon character of the molecule, i.e., hydrophobic character, increases
in higher alcohols.
SAQ 4
Arrange following compounds in order of their increasing boiling points:
HO OH HO
OH
Pentane 1,3-Propandiol 1-Butanol 2-Methyl-2-propanol
127
SAQ 5
Arrange following compounds in order of their increasing solubility in water:
HO OH
OH
Pentane 1,3-Propandiol 1-Butanol
15.6 CHEMICAL PROPERTIES

Recall the structure of an alcohol molecule. As mentioned earlier, alcohols
have two polar covalent bonds, the C−O bond and the O−H bond. Due to high
electronegativity of oxygen both the bonds are polarised so that oxygen is
electron rich (nucleophilic) and both carbon and hydrogen are electron
deficient (electrophilic). The nucleophilicity of oxygen is further enhanced by
the presence of two lone electrons pairs on oxygen.You will find that all these
structural characteristics will be very useful in predicting the reaction path and
mechanism of reactions of alcohols.
The chemical reactions of alcohols involve breaking of either the O−H bond or
the C−O bond. In this section, we shall first take up the reactions of O−H bond
and C−O bond. Then, we shall look at the oxidation reactions of alcohols. It is
observed that many reactions of alcohols are initiated by either accepting a
proton or donatinga proton. Thus before going in details of these types of
reactions of alcohols, let us review acidic and basic properties of alcohols.
15.6.1 Acidic and Basic Nature of Alcohols

Alcohols can function as both weak acids (proton donors) and weak bases
Molecules that act both (proton accepters) similar to water. Polar nature of O−H bond is mainly
as acids and as bases responsible for the acidic behavior of alcohols. Alcohols are much stronger
are called amphoteric acids than alkanes (by roughly 1030 times), and nearly that much stronger than
(ampho, Greek, both). ethers. An alcohol can lose a proton to a strong base yielding an alkoxide ion,
Examples are water, RO-. In the reaction given below, alcohol behaves as an acid.
alcohol, etc.
+ - - +
R OH + Na H RO Na + H2
Alcohol Sodium hydride Sodium alkoxide
Alkoxides are strong bases, generally stronger than hydroxides. To prepare an

alkoxide from an alcohol, we need a base stronger than the alkoxide itself,
such as, alkali metal hydrides, NaH, KH, etc.
The oxygen atom of the alcohol molecule has two lone pairs of electrons.
These lone pair electrons make alcohols act as a base. For example, in acidic
solutions, alcohols are protonated to form oxonium ion. In the reaction given
below, alcohol behaves as a base.
+
H2SO4 +
R O + H O H R O H + O H
H
H H H
Hyronium ion Oxonium ion
(weak acid) (strong acid)
128
Unit 15 Alcohols
In dilute aqueous solutions, alcohol has approximately the same pKa values as
water. For example, the pKa of methanol in water is 15.5, while that of pure
water is 15.74. Therefore, methanol is as acidic as water. Now we can
conclude that alcohols are both weak acids and weak base depending on the
reaction conditions.
strong acid strong base -

+
R O H R O R O
H H
Oxonium ion Alkoxide ion
Alcohols are both acidic and basic
As mentioned above, acidic nature of alcohol is due to the polar nature of the
O−H bond. The electron releasing/donating groups such as alkyl group if
attached to -carbon, increase electron density on oxygen tending to decrease
the polarity of O−H bond. This decreases the acid strength of substituted
alcohol. Reverse is true with electron attracting/withdrawing group. Electron
withdrawing group at -carbon, further increases the polarity of O−H bond. The
effect of substituents decreases with the distance from the carbon to which
O−H group is attached.
We can now write the order of decreasing acid strength.
H2O > CH3OH > primary > sec > tert-alcohols
SAQ 6
Arrange following alcohols in order of increasing acidity.
Cl
OH OH OH
Cl Cl Cl
The alkoxides of the
alkali metals are strong
15.6.2 Reactions of the O–H Bond bases (nucleophiles) that
enter into SN2
In the previous sub-section, we have seen that with strong base alcohols substitution of halogen
furnish alkoxides which are valuable both as strong bases and as from alkyl halides. This
nucleophiles. Strong acids can protonate alcohols into oxonim ions.This reaction, referred to as
protonation process converts −OH (a poor leaving group) into −OH2+ (a good the Williamson ether
synthesis, is best used to
leaving group) and enabling subsequent nucleophilic substitution or
prepare ethers.
elimination reactions to take place in alcohols similar to alkyl halides. Now, we
SN2
will take up reactions of alcohols in detail. - +
CH3O Na + C2H5−I →
Sodium iodoethane
i) Reaction with Active Metals:
methoxide
Strongly electropositive metals like K, Na, Mg, Al and Zn liberate hydrogen
CH3−OC2H5+Nal
from alcohols and form alkoxides, e.g.,
Ethyl methyl
ether
2C2H5OH + 2Na 2C2H5O-Na+ + H2 ↑
Ethanol Sodium ethoxide

129
In the above reaction, the oxygen-hydrogen bond of the alcohol is broken and
the alcohol, thus behaves as an acid. We have mentioned in the previous
subsection that alcohols are, however, weaker acids than water. Therefore,
the conjugate base of alcohols, the alkoxide ion, is a stronger base than the
hydroxide ion, the conjugate base of water. The order of reactivity for different
types of alcohols in this reaction is CH3OH > primary > sec. > tert. This order
is the same as given earlier for the acidity of alcohols.
ii) Esterification:
Another interesting reaction of alcohols is with acids to form esters and water.
In this reaction, the oxygen-hydrogen bond in the alcohol is broken.
RCOOH + R'OH RCOOR' + H2O
This reaction is known as esterification. These types of reactions will be

discussed again in greater detail in the third semester DSC course.
Any inorganic acid can be used in place of carboxylic acid to produce

inorganic ester. Inorganic esters are valuable commercial products. For
instance, nitroglycerin is readily prepared by the esterification of nitric acid with
glycerol.
CH2 OH CH2 ONO2
H2SO4
CH OH + 3 HNO 3 CH ONO2 + 3 H 2O
CH2 OH CH2 ONO2
1,2,3-Propanetriol 1,2,3-propane trinitrate
(glycerol) (nitroglycerin)
Nitroglycerin is an explosive used to make dynamite. Similarly, sodium

laurylsulphate, a synthetic detergent, can be obtained by esterification of lauryl
alcohol,
H2SO4 NaOH - +
CH3(CH2)10CH2OH CH3(CH2)10CH2OSO2OH CH3(CH2)10CH2OSO2O Na
1-Dodecanol 1-Dodecanyl hydrohen sulphate Sodium-1-Dodecanyl hydrohen sulphate
(lauryl alcohol) (lauryl hydrogen sulphate) (sodium lauryl hydrogen sulphate)
Synthetic detergent
Another important ester is cellulose trinitrate (gun cotton). It is a product obtained
when cellulose (a polysaccharide) is almost completely nitrated under
conditionscarefully controlled to prevent degradation of the cellulose molecule.
3n HNO3/H2SO4
[C 6H7O 2(OH)3]n (C6H7O 2(ONO 2)3]n
Cellulose Gun cotton
Gun cotton contains about 12-13% of nitrogen, is explosive and is used in the
manufacture of smokeless powder.
Esterification of cellulose with acetic anhydride gives cellulose acetate; it is an
ester but is not explosive. Cellulose acetate is used to produce thin fibers.
From such fiber, the acetate fabrics are woven. Photographic film is also
produced from cellulose acetate.
130
Unit 15 Alcohols
iii) Reaction with Grignard Regents:
Alcohols react with Grignard reagents to form alkanes.

Ether
R−OH + R'MgX R'H + Mg(OR)X
Ether
CH3−OH + C2H5MgI C2H6 + Mg(OCH3)I
Methanol Methyl magnesium Ethane
iodide
15.6.3 Reactions of the C−O bond

We have seen above that the breaking of O−H bond in alcohols is readily
achieved with strong bases. We have also mentioned that −OH group (a very
poor leaving group) can be changed into a − OH2+ (a better leaving group) by
strong acids. Subsequently, C−O may be broken; thereby leading to
substitution or elimination reactions. Details of these reactions are as follows.
i) Substitution Reactions of Alcohols: The reactions of alcohols with HX,

PX3, SOCl2, PCl5 to prepare alkyl halides have already been briefly
discussed in Unit 13.
R OH + HX R X + HX
Alcohol Hydrogen halide Alkyl halide
3R OH + PX 3 R X + H3PO4
Phosphorus trihalide Alkyl halide
R OH + SOCl2 R Cl + SO2 + HCl
Thionyl chloride Alkyl chloride
R OH + PCl 5 R Cl + POCl3 + HCl
Phosphorous Alkyl chloride
pentachloride
Let us first look more closely at substitution reaction of alcohol with

hydrogen halides (HX). Alcohols can undergo substitution reactions with
HX under acidic conditions or in the presence of Lewis acid like
anhydrous zinc chloride (ZnCl2). The general reaction can be
represented as,
H+
R OH + HX R X + HX
Alcohol or ZnCl2 Alkyl halide
Example
ZnCl2
CH3CH2CH2CH2 OH + HBr CH3CH2CH2CH2 Br + H2O
Heat
1-Butanol 1-Bromobutane
ZnCl2
(CH3)3 OH + HCl (CH3)3 Cl + H2O
2-Methyl-2-propanol 2-Methyl-2-chloropropane
If we compare substitution reactions of alcohols and alkyl halides, we can

notice that unlike alkyl halides, alcohols do not undergo substitution under
neutral or alkaline condition. The reaction requires acidic conditions
131
(protonation of −OH group)) or catalysts like ZnCI2. In Unit 13, we have seen
A tertiary R3C–OH most that Cl-, Br- and I- are good leaving-groups and weak bases. But, as you know,
easily gives a OH- is a strong base and thus, a very poor leaving group. In acidic solution,
carbocation and tends to alcohols get protonated to − OH2+ , which is a good leaving group because it is
react by the
SN1mechanism. It is lost as water, a weak base. A weak nucleophile, such as a halide ion can
very difficult for a primary displace the water molecule to yield an alkyl halide.
RCH2–OH to form a -
Strong acid X
carbocation, but the + +
primary structure is open R O + H O H R O H R X + O H
to backside attack, so an H
H H H
SN2 reaction is possible. Hyronium ion Oxonium ion Alkyl halide
Alcohol
A secondary alcohol (weak acid)
R2CH–OH may react by
The function of zinc chloride is similar to that of proton. Anhydrous zinc
either SN1or SN2
mechanism. chloride is a powerful Lewis-acid with empty orbitals that can accept electrons
from the oxygen atom of alcohol. The formation of a complex of ZnCI2, with the
alcohol oxygen weakens the C−O bond and thus, enhances the leaving ability
of the hydroxyl group.
In substitution reactions of alcohols, the reactivity of the hydrogen halides is as

follows:
HF < HCI < HBr < HI
Thus, the higher the acid strength and nucleophilicity of the halide ion, the
higher will be the reactivity towards ROH.
The order of reactivity of alcohols towards hydrogen halides is as follows:
Methyl < primary < sec < tert-alcohols
Increasing reactivity of ROH towards HX
This order of reactivity forms the basis for the Lucas test which is used to
differentiate primary, secondary and tertiary alcohols. The Lucas reagent is
made up of concentrated HCI and ZnCl2. Tertiary alcohols react immediately
upon shaking with the Lucas reagent to produce an immiscible upper layer of
alkyl chloride. Secondary alcohols react in 2-3 minutes, and primary alcohols
do not react unless the mixture is heated.
Mechanism
Like alkyl halides, primary alcohols react by the SN2 mechanism, tertiary
alcohols by SN1 mechanism, and secondary alcohol by either an SN1 or SN2
mechanism.
The mechanism for the reaction of primary alcohols is as follows:
Step 1
H O + HX
H
Addition of proton: When an aqueous solution of acid like HX is used, it forms
+ -
H O H + X a hydronium ion. Hydronium ion, actually acts as an acid and transfers proton
H to –OH group of an alcohol. The −OH group of the alcohol gives oxonium ion
on accepting proton from hydronium ion. This process converts −OH, a poor
132 leaving group, into − OH2+ which is a good leaving group.
Unit 15 Alcohols
fast and reversible

+ +
RCH2 O + H O H RCH2 O H + O H
H
H H H
An alcohol Hyronium ion An oxonium ion
Step 2
Nucleophile (halide ion) forms new bond with electrophilic carbon centre and
simultaneously bond is broken with the leaving group to give stable molecule
(an alkyl halide).
slow, rate
- + determining
X + RCH2 O H X CH2R + O H
SN2
H Alkylhalide H
The mechanism for the reaction of tertiary alcohols is as follows:
Step 1
Similar to the first step of the mechanism of the primary alcohol, proton is
transferred to convert −OH of a tert-alcohol, a poor leaving group, into − OH2+ ,
a good leaving group.
+ fast and reversible +

R3C O + H O H R3C O H + O H
H
H H H
A tert-alcohol Hyronium ion An oxonium ion
Step 2
With the loss of water, C−O bond of the alcohol is broken to give a stable
carbocation intermediate.
slow, rate R
+ determining +
R 3C O H R C + O H
SN1 H
H R
A tert-carbocation
intermediate
Step 3
A new bond is formed between electrophilic carbocation and nucleophilic
halide ion to form an alkyl halide molecule.
R R
+ - fast
R C + X R C X
R R
A tert-carbocation tert-Alkyl halide
intermediate
The key feature of nucleophilic substitution reactions with hydrogen halides is

conversion of −OH group into a good leaving group by the protonation. Such
substitution reactions have some limitations. Primary alcohols do not react 133
with HCl or HF as both chloride and fluoride ions are poor nucleophile in
comparison to bromide and iodide ions. Secondary and tertiary alcohols,
similar to secondary and tertiary alkyl halides, also tend to undergo
rearrangements during the SN1 reaction.
CH3 CH3 H CH3 H
H+Br-
CH3 C CH CH3 CH3 C C CH3 CH3 C C CH3
-
- Br +
CH3 OH H3C OH2 CH3
+
Secondary carbocation
3-Dimethyl-2-butanol
(less stable)
CH3 H - CH3 H
Br
CH3 C C CH3 CH3 C C CH3
+
CH3 Br CH3
Tertiary carbocation 2-Bromo-2,3-dimethylbutane

(more stable)
There is also a possibility of protonation of neucleophile in strong acidic

conditions unless our nucleophile is a weak acid as our halide ions. Because
of all such difficulties, several alternative methods for the preparation of alkyl
halides from alcohols have been developed.
Phosphorus and sulphur halides also convert the −OH group into a good
leaving group and provide a nucleophile, a halide ion, to replace the leaving
group.
Most widely used reagents for the conversion of primary and secondary
alcohols to alkyl halides are thionyl chlonde (SOCl2) and phosphorus trihalide
(PX3). These reagents undergo reaction under milder reaction conditions with
alcohols to form intermediate inorganic esters. The resulting inorganic ester
groups are good leaving groups that can be displaced by halide ions.
The reaction with thionyl
SOCl2
for conversion of OH Cl
alcohols to alkyl chloride + HCl + SO2
D
is preferred as by
products (SO2 and HCl) PX3
OH X
are gases and are + H3PO3
D
removed from reaction
mixture on heating.
Both these reactions produce good yield of alkyl halides. The mechanisms of
these reactions may be written as:
Mechanism of Reaction with Thionyl Chloride:
The mechanism of the transformation of the alcohols into corresponding alkyl

halides depends on the nature of alcohols. Primary alcohols undergo an SN2
reaction and tertiary alcohols follow an SN1 pathway. Secondary alcohols
follow both SN1 and SN2 pathways.
Step 1
Alcohol reacts with thinoyl chloride to form alkyl chlorosulphite, this converts
−OH, a poor leaving group, into a chlorosulphite that now has a good leaving
134 group.
Unit 15 Alcohols
O
O Cl
OH S S + H Cl
Cl Cl
O
Propanol Thionyl chloride Propyl chlorosulphite
Step 2
In this step nucleophile, i.e. chloride ion displaces leaving group to form the
alkyl halide.
- O Cl SN2 Cl -
Cl + + SO2 + Cl
S
O Chloropropane
Mechanism with tert-alcohols

O
O CH3
CH3 -
- Cl S
OH + S O Cl
Cl Cl
+ CH3 CH3
- Cl
Cl + SO2
An SN2 pathway is favoured in secondary alcohols when a base such as

pyridine is added to the reaction mixture.
Mechanism of Reaction with Phosphorus Trihalides:

Several phosphorus halides such as PCl3, PBr3 and PCl5 are commonly used
to convert alcohols to alkyl halides. Amongst them, PBr3 is the best reagent for
this purpose. Reaction of phosphorus tribromide with primary and secondary
alcohols follows SN2 pathway. With tertiary alcohols, phosphorus bromide
works poorly as in this case back side attack of halide ion on intermediate
product (trialkylphosphite) is hindered (SN2 condition) and also its ionisation is
slow (SN1 condition).
Step 1
In the first step of the reaction with PBr3, an alcohol forms trialkylphosphite.
3R OH + PBr3 (RO)3P + 3HBr
Step 2
By extracting a proton from hydrogen bromide, trialkylphosphite forms a good

leaving group and generates a nucleophile, bromide ion for next step.
+ -
(RO)3P + H Br (RO)2PH O R + Br
Good leaving group 135

Step 3
This step leads to substitution with formation of very stable phosphorus-
oxygen double bond. This provides the driving force for this step.
+ - SN2 -
(RO)2PH O R + Br (RO)2PH O + R Br
As we have seen that primary, secondary and tertiary alcohols react with
different reagents by different pathways. In Table 15.4, we have summarised
the best reagent used for the substitution reactions of alcohols leading to alkyl
halides.
Table 15.4: Summary of best reagent used for substitution reactions of

alcohols leading to akyl halides
Alcohol Chloride Bromide Iodide

*
Primary SOCl2 PBr3 P/I2
*
Secondary SOCl2 PBr3 P/I2
Tertiary HCl HBr HI
 Phosphorus triiodide is not a stable compound; therefore, it is generated in the

reaction mixture by the reaction of phosphorus with iodine.
Nucleophiles other than halides also bring about substitution reactions with
alcohols. But the –OH group of an alcohol has to be converted into a good
leaving group. This is commonly done by converting alcohols into alkyl
sulphonate esters. They have very good leaving group, a sulphonate ion.
Common sulphonate esters are methanesulphonate (also called mesylate),
abbreviated −OMs; trifluromethanesulphonate (also called triflate), abbreviated
−OTf; and p-toluenesulphonate (also called tosylate), abbreviated −OTs.
O O O
+ + +
H3C S OR F3C S OR H3C S OR
- - -
O O O
Methanesulphonate Trifluoromethane- p-Toluenesulphonate
sulphonate
Sulphonates can be prepared by treating an alcohol with alkyl/aryl sulphonyl

chloride [for example p-toluene sulphonyl chloride (CH3C6H4SO2Cl or TsCl)]
and base which is usually pyridine, triethylamine, or NaOH.
O O
+ OH Pyridine +
CH3 S Cl + CH3 S O
- -HCl -
O O
p-Toluenesulphonyl chloride Propanol Propyl-p-toluenesulphonate

(propyl tosylate)
Tosylate (−OTs) being a very good leaving group, can readily be displaced by
136 nucleophile.
Unit 15 Alcohols
OTs NaCN, DMSO CN
Propyl tosylate Butanenitrile

(n-propyl cynide)
A verity of useful products can be synthesised from alcohols using these two
step process.
ii) Dehydration of Alcohols to Alkenes: Another reaction of alcohols is
the dehydration. This involves cleavage of C−O bond along with loss of
a proton from the β position. It may be affected by heating alcohols to
673- 1073 K or heating to a lower temperature in the presence of a
catalyst such as alumina or a mineral acid, e.g., sulphuric acid. The
product of dehydration of an alcohol is an alkene or a mixture of alkenes.
The order of the ease of dehydration of alcohols is:
tert > sec > primary
Dehydration of primary alcohols gives only one product, e.g.,

H2SO4
CH3CH2CH2 OH CH3CH2 CH2 + H2O
Propanol 353 Propene
K
Primary alcohols undergo dehydration reaction by E2 path similar to the
dehydrohalogenation mechanism discussed in Unit 13.
For the above reaction the E2 mechanism can be written as,

H
+
H3O +
CH3CH2CH2 OH CH3CH CH2 O H
H
+
CH3CH2 CH2 + H3O
In the case of secondary or tertiary alcohols, a mixture of two alkenes is
formed, e.g.,
OH
H+/Heat
CH3CH2CHCH3 CH3CH CHCH3 + CH3CH2CH CH2
- H2O
2-Butanol 2-Butene 1-Butene
Like the dehydrohalogenation reaction of alkyl halides, the major product

in the above reaction is 2-butene, the more substituted alkene
(according to Saytzeff rule which was given earlier in Unit 13).
In secondary and tertiary alcohols, dehydration follows the E1 pathway.

A detailed discussion of the E1 mechanism has already been given in
Unit 13. Now let us write the mechanism for dehydration of 2-butanol.
Step 1
+
OH OH2
H3O+ - H2O +
CH3CH2CHCH3 CH3CH2CHCH3 CH3CH2CHCH3

Protonated Carbocation
137
Step 2
H
+ H+
CH3CH CHCH3 CH3CH CHCH3 (more favourable)
2-Butene
or
H H
+ H+
CH3CH CH CH2 CH3CH2CH CH2 (less favourable)
1-Butene
SAQ 7
Complete the following reaction and write its mechanism:
OH TsCl NaI
A B
Pyridine Acetone
SAQ 8
Draw the structure for the alkenes formed in the reactions given below and
also predict the major product in each case.
i) H2SO4
OH
OH
The combination of H2SO4
chromic acid and ii)
sulphuric acid is called
Jones reagent. This
reagent is suitable for the
oxidation of secondary 15.7 OXIDATION OF ALCOHOLS
alcohols to ketone and
primary alcohols to Alcohols undergo oxidation and the nature of the product depends on whether
carboxylic acid.
the alcohol is primary, secondary or tertiary. The common oxidising agents
The chromium trioxide used are acidic dichromate, acidic or alkaline potassium permanganate or hot
complex with pyridine is concentrated nitric acid or chromic acid (H2CrO4) or the chromium trioxide
available in two forms. (CrO3) complex with pyridine.
One is called Collin’s
reagent: It is prepared by A primary alcohol on oxidation gives an aldehyde, which on further oxidation
the addition of chromium gives a carboxylic acid. The oxidation products have the same number of
trioxide to pyridine. The carbon atoms as the alcohol, e.g.,
other is Corey’s reagent,
also called pyridinium [O] [O]
chromate complex
CH3CH2 OH CH3CHO CH3COOH
(PCC), It is made from
CrO3, HCl and pyridine. A secondary alcohol on oxidation gives a ketone with the same number of
Both these reagents are carbon atoms as the alcohol. Ketones are not further easily oxidised.
suitable for the selective However, drastic oxidations give a mixture of carboxylic acids containing a
oxidation of primary fewer carbon atoms than the alcohol:
alcohols to aldehydes.
[O] [O]
CH3CHOHCH2CH3 CH3COCH2CH3 2 CH3COOH
138
Unit 15 Alcohols
Tertiary alcohols are not easily oxidised in neutral or alkaline conditions. Acidic
oxidising agents convert a tertiary alcohol to the alkene and then it is oxidised
to a mixture of ketones and carboxylic acids, each having a lesser number of
carbon atoms than the alcohol. Oxidation of alkene was discussed in Unit 17
of first semester chemistry course.
[O]
No reaction
OH-
R3COH
[O] [O]
Alkene Ketone + Carboxylic acid
H+
Oxidation of alcohols can also be brought about by catalytic dehydrogenation.

In this process, vapours of the alcohol is heated over copper, for example,
Cu as cat.
CH3CH2 OH CH3CHO + H2O
573 K Ethanal
Ethanol
Cu as cat.
(CH 3)2CH OH (CH 3)2CO + H2O
573 K
2-Propanol Propanone
As mentioned above, tertiary alcohols are resistant to oxidation. When

vapours of tertiary alcohols are passed over copper heated at 573 K, they
undergo dehydration to give alkenes, for example,
CH3 CH2
Cu as cat.
CH3 C OH CH3 C + H2O
573 K
CH3 CH3
2-Methyl-2-propanol 2-Methylpropene
Silver catalyst is also employed. For example,

Ag as cat.
CH3 OH + 1/2O 2 HCHO + H2O
Metanol
Dehydrogenation is more often used for industrial preparation of aldehydes

and ketones.
SAQ 9
Write the product of treating each of the following alcohols with i) PCC, ii)
chromic acid.
a) 1-Butanol; b) 2-Butanol; c) Cyclopantanol
15.8 DIOLS
The dihydric alcohols are known as glycols or diols (in IUPAC nomenclature).
1,2-Ethanediol (ethylene glycol or simply glycol) can be prepared by the
hydroxylation oxidation of ethene with cold dilute alkaline potassium
permanganate:
H2C CH2 + H2O + [O] CH2 CH2
Ethene OH OH 139
Hydrolysis of ethene chlorohydrin or 1,2-dihalide with mild alkali, such as aq.

NaHCO3 or Na2CO3 also gives 1,2-ethenediol.
CH2 Cl CH2 OH
+ NaHCO 3 + NaCl + CO2
CH2 OH CH2 OH
CH2 Br H2O CH2 OH

+ Na 2CO3 + 2 NaBr + CO2
CH2 Br CH2 OH
1,2-Ethanediol is manufactured by the hydration of oxirane (ethylene oxide).

O
CH2 CH2
H2C CH2 + H2O
OH OH
This is carried out in acid solution at about 333 K or with water at 473 K under
pressure.
1,2-Ethanediol is taken as a typical example of diols. It shows the chemical

reactions of monohydric alcohols except that more vigorous conditions are
sometimes needed for reaction of the second of the two hydroxyl groups. For
example:
i) It reacts with sodium to form a monoalkoxide and at higher temperature
forms the dialkoxide:
- +
CH2 OH Na CH2 O Na
327 K + 1/2H 2
CH2 OH CH2 OH
- + - +
CH2 O Na Na CH2 O Na
- +
+ 1/2H 2
CH2 OH 423 K CH2 O Na
iii) It reacts with phosphorus halide to yield dihalide:
CH2 OH CH2 Br
3 + 2 PBr 3 3 + 2H 3PO3
CH2 OH CH2 Br
iv) It reacts with carboxylic acids to form esters:

O O
CH2 OH CH3COOH CH2 O C CH3 CH3COOH CH2 O C CH3

in excess
CH2 OH H+ CH2 OH CH2 O C CH3
H+
O
When esterified with a dibasic acid, it forms polymers, for example,
CH2 OH
+ n HOOC COOH
CH2 OH
Benzene-1,4-dicarboxylic acid
O O
H O C C O CH2 CH2 n
OH + (2n-1) H2O
140
Terylene
Unit 15 Alcohols
v) Acid-catalysed Dehydration of Glycols:

The products of acid-catalysed dehydration of diols are quite different
from those of acid catalysed dehydration of alcohols. For example,
reaction of 2,3-dimethyl-2,3-butanediol (commonly called pinacol) with
concentrated sulphuric acid gives 3,3-dimethyl-2-butanone (commonly
called pinacolone).
OH OH O CH3
H2SO4
H3C C C CH3 H3C C C CH3
CH3 CH3 CH3
2,3-dimethyl-2,3-butanediol 3,3-Dimethyl-2-btanone
(pinacol) (pinacolone)
You can notice two important features of this reaction:
i) dehydration product is a ketone
ii) migration of methyl group from one carbon to adjacent carbon
The acid catalysed conversion of pinacol to pinacolone is an example of a

rearrangement reaction and called as Pinacol-pinacolone or simply pinacol
rearrangement. The mechanism of the reaction can be given as shown:
Step 1
Protonation of hydroxyl group.

H
+
OH OH OH O H
+ rapid and
CH3 C C CH3 + H O H CH3 C C CH3 + H2O
reversible
CH3 CH3 H CH3 CH3
2,3-dimethyl-2,3-butanediol
(pinacol)
Step 2
Loss of H2O from oxonium ion to form tert-carboction intermediate.
H
+
OH O H OH
-H2O +
CH3 C C CH3 CH3 C C CH3
CH3 CH3 CH3 CH3

Step 3
Migration of methyl group from one carbon to adjacent carbon to form more
stable carbocation.
+
OH OH CH3 OH CH3
+
CH3 C C CH3 CH3 C C CH3 CH3 C C CH3
+ +
CH3 CH3 CH3 CH3
Carbocation intrmediate stabilised by charge
delocalisation 141
Step 4
Transfer of proton to solvent
+
H O CH3 O CH3
O H + CH3 C C CH3 CH3 C C CH3

H CH3 CH3
3,3-Dimethyl-2-butanone
(pinacolone)
vi) On oxidation with nitric acid, both the primary alcoholic groups are
oxidised, first to aldehyde and then to carboxyl groups. Ethanedioic acid
is finally oxidised to carbon dioxide and water,
CH2 OH [O] CH O [O] CH2 COOH [O] CH2 COOH [O]

2 CO2
CH2 OH CH2 OH CH O CH2 COOH
Oxidising agents such as periodic acid, HIO4.2H2O are used for the
cleavage of diols, into aldehydes or ketones.
OH O OH
O CHO
+ HIO 4 I
-
O O CHO
OH OH
The oxidative cleavage of diols with periodic acid is very useful in the
constitutional analysis of sugars.
1-2 Ethanediol is widely used as a solvent, antifreeze agent and in the

manufacture of terylene.
SAQ 10
Complete the following reaction:
OH
H2SO4
OH
SAQ 11
What products are formed when 2,3-butanediol is treated with HIO4?
15.9 LAB DETECTION

The reaction with sodium metal to evolve hydrogen gas is of some use for the
detection of alcohols. The presence of traces of moisture, however, affects the
characterisation. The presence of a hydroxyl group in a molecule is often
indicated by the formation of an ester upon treatment with an acid chloride or
an anhydride. Compounds like alcohols, phenols, primary and secondary
amines (those containing an active hydrogen atom) on treatment with benzoyl
142 chloride in the presence of dilute aqueous sodium hydroxide give benzoyl
Unit 15 Alcohols
derivatives (Schotten-Baumann reaction). Sometimes, 4-nitrobenzoyl or 3,5-

dinitrobenzoyl chlorides are used to prepare derivatives of alcohols and
phenols and thus, for the characterisation of these compounds.
NO 3 NO 3
O O
Pyridine
ROH + Cl C R O C
NO 3 NO 3
3,5-dinitrobenzoyl chloride 3,5-dinitrobenzoate
As mentioned earlier, alcohols of different classes can be differentiated on the

basis of their reaction rates with HCl/ZnCl2. If we take alcohol in a test tube
and add mixture of HCl/ZnCl2 the following results are obtained:
HCI/ZnCl2
primary alcohols No reaction at room temperature.
HCl/ZnCI2
secondary alcohol Reaction mixture gets cloudy in 5-10 minutes.
Tertiary, alkenyl, Reaction mixture gets cloudy immediately.

benzyl alcohols
15.10 SUMMARY
In this unit, we have described the chemistry of alcohols. We are summarising
below what we have studied:
 Alcohols are obtained by the hydrolysis of alkyl halides and reduction of

aldehydes and ketones. They are prepared on a large scale by hydration
of alkenes, catalytic treatment of water gas, catalytic oxidation of natural
gas and fermentation of starch or sugars.
 Alcohols are very weak acids. The molecules tend to associate

themselves by forming hydrogen bonds. They react with carboxylic acids
to form esters.
 Alcohols can undergo SN1 and SN2 reaction with hydrogen halides to form
alkyl halides. They can also be converted to alkyl halides by the reaction
with phosphorous halides and sulphur halides.
 Nucleophiles other than halides also bring about substitution reactions

with alcohols. But before that the −OH group of an alcohol has to be
converted into a good leaving group. This is commonly done by
converting alcohols into alkyl sulphonate esters.
 Dehydration of alcohols leads to alkenes. Oxidation or dehydrogenation of

alcohols gives mainly carbonyl compounds.
 Diols undergo pinacol-pinacolone rearrangement reaction under acidic

condition. 143
 Diols can be oxidised by periodic acid to two carbonyl species due to

cleavage of the C−C bond between the −OH groups.

1. Show a structural formula for each name and tell whether it is a primary,
secondary or a tertiary alcohol.
a) 3-pentanol
b) 2,2-dimethyl-1-propanol
c) 2-methyl-1-butanol
d) 3-methyl-2-pentanol
e) 1-methylcyclopentanol
2. Which compound from each pair has a higher boiling point and is more
soluble in water.
a) 1-chloropropane or propanol
b) 1-butanol or 2-methyl-2-propanol
c) 2-butanol or 2-propanol
3. Which is the stronger base, ethanol or 2-methyl-2-propanol? Explain.
4. Write the mechanism for the reaction of
a) ethyl alcohol with HBr
b) 3,3-dimethyl-2-butanol with HBr.
5. Complete the following reactions:

a) (CH3)3COH + HCl
Na
b) C2H5OH
H2O
6. Show all the alkenes that could possibly be formed by dehydration of each
alcohol given below. Which alkene would be produced in largest amount ?
a) 2-methyl-2-butanol
b) 2-pentanol
c) 2-methylcyclohexanol
d) 1,2-dimethylcycloxexanol
7. What product, if any, would be obtained by passing each of these alcohols

over copper metal at 573 K?
a) 1-propanol
b) 2-butanol
144
Unit 15 Alcohols
c) 2-propanol
d) 2-methyl-2-propanol
8. Give a simple chemical test that would distinguish primary alcohol from a
secondary alcohol and secondary alcohol from a tertiary alcohol.
15.12 ANSWERS
1. a) 2,2-Dimethyl-1-propanol or 2,2-Dimethylpropanol, primary
b) 2-Methyl-2-butanol, tertiary
c) 3,3-Dimethyl-2-butanol, secondary
d) 1-Methylcyclohexanol, tertiary
e) 2-hydroxycyclopentane-1-carbaldehyde, secondary
f) 3-Cyclohexene-1-ol or Cyclohex-3-en-1-ol, secondary
2. i) Preparation of 2-Butanol
OH
H+/H2O
a) CH3CH2CH CH2 CH3CH2CHCH3
Cl OH
-
OH /H2O
b) CH3CH2CHCH3 CH3CH2CHCH3
O OH
i) CH3MgX
c) CH3CH2CH CH3CH2CHCH3
ii H3O+
O OH
i) LiAlH4, ether
d) CH3CH2CCH3 CH3CH2CHCH3
ii) H2O
ii) Preparation of 1-Butanol
a) i) BH3
CH3CH2CH2 CH2 CH3CH2CH2CH2 OH
ii) H2O2/NaOH
b) OH-/H2O
CH3CH2CH2CH2 Cl CH3CH2CH2CH2 OH
O
i) C2H5MgBr/ether
c) H2C CH2 CH3CH2CH2CH2 OH
ii) H3O+/H2O
O or
i) C3H7MgBr/ether
H C H CH3CH2CH2CH2 OH
ii) H3O+/H2O
145
i) LiAlH4/ether
d) CH3CH2CH2CH2CHO CH3CH2CH2CH2 OH
ii) H2O
573 K
3. a) H 2C CH2 + H2O CH3CH2OH
70 atom
b) Cu Catalyst
CO + 2H2 CH3OH
533 K, 150 atom
c) Invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Cane Sugar Zymase
2C 2H5OH + 2CO 2
4. Order of increasing boiling point
Pentane < 2-Methyl-2-propanol < 1-Butanol < 1,3-Propanediol
Explanation: Boiling point mainly depends on two factors:
(i) The strength of inter molecular hydrogen bonding
(ii) van der Waals’ forces
In case of pentane, there is no possibility of hydrogen bonding, therefore,

this has the lowest boiling point.1,3-propanediol has two −OH groups
therefore, this alcohol has more sites within its molecule for
intermolecular hydrogen bonding than 1-butanol. Now, compare 1-
butanol and 2-methyl-2-propanol. Being larger surface area of 1-butanol,
this alcohol besides intermolecular hydrogen bonding association has
more effective van der Waals forces than 2-methyl-2-propanediol. Thus,
1-butanol has higher boiling point than 2-methyl-2-propanol.
5. Order of increasing solubility in water
Pentane < 1-Butanol < 1,3-Propandiol
Explanation: Pentane, is a nonpolar molecule, has the lowest solubility in

water. Due to the process of polar −OH group in 1-butanol and 1,3-
propanediol, they interact with water molecule by hydrogen bonding. 1,3-
propanediol is more soluble in water than 1-butanol as it has more sites
within its molecule for hydrogen bonding.
6. Chlorine atom being an electron withdrawing group stabilises the

negative charge in the alkoxide oxygen by electron attraction (Inductive
effect). Further, such inductive effect is increases with the number of
electronegative groups on -carbon of alcohol but decreases with
distance from the oxygen. Thus, on the basis of these facts, the order of
acidity will be
CH3CH2CH2CH2CCl2(OH) > CH3CH2CH2CH2CHCl(OH) >
CH3CH2CH2CH(Cl)CH2OH
146
Unit 15 Alcohols
7. O O
+ Pyridine +
CH3 S Cl + OH CH3 S O
-HCl
- - NaI I
O O
p-Toluenesulphonyl chloride Propanol propyl p-Toluenesulphonate

(propyl tosylate)
Mechanism
O O
- SN2
+ I + -
CH3 + I + CH3 S O
S O
- -
O O
p-Toluene sulphonate ion
(very weak base and being a stable
ion acts as very good leaving
group)
8. i)
H2SO 4
+
H2O
OH
3-Methyl-2-butanol 2-Methyl-2-butene 3-Methyl-1-butene
(Major product)
2-Methyl-2-butene has three alkyl groups (methyl groups) on the double bond
and 3-methyl-1-butene has only one substituent; thus, former will be the major
product as per the Saytzaff rule i.e. formation of more substituted alkene is
favoured.
ii) OH
H2SO4
+
-H2O
2-Methylvyclohexanol 1-Methylcyclohexene 3-Methylcyclohexene

Major product
1-Methylcyclohexene has three alkyl substituents on the double bond and 1-
Methylcyclohexene has two, therefore,1-Methylcyclohexene will be the major
product.
9. 1-Butanol, a primary alcohol, is oxidised to butanal with PCC and to butanoic acid
with chromic acid. On the other hand 2-butanone is a secondary alcohol oxidised
to butanone by both PCC and chromic acid. Cyclopentanol is also secondary
alcohol; it is oxidised to cyclopentanone by both oxidising agents.
H
10. OH O H O
H2SO4
+
+
-H2O
OH
O
O
-H+
or
11. The bond between the carbons bearing –OH group is cleaved and each −OH is
converted to a carbonyl group.
H3C CH3
HIO4
CH CH 2 CH3CHO
HO OH
147
Terminal Questions
1. a) OH
CH3CH2CHCH2CH3 (secondary)
b) CH3
CH3CCH2OH (Primary)
CH3
c) CH3
CH3CH2CHCH2OH (Primary)
d) CH3
CH 3CH 2CHCHCH 3 (secondary)

OH
e) CH3
(tertiary)
OH
2. Boiling point a) propanol b) 1-butanol c) 2-butanol

Solubility in water a) propanol b) 1-butanol c) 2-butanol
3. 2-Methyl-2-propanpl is less acidic and more basic as it has two electron

releasing methyl groups at -carbon.
4. See Subsec. 15.6.2.
5. a) (CH 3)3COH + HCl (CH 3)3CCl + H 2O
Na
b) C2H5OH C2H5ONa + 1/2 H 2
6. a) OH
+
2-Methyl-2-butanol 2-Methyl-2-butene 2-Methyl-1-butene
Major
b) OH
+
2-Pentanol 2-Pentene Pentene
Major
c) OH
2-Methylcyclohexanol 1-Methylcyclohexene 2-Methylcycloxexene

Major
d) OH
1,2-Dimethylcyclohexanol 1,2-Dimethylcyclohexene 2,3-Dimethylcycloxexene

Major
148
Unit 15 Alcohols
7. a) 1-propanal, b) 2-butanone
c) Propanone, d) 2-methylbutene
8. Lucas reagent (HCl/ZnCl2) is used to differentiate primary, secondary and

tertiary alcohols. Tertiary alcohols react immediately upon shaking with Lucas
reagent in a test tube. Secondary alcohols react in 2-3 minutes and primary
alcohols do not react with reagent unless the mixture is heated.
149
UNIT 16
PHENOLS
Structure
16.1 Introduction Reactions due to Phenolic
Expected Learning Outcomes Hydroxyl Group
16.2 Structure and Reactivity Reactions due to Aromatic Ring
16.3 Physical Properties Oxidation of Phenols
16.4 Preparation of Phenols Condensation Reactions
16.5 Chemical Properties Coupling Reaction
Acidity and Basicity of Alcohols Libermann’s Nitroso Reaction
and Phenols 16.6 Summary
Reactions of Phenols 16.7 Terminal Questions
16.8 Answers
16.1 INTRODUCTION
In the previous Unit, we have discussed the chemistry of alcohols. In this Unit,
we will discuss another class of compounds have hydroxyl group called
phenols. The phenols are grouped as a separate class of compounds because
their chemical properties are quite different from alcohols.
Phenols are aromatic compounds in which hydroxyl group(s) is attached to the

OH benzene nucleus. Their general formula is Ar−OH, where Ar is phenyl,
substituted phenyl, or some other aryl group. These compounds have several
applications and are indispensable in our daily life. Phenolic functional groups
are often encountered in a variety of household disinfectants,
H3C CH3 pharmaceuticals, agrochemicals and polymer materials. Phenol-formaldehyde
Cl resins, the polymers derived from phenols, for example, are the most widely
4-Chloro-3,5-dimethylphenol used industrial polymers.
(Dettol)
In this Unit, we will discuss general preparations and the chemical properties
of phenols. Phenols are important both as substrates and as reagent. Phenols
can be derivatised either at the hydroxyl group or the aromatic ring.

150  classify phenols;

Unit 16 Phenols
 explain physical properties of phenols;
 outline the preparation of phenols; and
 describe the reactions of phenols.
16.2 STRUCTURE AND REACTIVITY

Phenols are aromatic compounds in which hydroxyl groups are attached to the
benzene ring; so they have the hydroxyl group on an aryl sp2 hybridised
carbon. Before going to detail of their structure and reactivity, let us recall
some important aspects of their classification and nomenclature. Phenols are
classified as mono-, di- or trihydric on the basis of the number of −OH groups
present in the ring. Some examples of phenols are given below.
Monohydric Phenols
Although benzenol is the
CH3 CH3 systemic name of
OH
C6H5OH, the IUPAC
OH rules permit ‘phenol’ to
be instead.
OH
Benzenol 2-Methylbenzenol 4-Methylbenzenol
(phenol) (o-cresol) (p-cresol)
Dihydric Phenols
OH
OH OH
OH
OH
OH
1,2-Benzenediol 1,3-Benzenediol 1,4-Benzenediol
(catechol) (resorcinol) (quinol or hydroquinone)
Trihydric Phenols
OH OH OH
OH OH
HO OH OH
OH
1,3,5-Benzenetriol 1,2,4-Benzenetriol 1,2,3-Benzenetriol
(phloroglucinol) (hydroxyquinol) (pyrogallol)
The common names of important phenols are still widely used; therefore, in
this text we use both common names and IUPAC names. In the IUPAC
system, substituted phenols are named as derivatives of bezenols. Numbering
of the ring begins at the hydroxyl-substituted carbon and proceeds in the
direction that gives the lower number to next substituted carbon. Substituents are
cited in alphabetical order. The prefixes ortho (o), meta (m) and para (p) are also 151
used to indicate the relative positions of substituents. The dihydroxy and

trihydroxy derivatives of benzene are named as benzenediol and benzenetriol,
respectively with the relative positions of hydroxyl groups in ring. If one of
substituent is carboxyl or acyl group, then hydroxyl(s) group is treated as a
substituent. For example:
OH
O O
HO H3C
OH H
4-Hydroxybenzoic acid 2-hydroxy-4-methylbenzaldehyde
(p-hydroxybenzoic acid) (4-methylsalicyldehyde)
You might expect phenols to be very similar to alcohols as they also have the
hydroxyl group. But when we go in details of the structure of a phenol, we find
the bonded aromatic ring interacts with the −OH group and in many aspects
reactions of phenols are quite different from those of alcohols. Let us study in
details of the structure of a phenol.
The carbon-oxygen bond The hydroxyl functional group (−OH) in a phenol is bonded to a sp2 hybridised
lengths of phenol and aromatic carbon atom. The oxygen atom of hydroxyl group, similar to an
alcohol are 136 and 142
alcohol is sp3 hybridised. The two sp3 hybridised orbitals of oxygen form σ
pm, respectively.
bonds to carbon atom of aromatic ring and hydrogen atom and the remaining
two sp3 hybridised orbitals each contain a lone pair of electrons. Similar to aryl
halides, interaction between the delocalised electrons in the benzene ring and
the lone pairs on the oxygen atom is also possible in phenols (see Fig. 16.1).
This interaction causes partial double bond character in C−O bond. Thus,
because of these two factors i.e. the increased s character of the sp2
hybridised carbon and resonance delocalisation of electron pair of oxygen with
aromatic ring, the C−O bond in phenol will be shorter and stronger than of an
alcohol. This can be confirmed by measurement of bond lengths. The carbon-
oxygen bond lengths of phenol and alcohol are 136 and 142 pm, respectively.
p orbital of oxygen
containing lone pair
O
H
Fig. 16.1: Interaction of the lone pair of oxygen with the aromatic ring system
The geometry around oxygen atom of phenol is essentially the same as that in
alcohols. The C−O−C angle has the tetrahedral angle of 109o. Further, both
the C−O and the O−H bonds are polar in nature due to the high
electronegativity of the oxygen atom. All these structural aspects of phenols
152
Unit 16 Phenols
have an important effect on both the properties of the ring and of the −OH
group.
136 pm 142 pm
O H3C O
H H
109o 109o
sp2 sp3
Phenol Methanol
The delocalisation of lone pair electrons of oxygen onto benzene ring can be
shown by following resonating contributing structures:
+ OH + OH + OH
OH
_ _
The resonance effect shown by these contributing structures along with other
structural features discussed above can explain many of the unique properties
of phenols. Examples are as follows:
 Elecrophilic aromatic substitution in phenols is much faster than

benzene. This is because of the strong delocalisation effect of lone pair
electrons of oxygen. In phenols, the hydroxyl group activates the ring, and
therefore, it is ortho-para directing during electrophilic substitution
reactions. The ortho-para directing nature of hydroxyl group can be
understood by the resonating structures shown above for phenol, these
structures clearly indicate that benzene ring is relatively electron rich at
the positions ortho and para to hydroxyl group.
 Phenols generally do not undergo nucleophilic substitution reactions.

The resonance effect also reduces the partial positive charge on the
carbon bonded to the oxygen by spreading it over the whole delocalised
benzene ring system and thus, making this carbon less susceptible to
attack by nucleophile than the corresponding carbon in alcohols.
Because of this factor and partial double bond between carbon and
oxygen, phenols generally do not undergo nucleophilic substitution
reactions (see Fig. 16.2).
_
Nu:
-
d + d H
O
This bond is stronger

This carbon has less than in an alcohol
partial positive charge
than in an alcohol
Fig. 16.2: Phenols are less susceptible to attack by nucleophiles than alcohols.
 Phenols are more acidic than alcohols. Benzene ring also contributes
153
towards bond polarisation of O−H bond and stabilisation of phenoxide

ion formed after ionization of phenol. These factors result in more acidic
hydroxyl proton and more basic hydroxyl oxygen in phenols in compared
to alcohols.
We will further go in details of these properties in successive sections, but

before that try following SAQs.
SAQ 1
Write IUPAC names of the following:
i) OH ii) OH
CH3 CHO
iii) OH iv) COOH

CH3 OH
OCH3
COOH
v) OH
F
COOH
SAQ 2
Explain, why the C−O bond in phenols is shorter and stronger than the C−O
bond in alcohols?
16.3 PHYSICAL PROPERTIES

Like alcohols, the physical properties of phenols are also strongly influenced
by the hydroxyl group. Due to the polar nature of the O−H bond (both atoms
have different values of electronegativity); phenols form hydrogen bonds with
other phenol molecules and H-bonding systems like water. Thus, phenols also
have high boiling points and moderate solubility in water compared to
analogous aromatic hydrocarbons. On exposure to air and light they turn pink
due to auto-oxidation. The physical properties of some phenols are
summarised in Table 16.1.
154
Unit 16 Phenols
Table 16.1: Physical properties of some phenols
Name MP, K BP, K Solubility g/100 g H2O
Phenol 314 455 9.3
Catechol 377  45.0
Resorcinol 383  123.0
Hydroquinone 446  8.0
o-Nitrophenol 318  0.2

(volatile in steam)
p-Nitrophenol 387  1.7

(nonvolatile in steam)
In Table 16.1, we notice that ortho and para isomers of nitrophenol differ
considerably in their physical constants. How are we to account for these
differences? Let us see how these isomers undergo hydrogen bonding:
H
-
O
- O + O HO O
+ O H O
N
N +
N -
O
H
O
+
H N
OH O OH O OH Intramolecular
hydrogen boonding
H Intermolecular (o-nitrophenol)
Hydeogen bonding with hydrogen bonding
water molecules (p-nitrophenol)
From the above, we can expect that the p-isomer should have a higher melting
point and solubility in water due to the intermolecular hydrogen bonding
and its association with water molecules. On the other hand, o-nitrophenol has
intramolecular hydrogen bonding or hydrogen bonding within a single
molecule. It does not associate with other molecules or with water and,
therefore, has lower melting point and lower solubility.
SAQ 3
The melting points of 2-flurophenol and 4-flurophenol are 289.1 K and 321.6
K, respectively. How will you account for these differences?
16.4 PREPARATION OF PHENOLS

Phenols can be prepared from arylsulphonic acid, phenolic acids, diazonium
salts and from Grignard reagents. The general reactions of these methods of
preparation are summarised in Table 16.2. 155
Table 16.2: Preparation of Phenols
Fusion of arylsulphonates with sodium hydroxide

1. 573 K/NaOH
ArSO 3Na +
Ar OH
2. H
Phenol
Heating phenolic acid with soda-lime

OH OH
+ 2 NaOH (CaO) + Na 2CO3
COONa
Boiling diazonium salt with water

+ -
ArN 2 X + H 2O Ar OH + HX + N 2
Action of oxygen on Grignard reagent followed by hydrolysis

+
H /H2O
2ArMgX + O 2 2ArOMgX 2Ar OH
Let us study these reactions one by one.

i) Fusion of arylsulphonate with sodium hydroxide:
Phenol may be prepared by the fusion of sodium benzenesulphonate
obtained through sulphonation of benzene (Unit 11), with sodium
hydroxide. The sodium phenoxide produced in the reaction is converted
into the free phenol by treatment with acid.
- +
SO3H SO 3 Na
H2SO4 NaOH
Sodium
Benzene sulphonic
acid benzenesulphonate
573 K 2 NaOH
- +
OH O Na
+
+ H
+ Na + Na 2SO3 + H2O
Phenol Sodium phenoxide
ii) Decarboxylation of phenolic acids with soda-lime:

OH OH
+ 2NaOH (CaOH) + Na 2CO3
COONa Soda-lime
Sodium 2-hydroxy benzoate Phenol
(sodium salicylate)
iii) Boiling diazonium salt with water:

Aromatic amines react with nitrous acid to give diazonium salts which,
unlike their aliphatic analogues, are stable at low temperature and can be
isolated. The aqueous solution of the salt decomposes to phenol on boiling
with water with evolution of N2.
+
N N H2O
OH
-
Cl
N2 + HCl
Arydiazouium salt Phenol

156
Unit 16 Phenols
iv) Action of oxygen on Grignard reagent followed by hydrolysis:
Just as Grignard reagent adds to CO2, aryl Grignard reagents add to

molecular oxygen.
The intermediate reacts with another molecule of the Grignard reagent and
hydrolysis of the product gives phenol.
ArMgBr
ArMgBr + O 2 Ar O O MgBr
H+/H2O
2Ar O MgBr 2Ar OH + 2 Mg(OH)Br
Commercial Preparation
Phenols are of great commercial importance. In this section you will learn how
large quantities of these compounds are prepared from different abundant
natural sources.
From natural sources: On a commercial scale, phenols are obtained from coal
tar. Coal tar is fractionated and the middle oil is cooled when naphthalene
crystallises out. The liquid is treated with aqueous sodium hydroxide which
dissolves phenols. Carbon dioxide is passed into the liquid and the aqueous
layer is separated. Fractionation of remaining oil gives phenol (20%), cresols
(43%), xylenols (26%) and the residue is pitch.
From other aromatic hydrocabons:
a) Phenol can be obtained by the catalytic oxidation of methylbenzene

toluene) by air in presence of manganous and cupric salts.
CH3 OH
2O2, Cat.
+ CO2 + H2 O
Methylbenzene Phenol
(toluene)
b) The cumene process: (1-Methylethyl) benzene (cumene or

isopropylbenzene) is a constituent of crude oil and refined fuels. Oxidation
of cumene to hydroperoxide followed by decomposition by acid gives
phenol and an important by-product propanone (acetone):
CH3 CH3
H2SO4
C H + O2 C O O OH
CH3 CH3
(1-Methylethyl) benzene (1-Methylethyl) benzene
(cumene) hydroperoxide (cumene
hydroperoxide)
OH O
+ CH3 C CH3
Propanone
Phenol (acetone)
Synthetic cumene is made almost exclusively from benzene and propene via a
Friedel-Crafts reaction. 157
CH3
AlCl3
+ CH3CH CH2 C H
FC
CH3
Benzene Propene
(1-Methylethyl) benzene
(cumene)
c) The Dow process: Chlorobenzene and sodium hydroxide react at high

temperature and under pressure in the presence of a catalyst (copper
salts) to give phenols.
Cl OH
473 K
+ 2 NaOH + NaCl
Pressure, CuSO4
Chlorobenzene Phenol
When this process is applied to 1,2-dichlorobenzenes (catechol) is

obtained.
Cl OH
473 K
+ 2 NaOH
Pressure, CuSO4 + NaCl
Cl OH
1,2-Dichlorobenzene 1,2-Benzenediol
(catechol)
d) 1,2-Benzenediol (catechol) can be conveniently prepared by the action of

alkaline hydrogen peroxide on salicyladehyde. The reaction is an example
of Baeyer-Villiger rearrangement.
OH OH
3 NaOH
+ H2 O 2 + HCOONa + 3 H 2O
CHO ONa
Salicylaldehyde
H+/H2O
OH
+ 2 NaOH
OH
1,2-Benzenediol
(catechol)
e) 1,3-Benzenediol (resorcinol) is prepared industrially by the alkaline fusion

of benzene m-disulphonic acid:
SO 3H SO3Na ONa
NaOH fusion
+ 4 NaOH + 2Na 2SO3 + 2 H 2O
SO3H SO3Na ONa
Benzene-m-disulphonic H+/H2O
acid
OH
+ 2 NaOH
OH
1,3-Benzenediol
(resorcinol)
158
Unit 16 Phenols
f) 1,4-Benzenediol (quinol) is made commercially by the oxidation of aniline

with manganese dioxide and sulphuric acid. The product p-benzoquinone
is reduced to quinol with iron and hot water.
O OH
NH2
MnO2 Fe/H2O
H2SO4
Aniline O OH
p-Benzoquinone 1,4-Benzenediol
(quinol)
g) 1,2, 3-Benzenetriol (pyrogallol) is prepared by heating gallic acid (3,4,5-

trihydroxybenzoic acid) in a stream of carbon dioxide or by heating an
aqueous solution of gallic acid at 483 K under pressure:
OH OH
OH OH
483 K
+ CO2
HOOC OH OH
(3,4,5-Trihydroxybenzoic acid) 1,2,3-benzenetriol
(gallic acid) (pyrogallol)
h) 1,3,5-Benzenetriol (phloroglucinol) is obtained by the fusion of many plant

resins with alkali. It is also prepared by the reduction of
2,4,6−trinitrobenzoic acid to the amino derivative followed by reaction with
hot hydrochloric acid.
COOH COOH
O2N NO 2 HO OH
H2N NH2
Sn/HCl HCl
373 K
NO 2 NH2 OH
2,4,6-Trinitrobenzoic 1,3,5-Benzenetriol
acid (phloroglucinol)
SAQ 4
Complete the following reactions:
SO 3H + -
a) b) N2 Cl
1. NaOH/573 K
(?) H2O
2. H+/H2O (?)
c) CH(CH3)2 d) Cl
1. O2 1. NaOH/CuSO4
(?) (?)
2. H2SO4 2. H+/H2O
SAQ 5
How the following conversion can be carried out?
a) Benzene to phenol b) Phenylamine (Aniline) to phenol
c) Phenylmagnesium d) Chlorobenzene to phenol
bromide to phenol
159
16.5 CHEMICAL PROPERTIES

As stated earlier, phenols have very different chemical properties compared to
alcohols. One of the most important differences is that phenols are
significantly more acidic than alcohols. Therefore, it is worth comparing the
acidity of alcohols and phenols and the effect of substituents on it before
further going in details of various types of chemical reactions of phenols.
16.5.1 Acidity and Basicity of Alcohols and Phenols

Alcohols are neutral towards litmus. But in their reactions they behave both as
an acid and as a base depending upon the reaction conditions. For example,
in acidic solution, alcohols are protonated and thus the acid-base equilibrium
with alcohol acting as a base is established. It is the same type of reaction that
occurs between water and an acid. A protonated alcohol molecule is called an
oxonium ion.
+ - + -
R O + H Cl R O H + Cl
H H
Oxonium ion
An alcohol can also lose a proton to a strong base yielding an alkoxide ion,
RO. In this reaction, the alcohol behaves as an acid.
Alkoxides are strong bases, generally stronger than hydroxides. To prepare an

alkoxide from an alcohol, we need a base stronger than the alkoxide itself,
such as, alkali metal hydrides, NaH, KH, etc.
+ - - +
R OH + Na H R O Na + H2
In dilute aqueous solutions, alcohol has approximately same pKa values as

water. For example, the pKa of methanol in water is 15.5, while that of pure
water is 15.74. Therefore it is as acidic as water.
 +
CH3OH + H 2O CH3O + H 3O
On the other hand, phenols are distinctly acidic in character. Phenol, with a
pKa of 10.00 is a stronger acid than an alcohol or water. Unlike alkoxide ion of
alcohols, the phenoxide ion (ArO) is a weaker base than OH. Therefore, a
phenoxide can be prepared by treatment of the phenol with aqueous sodium
hydroxide.
unfavourable - +
CH3CH2 OH + NaOH CH3CH2O Na + H 2O
Ethanol Sodium ethoxide
pKa = 15.9
favourable - +
OH + NaOH O Na + H 2O
Phenol Sodium phenoxide

pKa = 10
160 We can explain the acidic character of phenol if we recall the fact that the
Unit 16 Phenols
degree of ionisation of a weak acid is determined by the relative stabilities of

the unionized compound and the anion:
+ -
HA H + A (if A is stabilised relative to HA,
acidity is increased)
The reason for the greater acidity of phenol compared to that of alcohol is that
the ionised product is resonance stabilised, with the negative charge
delocalised by the aromatic ring.
-
- -
O O O O
-
The negative charge in an alkoxide ion (RO) cannot be delocalised.
+ I effect of alkyl group
Therefore, alkoxide ion is of higher energy relative to the alcohol, and as a further increase the
result, alcohols are not as strong acid as phenols. Further, the alkyl group in intensity of negative
the alkoxide ion has a destabilising effect because of positive inductive (+I) charge on oxygen of
alkoxide ion; thus
effect (electron releasing effect) of the alkyl group. Therefore, addition of alkyl destabilises the alkoxide
groups to the carbon decreases the acidity of alcohols. We can now write ion.
the order of decreasing acid strength.
H2O > primary > sec > tert-alcohols
In phenols, substituents located ortho or para to the −OH group, can

dramatically influence the acidity of the phenol due to a combination of
inductive and resonance effects. The electron withdrawing groups enhance
the acidity while the electron donating substituents decrease the acidity.
OH OH OH OH OH
CH3 Cl
CH3 Cl
Phenol p-Cresol m-Cresol p-Chlorophenol m-Chloropheol
pKa 9.95 pKa 10.17 pKa 10.01 pKa 9.18 pKa 8.85
OH OH OH
O 2N NO 2
NO 2 H3PO 4
NO 2 NO 2
m-Nitropheol m-Nitropheol 2,4,6-Niropheol Phosphoric acid
pKa 7.15 pKa 8.28 pKa 0.38 pKa 2.1
The acid-weakening effect of alkyl substituents can be understood in the

following way. The +I effect of alkyl substituents are due to the higher
electronegativity of sp2 hybridised carbon of aromatic ring than sp3-hybridised
atom of an alkyl group. Thus, alkyl substituents are electron releasing towards
the aromatic ring. Because of electron releasing effect of alkyl substituent, it
will destabilise phenoxide ion contributing structures and in effect reduce the
acidity of alkyl substituted phenol. 161
CH3
The +I inductive effect of methyl group destabilises
this contributing structure
Halogens have –I effect as they are more electronegative than carbon, they
withdraw electron density from the aromatic ring and thus stabilise the
halophenoxide ion compared to phenoxide ion. As fluorine is most
electronegative among halogens, the fluorophenol will be the most acidic. This
effect will be less for chlorophenol and still less for bromophenol. In the case
of nitophenol both the inductive and resonance effects are observed.
Therefore, these phenols are highly acidic. 2,4,6-trinitophenol (picric acid) is a
stronger acid than phosphoric acid. In the case of nitophenols, if nito group is
ortho or para to hydroxyl group, it further contributes in negative charge
delocalisation as shown by following contributing structure on the right.
O O
+ +
- N - N -
O O O O
Delocalization of negative charge onto oxygen further

increase the resonance stabilization of phenoxide ion
Furthermore phenols, like alcohols, can be protonated by strong acids to give

the corresponding oxonium ions. Also, similar to alcohols, the hydroxy group
of phenols has amphoteric character. However, the basicity of phenols is even
less than that of the alcohols, because the lone electron pairs on the oxygen
are delocalised into benzene ring.
SAQ 6
4-Hydroxybenzaldehyde (p-hydroxybenzaldehyde) is more acidic (pKa = 7.3)
than phenol (pKa = 9.89). Explain.
16.5.2 Reactions of Phenols

In phenols, as mentioned earlier, the hydroxyl group is attached to an sp2
hybridised carbon of aromatic ring and the carbon oxygen bond of phenols has
considerable double bond character as evident from the resonance structures
shown for the delocalisation of lone pair of oxygen. Due to these factors, the
bond is shorter and stronger than a carbon oxygen single bond. As hydroxyl
group bonded to an aromatic ring is held tightly, therefore breaking up of the
C – O bond is very difficult. Consequently, the nucleophhilic substitution and
162
Unit 16 Phenols
elimination reactions so typical of an alcohol are generally not observed for a

phenol. Nucleophilic substitution on carbon atom of carbon oxygen bond is
also discouraged by the delocalisation of the positive charge created by more
electronegative oxygen over benzene ring.
This carbon is less positive than alcohol
d+ d
O
H
C-O bond is stonger than the alcohol
For example, hydrogen halides do not react at all with phenol and even
phosphorus pentachloride produces only a poor yield of chlorobenzene.
SN1 or SN2
R OH + HBr R Br + H 2O
Alcohol Alkyl bromide
Ar OH + HBr no reaction
Phenol
OH Cl
+ PCl5 + PCl3 + HCl
Very poor yield
Somehow hydroxyl group can be removed by distillation of phenol with Zinc

dust, but in this case again yield is very poor. Free radical mechanism is
involved in this reaction.
OH
+ Zn + ZnO
Phenols exhibit reactions mainly due to the phenolic hydroxy group and the
aromatic ring.
With this background, now let us study the reactions of phenols.
16.5.3 Reactions due to Phenolic Hydroxyl Group

i) Formation of phenoxides: We have already mentioned that phenols
are weak acids. They react with strong alkalis forming phenoxides and
water. This reactivity is in direct contrast to that of alcohols. We have
seen that alcohols form alkoxide only with strong bases like NaH and
metals like Na, K, Mg, etc.
- +
C 2H 5 OH + NaOH C 2H5 O Na + H 2 (not favoured)
Ehthanol Sodium ethoxide
pKa 15.9
- +
OH + NaOH O Na + H 2O (favoured)
Phenol pKa Sodium phenoxide

9.95.0
163
Carbonic acid is a stronger acid than phenol, therefore the equilibrium

Phenol is about 1 million for the reaction of phenol and bicarbonate ions lies far to the left.
times more acidic than
alcohols. However,
- +
phenol is not as strong OH + NaHCO 3 O Na + H 2CO3
an acid as carbonic acid
or a carboxylic acid. This Ehthanol Sodium Carbonic acid
Sodium phenoxide
affords a method for pKa 9.95 bicarbonate pKa 6.36
distinguishing phenol (weaker acid) (stronger acid)
from a carboxylic acid.
Phenol does not react Therefore, phenol does not react with an aqueous solution of sodium
with an aqueous solution bicarbonate, whereas carboxylic acid reacts to liberate carbon dioxide.
of sodium bicarbonate, - +
whereas carboxylic acid R COOH + NaHCO 3 R COO Na + CO2
reacts to liberate carbon
dioxide. The separation Again recall from earlier discussion that phenols are stronger acids than
of a mixture of phenol alcohols as the phenoxide ion is stabilised by resonance. No such
and a carboxylic acid is stabilisation is possible in the case of alkoxide ions.
based on the same
principle. ii) Alkylation: Similar to alcohols, phenols undergo reaction with alkyl
halide (Williamson ether synthesis) in presence of base.
OH O CH3
1. Aq. NaOH
+ H2O
2. CH3Br
Methyl phenyl ether

(anisole)
The reaction follows the SN2 mechanism

-
O OR
-
+ R X + X
iii) Esterification: Unlike alcohols, phenol reacts slowly with carboxylic

acids that we normally carry out its esterification with acyl halides (acid
halides) or acid anhydrides instead.
Phenols react with acyl halides or anhydrides in presence of a base such

as pyridine or NaOH to form esters. These reactions can be done under
milder conditions than those used for alcohols due to the greater acidity
of phenols as we have seen that phenols can be converted to phenoxide
ions with sodium hydroxide rather than very strong bases or metallic
sodium. It is important to note that phenoxide which formed in basic
reaction conditions is a better nucleophile than phenol. Thus, the
presence of base facilitates the ester formation.
O CH3
OH O
base C
+ C + HCl
H3C Cl O
Acetyl chloride Phenyl acetate
164
Unit 16 Phenols
O CH3
OH C
base + CH3COOH
+ (CH3CO)2O
O
Acetic anhydride Phenyl acetate
O
OH C O Ph
Cl 10% NaOH C
+ + HCl
O
Benzoyl chloride Phenyl benzoate
The reaction of phenols with benzoyl chloride in presence of 10 % NaOH is

known as Schotten-Baumann reaction. Unlike alcohols, esterification of
phenol does not occur with a carboxylic acid under acid catalyst as poor
availability of lone pairs of phenolic group for nucleophilic attack on the carbon
atom of carboxylic group.
Mechanism: Esterification of phenol is an example of nucleophilic acyl substitution

reaction.
Step 1: Fornation of phenoxide ion

- +
OH O Na
+ NaOH + H2O
Step 2: Phenoxide ion (as nucleophile) attacks on carbonyl carbon of acyl chloride
and replaces chloride ion (Addition elimination).
-
O O
C C
-
O R O R
O Cl
R
C O
+
Cl
iv) Reaction with Iron(III) Chloride: Phenols produce coloured complexes

when mixed with iron(III) chloride since phenols act as ligands in such
reactions. These reactions are often used as a test for phenols.
SAQ 7
Discuss the role of base in estrification reactions.
16.5.4 Reactions due to Aromatic Ring

As we mentioned earlier, the −OH group is a powerful activator in electrophilic
aromatic substitution reactions and directs substitution to the ortho and para
positions. Therefore, phenol is much more reactive towards electrophilic
substitution reactions than benzene. 165
i) Electrophilic aromatic substitution reaction: Phenol undergoes

electrophilic substitution quite readily. Sometimes phenolic group can be
too powerful activating group and it is difficult to control the reaction to
one substitution. For example, on shaking phenol with bromine water at
room temperature, 2,4,6-tribromophenol is formed:
OH OH
Br Br
2 + 3Br2 2
phenol Br
2,4,6-Tribromophenol
The activating power of phenolic group can be decreased by carrying
out reaction in less polar or nonplar solvents such as CHCl3, CCl4 or CS2
etc.. This is because, in more polar solvent such as water, phenol is

available mainly in the form of phenoxide ion (PhO ) which is more
reactive than Phenol. On the other hand, in less polar solvent, phenol
form dominates. Other way is by converting the phenol to ester that can
be removed by hydrolysis once electrophilic substitution has been
carried out. Since the ester is weak activating group and also bulky, it
will discourage ortho attack and para product will be the major product.
OH OH OH
Br
Br2
+
CHCl3 or CCl4 or CS2
Br
Base CH3COOCl O
O C
O CH3 OH
O CH3
1. NaOH
2. HCl
Br2
Br Br
Major product
Following resonating structures explain less reactivity of phenyl acetate

(acetoxybenzene):
+
O O
-
C O C O
Due to these resonating structures, oxygen electrons are less available to ring
On treatment with dilute nitric acid, phenol gives o- and p-nitrophenols.

Unlike nitration of benzene, there is no need of nitration mixture (conc.
166 HNO3 + H2SO4) because of high reactivity of phenol.
Unit 16 Phenols
OH OH OH
NO 2
298 K
+ HNO 3 +
(dil)
NO 2
Phenol 4-Nitrophenol 2-Nitrophenol
Phenol, when nitrated directly with concentrated nitric acid, undergoes

oxidation. For this reason, 2,4,6-trinitrophenol (picric acid) is obtained
through a synthesis that begins with chlorobenzene. The first product is
2,4-dinitrochlorobenzene, which is then easily hydrolysed to, 2,4-
dinitrophenol and the nitration continued to give picric acid in good yield.
Cl Cl
NO 2
H2SO4
+ 2HNO 3
(dil) 2H2O
NO 2
NaOH NaCl
OH OH
O 2N NO 2 NO 2
HNO3/ H2SO4
H2O
NO 2 NO 2
2,4,6-Trinitrophenol
(picric acid)
Phenol, when treated with sulphuric acid, yields both ortho and para
products,
OH OH OH
SO 3H
293 to 373 K
+ H2SO 4 +
(conc.)
2-Hydroxybenzene- SO 3H
sulphonic acid
4-Hydroxybenzene-
sulphonic acid
Phenol can easily undergo Friedel-Crafts alkylation or acylation.

Acylation products in presence of AlCl3 undergo Fries rearrangement.
OH OH OH
CH3
AlCl3
+ CH3Cl +
CH3 167
OH O C OH O OH
R
O C
AlCl3 Fries R
+ C +
R Cl 333 K rearrangement
D
C
O R
Similar to Friedel-Crafts acylation, acylation of phenol can also be
carried out with organic nitriles in presence of hydrogen chloride gas and
Lewis acid catalyst (e.g. ZnCl2, FeCl3, AlCl3 etc.). This reaction is known
as Hauben-Hoesch reaction. This reaction has been found to be very
useful with polyhydroxy phenol. In this reaction, phenol gives imine as
intermediate product which on hydrolysis gives aryl ketone.
OH HO H C OH O
3 + -
ZnCl2 NH 2 Cl C
+ CH3 C N CH3
HCl, 273 K H2O
HO HO HO
Imine 1-(2,4-dihyroxyphenyl)ethanone
ii) Reimer-Tiemann reaction: Phenols undergo the Reimer-Tiemann
reaction. In it an alkaline solution of phenol is heated with
trichloromethane (chloroform) and the product is acidified to give
2-hydroxybenzalohyde (salicylaldehyde).
OH OH
1. CHCl3/OH343 K
+
2. H /H2O
CHO
Phenol
2-Hydroxybenzaldehyde
(salicylaldehyde)
Mechanism: Reimer-Tiemann Reaction
Step 1: Formation of electrophilic dichloro carbene

: :
 
CHCl 3 + OH H2O + CCl 3 :CCl 2 + :Cl:
Dichlorocarbene
(electrophilic)
Step 2: Electrophilic addition of carbene to phenol.

+
O 
OH O
H CHCl2
H -
+ CCl2 CCl2
Phenoxide ion
intermediate
168 Step 3: Phenoxide formed in Step 2 reacts with strong base to form
Unit 16 Phenols
2-hydroxybenzaldehyde.
H
-  O
O H O O OH
C Cl C H C
- -Cl- H -
Cl + OH + Cl
Cl
iii) Kolbe reaction: On heating sodium or potassium phenoxide with carbon

dioxide and subsequent acidification, 2-hydroxybenzoic acid (salicyclic
acid) is formed. This is known as Kolbe reaction. In this reaction,
carbon of CO2 acts as an electrophile in aromatic substitution.

-
O Na
+ Od O OH
+ 323 K proton
+ Cd - transfer OH

O C
Od C
H
O
O
2-Hydroxybenzoic acid
(salicylic acid)
iv) Gattermann and Koch formylation: The introduction of a formyl group

into electronic rich aromatic rings by using CO/HCl/Lewis acid catalyst As HCN is very toxic
(AlCl3, AlBr3, FeCl3 etc.) is known as Gattermann-Koch formylation. Co- compound so R Adams
suggested modification
catalyst such as Cu2Cl2, TiCl4 or NiCl2 is needed to carry out reaction at
for the Gattermann
normal atmospheric pressure; however, no catalyst is needed at high synthesis. He generated
pressure (100-250 atm). HCN during reaction (in
situ) by the reaction of
Gattermann introduced a modification where HCN is mixed with HCl in Zn(CN)2 with HCl.
presence of ZnCl2 to formylate phenols. This modification is called the
Gattermann formylation or Gattermann synthesis. Formylation generally
occurs para to hyrooxyl groups. Both these reactions belong to the
category of electrophilic aromatic substitution.
Mechanism: Gattermann-Koch Formylation
Step 1: Formation of formylation

d
AlCl 3
- d+ +
O Cl - Cl O O
+ +
C H C C
H H
n
Step 2: Electrophilic substitution of formyl cation

O O
+
O C H C H
+
-H
+ C
+
HO H HO H HO
169
Gattermann Synthesis
Step 1: Formation of electrophilic [+CH=NH]
Zn(CN) 2 d d
ZnCl 2 ZnCl 2
HCl H
HCl +
H C N C N d+ HC NH
+ d+
Cl H
ZnCl 2
ZnCl 2
Step 2: Electrophilic substitution of [NC+=NH]
d
ZnCl 2 CH NH CH NH
+
+
-H
+ HC NH +
d+
HO HO H HO H
O
C H
H2O
D
HO
16.5.4 Oxidation of Phenols

Phenols are easily oxidised, but their products are often complex. The
The ability of
oxidation may occur with air alone (autoxidation) or with other oxidising
hydroquinone to
reduce silver ions to agents. The reaction of phenols with oxygen in the air is exploited industrially
silver metal is the by the use of phenol as antioxidants in gasoline, rubber and other products.
chemical basis of Phenols react with oxygen more readily than most other organic compounds
photography. and protect them from oxidation.
Hydroquinone is
developer fluid which OH O
reduces the light
activated silver ions at a mild
faster rate than the + H2O + H2O
condition
nonexposed silver ions.
In the fixing process
unreacted silver halide is O
converted into a water 1,4-Quinone
soluble silver complex of (1,4-benzoquinone)
sodium thiosulphate, and Hydroquinone and catechol are easily oxidised to quinones by mild oxidising agents
washed from film. The such as Ag+ of Fe3+.
result is the familiar
photographic negative. OH O OH O
OH O
[O] + [O] +
+ 2H + 2e + 2H + 2 e
[H] [H]
OH O
1,4-Benzenediol 1,4-Quinone 1,2-Benzenediol 1,2-Quinone
(hydroquinone) (1,4-benzoquinone) (catechol)
170
Unit 16 Phenols
16.5.5 Condensation Reactions

Condensation of phenols with phthalic anhydride in the presence of a
dehydrating agent gives a class of compounds known as phthaleins. These
are dyes.
By heating a mixture of phenol and phthalic anhydride in the presence of

concentrated sulphuric acid, phenolphthalein is formed:
O HO OH
OH
C
H2O
2 + O
C
O
O C
Phenol
O
Phenolphthalein (colourless)
Phenolphthalein is colourless in acidic medium. On addition of alkali, a pink

coloration develops due to the quinoid form. Addition of excess alkali
regenerates the benzenoid structure which is colourless. Phenolphthalein is
commonly used in the laboratory as a pH indicator. At pH below 8.5, the
molecule exists in colourless form and at pH~9 and above, in pink form.
Phenolphthalein as pH indicator
-
HO OH O O 
O
O
C C C
OH-
O
H+ - -
C CO2 CO2
O
Benzenoid (colourless) Quinoid (pink) exists
exist below pH 8.5 at pH~9 and above
The condensation of phenol with excess of methanal (formaldehyde) in the The electric resistance of
presence of dilute sodium hydroxide gives polymer which is known as Bakalite makes it
Bakelite. These are phenol methanol (phenol-formaldehyde) resins which are especially useful for
electric plugs, switches
three-dimensional polymer of the following possible structure: and tools.
OH OH
CH2 CH2
OH
OH
nHCHO + n
CH2 OH CH2 + H 2O
Methanal
Phenol CH2 CH2
OH OH
segment of Bakelite polymer
171
16.5.6 Coupling Reaction

Phenols couple with diazonium salts in alkaline conditions to form azo dyes.
This reaction follows electrophilic substitution mechanism.
+ - 1) NaOH
N2Cl + OH
2) H+/H2O
N N OH
16.5.7 Libermann’s Nitroso Reaction

Phenol reacts with sodium nitrite and concentrated sulphuric acid and forms a
green or blue coloured complex. This blue colour of complex changes to red
on dilution. The red colour of complex change to blue, if we change the acidic
medium to alkaline.
OH OH O
NaNO2/H2SO4
Phenol
+ NOH
OH NO
p-Nitrosophenol O
- H2O NaOH
HSO 4
N OH
N OH
Isophenol hydrogensulphate Indophenol

(green or blue) (red)
- +
O O Na
- + N O
N O Na
Sodium salt of indophenol
SAQ 8
Treatment of phenol with trichloromethane (chloroform) and aqueous sodium
hydroxide gives:
a) 2-chlorophenol b) 2-hydroxybenzaldehyde
c) 3-hydroxybenzaldehyde d) 3-chlorophenol
172
Unit 16 Phenols
SAQ 9
How will you bring about following conversions?
a) Phenol to phenyl benzoate b) Phenol to 4-hydroxybenzaldehyde
c) Phenol to 4-bromophenol d) Chlorobenzene to picric acid
16.6 SUMMARY
In this unit we have described the chemistry of phenols. We are summarising
below what we have studied:
 Phenols are polar compounds and the –OH group of phenols

participates in hydrogen bonding. Therefore, the boiling points and
melting points of phenols are higher than aryl halides.
 Phenols are obtained by the decarboxylation of phenolic acid, action of

water on diazonium salts and from Grignard reagent. They are prepared
on a commercial scale by catalytic oxidation of methylbenzene (toluene)
or decomposition of cumene pereoxide or from chlorobenzene by Dow
process. Phenols are also obtained from coal tar.
 Phenols are stronger acids than alcohols. They are easily converted to
phenoxide ions on treatment with aqueous sodium hydroxide.
 Electron releasing substituents attached to the ring, decrease acidity of

phenols. Strongly electron withdrawing groups such as –NO2 at ortho
and para positions increase the acidity many fold.
 The –OH group pf phenol is powerful activator substituent and

electrophilic aromatic substitution occurs readily in phenols.
 Phenol undergoes electrophilic substitution (nitration, halogenation,

Friedel-Crafts reaction, sulphonation, etc.) quite readily giving a mixture
ortho- and para-derivatives.
 On heating phenol with trichloromethane (chloroform) and potassium

hydroxide, 2-hydroxy benzaldehyde is obtained. On passing carbon
dioxide in a mixture of phenol and aq. sodium hydroxide, o-hydroxy
benzoic acid is formed.
 On condensation with phthalic anhydride in the presence of a

dehydrating agent, phenol gives phthalein dyes. With methanal, phenol
gives a polymer, Bakelite.

1. Name the following compounds:
OH OH
OH
a) b)
C2H5
OH NO 2 173
OH OH
CH3
c) d)
Cl
CHO F
2. Write chemical reaction for each of the following reactions.
a) Sodium salicylate + soda lime
b) Benzene + propene + AlCl3 + Heat
c) 1,2-Dichlorobenzene + NaOH + CuSO4 + Heat
d) Phenyldiazonium salt + H2O
3. Which compound in each of the following pairs is more acidic? Explain
a) Cyclohexanol or phenol;
b) 2,4-Dinitophenol or 3,5-dinitophenol;
c) p-Nitrophenol or m-nitrophenol;
d) 4-Hyroxybenzaldehyde or phenol.
4. Write the mechanism of the formation of salicylic acid from phenol.
5. How will you bring about following conversions?
a) Phenol to anisol
b) 1,4-Benzenediol to 1,4-quinone
c) Phenol to monosubstituted bromophenol
d) 1,3,5-benzenetriol to 1-(2,4,6-trihydroxyphenyl)ethanone
e) Phenyl acetate to 1-(2-hyroxyphenyl)ethanone.
6. Identify compounds A to C in the synthetic sequence given below:

NaOH
i) Phenol + CH3COCl A
ii) A + Br2 B
∆
iii) B + HCl C
7. Write all the steps involved in following reaction:

OH
CO/HCl/AlCl3
8. How will you test the presence of phenolic group?
9. Outline a reasonable preparation route of following:
a) 2,4,6-Trinitophenol from chlorobenzene
174 b) 4-Nitrophenyl phenyl ether from chlorobezene and phenol.

Unit 16 Phenols
16.8 ANSWERS
1. i) 3-Methyl benzenol (m-cresol)
ii) 3-Hyroxybenzaldehyde (m-hyroxybenzaldehyde)
iii) 4-Hydroxy-3-methylbenzoic acid
iv) 2-Hydroxy-3-methoxybenzoic acid
v) 2-Fluoro-4-hyroxybenzoic acid
2. Two factors are mainly responsible for this, These are
i) C-O bond is formed by the overlapping of sp2 orbital of carbon of

benzene ring which has more s character and sp3 of oxygen atom.
ii) The lone pairs on the oxygen atom on phenol can overlap with the
delocalised ring system of benzene.
3. In case of o-flurophenol, fluorine atom is more electronegative than

hydrogen atom of hydroxyl group attached to aromatic ring. This leads to
intra-molecular hydrogen bonding within a single molecule. On the other
hand, p-flurophenol has intermolecular hydrogen bonding. Therefore,
o-flurophenol has lower melting point than p-flurophenol.
SO3H OH
4. 1. NaOH/573 K
a)
2. H+/H2O
+ -
N2 Cl OH
H2O
b)
CH(CH3)2 OH
1. O2
c)
2. H2SO4
Cl OH
1. NaOH/CuSO4
d)
2. H+/H2O
- +
SO3H SO Na
H2SO4 NaOH
5. a) NaOH
573 K
ONa OH
H+/H2O
+ -
NH2 N2 Cl OH
b) HCl H2O
+ NaNO 2
-N2
175
C6H5MgBr
c) C6H5MgBr + O2 C6H5 O O MgBr
OH
H+/H2O
2 C 6 H5 O MgBr + 2Mg(OH)Br
Cl OH
d) 473 K
+ 2NaOH + NaCl
Pressure, CuSO4
6. Similar to nitro group, aldehyde group contributes in delocalisation of

negative charge of phenoxide ion.
O O
C C -
H O H O
7. Base is used as a catalyst to increase nucleophilicity by converting the

nucleophile to an anion nucleophile. In case of phenols, the phenoxide
ion is better nucleophile than unionised phenol.
8. 2-Hyroxybenzaldehyde
O
OH O Ph
Cl 10% NaOH C
9. a) + + HCl
O
Benzoyl chloride Phenyl benzoate
OH OH
CO/HCl/AlCl3
b) or
or HCN/HCl/ZnCl2
CHO
OH O C OH O OH
H
O C
AlCl3 Fries H
+ C +
H Cl rearrangement
333 K
D
C
O H
c) See sub-section 16.5.4.
d) See sub-section 16.5.4.

176
Unit 16 Phenols
Terminal Questions
a a) 1,2,4-Benzenetriol; c) 2-Ethyl-4-nitophenol;
c) 3-Methyl-4-hyroxybenzaldehyde; d) 3-Chloro-4-fluorophenol.
2. OH OH
a) 2NaOH(CaOH)
+ + Na 2CO3
D
COONa
b) CH3
AlCl3 CH3
+ H2C CHCH3
D
c) Cl OH
473 K
+ 2NaOH + 2NaCl
Pressure, CuSO4
Cl OH
d) N
+
NCl
-
OH
H2O
+ N2 + HCl
3. a) Phenol; b) 2,4-Dinitophenol; c) p-Nitrophenol; d) 4-Hydroxybenzaldehyde

Explanation: Electron withdrawing group substituents increases the acidity of phenol,
if such groups are at ortho and para to hydroxyl group this effect is more
pronounced.
4. See page 169, Kolbe reaction.
OH OCH3
aq. NaOH
5. a) + CH3I
COONa
OH O
+ 3+ [O]
b) + Ag or Fe
HO O
OH OH OH
Non polar Solvent
c) + Br2 +
such as CS2, CCl4
Br Br
HO OH 1. ZnCl2//HCl, 273
HO OH
d) + N CHCH3
2. H2O CH3
OH OH O
O AlCl3 OH OH
e) +
O D
O O
177
O O OH
6. A = B= C=
O O
Br Br
7. Step 1: Formation of formulation
d
AlCl 3
- d+
+
O Cl - Cl O O
+ +
C H C C
H H
n
Step 2: Electrophilic substitution of formyl cation
O O
+
O C H C H
+
-H
+ C
+
HO H HO H HO
8. a) FeCl3 solution test; b) Libermann’s nitroso reaction

9. a) Cl Cl
NO 2
H2SO4
+ 2HNO 3
(dil) 2H2O
NO 2
NaOH NaCl
OH OH
O 2N NO 2 NO 2
HNO3/ H2SO4
H2O
NO 2 NO 2
2,4,6-Trinitrophenol
(picric acid)
Cl
Cl
Phenol
b)
+ 2HNO 3/H2SO4
NaOH
O Ph
NO 2
NO 2
178
Unit 17 Ethers
UNIT 17
ETHERS
Structure
17.1 Introduction Physical Properties
Expected Learning Outcomes Reactions of Open Chain Ethers
17.2 Classification Reactions of Epoxides
17.3 Preparation of Ethers 17.5 Crown Ethers and Cryptands

Preparation of Open Chain 17.6 Industrial Uses
Ethers
17.7 Summary
Preparation of Epoxides
17.4 Properties of Ethers
17.9 Answers
17.1 INTRODUCTION
In the previous Unit 15, while discussing the chemistry of alcohols, it was The Nobel Prize for
pointed out that mono alkyl derivatives of water are called alcohols and dialkyl Chemistry in 1987 was
derivatives of water are called ethers. In this unit, we will study the chemistry given to Charles J.
of ethers in detail. Pedersen, Donald J.
Cramand Jean-Marie
In this unit, we first discuss the structure and classification of ethers. Then, we Lehn, for their efforts in
will study the preparations, physical properties and chemical properties of both discovering and
open chain ethers and a group of cyclic ethers, called epoxides. We shall also determining uses of
crown ethers and
touch on a special group of macrocyclic (large ring) compounds, called crown
cryptands, thus
ethers and cryptands.
launching the new
growing field of
Expected Learning Outcomes Supramolecular
Chemistry.
 list different types of ethers such as open chain ethers, epoxides, crown
ethers and cryptands;
 outline the preparation of open chain ethers and epoxides;
 explain the physical properties of ethers;
 describe the chemical properties of open chain ethers and epoxides;

179
 describe the crown ethers and cryptands; and
 state the industrial uses of ethers and related compounds.
17.2 CLASSIFICATION
Like water and alcohols, ether molecule contains asp3hybridised oxygen atom,
which is bonded to two carbon atoms. Fig. 17.1 shows the structure of
dimethyl ether [CH3OCH3] also with its ball-stick model. In this molecule, two
sp3hybrid orbitals of oxygen form two σ bonds with the two carbon atoms.
Similar to water molecule the other two sp3 hybrid orbitals of oxygen each
contain an unshared pair of electrons. The C−O−C bond angle in dimethyl
ether is 110.3, a value close to the tetrahedral angle of 109.5.
O 
H H
H 110o H
H H
Bent molecular gemetry
Oxygen is sp3 hybridised
Tetrahedral angle
Fig. 17.1: Structure of dimethyl ether along with its Ball-and-Stick model. Here μ
represents net dipole moment in the molecule.
The groups bonded to the ether oxygen can be alkyl, aryl, ethenyl or any other
carbon containing group. Aliphatic ethers may be simple or symmetrical in
which both the alkyl groups are the same or mixed i.e. unsymmetrical in which
the two alkyl groups are different. Just to recall, in IUPAC system of
nomenclature, ethers are named by selecting the longer carbon chain as the
parent alkane and namely the −OR group bonded to it as an alkoxy group.
Common name are derived by listing the alkyl group bonded to oxygen in
alphabetical order and adding the word ether. Now consider few examples of
simple ethers (name given in brackets are common names):
CH3
CH3CH2 O CH2CH3 CH3 O C CH3
CH3
Ethoxyethane 2-Methoxy-2-methylpropane
(Diethyl ether) (t-Butylmethyl ether)
Simple Ether Mixed Ether
O
CH3 CH3CH2 O CH2 CH2 OH
2-Ethoxyethanol
Methoxycyclohexane
O
CH3
CH3CH2 O CH CH2
Ethoxyethene
Methoxybenzene
(Anisole)
180
Unit 17 Ethers
Ethers can be either open chain or cyclic. When the ring size (including the
oxygen atom) is five or greater, the chemistry of the cyclic ether is similar to
that of an open chain ethers. Three membered cyclic ethers are called
oxiranes (IUPAC name), which are often known as epoxides. Because of
Baeyer strain associated with small rings, epoxides are more reactive than
other ethers.
O O
O
O
Oxirane Oxolane 1,4-Dioxane
(Ethylene oxide) (Tetrahydrofuran, THF)
Large ring system with repeating −OCH2CH2 – units are called crown ethers.
They are macro-monocyclic polyethers. These compounds are valuable
reagents which can be used to help dissolve inorganic salts in organic
solvents. Crown ethers are named as x-crown-y; where x is the total number
of atoms in the ring and y is the total number of oxygen atom in the ring. For
example,
O
O O
O O
O
18-Crown-6
A crown ether with a total number of 18 atoms and 6 oxygen atoms in the ring
There is another class of compounds, similar to crown ethers, called

cryptands. These are macro-polycyclic polymers having additional bridge(s).
These compounds show higher complexing ability and selectivity towards a
variety of metal ions in comparison with crown ethers. In the example of
cryptand [2.2.2.] given below, the numbers in the brackets indicate the
numbers of ether oxygen atoms in the chains between the bridgehead
nitrogen atoms.
O O
N O N
O
O O
Cryptands [2.2.2]
Ethers occur widely in nature, some examples of naturally occurring ethers

are:
OH OCH3
OCH3
O CH3
OH
H2C CH CH2 HC CH CH3

Guaicol
(Beech-wood tar) Eugenol Anethol (Aniseed oil)
(Oil of cloves) 181
O OH
O OCH3
H2C CH CH2 CHO

Safrole Vanilla
(Camphol oil) (Vanilla beans)
SAQ 1
Write IUPAC and common names for the following ethers:
a) CH3 b) CH3 CH2 O CH CH CH3

CH3CH2 O CH3
CH3
c) O d) O
CH2CH3
17.3 PREPARATION OF ETHERS

In this section, we will discuss the preparation of open chain ethers and
epoxides.
17.3.1 Preparation of Open Chain Ethers

Ethers are commonly prepared from alcohols. There are two methods:
i) Acid catalysed dehydration
ii) Nucleophilic displacement (Williamson ether synthesis)
i) Acid Catalysed Dehydration
In precious Unit 15, we have described the conversion of alcohols to alkenes

in the presence of sulphuric acid. When an alcohol is reacted with H2SO4, a
series of reversible reactions occur under different reaction conditions. Which
reaction product predominates depends on the structure of the alcohol, the
relative concentration of reactants, and temperature of the reaction mixture.
273 K ROSO2OH + ROSO2OR + H2O
413 K
R OH + H2SO4 R O R + H2O
Primary alcohol 443 K
Alkene + H2O
As shown above, primary alcohols give alkyl hydrogen sulphate and

dialkylsulphate at low temperatures, symmetrical ethers at moderate
temperature and alkenes at high temperature.
182
Unit 17 Ethers
In case of secondary alcohols, yields of ethers are lower because of

competition from acid-catalysed dehydration. In case of tertiary alcohols,
dehydration to an alkene is the only reaction.
Diethyl ether is synthesised on an industrial scale by the acid-catalysed

dehydration of ethanol.
H2SO4
2CH3CH2OH CH3CH2OCH2CH3 + H2O
413 K
Reaction Mechanism: Acid-catalysed dehydration of ethanol:
It follows the SN2 mechanism. Detailed steps are as follows:
Step 1: Acid converts −OH, a poor leaving group into − OH2 a better leaving
group
O O
fast + -
CH3 CH2 O H + H O S OH CH3 CH2 O H + O S OH
O H O
An oxonium ion
Step 2: The protonated ethanol is attacked by another molecule of ethanol

(nucleophile) in an SN2 process, thus, displacing H2O.
SN2 +
+
CH3 CH2 O H + H3C CH2 O H CH3 CH2 O CH2 CH3 + H2O
H H
An oxonium ion
Step 3: Deprotonation
H
+ Proton transfer +
CH3 CH2 O CH2 CH3 + O H CH3 CH2 O CH2 CH3 + H3O
Notice that a proton is used in the first step of the mechanism and then
another proton is liberated in the last step of the mechanism. Therefore, in this
reaction, the acids behave as a catalyst.
ii) Williamson Ether Synthesis
Ethers are also prepared by Williamson ether synthesis. This method is the
most common general method for the preparation of ethers. This process is
named after Alexander Williamson, a British scientist who first demonstrated
this method in 1850 as a method of preparing diethyl ether. This method
involves nucleophilic displacement of halide ion or other good leaving group by
an alkoxide ion (SN2 mechanism). If alcohols are starting material, one alcohol
preferable primary alcohol is converted to alkyl halide (R−X), another alcohol
is converted to alkoxide, using strong base such as sodium hydride (NaH),
and then, the two products are heated together.
NaH R Cl
R OH R ONa R O R + Na +X-
DMF SN2
183
Mechanism: Williamson Ether Synthesis: This is a two step reaction.
Step 1: Hydride ion function as a base and deprotonates the alcohol.
Na+H- -
R O H R O Na+
DMF
Step 2: The resulting alkoxide ion then functions as nucleophile and attacks
the electrophilic carbon centre of alkyl halide and displacing halide ion.
SN2
R O Na- + + R X R O R + Na + X -
As mentioned earlier, because of steric effect, the tendency for alkyl halide to
undergo SN2 reaction is primary>sec>tert. Therefore, this process works best
with methyl or primary alkyl halides. Secondary alkyl halides are less efficient
because elimination is favoured over substitution and tertiary alkyl cannot be
used. This limitation must be kept in mind while designing a synthesis of
MTBE was used to ethers. For example consider the synthesis of tert-butylmethyl ether which is
improve octane rating of also known as methyl-tert-butyl ether (MTBE). There can be two possible
gasoline until it was
routes, one by the reaction of butyl alcohol and bromomethane or other by the
observed the MTBE
might contribute to reaction of methanol with 2-bromo-2-methylpropane (tert-butyl bromide). The
ground water first route is efficient because it takes place through a primary alkyl halide i.e.
contamination. bromomethane; which is suitable for SN2 reaction. On the other hand; the
second route does not work because it employs a tertiary alkyl halide which
will undergo elimination reaction (E2) rather than substitution.
Route 1:
CH3 CH3
(1) Na+H-/DMF
CH3 C OH CH3 C O CH3
(2) CH3Br
CH3 CH3
2-Methoxy-2-methylpropane
(tert-butylmethyl ether)
Route 2:
CH3
(1) Na+H-/DMF + -
CH3 OH CH3 C CH2 + CH3 OH + Na Br
(2) (CH3)3CBr
2-methylpropene
This method can also be used to prepare phenolic ethers.

OH O
(1) Na+H-/DMF CH3 -
+ Na+ Br
(2) CH3Br
Methoxybenzen(Anisole)
If you wish to prepare methoxybenzene by the reaction of methanol and

chlorobenezene in presence of strong base; this reaction does not work.
Because the chlorine atom in chlorobenezene is attached to sp2 carbon and
184 SN2 process does not occur at sp2-hybridised centre.
Unit 17 Ethers
Ethers can also be prepared by the reaction of alcohols with alkenes. Recall
the oxymercuration-demercuration reaction of alkenes. If alcohol is used in
place of water, the final product is ether which is result of the addition of
alcohol across the alkene. This addition reaction follows Markovnikov
mechanism.
OR
(1) Hg(OAc)2, ROH
H3C CH CH2 H3C CH CH3
(2) NaBH4
Similar to above reaction, alcohol can also be added to alkenes in the

presence of acid to give ethers.
CH3
H3O+
CH3 CH CH2 + CH3 OH CH3 C O CH3
H
Mechanism: Acid catalyzed addition of an alcohol to an alkene.
This reaction follows SN1 mechanism.
Step 1: Proton transfer from the acid to the alkene gives a carbocation
intermediate.
+
+
H3C CH CH2 + H O CH3 CH3 CH CH3 + HO CH3
H
Protonated metanol Carbocation
Step 2: Reaction of the carbocation intermediate (an electrophile) with the

alcohol (a nucleophile) gives an oxonium ion.
H + CH3
O
+
H3C CH CH3 + HO CH3 CH3 C CH3
H
Step 3: Proton transfer to solvent
H3C + H
O OCH3
+
CH3 C CH3 + O CH3 CH3 C CH3 + CH3 OH2
H H H
This method is used for the industrial production of MTBE. This method is only
suitable for the reactions of alkenes which can produce stable carbocations
with methanol or primary alcohols.
SAQ 2
Show the reagents that can best be used to prepare following ethers by
Williamson ether synthesis:
a) CH3CH2 O Ph b) OCH3
H3C
CH3
185
17.3.2 Preparation of Epoxides

Epoxides are obtained by the reaction of alkenes with peracids. This is most
common method for synthesis of epoxides. Among per acids meta-
chloroperoxybenezoic acid (MCPBA) is the most commonly used per acid.
O
C H
OOH CH Cl COOH
2 2
+ O +
H
Cl
Cl
Cyclohexene meta-chloroperoxybenzoic 1,2-Epoxycyclohexane
acoid (MCPBA) (cyclohexene oxide)
This reaction is stereo specific (not entioselective); that is, the cis alkene give
cis epoxides and trans alkene give trans epoxides.
H O O
H H H H3C CH3
MCPBA
C C
H3C
+ H H
CH3 CH3
H3C
cis-2-Butene cis-2,3-Dimethyloxirane
(a pair of enantiomers)
H O O
CH3 H CH3 H3C H
MCPBA
C C +
H3C H H CH3
H3C H
tans-2-Butene tans-2,3-Dimethyloxirane
(a pair of enantiomers)
Mechanism: Epoxidation of an alkene by peracids.
In this reaction, bond-making and band-breaking steps are taking place

simultaneously i.e. in concerted way.
R' R'
O C
HO C
H O
O
O
H O
H H H
R R R R
Industrial preparation of oxirane (ethylene oxide) is carried out by passing a

mixture of ethylene and air (or oxygen) over a silver catalyst.
O
Ag 2
2 H2C CH2 + O2 H2C CH2
Oxirane
(ethylenew oxide)
This method only works for the production of oxirane from ethylene. There are
186 other methods also by which, we can prepare epoxides. In the previous Unit
Unit 17 Ethers
15, we have seen that alkenes can be converted to halohydrins when they are
treated with halogens in presence of water.
Br2/H2O OH
+ Enantiomer
Br
The halohydrin obtained from above reaction can be converted into epoxides
upon treatment with a strong base.
OH
NaOH
O
Br
This reaction follows intra molecular SN2 mechanism.
Mechanism: Epoxide formation from halohydrin.
Step 1: Hydroxide ion or other base abstract a proton from the hydroxyl group
of halohydrin to form an alkoxide ion.
-
O OH -
H O
+ H2O
Br Br
Step 2: Alkoxide ion formed in Step 1, functions as a nucleophile in an

intramolecular SN2 reaction, removing the halide as a leaving group.
-
O
-
O
O + Br-
Br
Br
As with all SN2 reactions, attack of the nucleophile is from the back side of the
C – X bond and causing inversion of configuration at the site of substitution.
The stereochemical outcome of this conversion is the same as the reaction of

peracids with alkene. That is, substituents that are cis to each other in the
starting alkene remain cis to each other in the epoxide; and similarly
substituents that are trans to each other in the starting alkene remain trans to
each other in the epoxide.
peracid
H H O O
H H R R
C C +
R R (1) Br2/H2O R R H H
(2) NaOH
187
Both the conversion routes provide a racemic mixture. In recent past,

Prof. Barry Sharpless developed a catalyst for the asymmetric
(stereoselective) epoxidation of allylic alcohols. The Sharpless’ catalyst
consists of titanium tetraisopropoxide [Ti(O-iPr)4], and pure enantiomer of
diethyl tartrate [(+) or () DET].
CH3 OH
CH3 CH3 COOC2H5
CH3 O H5C2OOC
O Ti O HO (2S,3S)-(-)-Diethyl tartrate
CH3 + (-) DET
O
H3C H3C OH
CH3 COOC2H5
H5C2OOC
Titanium tetraisopropoxide HO (2R,3R)-(+)-Diethyl tartrate
(+) DET
In the presence of any one of the above chiral catalyst, an oxidising agent
such as tert-butylhydroperoxide converts an allylic alcohol to enantioselective
epoxide. The stereochemical outcome of the reaction depends on whether the
chiral catalyst used was (+) DET or (–) DET.
In Fig.17.2, we have shown that how oxygen is delivered to either the top face
or the bottom face of the alkene, depending on which enantiomer of diethyl
tartrate is used.
With(-)DET, oxygen is
delivered from the top face
O OH
3
3 R
R OH 1
R
2 R
2 3
R R
R
1
R
2
1
OH
R
O
With(+)DET, oxygen is
delivered from the bottom face
Fig. 17.1: Sharpless asymmetric Epoxidation.
Sharpless along with William Knowles and Ryoji Noyori received the 2001
Noble Prize in Chemistry for their pioneering work in the field of asymmetric
synthesis.
SAQ 3
Explain why the following reaction is not preferred for the preparation of ether.
H2SO4
H3C OH + H3C OH
188
Unit 17 Ethers
SAQ 4
Predict the major product of these reactions:
warm
a) CH3CH2OH + H2SO4
413
b) CH3CH2ONa + Br
c) CH3ONa + (CH3)3CCl
d) ONa + CH3CH2Br
17.4 PROPERTIES OF ETHERS

Before studying the reactions of open chain ethers and epoxides in detail, let
us first understand their physical properties.
17.4.1 Physical Properties

As discussed earlier, the geometry of the oxygen atom in ethers is similar to
water and alcohols. Oxygen atom is sp3 hybrised and the orbitals are arranged
in a tetrahedral shape. Thus, similar to water and alcohols, due to the high
electronegativity of oxygen atom, ethers are polar compounds with dipole
moment 3.9  1030 C m for diethyl ether. But they are not as polar as water,
6.0  1030 C m and alcohols, 5.7  1030 C m (for methanol). Because of the
weak dipole – dipole interactions, ethers have lower building points as
compared to those of alcohols containing the same number of carbon atoms
and are close to those of hydrocarbons of having comparable carbon
numbers. Another factor which also influences the boiling points of compounds
is intermolecular hydrogen bonding, which is present in case of alcohols and
not feasible in case of ethers because they do not have hydrogen attached to Only very weak
dipole-dople interaction
the oxygen and thus they cannot function as hydrogen bond donors. H H
d
H d O H
d H
 
 d d
CH3CH2OH CH3 O CH3 CH3CH2CH3 O
H H d H
H H
Boiling point Ethanol Dimethyl ether Propane H
H
352 K 249 K 273 K
Steric factor further
weaken the dipole-dipole
As ethers cannot act as hydrogen bond donors they are much less soluble in interaction
water than alcohols. However, they can act as hydrogen bond acceptors,
which make them more soluble in water than hydrocarbons.
CH3
d
d d d
O ------ H O
d
d
H -------
CH3
189
We are summarizing the physical properties of some of ethers in Table 17.1.

For the comparison, boiling points of some alcohols are also given.
Table 17.1: Physical properties of some ethers
3
Name Formula Bp,K Solubility in H2O Density kg/dm
Diethyl ether CH3OCH3 249 Miscible Gas
Ethanol CH3CH2OH 351 (Highly soluble) 0.79

3
Diethyl ether C2H5OC2H5 307.6 8 g/100 cm 0.71
3
1-Butanol CH3(CH2)2CH2OH 380 8.3 g/100 cm 0.81
Methyl phenyl C6H5−O−CH3 427

ether (anisole)
Tetra hydro 339 Miscible 0.89

O
furan (THF)
Oxirane O 286.5 Miscible 8.88 (at 283 K)
Before studying the reactions of ethers, try following SAQ.
SAQ 5
To what effect can you attribute for water solubility of ethers?
17.4.2 Reactions of Open Chain Ethers

Ethers are quite unreactive and behave more like alkanes than like organic
compounds containing functional groups. As a result, they are ideal choice as
solvent for many reactions. The bond between carbon and oxygen in ether is
called the ether linkage. This ether linkage is not affected by even strong
bases, oxidising agents such as potassium dichromate or potassium
permanganate. However, due to the presence of highly electronegative
oxygen atom in ether, the carbon atoms bonded to oxygen behave as
electrophilic centres at which nucleophilic reaction can occur.
d
H d O d H
C C
H H
H H
Further due to the presence of lone pair on oxygen, ethers behave as Lewis
bases (electron-pair donors). Therefore, with strong acids, ethers give
oxonium salts:
H
+
+ H HSO -4
+
R O R O HSO 4-
CH3 CH3
190 Oxonium salt
Unit 17 Ethers
The solubility of ethers in sulphuric acid is, thus, a convenient method for
distinguishing between ethers and hydrocarbons and alkyl halides. Similarly,
ethers react with Lewis acid to form Lewis complexes.
R R
+ -
O + BF3 O BF3
R R
Further, this Lewis complex treatment with alkyl fluoride gives a tertiary
oxonium salt, trialkyloxoniumtetrafluoroborate.
+ - + -
R2O BF3 + RF R3O BF4
The product of above reaction i.e. the, trialkyloxoniumtetrafluoroborates are

powerful alkylating agents in many reactions.
As shown above, ethers have two electrophilic centres. Therefore, ethers may
undergo nucleophilic substitutive reaction. But in the case of ethers,
nucleophilic substitution reaction can only be possible with a reagent that can
react first with the oxygen atom of ether to form a good leaving group and then
also provide a good nucleophile to displace it. The strong acids such as HBr
and HI fulfill these criteria. In such reactions, cleavage of the ether linkage (C If the ether is
– O) takes place. These reactions are called acidic cleavage reaction of unsymmetrical, the
nucleophile prefers to
ethers. attack on less hindered
electrophilic carbon
1. Acidic Cleavage centre of ether. Recall
the order of reactivity of
Ethers are cleared using hot, aqueous hydrobromic acid (48%) or hydroiodic SN2 reactions:
acid (57%). For example diethyl ether reacts with hot concentrated HBr to give
two molecules of bromoethane. CH3 > primary > Sec >
tert
heat
CH3CH2–O–CH2CH3 + 2HBr 2CH3CH2Br + H2O
Mechanism: Acid cleavage of ethers:

Step 1: Protonation of ether molecule leads to formation of a good leaving
group.
+
CH3CH2 O CH2CH3 + H3O
+ H3CCH2 O CH2CH3 + H2O
H
An oxonium ion
(protonated ether)
Step 2: Nucleophilic substitution reaction (SN2): A bromide ion (Br-) functions

as a nucleophile and attacks at electrophilic centre of oxonium ion by
displacing an alcohol as a leaving group.
.. +
- + CH3CH2 O CH2CH3 CH3CH2 Br + HO CH2CH3
Br
H
191
This cleavage produces one molecule of bromoethane and one molecule of

ethanol. In presence of excess concentrated HBr, ethanol is converted into
second molecule of bromoethane by another SN2 reaction:
-
+ Br
+ CH3CH2 O H CH3CH2 Br + H2O
CH3CH2 OH + H3O
- H 2O H
The acid cleavage of dialkyl ethers depends on the nature of the carbon
bonded to oxygen. If both carbons are primary, cleavage involves an SN2
mechanism as illustrated above. Otherwise cleavage is by an SN1 mechanism.
For example, tertiary butyl ethers, allylic and benzylic ethers follow SN1
mechanism. These ethers require much milder reaction conditions. For
example 2-ethoxy-2-methylpropane after protonation, cleaves to produce
stable tert-carbocation.
CH3 CH3
-
H+ Br + -
H3C C O CH2CH3 H3C C O CH2CH3 + Br
CH3 CH3 H
The Zeisel procedure of
estimation of the number SN1
of methoxyl (CH3O ) or
ethoxyl (C2H5O ) groups CH3 - CH3
Br
in alkyl and aryl ethers is +
H3C C Br H3C C + HO CH2CH3
based on acid cleavage
reactions of ethers. This CH3 CH3
method consists of ether tert-carbocation
cleavage with excess of
HI, followed by distillation Finally, the reaction of carboction with nucleophile completes the reaction.
of volatile iodomethane
or iodoethane from the Acid cleavage reactions have great importance in synthetic chemistry. The
reaction mixture. Then, hydroxyl group in a poly functional compound can be protected by converting it
the iodoalkenes are
into ether and later, after completion of a chemical transformation, the
treated with an ethanolic
solution of silver nitrate molecule can be regenerated after treatment with concentrate dhydroiodic
and the silver iodide so acid. As HBr and HI are strong acids, therefore, we generally prefer mild
formed is weighed. reagents such as iodotrimethylsilane or trimethylsilyl iodide (TMSI)[(CH3)3SiI]
for ether cleavage. In first step, it reacts with ether and converts ether oxygen
atom to a good leaving group.
−
R CH3 CH3
CH3
+ R O Si CH3
R O + H3C Si I O Si CH3
Both HI and HBr can be CH3 R CH3 CH3 + R I
R
-
used to cleave ethers. Trimethylsilyl iodide I An alkyltrimethylsilyl ether
HCl is less efficient and (TMSI)
HF does not cause
cleavage of ether. The Alcohol can be obtained by the hydrolysis of alkylmethylsillyl ether.
reactivity is a result of
the relative CH3 CH3
CH3
nucleophilicity of the
halide ions. 2R O Si CH3 + H2O 2R OH + CH3 Si O Si CH3
CH3 CH3 CH3
192
Unit 17 Ethers
Aromatic ethers, such as anisole, yield the alkyl halide and phenol, not
halobenezene and alcohol. This is because; sp2-hybridised carbon does not
undergo reaction by an SN2 or SN1 path.
sp2 carbon
O OH
CH3 273 K
+ HI + CH3I
Anisole HI
No reaction
SAQ 6
Account for the fact that following reaction gives CH3I and (CH3)2CHOH as the
initial major product rather than CH3OH and (CH3)2CHOI.
HI
CH3 CH O CH3 CH3 CH OH + H3C I
CH3 CH3
SAQ 7
Write detail mechanism pathway for the following reactions:
a) H3C + HBr
H3C O
b) O OH
HI
c) O CH3
HI
CH3
CH3
2. Autoxidation of Ethers
Ethers undergo autoxidation in the presence of atmospheric oxygen to form

hydroperoxides:
O OH
O2
CH3CH2 O CH2CH3 CH3CH2 O CH CH3
slow A hydroperoxide
This process takes place via a free radical mechanism. The oxidised product,
hydroperoxides decompose violently when heated. The presence of
hydroperoxidein ether may cause laboratory explosion when ether is distilled
for the purification. Therefore, it is important to know the concentration of
hydroperoxide before distillation. To prevent the formation of peroxides, some 193
ethanol or a small amount of cuprous compound, e.g., cuprous oxide is added.

It is also advised that never use ethers past their expiration date.
17.4.3 Reactions of Epoxides

It has been stated earlier that because of the strain associated with three-
membered ring, epoxides are highly reactive compounds,. The characteristic
reaction of epoxides is nucleophilic substitution reaction. In this reaction, ring
opening takes place which can be initiated either by acid (acid-catalysed ring
opening) or by nucleophile (nucleophilic ring opening). The general reaction
An epoxide ring cannot
have normal sp bond
3 can be written as:
o
angles of 109 ; instead,
HO H
the inter nuclear angles O H+
H
o
are about 60 , a H + HNu
H
C R
geometric requirement of R
R R Nu
the three membered ring.
The orbitals forming the
Characteristic reaction of epoxides
ring bonds are incapable
of maximum overlap. Acid-catalysed Opening
Therefore, epoxide ring
are - strained. The Like other ethers, epoxides undergo carbon-oxygen bond cleavage when
polarity of the C−O bond, treated with an acid. However, because of their high reactivity much milder
along with the ring strain,
acidic conditions are employed than for cleavage of open chain ethers. For
contributes to the high
reactivity of epoxides
example, acid-catalysed ring opening of oxirane gives 1, 2-ethane diol
compared to the (ethylene glycol) when treated with aqueous sulphuric acid.
reactivity of other ethers. O +
d + H3O HOCH2CH2OH
O
d d
H2C CH2 Mechanism: Acid-catalysed hydrolysis of an expoxide
sp3 carbon polar Step 1: Protonation: Proton is transferred from the acid to oxygen of the
and strained
epoxide to give bridged oxonium ion intermediate
H
+
O + O
H O H + H2 O
Step 2: Ring Opening: Nucleophile attacks from back side on a bridged

oxonium ion and open the three membered ring.
H H OH
+ SN2
O O H H2C CH2
+
+
O
H H
Step 3: Proton Transfer: In this final step proton is transferred to solvent.
OH OH
+
H2C CH2 H2C CH2 + H3 O
+ H O H OH
O
H H
194
Unit 17 Ethers
In these reactions, the attack of the nucleophile is anti to the bridge oxonium
ion. Thus, the stereochemistry of acid-catalysed ring opening is SN2 like.
+ OH OH
H 3O
O +
OH OH
1,2-Epoxy cyclohexane trans-1,2-Cyclohexanediol

(Racemic mixture)
But regiochemistry of these reactions depends on the nature of the epoxides.
For example, if one side is primary and other side is secondary, the
nucleophile will attack on the less hindered primary position following
predominantly SN2 mechanism. On the other hand, if one side of the epoxides
is a tertiary the nucleophile with attack on more substituted tertiary position
rather on the primary following predominantly SN1 process.
OH Cl
HCl/ether
O H3C CH CH2 + H3C CH CH2
H3C SN2 Cl OH
1,2-Epoxypropane 1-Chloro-2-propanol 2-Chloro-1-propanol
90 % 10 %
Cl OH
HCl/ether
O H3C C
H3C CH2 + H3C C CH2
SN1 CH3 OH
H3C CH3 Cl
2-Methyl-1,2-Epoxypropane 2-Chloro-2-methyl- 2-Chloro-2-methyl-

1-propanol 2-propanol
60 % 40 %
But in reality in SN1 process, a pure carbocation does not form as we would
expect for this process. Instead, an unshared electron pair on the oxygen atom
maintains an interaction with the neighbouring carbon atom, which then bears
only a partial positive charge. The tertiary position is significantly better at
supporting a partial positive charge, so this position has significantly more
partial carbocation character than the primary position or in other words more
substituted carbon centre is better electrophile and therefore, more susceptible
to nucleophilic attack. Because of the bridged carbocation stereochemistry of
epoxides, reactions though following SN1 process are SN2 like. Above two acid
catalysed reactions can now be illustrated as:
H
+ SN2 OH
+ O H H3C
O H H3O H3C
H3C .. - C CH2 Cl
H :Cl: H
H ..
H H
Dominatinf factor: Steric
H
+ Cl
O
+ H3C d  d SN1
O H H3 O H3C C CH2 OH
H3C H .. -
H3C H :Cl: .. CH3
H3C H
Dominatinf factor:
electronic effect 195
SAQ 8
Predict the product of the reaction below, and draw likely structure of oxonium
ion intermediate.
CH3
H2SO4
O
CH3OH
Nucleophilic Ring Opening
Unlike ethers, epoxides undergo ring-opening reaction with a variety of

nucleophiles because of the strain associated with ring. Good nucleophiles
attack on epoxides by an SN2 mechanism and shows SN2 like stereo
selectivity and regioslectivity (inversion of configuration and nucleophile
attacks the less substituted position).
OH
i) RONa
ii) H2O HO CN
i) NaCN
ii) H2O HO SH
i) NaSH
O ii) H2O HO R
i) RMgX
ii) H2O HO H
i) LiH
ii) H2O CH
HO
i) HC CNa
ii) H2O HO
Mechanism: Nucleophilic opening of an epoxide ring
Step 1: Nucleophile attacks from backside on the less hindered carbon of the
epoxide and opens the ring by cleaving the C−O bond.
Na+ O-
O -
SN2
+ H3C O Na+ CH CH2
H3C H3C
OCH3
Alkoxide ion
Step 2: The resulting alkoxide ion from Step 1 gets protonated by solvent
system of reaction.
-
Na + O
O HO
CH CH2 + H CH3 -
CH CH2 + H3C O
H3C OCH3 H3C OCH3
196
Unit 17 Ethers
SAQ 9
For each of the following, predict the product:
O i) CH3MgBr O i) NaCN
i) ii)
ii) H2O
CH3 ii) H2O
iii) O iv) H3C O i) H2SO4
CH3 ii) CH3OH

i) LiAlH4
ii) H2O CH3
Epoxides play important role as building block in organic synthesis. Ethylene

oxide can be used to introduce two carbons in a molecule. For example,
consider an alkyl halide as starting material and by using an epoxide, we can
introduce two carbon atoms in the structure of the alkyl halide:
i) Mg/diethyl ether
O
ii) R
R Br OH
iii) H2O
The −OH group of the product obtained from above reaction can be easily be
modified by replacement with another nucleophile such as ammonia, halide,
CN, N3- , SH etc. to get desired final or intermediate product. Epoxides can
also be used for introducing functional group(s) in a molecule. You may have
noticed that ring opening of an epoxide provides two functional groups on
adjacent carbon centres.
O Nu Nu
HO
For further understanding consider the following conversion:
CH3 CH3
OMe
OH
Find product can be achieved by using following synthesis route:
CH3 CH3 CH3

Br2 Br -HBr
hn Base
MCPBA
CH3 CH3
+
MeOH/H 3O
OCH3 O
OH 197
SAQ 10
How would you prepare 1-butanol from ethanol?
17.5 CROWN ETHERS AND CRYPTANDS

As mentioned earlier, structure of crown ethers are consisting of the repeating
– OCH2CH2 – units. They are polymers of 1, 2-ethandiol. Crown ethers and
cryptands have the ability to form complexes even with most reluctant alkali
metal ions. This has made the coordination chemistry of alkali metals richer.
Crown ethers are prepared by a variant of the Williamson ether synthesis in

which an alkoxide ion displaces a tosylate ion (It is a better leaving group than
halide ions) by an SN2 mechanism. A general procedure used for the synthesis
of crown ethers is illustrated below.
OTs
OH OH TsO OH
O - + O O O O
(CH3)3CO K
O O O O O
.. - +
O OH O: K TsO O
..
H 3C S O_
Tosylate ion, OTs

-
O
Tosylate ion is an O
excellent leaving group. O O
O O
O O O O
O O
1
8
-
C9
o0
r
w%
n
-
6
The unique feature of crown ether is that they can chelate metal ions and give
metal complexes which are soluble in non-polar organic solvents. In this form,
the crown ether is referred to as the host, while the metal ion is called guest.
For example, purple benzene is a reagent in which KMnO4, complexed by
18-crown-6, is dissolved in benzene. This is a very useful reagent for the
oxidation of water insoluble organic compounds.
O
O O
+ -
K MnO 4
O O
O
18-Crown-6 complex
Crown ethers are specific for the cation they bind, and this is related to the
size of the cavity. As show above, 18-crown-6 binds K+ preferentially, but
198 smaller crown ethers can bind Li+ or Na+
Unit 17 Ethers
O
O O
Li
+ O + O
Na
O O
O O
12-Crown-4 15-Crown-5
To further optimizing binding capabilities of crown ethers, Jean-Marie Lehan,

who shared the 1987 Nobel Prize, developed double-cyclic crown ethers. He
named them cryptands. These compounds are like crown ethers except they
have addition ‘bridge’ which provides extra strength to hold the ion. In other
words, if regular crown ether surrounds an ion, a cryptand locks it up. A typical
cryptand is prepared by making a diamide from a diaza crown ether. The
amide groups are subsequently reduced.
Cl Cl
O O O O O O
O O
H N N H O N O O N O
O O O O
[H]
O O
N O N
O
O O
[2.2.2] Cryptand
17.6 INDUSTRIAL USAGE

Ethers are widely used as solvents for oils, fats, gums, resins etc. Diethyl ether
is used as refrigerant. It is also used as a solvent for extraction of organic
matter, and in the laboratory for preparation of Grignard reagents. Diethyl
ether was also used as inhalation anesthetic, but due to its side effects, it is
now replaced by halogenated ethers such as enflurane [F2CHOCF2CHClF],
isoflurane [(F2CHOCHClCF3)], sevoflurane [CH2FOCH(CF3)2], etc. Dimethyl
ethers are used as a catalyst in industrial polymerisation process, alternative
fuel, a foam expansion agent, and as an aerosol propellent for a variety of
products that include adhesives, sealants, foam in a can, coating, paints,
automotive care products, tropical cooling spray, hair spray, sun screen and a
variety of other personal care and household products.
Because of the inert nature of the ethers, many ethers such as tetra
hydrofuran (THF), 1,4-dioxane, etc. are excellent solvents for carrying out
many organic reactions. Epoxides are used as intermediates in the
preparation and manufacturing of other basic organic chemicals.
Crown ethers have great advantages in synthetic organic chemistry. One is

that an ionic reagent can be dissolved in an organic phase where it can react 199
with a water-insoluble organic compound. A second advantage is that the

nucleophilicity of an ion such as CN or CH3COO is greatly enhanced in non
polar solvents, where the anion is poorly solvated, or naked. An example of
how a crown ether increases the rate of substitution reaction in preparation of
the benzyl methyl ether in acetonitrile (methyl cyanide) which does not
dissolve ionic compound is shown below.
CH3CN
- + + -
CH2 Br + CH3 O K CH2 OCH3 + K Br
5 % yield with no crown ether

100 % yield with 18-crown-6 ether
Crown ethers generally form characteristic coloured complexes with metal
ions, this property can be used for the detection of the metal ions.
17.7 SUMMARY
What we have studied in this unit, can be summarised as follows:
 Ethers can be prepared using the Williamson ether synthesis, which is

an SN2 reaction. On commercial scale, diethyl ether is prepared through
the dehydration of ethanol in strong acid.
 Epoxides can be prepared by the reaction of peracid with alkenes or by

the reaction of halohydrin with alkali.
 Ethers are less reactive than alcohols and they undergo ether cleavage
by reaction with HBr and HI. This acid catalysed cleavage takes place
via SN2 or SN1 mechanism. The exact mechanism being determined by
the substituent on carbon atoms bonded to oxygen.
 Unlike ethers, epoxides are quite reactive and their ring opening reaction
requires milder reaction conditions. The ring opening reaction may be
initiated by acid or by nucleophile.
 The unique feature of crown ethers and cryptands is that they can
selectivity chelate metal ions and give complexes which are soluble in
non polar solvents.
 Ethers have many industrial uses.

1. Among ethyl alcohol and diethyl ether, which will have greater solubility
in water? Explain.
2. Write the major product obtained from the following reactions:
i) H3C Cl - +
EtO Na
CH3
Cl
- +
ii) H3C EtO Na
CH3
200 CH3
Unit 17 Ethers
3. Write equation to show how would you prepare the following

compounds?
i) CH2CH2CH2OH
OCH3
ii) CHCH3
4. How are the methoxy and ethoxy groups estimated in a

compound?
5. Give two important features of the crown ethers.
6. How would you prepare 1,4-dioxane from oxirane?
7. Predict the products for each of the following:
CH3
i) Hg(OAc)2, EtOH
a) H C CH2 ii) NaBH4

3
HI
b)
O
O CH3
c) HBr
i) PhMgBr
O
d)
ii) H3O+
CH3
O i) LiAlH4
e) H3C ii) H3O+
O H2SO4/EtOH
H3C
f)
CH3
Et
17.9 ANSWERS
1. a) 2-Ethoxy-2-methyl propane; b) 1-Ethoxypropene;
c) Ethoxybenzene; d) Cyclohexyloxycyclohexane.
2. a) Following route will be followed:

201
NaOH C2H5Cl
Ph OH Ph ONa Ph O C2 H5
Other route using ethanol and chlorobenzene does not work as

replacement of chlorine from sp2 is very difficult.
b) Following route will be preferred:
OH ONa OCH3
NaH CH3Cl
H3C H3C H3C
CH3 CH3 CH3
2-Methoxybutane
Other route using 2-chlorobutane and methanol gives considerably more

elimination products.
3. From this reaction we expect a mixture of three ethers: diethyl ether,
dibutyl ether and butyl ethyl ether. It is very difficult to separate these
three ethers from reaction mixture in pure form.
4. a) CH3CH2OCH2CH3; b) No reaction, c) CH3C(CH3)=CH2) CH3;

d) PhOCH2CH3.
5. Water solubility of ether can be attributed to hydrogen bonding between
oxygen of ether with water.
H3C O H O
H
CH3
6. This reaction follows SN2 pathway, therefore iodide ion prefers to attack
on less hindered methyl carbon of 2-methoxypropane.
+ SN1/E 1 H C +
H3C H3 O H3C 3
C
+
7. a) +
O H3C O
H3C O H3C
H H
E1 -
Br SN1
H3C SN2 H3C
H3C Br
+ - Br
H3C O H3O /Br H3C
H3C Br O
H
H
-
I
2
H
sp carbon
+ OH
O CH3 O CH3
+
b) H3O + CH3CH2
sp3 carbon
HI
H
+
+ CH3
O CH3 H3O O CH3 OH
C C +
c) + C CH3
CH3 CH3
H3C H3C CH3
-
SN2 I- SN1 I
I CH3
+
I C CH3
202 CH3
Unit 17 Ethers
CH3 CH3 CH3

+
H3 O d CH 3OH OCH 3
8. O +
OH SN1
OH
Nucleophile will attack from backside on tert carbon. This position is

better at supporting partial positive charge. Therefore, this position has
more carbocation character than sec. position.
9. i) CH3CH2CH2OH
ii) Reaction will follow SN2 pathway. Nucleophile will attack on less
hindered position.
NC OH
CH3
iii) Reaction will follow SN2 pathway. Nucleophile will attack on less
hindered position.
HO
CH3
iv) Reaction will follow SN1 pathway. Nucleophile will attack on tert
position.
CH3
OH
H3C H
H3CO CH3
i) Mg/ether
ii) O
HBr
H3C CH2 OH H3C CH2 Br CH3CH2CH2CH2OH
10.
+
iii) H3O
Terminal Questions
1. Ethanol has greater solubility in water as it is more polar than ether and
ethanol molecules act both as hydrogen bond donor as well as hydrogen
bond acceptor. Ether is less soluble in water as its molecules cannot act
as hydrogen bond donor. It only acts as hydrogen bond acceptor.
2. i) H3C O CH3 ii) H3C

CH3
H3C CH3
203
i) Mg/ether
ii) O
3. i) CH2Br CH2CH2CH2OH
+
iii) H3O
ONa OCH 3
CH3 CH3
+ CH 3I
ii)
4. Methoxy or ethoxy group in an organic compound are estimated by the

Zeisel method. In this method, the organic compound is first heated with
excess of HI followed by distillation of volatile iodomethane or iodoethane
from the reaction mixture. Then the iodomethane or iodoethane is treated
with ethanolic solution of silver nitrate, and silver iodide so formed is
weighed.
5. i) Crown ethers can selectively chelate metal ions and give metal
complexes, which are soluble in non polar organic solvents.
ii) Nucleophilicity of certain anions can be enhanced by the crown
ethers and hence increased the rate of reactions of such reactions.
O H3O+ H3O+
6. HO HO + + HO
OH O H OH
H - H2O
H
O O O +
H3O+ O
O O
+
H O
+ HO
HO HO
H H
CH3 H3C OEt
i) Hg(OAc)2, EtOH
C
7. a) ii) NaBH3 H3C CH3
H3C CH2
HI I
b)
O OH
O CH3 Br
c) HBr
+ C2H5Br + H2O
i) PhMgBr
O OH
d) Ph
CH3 ii) H3O+
CH3
i) LiAlH4 OH
O
e) H3C H3C
ii) H3O+ CH3
Et OH
O H2SO4/EtOH
f) H3C H3C H
Et CH3 EtO CH3
204
Unit 18 Aldehydes and Ketones
UNIT 18
ALDEHYDES AND KETONS
Structure
18.1 Introduction Nucleophilic Addition Reactions
Expected Learning Outcomes Reactions Involving -Hydrogen
18.2 Structure and Physical Oxidation

Properties
Reduction
Structure of the Carbonyl Group
Condensation
Physical Properties
Specific Reactions of Aldehydes
18.3 Preparation and Ketones
General Methods of Preparation 18.5 Industrial Uses

of Aldehydes and Ketones
18.6 Lab Detection
Industrial Methods of Preparation
18.7 Summary
of Aldehydes and Ketones
18.4 Reactions of Aldehydes and
Ketones 18.9 Answers
18.1 INTRODUCTION
In previous units, you have studied the chemistry of alcohols and phenols
ethers. In this unit, we deal with aldehydes and ketones. Both these classes of
organic compounds have a carbonyl group, >C=O. A ketone has two alkyl (or
aryl) or one alkyl and one aryl groups attached to the carbonyl carbon, while
an aldehyde has at least one hydrogen atom attached to the carbonyl carbon.
The other group in an aldehyde can be alkyl or aryl.
The remarkable reactivity of the carbonyl group makes the chemistry of

aldehydes and ketones the backbone of synthetic organic chemistry. The
double bond between the carbon and oxygen atoms in these compounds
serves as a model for the reaction of many other functional groups containing
 bonds between dissimilar atoms. Although the reactions of carbonyl
compounds are quite simple, their synthetic utility is enormous. Addition and
substitution reactions are of major interest. In this unit, you will learn the basic
principles which are responsible for the extreme reactivity of these compounds
and on the basis of which reliable predictions can be made.
205
Here, we will first consider the preparation of aldehydes and ketones and then
the characteristic reactions of the carbonyl-group. Finally, we will study
industrial uses of aldehydes and ketones and the methods used for their
detection. Aromatic aldehydes and ketones unlike aryl halides and phenols do
not much differ from aliphatic aldehydes and ketones, you will study them in
the next unit.

 explain the nucleophilic addition reactions of aldehydes and ketones on
the basis of the structure of carbonyl group;
 describe the physical properties of aldehydes and ketones;
 list and discuss the preparation of aldehydes and ketones;

 describe the commercial methods of preparation of methanol, ethanol
and propanone;
 explain the relative reactivity of aldehydes and ketones;
 describe the reactions of aldehydes and ketones;

 discuss the lab detection of carbonyl compounds and the test which
distinguishes aldehydes from ketones; and
 state the industrial uses of aldehyde and ketones.
18.2 STRUCTURE AND PHYSICAL PROPERTIES

Before going in details of the chemistry of aldehydes and ketons, let us recall
the nomenclature pattern of these compounds. The common names of
aldehydes are derived from the common name of the corresponding
carboxylic acid, with the ending -ic or -oic acid replaced by -aldehyde. In the
IUPAC system, aldehydes are treated as derivatives of the alkanes, with
ending -e replaced by -al. Thus, an alkane becomes an alkanal. Cyclic and
aromatic aldehydes are named as cyclic alkane- or aryl-substituted
carbaldehydes. In the examples given below, common names are written in
parenthesis.
O O O O O O
OH H H H3C OH H3C CH3 OH H

H
M
e
t
h
a
n
a
l
E
t
h
a
n
a
l
Benzenecarbaldehyde
F
o
r
m
i
c
a
c
i
d
F
o
r
m
a
l
d
e
h
y
d
e
A
c
e
t
i
c
a
c
i
d
A
c
e
t
a
l
d
e
h
y
d
e
( ( )
( ) ) (Benzoic acid) (Benzaldehyde)
In the IUPAC system, ketones are called alkanones, the ending -e of the
alkane replaced with -one. On the other hand, aromatic ketones are named as
aryl-substituted alkanones. To indicate the position of carbonyl group in chain,
the parent chain is numbered from the direction that gives the carbonyl carbon
the smaller number regardless of the presence of substituents or the
halogens, hydroxyl, C=C or C≡C functional groups. Cyclic ketones are simply
called cycloalkanones and aromatic ketones are named as aryl-substituted
206 alkanone.
O O O O O
C C C C C
CH3 H3C 2
CH2CH3
3
CH2CH3 CH3
H3C CH 3CH 2
1 3
3
-
P
e
n
t
a
n
o
n
e
P
r
o
p
a
n
o
n
e
2
-
B
u
t
a
n
o
n
e
1
-
P
h
e
n
y
l
e
t
h
a
n
o
n
e
D
i
p
h
e
n
y
l
m
e
t
h
a
n
o
n
e
D
i
e
t
h
y
l
k
e
t
o
n
e
A
c
e
t
o
n
e
E
t
h
y
l
m
e
t
h
y
l
k
e
t
o
n
e
A
c
e
t
o
p
h
e
n
o
n
e
B
e
n
z
o
p
h
e
n
o
n
e
( )( ) ( ) ( ) ( )
The IUPAC system still retains the common names for formaldehyde,
acetaldehyde, bezaldehyde, acetone and benzophenone.
SAQ 1
Name of the following compounds:
a) O b) CHO
c) O d) O
CH3
18.2.1 Structure of the Carbonyl Group

In order to understand the chemistry of the carbonyl group, there is a need to
look in to details of the structure of the carbonyl group. According to valence
bond theory, the carbon-oxygen double bond consists of one  bond formed
by the overlap of sp2 hybrid orbitals of carbon and oxygen and one  bond
formed by the overlap of parallel 2p orbitals. The two nonbonding pairs of
electrons (unshared electrons pairs) on oxygen lie in the remaining sp2 hybrid
orbitals of oxygen. The sp2 hybridisation means that the carbonyl group has to
be planar, and the angle between the substituent is close to 120. Fig. 18.1
illustrates all these features for the methanal (CH2O) molecule. You can notice
that the orbital arrangements are somewhat similar to carbon-carbon double
bond of alkenes. But when we compare electronic arrangement, we can notice
two important differences. First, oxygen atom of carbonyl group bears two
nonbonding pairs of electrons located in two sp2 hybrid orbitals.
Remaining two sp2 orbitals of C O  bond made from overlap of p orbitals of
carbon form bond with hydrohen carbon and oxygen
120o H
d+ d-
120o C O C O
120o
H Two lone pairs occupy two sp2
orbitals of oxygen
+ -
C O C O C O  -bond made from overlap of
sp2 orbitals of carbon and oxygen
(a) (b)
Fig.18.1: (a) Molecular structure of carbonyl group, (b) Orbital picture of

methanal.
207
Second, carbonyl group oxygen is more electronegative than carbon
[electronegativity of oxygen on the Pauling Scale = 3.44 and electronegativity
of carbon on the Pauling Scale = 2.55]. Therefore, similar to ether group
carbon-oxygen double bond is polar with oxygen bearing a partial negative
charge and carbon bearing a partial positive charge. These two factors
contribute to the high reactivity of the carbonyl group.
In addition, the resonance structures shown in Fig. 18.1(a) emphasise that

carbon is an electrophilic site (electron deficient centre) and the oxygen is a
nucleophilic site (electron rich centre). Thus, we can say that the carbonyl
carbon acts as a Lewis acid and the carbonyl oxygen acts as a Lewis base. As
a result, carbonyl carbon is susceptible to attack by a nucleophile. The
electrophilicity of carbon centre is further enhanced when reaction is carried
out in acidic medium due to the protonation of oxygen atom.
R R
+
C O + H3O + C OH
R Protonation R
Now, we will apply molecular orbital approach to further understand the

chemistry of the carbonyl group. A good approximation for reactivity can be
found by looking at the frontier molecular orbitals [highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)]. In case of
carbonyl group,  and * are the HOMO and LUMO, respectively. Fig. 18.2
shows, how  and * orbitals are formed on mixing of two p atomic orbitals of
carbon and oxygen.
(b) Out of phase addition C O

*
*
C
O
(a) In phase addition

C O


Fig. 18.2: Molecular mixing diagram for the creation of π bond in carbonyl
group: (a) HOMO and (b) LUMO.
In the above diagram you can notice that p orbital of oxygen is lower in energy
because oxygen is more electronegative than carbon. According to MO
theory, when the two combining atomic orbitals are not equal in energy, the
resulting molecular orbitals have a greater contribution from the atomic orbital
that is closest in energy. Thus, the bonding  orbital has larger contribution
from the oxygen, therefore has larger coefficient at the oxygen atom, and
208 conversely, the anti-bonding * orbital has a larger contribution from the
carbon. Further, only the bonding orbital is occupied, the electron density in
the bond is concentrated on oxygen. The resultant bond is said to be
polarised. Polarisation of the bond means that there is an uneven distribution
of electron density between the two combining atoms leading to the buildup of
positive charge on the carbon and negative charge on the oxygen and of the
carbonyl bond.
Conversely, unfilled antibonding * orbital, is polarised in the opposite

direction, with larger coefficient at the carbon atom. Thus, when the carbonyl
group reacts with a nucleophile, electrons move from the HOMO of the
nucleophile into the LUMO of the electrophile, in other words * orbital of the
carbonyl bond. The greater coefficient of the * orbital at carbon means a
better HOMO-LUMO interaction. It can be concluded that larger coefficient on
oxygen in the filled (bonding) orbital explains why the oxygen atom acts as
Lewis base (nucleophilic centre). The larger coefficient on carbon in the empty
antibonding, * orbital explains why it behaves as a Lewis acid (electrophilic
centre).
It can now be summarised that all the concepts discussed above lead to the
same conclusion, that is, in aldehydes and ketones, the carbon of carbonyl
group is an electrophilic site and oxygen is a nucleophilic site. Thus, because
of these structural features, these compounds undergo a wide variety of
reactions with most involving nucleopholic addition.
The Angle of Nuecleophilic Attack
When a nucleophile (Nu-) approaches the carbon atom, the electron pair in its
HOMO starts to interact with the LUMO (antibonding, *) to form a new 
bond. This interaction leads to breaking of the  bond, leaving only the C–O, 
bond intact. The nucleophilic addition to carbonyl group can be illustrated as
follows:
Nu -
Nu
d+ d- -
C O C O C O
sp2 hybridised
sp3 hybridised carcon
carbon
Nu -
New  bond
Nu -
C O C O -
C O
*
LUMO Electron on HOMO of Nu- being
to intract with LUMO of carbon
Nu
while at the same time C O -
C O

HUMO Electron from  bond end up
Filling of * causes as negative charge on oxygen
 bond to break
Fig. 18.3: Orbital interaction during nucleophilic attack. 209

Fig. 18.3 shows how the trigonal, planar sp2 hybridised carbon atom of the
carbonyl group changes to a tetrahedral sp3 hybridised state in the product.
Burgi and Dunitz Molecular orbital calculations also suggested that HOMO of the nucleophile
deduced this trajectory approaches from a particular angle; that is, 107 to the plane of the carbonyl
by examining crystal group. This approach route is known as the Burgi-Dunitz trajectory.
structures of compounds
containing both a
The possible explanation for this angle of attack is that due to repulsion of the
nucleophilic nitrogen
atom an electrophilic HOMO by the electron density in the carbonyl  bond, the lobs of LUMO, *
carbonyl group. are already at an angle as shown below.
107o
C O
* MO
Burgi-Dunitz angle
Any other portion of the molecule, that gets in the way of the Burgi-Dunitz
trajectory, will greatly reduce the rate of nucleophilic addition to carbonyl group
and this is the one of the reasons why aldehydes react faster than ketones in
the nucleophillic reactions.
18.2.2 Physical Properties

As we have mentioned above, the aldehydes and ketones are polar
The bond dipole moment
of a carbonyl group is compounds due to presence of carbonyl group and these compounds possess
2.3 D intermolecular dipole-dipole attraction. Due to these interactions, molecules
have higher boiling points than nonpolar compounds of similar molecular
weight. The boiling points of aldehydes and ketones are, however, much lower
than the boiling points of the corresponding alcohols. This is due to the fact
that the molecules of aldehydes and ketones are held together by the much
weaker electrostatic interaction between dipoles whereas alcohols are held
together by strong hydrogen bonds.
The partial solubility and the formation of hydrates can be explained by the
formation of hydrogen bonds between carbonyl compounds and water. The
unshared electron pairs on oxygen are responsible for such hydrogen
bonding. The carbonyl-carbonyl and carbonyl-water interactions are illustrated
in the following structures:
R R R
O O O H O
R R R H
Dipole-dipole intraction between the Hydrogen bonding between carbonyl

molecules of carbonyl compounds compound and water
As the hydrophobic hydrocarbon part of the molecule increases in size, water

solubility decreases. The physical properties of some aldehydes and ketones
210 are summarized in Table 18.2.
Table 18.2: Physical properties of some aldehydes and ketones
Aldehydes Structure BP, K Solubility in H2O

Formula
IUAPC Common Name
Methanal Formaldehyde HCHO 252 miscible
Ethanal Acetaldehyde CH3CHO 293 miscible

3
Propanal Propionaldehyde CH3CH2CHO 322 16 g/100 cm
3
Butanal Butyraldehyde CH3CH2CH2CHO 349 7 g/100 cm
Benzaldehyde Benzaldehyde C6H5CHO 451 slightly
Ketones:
Propanone Acetone CH3COCH3 329 miscible

3
2-Butanone Methy ethyl CH3COCH2CH3 353 26 g/100 cm
ketone
Phenylethanone Acetophenone C6H5COCH3 475 insoluble
Diphenyl Benzophenone C6H5COC6H5 579 insoluble

methanone
SAQ 2
Without consulting Tables given for physical properties of organic compounds,
identify which compound in each pair would have the higher boiling point.
a) 1-Pentanal or 1-pentanol
b) 3-Methyl-2-butanone or 2-methylbutane
c) 2-Pentanone or 2-pentanol
d) Cyclohexanone or cyclohexane
e) Pentane or 1-pentanal
18.3 PREPARATION
We have already learned several reactions that can be used for the
preparation of aldehydes and ketones. Recall the oxidation of alkenes with
ozone, hydration of alkynes and oxidation or dehydrogenation of alcohols.
In this section, we will first consider the general methods for the preparation of
aliphatic aldehydes and ketones and then follow them up with industrial
methods for the production of methanal, ethanal and propanone.
18.3.1 General Methods of Preparation of Aldehydes

and Ketones
Aldehydes and ketones can be prepared from alkenes, alkynes, alcohols,
carboxylic acids and their derivatives. We are summarising the general
reactions of these methods of preparation in Table 18.3. 211
Table 18.3: Preparation of Aldehydes and Ketones
From Alkenes: Ozonolysis of alkenes
R R (i) O3 R
C C 2 C O
ii) Zn/H2O
R R R
From Alkynes: hydration of alkynes

H
R
C
Hg2+/H3O+
R C C R H C O
R
From Alcohols
OH
R
[O]
R C H C O
or dehyrogenation Cat.
R R
From Carboxylic Acids and their Derivatives

R
(RCOO) 2Ca C O + CaCO 3
Calcium salts of R
carboxylic acid
MnO
R
2 RCOOH C O + CO 2 + H2O
573 K
R
H2/Pd/BaSO4
RCOCl RCHO + HCl
Rosenmund's Method
O
AlCl3 R
RCOCl +
Friedel-Crafts Reacrtion
From the Stephen’s Method
SnCl2/HCl
2 RCN 2 RCHO + (NH 4)2SnCl 6
The preparation of aldehydes and ketones from alkenes and alkynes has been
discussed in Unit 7 and Unit 8, respectively. Here, we will consider preparation
of these compounds from alcohols, and carboxylic acids and their derivatives.
i) From Alcohols
As mentioned in Unit 12, primary alcohols give aldehydes and secondary

alcohols give ketones on dehydrogenation/oxidation. The tertiary alcohols are
resistant to dehydrogenation/oxidation because the carbon bearing the –OH
group is already bonded to three carbon and, therefore, cannot form any
additional carbon-oxygen bond. This is the most common way of synthesising
aldehydes and ketones in the laboratory. We generally use the following
212 oxidising agents for the oxidation of alcohols:
i) alkaline potassium permanganate solution
A solution of chromic
ii) hot, concentrated HNO3 acid in aqueous
sulphuric acid is known
as the Jones reagent.
iii) chromic acid (H2CrO4)
This reagent is used to
distinguish between
iv) chromium trioxide (CrO3) complex with pyridine or with pyridine and HCl aldehydes and ketones.
(PDC and PCC) Aldehydes give a
positive test, but ketones
The first three methods generally lead to over oxidation of primary alcohols to do not. Primary and
carboxylic acids. The chromium trioxide complex is most commonly used for secondary alcohols also
give positive test with
oxidation of a primary alcohol to an aldehyde. This reagent is prepared by Jones reagent but
dissolving CrO3 in aqueous HCl and adding pyridine to precipitate pyridinium tertiary alcohols do not.
chlorochromate (PCC) as solid. PCC oxidation is carried out in aprotic solvent
This regent is also
such as dichloromethane.
selective and does not
O oxidise alkene and
OH alkyne units if present in
PCC/CH2Cl2
same molecule.
H H
H2CrO4/H2O, acetone
O
OH
Another reagent used for oxidation of secondary alcohols is alumimium

tertiary-butoxide. It is used in the Oppenauer oxidation. In this method, the
reaction mixture is first heated and then propanone (acetone) is added:
OH R Oppenaure oxidation is
reversible and the
R CH R + Al( tert-BuO)3 (R CH O)3Al + 3 tert-BuOH reverse reaction is
known as the Meerwein-
R O CH3 Ponndorf-Varley
reduction.
(R CH O)3Al + 3 CH3COCH3 C + ( CH3 CH O)3Al
R R
ii) From Carboxylic Acids and their Derivatives
Carboxylic acids can be converted into aldehydes and ketones either by

heating their calcium salts or by passing vapours of the acid over heated
manganous oxide or by reduction of acid chlorides with hydrogen in the
presence of palladium over barium sulphate (Rosenmund’s method). We will
consider these reactions in more detail in third semester course. General
equations for these reactions are given below:
From Calcium Salts of Carboxylic Acids

O
Heat C CaCO3
(HCOO)2Ca H H +
Calcium methanote Methanal
O
Heat
(HCOO)2Ca + (CH3COO)2Ca C + 2CaCO3
H3C H
Calcium methanote Calcium ethanoate
Ethanal
213
O
(RCOO)2Ca Heat
C CaCO3
R R +
Calcium salt of
carboxylic acid Ketone
O
Heat + 2CaCO3
(C6H5COO)2Ca + (CH3COO)2Ca C
Ph CH3
Calcium benzoate Calcium ethanoate
Phenyl ethanone
(acetophenone)
(Mixture of calciun salt of carboxylic acids) unsymmetrical ketone
From the Reaction of Carboxylic Acids with Manganese(II) oxide

O
MnO/573 K
C
2HCOOH H H + CO2 + H2O
Methanoic acid Methanal
O
MnO/573 K
RCOOH + HCOOH C CO2 + H2O
H3C H +
Carboxylic acid Methanoic acid Aldehyde
O
MnO/573 K
2RCOOH C + CO2 + H2O
R R
Carboxylic acid Ketone
O
MnO/573 K C + CO2 + H2O
RCOOH + R'COOH R'
R
(Mixture of caboxylic acids) unsymmetrical ketone
Please note that for aldehydes other than methanal and for unsymmetrical
ketones, a mixture of acids and their calcium salts in molar proportion is taken.
From Acid Chlorides by the Rosenmund’s Method
O O
H2/Pd (BaSO4)
C C + HCl
R Cl R H
Carboxylic acid Aldehyde
where R = CH3 or C6H5
BaSO4 poisons the catalyst and helps to stop the reduction at the aldehydes
stage.
iii) From the Stephen’s Method
Reduction of an alkyl cyanide with stannous chloride and hydrochloric acid

followed by hydrolysis with steam gives aldehydes (Stephen’s method):
O
SnCl2 H2O
C
R C N
HCl
[RCHNH 2]2SnCl6 R H + (NH 4)2SnCl6
Alkyl cyanide Aldehyde
214 where R = CH3 or C6H5

SAQ 3
An organic compound A (molecular formula C3H7Cl) was treated with aqueous
sodium hydroxide and the vapours of the product obtained were passed over
heated copper to give propanone (acetone). A is
a) 1-chloropropane b) 2-chloropropane c) chlorocylclopropane
18.3.2 Industrial Methods of Preparation of Aldehydes

and Ketones
The industrial preparation of some common carbonyl compounds are
described below:
Methanal
It is manufactured from methanol by following two processes:
i) Oxidation of methanol using silver or copper catalyst.
O
O Ag/air/773 K Cu/573 K
CH3OH C + H2
H2O + C
H H
H H
Although the silver catalyst is expensive no silver is lost and catalyst is

easily regenerated and can be recycled.
ii) Oxidation using zinc-chromium or iron-molybdenum oxide catalyst.

O
[O]
CH3OH C + H2
catalyst H H
Methanol itself is made from enriched water gas.
Cu as cat.
CO + 4H 2 CH3OH
523 K, 70 atm.
Ethanal
The following methods can be used for the manufacture of ethanol:
i) By passing a mixture of ethene and oxygen under pressure over

palladium (II)/Cupric chloride catalyst in water at 323 K, ethanal is
produced:
O
PdCl2, CuCl2/H2O
H2C CH2 + 1/2O 2 C
523 K, 70 atm. H3C H
This process is called Wacker process. Since ethene is cheaper than

ethyne, this process has superseded the two older routes outlined
below:
215
ii) By passing ethyne through dilute sulphuric acid, with mercury(II)
sulphate as catalyst at 336 K.
O
H2SO4/Hg2+
HC CH + H2O C
H3C H
iii) By the oxidation of ethanol (which is manufactured from ethene) in the

gas phase over a silver or copper catalyst:
O
O Ag/air/773 K Cu/773 K
CH3CH2 OH C + H2
H2O + C H3C H
H3C H
Propanone
Dehydrogenation of 2-propanol over heated copper or zinc oxide or air

oxidation over heated silver gives propanone. 2-Propanol is obtained from
propene.
O O
Ag/air/heat Cu or ZnO/heat
(CH3)2CH2 OH C + H2
H2O + C CH3
H3C CH3 H3C
Propanone can also be manufactured by the direct oxidation of propene from

natural gas with oxygen or air, catalysed by a mixture of palladium and
cuprous chlorides (The Wacker Process).
O
PdCl2, CuCl2/H2O
H3C CH CH2 + 1/2O 2 C
523 K, 70 atm. H3C CH3
We have already seen in Unit 16 that propanone is obtained as a by-product

in the oxidation of cumene to phenol.
SAQ 4
How will you convert propene to acetone?
18.4 REACTIONS OF ALDEHYDES AND

KETONES
We can group together the reactions of aldehyde and ketones into four
categories (a) reactions of the carbonyl group, (b) reactions of the ‘’
hydrogen (acidic hydrogen) attached to the carbon adjacent carbonyl group,
(c) oxidation reactions and (d) reduction reactions.
As stated earlier, the carbon-oxygen double bond is polar which leads to ionic
addition to the carbonyl π bond. A carbonyl compound may first be attacked
either by a nucleophile or by an electrophile. Therefore, with most reagents,
216 carbonyl additions show the same overall course, i.e., addition of the negative,
nucleophilic part of the reagent to the carbon atom and addition of the positive
electrophilic part to the oxygen atom.
O Attack by electrophiles
R C
C R
Acidic hydrogen H R
Attack by nucleophiles
In acidic medium, the proton first adds to the carbonyl oxygen. This further
increases the electrophilic nature of the carbonyl carbon.
R R R
+ +
C O + H3O C OH
+
C OH
R R R
Resonance structures of
protonated carbonyl group
Hence, nucleophilic additions to the carbonyl compounds are very often

catalysed by acids. We turn now our attention on the nature of α hydrogen
atoms attached to carbon next to carbonyl group. The carbonyl group induces
enhanced acidity of these hydrogens. Moving or removing these α hydrogens
may lead to either of two electron-rich species: enols or enolate ions. Both
enol and enolate ion behave as nucleophiles and are capable of attacking
electrophilic species such as protons, halogens and even carbon centre of
carbonyl compounds. A brief description of the reactions due to α hydrogen is
included in this unit.
+
E
OH
O
R C
C C R
R C R
R R
Acidic hydrogen H Enol form
--
B -
R - O R O
CH C C C Enolate ion
+ R
R R E R
Before going into details of the reactions of carbonyl compounds, let us study
the relative reactivity of aldehydes and ketones.
The relative reactivity of aldehydes and ketones in addition reactions may be

attributed partly to the extent of polarisation on the carbonyl carbon. The more
polarised the carbonyl group the greater the positive charge on the carbonyl
carbon. A greater positive charge means higher reactivity. If this partial
positive charge is dispersed throughout the molecule, then the carbonyl
compound is less reactive.
As you already know the alkyl group is electron releasing (+I effect).
Therefore, in ketones, due to the presence of two alkyl groups, the carbon of
the carbonyl group will be less electron deficient than in aldehydes. Hence,
ketones will be less reactive than aldehydes. Further, methanal with no alkyl 217
groups attached to the carbonyl carbon is more reactive than ethanal and
other susbstituted aldehydes.
R H R R H
C O C O C O C O C O
Ph Ph R H H
Increasing reactivity
The most reactive aldehyde is trichloroethanal (chloral), Cl3CCHO, in which

electron withdrawal by the three chlorine atoms depletes the electrons density
on the carbonyl carbon so much that it forms stable hydrates.
Steric factors also play a role in the relative reactivity of aldehydes and
ketones. Since hybridisation of the carbonyl carbon changes from sp2 in the
starting material to sp3 in the addition product, ketones are less reactive than
aldehydes because of the un-favourable steric interaction between the two
alkyl groups and the other two groups in the product. Lack of such steric
hindrance in the product is another reason for the higher reactivity of
methanal.
A carbonyl group attached to an aromatic ring is less reactive in addition

reactions than it is in aliphatic aldehydes and ketones. This can be attributed
to resonance interaction in between the carbonyl group and the aromatic ring:
- - - -
H3C O H3C + O H3C O H3C O H3C O
C C C C C
C C C C C
+ +
+
Resonating structures of phenylethanone (acetophenone)
The result of this interaction is a weakening of the positive charge on the

carbonyl carbon atom through dispersal of the charge into the ring.
With the above general ideas, it will be easier to understand the reactions of
aldehydes and ketones. Many of the reactions given below are shown by all
aldehydes and ketones, but some members show exceptional behaviour
which we will take up separately.
18.4.1 Nucleophilic Addition Reactions

The main reaction of aldehydes and ketones is nucleophilic addition to the
partially positive carbon of the carbonyl group. This addition can take place by
two pathways: i) nucleophilic addition-protonation and ii) electrophilic
protonation or addition of other Lewis acid –nucleophilic addition. We will now
take up the mechanism of both the pathways in detail.
The Mechanism of Nucleophilic Addition-Protonation
Necleophilic addition reactions in neutral or more commonly in basic condition

follow the mechanism as shown below:
218
Step 1: Nucleophilic attack
-
Nu: -
R d+ d+ O:
C O Nu C
R
R
R
Notice how the nucleophile approaches the electrophilic carbon and breaks
the π bond of carbonyl group. This also results in rehybridisation of carbonyl
carbon from sp2 to sp3 and the electron pair of the π bond moves over the
oxygen, thereby producing an alkoxide .
Step 2: Protonation
H H
- O
O OH
Nu C -
R Nu C + HO
R
R
R
In second step, alkoxide ion abstracts a proton from protic solvents such as
water or alcohol to yield the final addition product.
Protonation - Nucleophilic Addition
This mechanism predominates under acidic condition and begins with the
attack of a electrophilic proton or other Lewis acid on nucleophilic oxygen
(Lewis base) of carbonyl group. Protonation increases the electron deficiency
of the carbonyl carbon and makes it more reactive toward nucleophile.
Step 1: Protonation
H + H
O
R d+ d- R R
H + +
C O C OH C OH + H2O
R R
R
Step 2 and 3: Nucleophilic attack and deprotonation
The carbocation formed in step 1 reacts with the nucleophile, followed by loss
of a proton which completes the addition process.
R HNu + Nu
+ NuH + H2 O
C OH C OH C OH
R + R
R - H 3O
R R
Weakly basic nucleophiles follow this mechanism. The acidic conditions are
not suited for strong basic nucleophile. It is also important to note that in
normal situation, in both the mechanisms the nucleophile can approach the
carbonyl carbon from either side with equal probability. As a result, the
carbonyl addition product will consist of racemic mixture if it is a chiral rectant.
219
Approach from the top Nu
face Nu
-
C O C OH
R' R'
R' R +
- H3 O R
Nu: C O + +
R R' R'
-
C O C OH
Approach from the
R R
bottom face Nu Nu
Formation of new A recmic mixture
chiral centre
But in recent past, many stereoselective neucleophilic addition reactions have

been designed. The stereoslectivity of such reactions are either substrate
controlled or reagent controlled or controlled by a catalyst. Details of such
types of reactions will be studied in higher classes.
A wide variety of nucleophiles can attack the carbonyl group of aldehydes and
ketones. We can categories the nuclephilic addition reactions on the basis of
the nature of attacking atom in the following groups:
i) Addition of carbon nucleophiles
ii) Addition of oxygen nucleophiles
iii) Addition of sulphur nucleophiles
iv) Addition of nitrogen nucleophiles
v) Addition of hydrogen nucleophile
i) Addition of Carbon Nucleophiles
Following types of carbon nucleophiles undergo addition reaction with

aldehydes and ketones:
-
:C≡N: RC≡C:- RMgX RLi
Cyanide ion An anion of a Grignard Organolithium
terminal alkyne reagent reagent
Additions of such nucleophiles have lot of significance in synthetic organic

chemistry because a new carbon-carbon bond is formed in the process. These
reactions are carried out in neutral conditions or basic conditions and they
follow two step nucleophilic addition-protonation mechanism.
Addition of Hydrogen Cyanide
Aldehydes and ketones react with hydrogen cyanide to form nitriles

(cyanohydrins), for example, HCN adds to ethanal to form 2-
hyroxypropanenitrile (acetaldehyde cyanohydrin).
H
H
C O + HCN H3C C OH
H3C CN
2-Hydroxypropanenitrile
220 75 % yield
These reactions are reversible and occur very slowly as cyanide ion is a poor
electron donor (weak nucleophile), but their rates are greatly increased by the
addition of alkali. This is because added alkali increases the concentration of
the cyanide ion,
- -
HCN + OH :C N + H2O
It is difficult to handle HCN because it is volatile nature (b.p. = 26 oC) at room

temperature and is also toxic in nature. Therefore, appropriate mixture of
KCN/NaCN and HCl is used in place of HCN. For aldehydes and simple
ketones, the position of equilibrium favours nitrile formation. Nitrile formation is
not a useful reaction for aromatic ketones and sterically hindered aliphatic
ketones as the position of equilibrium for these compounds favours starting
materials.
Nitriles are useful in synthesis as they can be modified by further reactions.

Hydrolysis of nitriles gives -hydroxyacids and their reduction gives primary
amines:
H H + H
2H2/Ni H3 O
H3C C OH H3C C OH H3C C OH
or 1. LiAlH4, 2. H3O+ CN
CH2NH 2 COOH
1-Amino-2-propanol 2-Hydroxypropanoic acid
An important consequence of the hydrogen cyanide addition reaction is that
one more carbon atom is added to the carbon chain. For example,
H H + H
KCN/HCl H3O
C O RCH2 C OH RCH2 C OH
RCH2 CN COOH
-H 2O
reduction
RCH2CH2CHO RCH CH COOH
Higher aldehyde
Thus, nitriles are valuable intermediates for the synthesis of other useful
organic compounds.
SAQ 5
Arrange the following carbonyl compounds in order of favourability of
formation of nitriles:
Propanal, propanone, methanal and 1-phenylethanone
SAQ 6
How will you prepare butanal from propanal?
Addition of Anions of Terminal Alkynes
As discussed earlier that the hydrogen atom of a terminal alkyne is weakly

acidic, and it reacts with a suitable base to generate a conjugate base, the 221
alkyne anion. Alkyne anions are carbanions and classified as strong
nucleophiles. Alkyne ions undergo addition reactions with the carbonyl group
of aldehydes and ketones. In the following example, addition of the sodium
acetylide to cyclopentanone followed by hydrolysis in aqueous acid gives
1-ethynylcyclopentanol.
- +
O HC C O Na HC C OH
+
H 3O
H C C Na +
Sodium acetylide
1-Ethynylcyclopentanol
This reaction is also very useful in synthesis as both the functional groups of
adduct (alkynyl alcohol) can be further modified. For example, acid catalysed
hydration of 1-ethynylcyclopentanol gives an α-hydroxyketone and its
hydroboration followed by oxidation with alkaline hydrogen peroxide gives a
β-hydroxyaldehyde.
O
HO C CH3
+
HgSO 4, H3O
HO C CH
-Hydroxyketone
O
HO CH2 CH
BH3
H2O 2, NaOH
b-Hydroxyaldehyde
Addition of Grignard Reagents
The special significance of the addition of the Grignard reagents on a carbonyl

group of aldehydes and ketones is that they provide excellent way to form new
carbon-carbon bond. General reaction of the addition of Grignard reagent to
aldehydes or ketone is that
1 1
1 R R
- + R H3O
+
d d ether 2+
R MgX + C O R C OMgX R C OH+ Mg
2 2 2
R R R
This reaction was discussed in earlier unit. As mentioned earlier, the carbon-
magnesium bond of a Grignard reagent is polar in nature because of the
difference in electronegativity between carbon and magnesium
(2.5 – 1.2 = 1.3). In this bond, carbon bears a partial negative charge and
magnesium bears a partial positive charge. Therefore, Grignard reagent is a
good nucleophile and adds to carbonyl group of the aldehydes and ketones to
form adduct, which on protonation in aqueous acid gives an alcohol. The
reaction of Grignard reagent with methanal (formadehyde) gave primary
222 alcohol, with other aldehydes gave secondary alcohols and with ketones gave
tertiary alcohols. Grignard reactions must be performed in dry ether. Even
traces of moisture can be neutralised the reagent. Let us study the mechanism
of the reaction of Grignard reagent with carbonyl compounds.
Mechanism: Reaction of Grignard reagent with aldehydes and ketones
When a Grignard reagent is mixed with an aldehyde or ketone, the negative

hydrocarbon group quickly attacks the positive carbonyl carbon and provides
the two electrons needed for the new carbon-carbon bond. The  electrons
are displaced to the oxygen, forming alkoxoide ion in the form of alcohol salt
(–O-[MgX]+. The alkoxide ion is strong base and when treated with an aqueous
acid such as HCl during work up, it is protonated to form alcohol.
Step 1: New bond formation between a nucleophile and an electrophile

- +
O O [MgX]
d- d+ ether 2
R MgX + C R C R
1 2
R R 1
R
Step 2: Protonation
+
[MgX] O- OH
2 + 2
R C R + H O H R C R + H2O
1 1
R H R
SAQ 7
How will you prepare primary, secondary and tertiary alcohols from same
Grignard reagent?
Addition of Organolithium Compounds
Because of high electropositivity of lithium atom, organolithium compounds

have greater negative charge on carbon. Therefore, they are generally more
reactive in nucleophilic addition reactions than organomagnesium compounds.
These compounds are very useful in addition reactions to sterically hindered
ketones. In the following example, the Grignard reagent does not react with
ketone but the organolithium does since it is stronger nucleophile.
CH3 CH3 - +
- + O O Li
O [MxBr] BrMg Li
CH3
CH3 H3C CH3
H3C CH3 H3C CH3
H3C CH3
CH3 CH3 CH3 CH3 H3C CH3
+
H3 O
OH
H3C CH3
H3C CH
H3C CH3 3
223
SAQ 8
Write the reaction mechanism of the following reaction:
PhCHO + BuLi → PhCH(Bu)OH
Wittig Reaction
A very important method of synthesis of alkenes known as Wittig reaction

involves the reaction between an aldehyde or ketone and a phosphorus ylide.
Phosphorus ylides contain a carbanion which is stabilised by an adjacent
positively charged phosphorus group.
H3C CH3 H3C CH3

C O + (C6H5)3P+ C
-
C C + (C6H5)3P O
H3C CH3 H3C CH3
Aldehyde Ylide Alkene Triphenylphosphine oxide
or ketone
In this reaction, the oxygen of the carbonyl group is substituted by an alkene

group, triphenyl phosphine oxide being the other product.
Phosphorus ylides are prepared from haloalkanes by two step sequence: the
first step is the SN2 displacement of halide by triphenylphosphine [(C6H5)3P] to
give an alkyltriphenylphosphonium salt.
R
C
H
+
6
6
R
C
H
X
+
-
2
(C6H5)3P (C6H5)3P CH2 X

An alkyltriphenylphosphonium halide
α-Hydrohen atoms on the alkyl group of an alkyltriphenylphosphonium ion now

become weakly acidic in nature due to the presence of adjacent positively
charged phosphorus atom and can be removed by very strong base such as
butyllithium (BuLi) or sodium hydride. (NaH) to give ylide.
_
+
H - + RCH P(C6H5)3
d d THF
+ -
(C6H5)3P CHR X + CH3CH2CH2CH2 Li + CH3CH2CH2CH3 + LiX
RCH P(C6H5)3
Ylide
Mechanism
The carbanion in the ylide is nucleophilic and can attack the carbonyl group.
The result is a dipolar intermediate called a betaine. The betaine is short lived
and collapses to a four membered oxaphosphacyclobutane (oxaphosphetane)
ring. This substance finally breaks to give alkene and
triphenylphenylphosphine oxide. The driving force for the last step is the
formation of very strong phosphorus-oxygen double bond.
224
Step 1: Bond formation between a nucleophile and an electrophile
H R R
+ -
(C6H5)3P C + C O CH2 C R
H R +
O
-
(C6H5)3P
A betaine
Step 2: Formation of four membered ring
R R
CH2 C R CH2 C R
+ -
(C6H5)3P O O
(C6H5)3P
Step 3: Braking of four membered ring to more stable products

R
CH3
CH2 C R
CH2 C + (C6H5)3P O
(C6H5)3P O
CH3
An alkene Triphenylphosphine oxide
Wittig reactions display useful steroselectivity. The reaction of non-conjugated

ylides (unstabilised ylides) and aldehydes typically results in Z (cis) alkenes as
major product and conjugated ylides (stabilised ylides) frequently result in
trans products. Because of this, Wittig reaction is of considerable importance
in industrial synthesis. Much of the synthetic vitamin A is manufactured by a
reaction sequence involving Wittig reaction.
SAQ 9
Show how the following alkene can be synthesised by the Wittig reaction:
CH CH3
ii) Addition of Oxygen Nucleophiles
In this section, we examine nucleophilic addition reactions of aldeydes and

ketones with water and alcohols. Both water and alcohols are very weak
nucleophiles. Therefore, these reactions are reversible and the position of
equilibrium depends on the reactivity of carbonyl group of aldehydes and
ketones.
Addition of Water
Aldehydes and ketones react with water to form 1,1-diols (Geminal diol) or
hydrates. These compounds are unstable and are rarely isolated. The reaction
is catalysed by acid or base. Hydration reaction is reversible and in most
cases, equilibrium strongly favous the carbonyl group.
225
OH
H3C Acid or base
C O + H2O H3C C OH
H3C CH3
A hydrate (a geminal diol)
Stable hydrates are known in few cases but they are rather exceptions, For
example, hydrates of 2,2,2-trichloroethanal (chloral ) methanal
(formaldehyde).
H OH
C O + H2O H C OH
H H
Methanediol
(>99 %)
The position of equilibrium depends on the reactivity of the carbonyl group and
is influenced by a combination of electronic and steric effects. With increase in
size of alkyl substituent on carbonyl group, the reactivity of the carbonyl
compounds decreases, For example,
H3C OH
C O + H2O H3C C OH
H H
Ethanediol
(58 %)
H3C OH
C O + H2O H3C C OH
H3C CH3
2,2-Propanediol
(O.14 %)
As discussed earlier, the carbon atom of carbonyl group has carbocation

character. Methanal has no alkyl substituent to stabilise its carbonyl group and
is converted almost completely into corresponding diol. The carbonyl group of
ethanal is stabilised by one alkyl substituent and carbonyl of propanone by two
alkyl substituents. Thus ethanal gives 58 % of 1,2-ehanediol while propanone
gives 0.15 % of 2,2-diol product. The reactivity of carbonyl group can be
increased by increasing carbocation character of carbon atom of carbonyl
group. This can be done by attaching electron withdrawing group to carbonyl
group. For example, in contrast to almost negligible hydration of propanone,
hexafluoroproanone is completely hydrated.
CF3 OH
C O + H2O F 3C C OH
CF3 CF3
(100 %)
Above observations can also be explained on the basis of steric factor. The
carbon atom that bears two hydroxyl groups is sp3 hybridised. Its substituents
are more crowded than are in the starting aldehyde or ketone. Increased
crowding can be better tolerated when the substituents are hydrogen than
226 when they are alkyl groups. Thus, diol of methanal is least crowded and hence
formed in larger amount. Diol of propanone on the other hand is more
crowded, therefore, is formed in a lesser amount. The amount of diol of
ethanal is formed between the above two limits. In real situation, the reactivity
of aldehydes and ketones for the formation of diol depends on the combined
effect of electronic and steric factors.
SAQ 10
Which of the following compounds do you predict would form hydrates and
why?
Cl3CCOCCl3, CH3CH2COCH3
SAQ 11
Write the mechanism of both acid and base catalysed hydration reactions.
Addition of Alcohols
We have seen above that the addition reactions of water are reversible and
the equilibrium is generally unfavourable. Therefore, addition reactions of
water to aldehydes and ketones are generally not of much significance. On the
other hand, alcohols undergo appreciable nucleophilic addition reactions to
aldehydes and ketones. Let us study these reactions in some more detail.
Aldehydes and ketones give first hemi-acetals (half-acetal) and hemiketals on
reaction with an alcohol, respectively. With excess of alcohol, they give
acetals and ketals. All these reactions are catalysed by acid or base.
OH OR'
R
Acid or base Acid
C O + R'OH R C R' + R'OH R C R'
H H H
A hemiacetal An acetal
OH OR'
R
Acid or base Acid
C O + R'OH R C R' + R'OH R C R'
R R R
A hemiketal A ketal
Hemiacetals are generally unstable and exist only in minor

concentration in the equilibrium mixture. Exception are those from
reactive carbonyl compounds such as methanal or
2,2,2-trichloroethanal.Five and six membered cyclic hemiacetals also
are quite stable. Such hemiacetals are common in sugar chemistry. For
example in aqueous solution, the cyclic forms constitute more than 99%
of the mixture.
OH OH
OH H O H
H H
H or HO-
H H H O H H H
HO HO OH
OH OH OH OH
Aldehyde form Cyclic hemiacetal

(0.003 %) (two stereoisomers)
(90 %)
227
Hemiacetals are generally not stable relative to starting materials, but they
react further with alcohols to form acetals. Acetals are more stable than
hemiacetals and can be isolated in good yield under the proper conditions.
Like other ethers, acetals are good solvents. They are stable to bases and
oxidising agents, but are cleaved even by dilute acids. The mechanism of
cleavage reaction is just the reverse of that for the formation of the acetals.
This property of acetals is used in synthesis to protect the carbonyl function
from reacting while a substitution or addition reactions is carried out elsewhere
in the molecule. After the reaction the acetal is then hydrolysed back to the
aldehyde. The example below illustrates the utility of such protection in
synthetic reactions,
O OC2H5
C2H5OH/HCl (CH3)2NH:
Cl CH2 C H Cl CH2 CH OC2H5
Protection
OC2H5 O
dil. acid
(CH3)2N CH2 CH OC2H5 (CH3)2NCH2 C H
Regeneration
Let’s study the mechanism of base-catalysed and acid-catalysed formation of

a hemiacetal.
Mechanism: Base catalysed formation of hemiacetals
Step1: Alkoxide ion is formed by the proton transfer from ROH to the base.
- -
B: + R OH BH + RO
Step 2: Nucleophilic attack on the elctrophilic carbon of carbonyl group.
H H
- -
C O + O R R C O
R OR
Step 3: Protonation of above addition compound.

H H
- -
R C O + H O R R C OH + O R
OR OR
Mechanism: Acid Catalysed formation of hemiacetals
Step 1: In presence of strong acids such as HCl or sulphuric acid, alcohol

molecules get protonated and this protonated alcohol will act as
proton source in next step.
+ -
H O R+ H Cl H O R + Cl
H
Step 2: Proton from protonated alcohol is transferred to the oxygen of

228 carbonyl group.
H H
+ +
C O + H O R C O H + HO R
R R
H
Step 3: Attack of a nucleophile (alcohol molecule) to the protonated carbonyl

group.
H H
+
C O H + HO R R C OH
+
R O
H R
Step 4: Transfer of proton from oxonium ion to an alcohol molecule.
H H H
+
R C OH + O R R C OH + H O R
+
O OR H
R H
Hemiacetal
Formation of acetal from hemiacetal is catalysed by acid, not by base as it is

difficult to displace, poor leaving group like −OH directly by a nucleophile. The
mechanism of this reaction is as followed.
Mechanism: Acid catalysed formation of an Acetal
Step 1: Protonation of hydroxyl group of hemiacetal to form oxonium ion.
H H H
+ +
R C OH + H O R R C O + HO R
OR H OR H
Hemiacetal An oxonium ion
Step 2: Loss of water molecule to form resonance stabilised carbocation.
H H H
+ + +
R C O C O R H CH OR + H2O
OR H R R
A resonance stabilised carbocation
Step 3: Nucleophilic attack on positively charged carbon atom of the carbonyl

group to form protonated acetal.
R + H
H O
+
R OH + C O R H C O R
R R
A protonated acetal
Step 4: Proton transfer from protonated acetal to alcohol molecule. 229

R + H
O OR
+
H C O R + R OH H C O R +H O R
R R H
An acetal
It is much more difficult to obtain ketals from ketones, as in most of cases the
equilibrium favour reactants rather than products. In such situation, formation
of acetal/ketal is favoured by the removing one of products, water from
reaction mixture using special distillation technique.
Notice that acetal/ketal formation requires one mole of aldehyde or ketone and
two moles of the alcohol. Alternatively, alcohols having two hydroxyl groups
can be used in equimolar ratio to prepare cyclic acetals/ketals. Cyclic acetals
or ketals are often used for protecting carbonyl group because they are easy
to prepare. Sulphuric acid and p-toluinesulphonic acid (TsOH) are commonly
used acids for the preparation of hemiacetal/hemiketals and acetals/ketals.
R R O
OH Acid
C O + HO
R R O
SAQ 12
How will you accomplish the following conversion?
O O O
O CH3 H3C OH
H3C
iii) Addition of Sulphur Nucleophiles
Thiols and sulphur analogs of alcohols react with aldehydes and ketones by
the mechanism identical with the one discussed above for alcohols. These
reactions can be catalysed by Lewis acids such as BF3 or ZnCl2. Reactions
are generally carried out in ether solvent. Cyclic thioacetals/thioketals are
particularly easy to prepare.
O
S S
ZnCl2/ether
+ HS
SH
Cyclic thioketal
Thioacetals/thioketals are stable in aqueous acids. Their hydrolysis is

carried out using mercuric chloride in aqueous acetonitrile.
Thioacetals/thioketals can be desulphurised to the corresponding
alkanes by the treatment with Raney nickel.
O
Raney Ni, H2
S S H2O, HgCl2,
CH3CN, CaCO3
230 Cyclic thioacetal

Addition of sodium bisulphate (NaHSO3)
The reaction with sodium bisulphate (sodium hydrogen sulphite) gives the
bisulphite adduct.
R OH
+ - - +
C O + Na HSO 3 R C SO3Na
R
R
The bisulphite adducts are crystalline solids. On heating with dilute acid or
aqueous sodium carbonate, they regenerate the carbonyl compound. This
reaction is often used for separation and purification of aldehydes and
ketones. The mechanism of this reaction is given below:
Mechanism: Formation of bisulphite a dduct
The reaction occurs by nucleophilic attack of the lone pair of sulphur on

the carbonyl carbon of aldehde or ketone, just like the attack of cyanide.
This leads to a positively charged sulphur atom and a simple proton
transfer leads to the product.
Addition of sulphur R
R O R
nucleophile Protontransfer R C OH
- + R -
C O + S O Na C O
+ - S O
R OH + H Na O
S O
+ - O
Na O
O Bisulphite addition
compound
iv) Addition of Nitrogen Nucleophiles
Nitrogen nucleophiles such as ammonia and its derivatives may be regarded
as nitogen analog of water and alcohols. They add to carbonyl group of
aldehydes and ketones in same fashion. However, in certain cases addition
products lose water, furnishing either of two new dehydrated products: imines
(Schiff bases) and enamines.
Addition of Ammonia and its mono substituted derivatives (GNH2)
Addition of ammonia is a reversible reaction with an unfavourable equilibrium. Organic reactions in

However, certain mono substituted ammonia derivatives are added to which two molecules of
carbonyl compounds to give imines or Schiff bases. Imine is a condensation starting materiel react
together to form a main
product in which the initial addition is followed by dehydration to form a product plus a byproduct
carbon-nitrogen double bond. The net result is substitution of oxygen by of considerably lower
nitrogen group. Imines are generally unstable unless C=N group is part of an molecular mass such as
H2O or CO etc. are
extended system of conjugation and are difficult to isolate from reaction referred to as
mixture. The general reaction can be summed up as follows: condensation reactions
and the main product is
OH R called condensation
R H3O+
H3O+ product.
C O + H2NG R C NHG C NG + H2O
R R Removal of water favours
R formation of the imine
Addition product Imine
G = Groups mentioned in Table 18.5 231

These reactions are catalyzed by acids. While protonation of carbonyl
compounds increases their reactivity towards nucleophiles. But on the other
hand, protonation of the reagent, H2NG will lower its nucleophilic character as
depicted below:
R R R
+ +
+ -H2O C OH
C O + H O H C OH
R R R
H
More electrophilic carbon
+ - H2O +
H2NG + H O H H3NG
H Conjugate acid, nitogen can
not act as nucleophile
Therefore, an optimum pH has to be maintained during the reaction. The

optimum pH for the reaction depends on the nature of G in H2NG. It is to be
adjusted such that all of H2NG is not converted to H3N+G and at the same time
there is sufficient concentration of the conjugate acid of the carbonyl
compound to activate it.
The names of reactants with different G, general condensation products and

their class are given in Table 18.5. Many of these condensation products are
crystalline solids with sharp melting points. For this reason they are frequently
employed for the preparation of aldehyde and ketone derivatives needed for
identification.
Table 18.5: Addition of ammonia derivatives
G of product Ammonia derivative Condensation Class

product
-R/-Ar RNH2,/ArNH2 >C = NR/.C= NAr Imine

Alkyl/aryl Primary aliphatic (Schiff base)
amine/aromatic amine
-OH NH2OH >C =NOH Oxime

Hydroxylamine
-NH2 H2NNH2 >C =NNH2 Hydrazone

Hydrazine
-NHC6H5 H2NNHC6H5 >C= NNHC6H5 Phenylhyrazone

Phenyl hydrazine
-NHNHCONH2 NH2NHCONH2 >C= NNHCONH2 Semicarbazone

Semicarbazide
O 2N O 2N O2N
2,4-
NH NO2 H2 N NH NO2 C NH NO2
dinitrodiphenylhyrazone
2,4-Diphenylhyrazine
232
Mechanism: Formation of imine from an Aldehyde or Ketone
A six step mechanism for the formation of imine is shown below. The first
three steps produce intermediate hemiaminal (carbinolamine) and last three
steps convert this intermediate to imine.
R R OH H
+ + -
C O + H A C O H + H2NG R C N G + :A
R - A- R
R H
Protonation of carbonyl Nucleophilic addition to Deprotonation
group carbonyl carbon
-AH
H + H
H O H OH H
R R
C NG C
+
NG + A
- R C N G H A +R C N G
-AH - H2O - : A-
R R R R A hemiaminal
Imine Deprotonation Loss of water molecule Protonation of hydroxyl group
Imines are useful compounds both in synthetic organic chemistry and in

biological systems. They are used for the synthesis of complex amines. When
the hydrazones are heated with potassium hydroxide or sodium ethoxide,
alkanes are formed with the loss of nitrogen:
R R
KOH, 423 K
C NNH2 R C H + N2
1,2-ethanediol
R H
Thus the carbonyl group is converted into a methylene group via a hydrazine.
This reaction is known as the Wolff Kishner reaction or Wolff Kishner
reduction. In this reaction, base mediates hydrogen shifts. The detailed
mechanism is given below.
R H R R
- - H2O - -
C N N + OH C N N H C N N H
R H R R
H OH
Deprotonation Protonation
R R R
CH N N H +
-
OH CH
- - Irreversible
N N CH N N
R loss of N2
Azo intermediate Deprotonation R R
- H
OH
-
R C H + H OH R C H
R R
Protonation
Like hydrazones, semicabozones can also be used in the above reaction.
Addition of Secondary Amines:
Secondary amines react with aldehydes and ketones to form enamines (en =
carbon-carbon double bond, amine =amino group). The mechanism for the
formation of an enamine is very similar to that for the formation of an imine
except last step: 233
R H R
+
N N
RNH2
RNH2
O An imine
R + R R R
N N
R2NH H H
R2NH
An enamine
Enamines behave as carbon nucleophiles during organic reactions because of

following resonance structures.
R R R + R
N N
H
-
C H
We will further go in detail of enamine chemistry and their use in synthetic

organic chemistry at higher level.
v) Addition of Hydrogen Nucleophiles
Addition of hydride donors such as lithium aluminum hydride (LiAlH4) or

sodium borohydride (NaBH4) or LiH to aldehydes and ketones gives alcohols.
This addition reaction is also called a redox reaction as the reduction of a
carbonyl compound to an alcohol takes place. In this unit, our discussion is
only focussed on the addition reaction of lithium aluminum hydride and sodium
borohydride. Both these reagents function as delivery agent of hydride (H-).
Lithium aluminum hydride is a very powerful donor of hydride. It reduces not

only the carbonyl group of aldehydes and ketones rapidly but also those of
carboxylic acid and their other functional derivatives. On the other hand,
sodium borohydride is less reactive and, therefore a much more selective
reagent, reducing only the carbonyl group of aldehydes and ketones. Because
of high reactivity of lithium aluminum hydride, non protic solvents such as
diethyl ether or tetrahydrofuran (THF) are used for carrying out the reaction
and protic solvents such as methanol or alcohols are used for the reactions of
sodium borohydride.
R
R
R O R OH
R + H O +
Ether - 3
4 C O + LiAlH 4 O Al O Li 4 R C H
R R O R R
R
R
R
R
R O R OH
R + H2O
Methanol - Na
4 C O + NaBH 4 O B O 4 R C H
R R O R R
R
R
234 A tetraalkyl borate
Mechanism: Addition of Hydride using Sodium Borohydride
Step 1: Nucleophilic hydride ion adds to the electrophilic carbonyl carbon

atom.
H R H
R
- + -
C O+ H B H Na R C O + B
R H H
H H
Step 2: The alkoxide ion produced in the first step can help stabilise the
electron-deficient BH3 molecule by adding to its empty p orbital.
Now we have a tetravalent boron anion again, which could
transfer a second hydride to another carbonyl group.
R H H
R H R
- -
- R C O B H + C O R C O
R C O + B
H H R R
H H
H
Second molecule of carbonyl
compound
This process can continue so that, in principle, all four hydrogen

atoms could be transferred to molecules of aldehyde to form
tetraalkyl borate.
Step 3: Reaction is completed with the addition of proton. Water or

alcohol solvent provides the proton needed to form the alcohol
from the alkoxide ion.
R H R
- + H2O -
R C O B H Na R C OH + BH3 + OH
H H H
SAQ 13
Write the mechanism for the addition of hydride to a carbonyl compound using
LiAlH4.
18.4.2 Reactions Involving -Hydrogen

Another important characteristic of carbonyl compounds is the acidity of
hydrogen atoms on carbon atom alpha to the carbonyl group, called
-hydrogens. We have already encountered C−H acidity in the alkynes in
earlier Unit of first semester course. Propanone is about 100,000 times
stronger as acid compared to ethyne. Because of the reactivity of the -
hydrogens, aldehydes and ketones may exist as equilibrium mixtures of the
two isomeric forms, a keto from and an enol form.
H O
H C C H
H
Ethanal has three  hydrogens 235
CH3 OH
CH3 O
H3C CH C CH3 H3C C C CH3
Keto form Enol form
This type of isomerism in which there is dynamic equilibrium between the two
forms is called tautomerism, and the isomers are called tautomers. In the pure
liquid state or in neutral solutions, only traces of the enol form are present
since enol form is less stable than the keto form.
Conversion of keto form to enol form is called enolisation. This conversion can
be achieved by catalytic reaction with both acids and bases as shown in the
following equations.
Base-catalysed enolisation
-
O O O H
- -H2O -
HO + H CH2 C CH3 H2C C CH3 H2C C CH3 + O H
Enolate ion
OH
-OH-
H2C C CH3
Acid-catalysed enolisation
+
OH OH
O
-A-
H CH2 C CH3 + H A H CH2 C CH3 H2C C CH3
- Oxonium ion
A
O
-HA
H3C C CH3
Strong acids give rise to weak conjugated bases on ionisation. The ionisation
of propaone produces -CH2COCH3 in which the negative change is
delocalised and hence, it as a weak base. On the other hand, ionisation of
CH4 produces -CH3 which is a very strong base and, therefore, CH4 is a very
weak acid. The stabilisation of the anion by resonance is responsible for the
greater acidity of propanone relative to methane and ethyne.
Enols and enolate ions are important reaction intermediates because they
react further as nucleophiles on electrophilic carbon centres to create new
carbon-carbon bonds. We will now discuss those reactions of the carbonyl
compounds in which -hydrogens are involved.
Aldol Reaction
Aldol is a composite When an enol or enolate ion adds to another molecule of the aldehyde or the
word for aldehyde + ketone, the reaction is called the aldol. This reaction is either base- or acid-
alcohol. catalysed. The mechanism of the aldol raction involving self-condensation of
two molecules of ethanal in presence of a basic catalyst is shown as an
236 example:
-
O O O
-H2O -
- H2C C H
HO + H CH2 C H H2C C H
-
O O O O
-
H3C C H+ CH2 C H H3C CH CH2 C H
Nucleophile
OH O
-H2O
H3C CH CH2 C H
-OH
b-Hydoxyaldehyde (Aldol)
The mechanism of acid catalysed aldol reaction involves following steps;
Step 1: Acid catalysed enol formation
O OH
A-
H CH2 C H + H A H2C C H
Step 2: Oxonium ion formation of second molecule of an aldehyde or a

ketone.
+
O OH
-
H3C C H + H A H3C C H + A
Step 3 and 4: Nuclephilic enol attacks on electrophilc carbon atom of

the oxonium ion and oxonium ion transfer its proton to
conjugate base, A-of acid HA.
+ +
OH OH OH OH
A-
CH3 C H + H2C C H CH3 CH CH2 C H
Nucleophile -HA
OH O
CH3 CH CH2 C H
Aldol
Ketones containing -hydrogen are also capable of aldol-type of reaction. In

the aldol reaction, one chiral centre is created so we expect two stereoisomers
are produced as two 1:1 mixture of enantiomers. Chemists have been trying to
carry out aldol and other enolate reactions in such manner that they give
enantioselective products. You may study such reactions in your higher
classes.
Aldehydes lacking -hydrogens enter into a mixed aldol condensation with

other aldehydes having -hydrogens. They do this by acting as the carbanion
acceptors. For example, benzaldehyde reacts with acetaldehyde to produce
cinnamaldehyde, an , b-unsaturated aromatic aldehyde used as a flavouring
agent: 237
O O
O CH CH C H
H OH-
+ C
H3C H
3-Phenylprop-2-enal
(cinnamaldehyde)
-Halogenation
Aldehydes and ketones having -hydrgen react at the -carbon with halogens
such as bromine or chlorine to form -haloaldehydes and -haloketones.. e.g.,
O O
C C Br
CH3 CH3COOH CH2
+ Br2
1-Phenylethanone 2-Bromo-1-Phenylethanone
(acetiphenone) (-bromoacetophenone)
Halogenation reactions on -carbon can be catalysed by both acid and base.

Acid catalysed halogenations are generally stopped at single halogen
substitution. But in the case of base catalysed halogenation, -substituted
halogen increases acidity of remaining -hydrogens; thus, they can be
removed by base with much more ease and, therefore, successive
halogenations are more rapid.
Mechanism: Acid catalysed -halogenation of an aldehde or a ketone
Step 1: Enol is formed by catalytic reaction of acid with an aldehyde or a

ketone.
O O H
H-A -
H3C C H H2C C + A
slow
H
Step 2 and 3: The nucleophilic enol then attacks on electrophilic end of
polarised halogen molecule and gives α-substituted
intermediate which in final step transfer its proton to conjugated
base of acid to gives an α-haloaldehyde or an α-haloketone.
H +
- O H O H
d +
d fast - A-
Br Br + H2C C Br + Br C C
H H fast
H H
O
Br C C + H-A
H
H
-Haloaldehyde
Mechanism: Base catalysed α-halogenation of an aldehyde or a ketone
In the first step, base removes an α-hydrogen from an aldehyde or a ketone to

form enolate ion. In next step, this enolate ion attacks on electrophilic halogen
238 to gives an α-haloaldehyde or an α-haloketone.
H O -
O
slow
H C C H H2C C + H2O
-
OH H
H Enolate ion
- H O
+ -
O
d d fast -
Br Br + H2C C Br + Br C C
H H
H
-Haloaldehyde
Because of high reactivity of the remaining α hydrogens, base catalysed

halogenation tends to give polyhalogenation products. For this reason base
catalysed halogenations have less synthetic use.
Furthermore, when ethanal or methyl ketones are warmed with an alkalie

solution of chlorine, bromine, or iodine, the product is trichlromethane
(chloroform), tribrimomethane (bromoform), or tri-iodomethane (iodoform),
respectively. This reaction is called the haloform (trihalomethane) reaction and
appears to take place in two stages:
Stage 1: Halogenation
H O Cl O
H C C H + 3Cl2 + 2NaOH Cl C C H + H2O + 3NaCl
H Cl
Stage 2: Cleavage
-
Cl O O O
+ - -
Cl C C H OH Cl3C C H CCl3 + H C OH
Cl OH Methanioic acid
O
-
Cl3CH + H C O
Trichloromethane
(cloroform)
The first step is polyhalogenation via the enlolate ion. The second step is Ethanol or 2-propanol
cleavage of the polarised Cl3C−C bond by base through an addition also gives idoform test
as these compounds are
elimination mechanism. The haloform reaction is useful not only as a oxidised by iodine during
preparartive method for the haloforms but also as a diagnostic test for the reaction to ethanal and
presence of the methyl ketone group or a group capable of giving methyl propanone, respectivily.
ketone group under the dehydrogenation. In practice, a solution of iodine is 2CH 3CH 2OH + I 2
added to the aqueous alkaline solution of the compound to be tested. A CH 3CHO + 2HI
positive reaction will yield tri-iodomethane (iodoform), CHI3, a bright yellow 2CH 3CHOHCH 3 + I2
solid which may be identified by its sharp pungent odour and its melting point. CH 3COCH 3 + 2HI
Trichloromethane and tribromomethane are liquids.
R R - O
I2/OH- OH -
C O C O I3 H + H C O
H3C CI3 Triiodomethane
(idoform) 239
SAQ 14
A carbonyl compound does not form iodoform on being heated with iodine and
sodium hyroxide. It is:
a) ethanal
b) propanone
c) benzaldehyde
d) phenylethanone
18.4.3 Oxidation
Aldehydes are oxidised so easily that even the mildest oxidising reagents will
serve to bring about their conversion to acids. Ketones, on the other hand, are
fairly resistant to oxidation. The oxidation of ketones, when forced by the use
of strong oxidizing reagents and heat, results in the rupture of carbon-carbon
bonds to produce acids.
O O O
KMnO4/H3O
H3C C CH2CH3 H3C C OH + CH3CH2 C OH
The ease with which oxidation of aldehydes takes place, provides a simple
method for distinguishing between aldehydes and ketones. Mild oxidising
agents may be used for this purpose. Tollen’s reagent, an ammonical
solution of silver oxide, Ag(NH3)2OH, Fehling’s solution, an alkaline solution
of cupric ion complexed with sodium potassium tartrate and Benedicts
solution, an alkaline solution of cupric ion complexed with sodium citrate, are
the three reagents commonly used to detect the presence of an aldehyde
group.
When Tollen’s reagent is used to oxidise an aldehyde, the silver ion is reduced
to the metallic form and, if the reaction is carried out in a clean test tube, a
silver mirror is formed.
O O
2Ag(NH3)2OH - +
R C H R C O NH4 + 2Ag + H2O + 3NH 3
When Fehling’s and Benedict’s solutions are used to oxidise an aldehyde, the
complexed deep blue cupric ion is reduced to red cuprous oxide.
O O
2Cu(OH)2/NaOH
-
+
R C H R C O Na + Cu2O + 3H 2O
Aromatic aldehydes react with the Tollen’s reagent but do not react with either
Fehling’s or Benedict’s solution. A method of distinguishing aliphatic aldehyde
from aromatic aldehydes is thus provided by this difference in reactivity
240 between the two types of reagents.
18.4.4 Reduction
Both aldehydes and ketones undergo reduction and the nature of the product
depends on the reagent used for the purpose. Catalytic hydrogenation of
aldehydes and ketones gives primary and secondary alcohols, respectively.
Reduction with dissolving metals (e.g., sodium-alcohol) gives alcohols similar
to metallic hydrides (lithium aluminium hydride or sodium borohydride).
O OH
Pt or Ni, presuure
R C H + H2 R C H
H
Primary alcohol
O OH
Pt or Ni, presuure
R C R + H2 R C H
R
Secondary alcohol
Alkanes are formed when carbonyl compounds are reduced with zinc
amalgam and hydrochloric acid. This reaction is known as the Clemmensen
reduction.
H
R
Zn(Hg)HCl
C O R C H
R H
An alternative to the Clemmensen reduction for an acid sensitive ketone is the

Wolff-Kishner reduction. As mentioned earlier, this employs hydrazine
(NH2NH2) and potassium hydroxide. The solvent is 1, 2-ethanediol (glycol).
R H
KOH, 423 K
C O + NH 2NH 2 R C H
1,2-ethanediol
R R
18.4.5 Specific Reactions of Aldehydes and Ketones

Methanal
Methanal (formaldehyde) gives many of the general reactions of carbonyl
compounds above but as it does not have  hydrogens and therefore, it does
not undergo those reactions in which -hydrogens are involved. Thus, for
example, it does not undergo base-catalysed self condensation. On treatment
with aqueous sodium or potassium hydroxide it forms methanol and
methanoate ion. This reaction is known as the Cannizzaro reaction.
- -
2HCHO + OH HCOOO + CH3OH
Metanoate ion Methano
Benzaldehyde which also does not have any -hydrogen undergoes the
Cannizzaro reaction as well, e.g.,
- -
2C 6H5CHO + OH C6H5COO + C6H5CH2OH
Benzoate ion Benzyl alcohol 241
Mechanism: Cannizzaro reaction
Reaction is initiated by the addition of hydroxide ion to the carbonyl carbon to

form an addition intermediate, which transfers a hydride to a second molecule
of methanal in the rate determining step. After the proton transfer in final step,
final product are methanol and eathanoate ion.
- -
O O O O O
- fast slow
H C H + OH H C H + H C H H C OH + H C H
OH H
Hydride transfer
O OH
-
H C O + H C H
H
Treatment of methanal with ammonia gives hexamethylenetetramine:
Hexamethylenetetramine is also called urotropin and has following cyclic
structure.
CH2
NO 2 CH2 NO 2
N N N
N
CH2 CH2 HNO3
HCHO + NH 3 N CH2
CH2
CH2 CH2 N
CH2
N NO 2
Hexamethylenetetramine Cyclonite(RDX)
Hexamethylenetetramine is medicinally useful as a urinary antiseptic

(urotropine) and is also oxidized by nitric acid to the important military
explosive cyclonite (RDX).
Methanal is also used as a methylating agent:

C2H5NH 2 + HCHO + HCOOH C2H5NHCH 3 + CO2 + H2O
Aldehydes
Here we will consider reactions which are given by aldehydes only and not by
ketones. Aldehydes restore the magenta colour of Schiff’s reagent (aqueous
rosaniline hydrochloride solution whose magenta colour has been discharged
by sulphur dioxide).
As mentioned earlier, aldehydes are very easily oxidised. Hence, they reduce
Tollens’ reagent to metallic silver, and Fehling’s and Benedict’s solutions to
cuprous oxide.
Aldehydes (except methanal) on being warmed with concentrated sodium

hydroxide solution, undergo aldol condensations and dehydration. Methanal
and ethanal polymerise readily, propanone does not. The polymer of
formaldehyde is known as paraformaldehyde, HO(CH2O)nH, with n having an
average value of 30. Paraformaldehyde is an amorphous white solid which is
prepared by slowly evaporating formalin (a 37-40% aqueous solution of
242 methanal) under reduced pressure.
H
H2C O + H2O HO CH2 OH + n H2C O HO [ C ] n H
H
Depolymerisatin of paraformaldehyde is brought about by heating. This facile
change of state from solid to gaseous allows methanal to be easily stored and
used.
When treated with acid at a low temperature, ethanal undergoes addition to

give a cyclic trimer, paraldehyde (b.p. 389 K). Paraldehyde, when warmed, is
depolymerised to regenerate ethanal. Like methanal, ethanal can also be
easily stored and is used in the form of paraldehyde.
H3C H
O
Acid O O
H3C C H
H CH3
O
H3C H
Paraldehyde
Finally in the following subsection, we will see the reactions which are given
by ketones only and not by aldehydes.
Ketones
Ketones react with ammonia to give complex condensation products.
Treatment with nitrous acid converts ketones to oximino derivatives, e.g.,
O O
H3C C CH3 + HNO 2 H3C C CH NOH
When reduced with magnesium amalagam and water, ketones give dimers.
The dimer from propanone is called pinacol.
O CH3 CH3
Mg-Hg/H2O
H3C C CH3 H3C C C CH3
OH OH
Pinacol
Treatment of ketones with preacids gives esters. This reaction is known as

Baeyer-Villiger oxidation:
O
R C R + R'COOOH RCOOR + R'COOH
18.5 INDUSTRIAL USE

Methanal is perhaps the most important member of the aldehyde family. Its
industrial importance lies principally in its ability to copolymerise with phenol
and with urea to produce bakelite and urea methanal resins, respectively. 243
Methanal is also an antiseptic and disinfectant. As formalin, it is used to
preserve anatomical specimens, in the manufacture of dyes, gelatin and
casein.
Ethanal is used for preparing ethanol, ethanoic acid, phenolic resins, synthetic
drugs and rubber accelerators. Its trimer, paraldehyde (CH3CHO)3, is used in
medicine as a hypnotic.
Propanone is used as a solvent for celluloid, lacquers, cellulose acetate and

nitrate and in the preparation of sulphonal and ketene (CH2=C=O) for
synthesis of organic compounds. Other ketones are used as solvents for
resins and synthetic rubber.
Benzaldehyde is used in perfumery, for preparation of dyes for flavouring

purposes and for the preparation of , b-unsaturated derivatives.
Phenylethanone (acetophenone) is used in perfumery and as hypnotic

(hypnone). It is also used in the preparation of many organic compounds
which are used in synthesis such as, phenacyl halides 1, 3-diketones, etc.
Some insecticides are prepared from the condensation of carbonyl compound,

e.g., DDT (Unit 11) is obtained by heating trichloroethanal (chloral) with
chlorobenzene in the presence of concentrated sulphuric acid.
18.6 LAB DETECTION

Both aldehydes and ketones on heating with an alcoholic solution of
2,4-dinitrophenyl hydrazine (DNP) in acidic medium give orange red
crystalline hydrazine derivatives which are identified by their characteristic
melting points.
O2N O2N
O R
R C R + H2N NH NO 2 C N NH NO 2
R
Aldehyde or Ketone 2,4-Dinitrophenyl hydrazine 2,4-Dinitrophenyl hyrazone
Aldehydes reduce Tollens’ reagent and Fehling or Benedict solutions, while

ketones do not. These tests provide methods for distinguishing between
aldehydes and ketones. Glucose (an aldehyde) when heated with Fehling
solution gives red precipitate. This test is both qualitative as well as
quantitative. It is used to estimate the amount of glucose in a sample of urine
of diabetic patients. As mentioned in Section 18.4.2, ethanal and methyl
ketones are characterised through the tri-iodomethane test (iodoform test).
SAQ 15
How might you use simple test tube reactions to distinguish between:
a) Benzaldehyde and ethanol
b) Ethanal and propanone

244
18.7 SUMMARY
In this unit, we have described the chemistry of aldehydes and ketones. We
summarise below what we have studied so far:
 Aldehydes and ketones have carbonyl (> C=O) group which is quite
reactive. Ketones can be regarded as alkyl or aryl derivatives of
aldehydes.
 Aldehydes and ketones are prepared by oxidation or dehydrogenation of

alcohols, decomposition of calcium salt of carboxylic acids or catalytic
decomposition of carboxylic acids, Rosemund’s method and Stephen’s
method.
 Methanal is commercially obtained by the catalytic oxidation of methanol.

Ethanal and propanone are prepared industrially either by hydration of
alkynes or catalytic oxidation of alkenes. Propanone is also obtained from
oxidation of natural gas and as a by-product in the oxidation of cumene.
 The > C = O function in aldehydes and ketones undergoes addition

reaction. As it has a polarized caron oxygen double bond, nucleophiles
add to the carbonyl carbon atom and electrophiles add to the carbonyl
oxygen atom.
R d+ d+
- C O
Nu: E+
R
Carbonyl group is attached by a variety of reagents such as HCN,

NaHSO3, ROH, ammonia derivatives, RMgX etc. to give addition
products.
 The reaction of aldehydes and ketones with phosphorous ylildes gives

alkenes (Wittig reaction). In certain aldehydes and ketones, where
-hydrogens are present, acid or base catalysed enolisation, base-
catalysed halogenation, haloform reaction and aldol condensation, etc.,
are observed.
 Aldehydes can be oxidised to carboxylic acid; ketones cannot be oxidised

without breaking carbon-carbon bonds. The carbonyl group of an
aldehyde or ketone can be reduced to alcohol by either catalytic
hydrogenation or metallic hydrides. They can also be reduced to alkanes
by either the Wolff-Kishner or Clemmensen reduction.
 Methanal reacts with aq. NaOH to give a mixture of alcohol and

carboxylate ion (Cannizzaro reaction). Methanal reacts with ammonia to
form hexamethylenetetramine. Methanal and ethanal readily polymerise.
 Ketones from oximino derivatives with HNO2, are oxidised to esters with
peracids and form pinacols with magnesium amalgam water.
 Detection of carbonyl group is achieved by the formation of crystalline 2,

4-dinitrophenyl hydrazones. Aldehydes are detected by the reduction of
ammoniacal silver nitrate or Fehling solution and by Schiffs’ reagent. 245

1. Predict the products in the following reactions:
CrO3
a) RCH2OH
Pyridine
H3O+
b) HC CH
Hg2+
O
H2/Pd(BaSO4)
c) H3C C Cl
1. SnCl2/HCl
d) H3C C N
2. H2O
2. Write a mechanism for the reaction of:
a) addition of methanol to propanal.
b) addition of hydrazine to cyclohexanone.
3. Predict the products:
O
H3O+
a) H3C C CH3 + H2NNH 2
O
DMSO
b) CH3CH2 C CH3 + CH2P(C6H5)3
c) CH3CHO + Ag(NH 3)OH

O
OH-
d) H3C C CH3 + Br2
O
H2NNH2, NaOH
e) CH3CH2CH2 C CH3
1,2-ethanediol
O
Zn(Hg), HCl
e) H3C C CH3
4. Show how to bring about the following conversions using Wittig reaction:
a) acetone to 2-methyl-2-butene
b) cyclohexanone to methylenecyclohexane
5. Write equations for the following named reactions.
a) Oppenaur oxidation
b) Cannizzaro reaction
d) Aldol condensation
246 e) Baeyer-Villiger oxidation

18.9 ANSWERS
1. a) 3-methyl-3-butenal; b) cyclohaxanecarbaldehyde;
c) cyclohexanone; d) 1-phenylbutanone
2. a) 1-pentanol; b) 3-methyl-2-butanone; c) 2-pentanol; d) cyclohexanone; e)

1-pentanal
3. 2-Chloropropane
4. Propanone can be manufactured by the direct oxidation of propene from

natural gas with oxygen or air, catalysed by a mixture of palladium and
cuprous chlorides (The Wacker Process).
O
PdCl2, CuCl2/H2O
CH3 CH CH2 + 1/2O 2 C
523 K, 70 atm. H3C CH3
5. Methanal > propanal > propanone > 1-phenylethanone
6. H + H
KCN/HCl H3 O
CH3CH2CHO CH3CH2 C OH CH3CH2 C OH
Propanal CN COOH
-H2O
reduction
CH3CH2CH2CHO CH3CH2 CH COOH
Butanal
7. Reaction of a Grignard reagent with methanal gives primary alcohol,

reaction with other aldehydes gives secondary alcohols and reaction with
ketones gives tertiary alcohols.
8. The mechanism will be same as for the reaction of Grignard reagent with
aldehydes and ketones.
9. It can be prepared using cyclohexanone and ylide prepared from

chloroethane.
10. As discussed in text, reactivity of carbonyl group can be increases by

increasing carbocation character of carbon atom of carbonyl group.
Cl3CCOCCl3 has electron withdrawing group (−CCl3) attached to carbonyl
group. Therefore this will form hydrates.
11. Mechanism of base catalysed hydration reaction:

Step 1
- -
B: + H OH BH + HO
Step 2
H H
- -
C O + O H R C O
R OH
247
Step 3
H H
- -
R C O + H O H R C OH + O H
OH OH
Mechanism of Acid catalysed hydration reaction:
Step 1
+ -
H O H +H Cl H O H + Cl
H
Step 2
H fast H
+ +
C O + H O H C O H + HO H
R R
H
Step 3
H H
+
C O H + HO H R C OH
+
R O
H H
Step 4
H H H
+
R C OH + O H R C OH + H O H
+
O OH H
H H
Hydrate
12. First we have to protect ketone group by forming cyclic acetal, than
acetal is hydrogenated to convert easter group to alcohol. Final it is
treated with either base or acid back to ketone.
O
O O acid/base O O
O CH3 H3C O CH3
H3C
[H]
O
H Acid/Base
H3C O O O
H
H3C O
13. Step 1
H R H
R
- + -
C O +H Al H Li R C O + Al
R H H H
H
248
Step 2
R H H
R H R
- - -
- R C O Al H + C O R C O
R C O + Al
H H R R
H H
H
Second molecule of carbonyl
compound
Step 3
R H R
- - + H2O or ROH
R C O Al HLi R C OH
H H H
14. c; as it is not having -hydrogens.
15. a) Ethanal reduces both Tollen’s reagent and Fehling’s solution.

Benzaldehyde can reduce Tollen’s reagent but it does not reduce
Fehling’s solution. Ethanal also gives iodoform test.
b) Ethanal reduces both Tollen’s reagent and Fehling solution propanone

does not.
Terminal Questions
O
CrO3
1. a) RCH2OH H3C C H
Pyridine
O
H3O+
b) HC CH RCH2 C R
Hg2+
O O
H2/Pd(BaSO4)
c) H3C C Cl R C H
1. SnCl2/HCl O
d) H3C C N R C H
2. H2O
2. a)
O + OH
H O H HO CH3
CH3CH2 C CH3 + H CH3CH2 C CH3
+
+
OH + HOH OCH3
+H3O HO CH3
CH3CH2 C CH3 CH3CH2 C CH3 CH3CH2 C CH3
-H3O+ +H3O+
H OCH3 OCH3 OCH3
+ -H3O+
b) H
+
N NH2
H3O+ -H2O
O + H2N NH2 H N NH2
OH
249
O NOH
H3O+
3. a) H3C C CH3 + H2NNH 2 H3C C CH3
O CH2
DMSO
b) CH3CH2 C CH3 + CH2P(C6H5)3 CH3CH2 C CH3
O
c) CH3CHO + Ag(NH 3)OH - +
H3C C O NH 4 + 2Ag + H2O + 3NH 3
O
OH- -
d) H3C C CH3 + Br2 CH3COO + CHBr3
O
H2NNH2, NaOH
e) CH3CH2CH2 C CH3 CH3CH2CH2CH3CH3
1,2-ethanediol
O
Zn(Hg), HCl
f) H3C C CH3 CH3CH2CH3
4. a) H3C H3C
O + (C6H5)3PCHCH3
H3C H3C CH3
b) O + (C6H5)3PCH2 CH2
OH O O OH
Al(tert-BuO)3
5. a) R HC R + H3C C CH3 R C R + H3C HC CH3
- -
b) 2HCHO + OH HCOO + CH3OH
OH
c) 2CH3CHO H3C HC CH2CHO or H3C CH CH2CHO
O
d) R C R + R'COOOH RCOOR + R'COOH
250
Unit 19 Aromatic Aldehydes and Ketones
UNIT 19
AROMATIC ALDEHYDES
AND KETONS
Structure
19.1 Introduction Acetophenone
Expected Learning Outcomes Reactions due to the Benzene

Ring
19.2 Preparation of Bezaldehyde
and Acetophenone 19.4 Summary
19.3 Reactions of Aryl Aldehydes 19.5 Terminal Questions
and Ketones
19.6 Answers
Benzaldehyde
19.1 INTRODUCTION
In the previous unit, we have already discussed the chemistry of aliphatic
aldehydes and ketones. Aromatic aldehydes and ketones also show the usual
reactions associated with carbonyl group but they display some unique
reactions arising from the influence of the aromatic group. Benzaldehyde and
phenylethanone (acetophenone) are the simplest example of aromatic
aldehydes and ketones, respectively. Benzaldehyde is present in bitter
almonds in the form of its glucoside, amygdalin (C20H27O11N). When
amygdalin is boiled with dilute acids, it hydrolyses and converts into
benzaldehyde, HCN and glucose. Phenylethanone, which is known by its
preferred name acetophenone, is naturally found in several fruits. It has Amygdalin
distinct organic scent. Thus, it is often used in scenting lotions and flavoring
foods. Acetophenone has also been used in medicine as hypnotic under the
trade name hypnone. In this unit, we will take up preparations and reactions of
benzaldehyde and acetophenone in detail.

 explain how aromatic aldehydes and ketones can be prepared; and
 describe the reactions due to both carbonyl group and aromatic ring of
aromatic aldehydes and ketones.
251
19.2 PREPARATION OF BEZALDEHYDE AND

ACETOPHENONE
Benzaldehyde can be obtained by the following methods.
i) By Hydrolysis of (dichloromethyl)benzene (benzal chloride)
Benzaldehyde is prepared by the hydrolysis of (dichloromethyl)benzene

(benzal chloride) in either aqueous acid or aqueous alkali.
- +
C6H5CHCl2 + OH or H 3O C6H5CHO
ii) By oxidation of (chloromethyl)benzene
Mild oxidising agents like copper or lead nitrate convert

(chloromethyl)benzene (benzyl chloride) into benzaldehyde while
reagents like HNO3 convert it into benzoic acid.
aq. PbNO3
2 C6H5CH2Cl 2C 6H5CHO + PbCl2 + 2HNO 3
(Chloromethyl)benzene can also be converted to benzaldeyde by the

Sommelet reaction. This reaction involves refluxing
(chloromethyl)benzene in aqueous solution with
hexamethylenetetramine followed by hydrolysis.
N N
X-
+
N N N N Ar ArCHO
Ar- X + N CHCl3 N H2O
iii) Oxidation of methylbenzene (toluene)/phenylmethanol (benzyl

alcohol)
Methylbenzene (toluene) can be oxidised with chromium trioxide and

ethanoic anhydride (acetic anhydride) or with chromyl chloride (Etard'
reaction) to gives benzaldehyde:
CrO3/(CH3CO)2O H3O+
C6H5CH3 C6H5CH(OAc)2 C6H5CHO
or CrOCl2
In this preparation, acetic anhydride prevents further oxidation of

benzaldehyde by converting it into diacetate. Subsequent hydrolysis
generates the aldehyde group. Phenylmethanol (benzyl alcohol) can
also be oxidised to benzadehyde using chromium trioxide in acetic acid.
CrO3, AcOH
C6H5CH2OH C6H5CHO
iv) By direct formylation of benzene
There are several methods for the introduction of the formyl group
(CHO) into aromatic ring. You have already studied Gattermann-Koch
formylation and Gattermann synthesis in the previous unit. In
252 Gattermann-Koch reaction carbon monoxide and hydrogen chloride are
passed through a solution containing benzene and aluminium chloride.

Formyl cation (H C =O) formed during reaction undergoes electrophilic
substitution with benzene.
H CHO CHO
+ +
[HC=O][AlCl4-] -
AlCl 4 + HCl + AlCl 3
In a related reaction, Gattermann synthesis, the carbon monoxide is

replaced by hydrogen cyanide. This reaction precedes via aryl imine
followed by treatment with water.
AlCl 3 +
HCl + HCN HN CHCl
HC NH CHO
+
HN CHCl H2O
HCl + NH 4Cl
AlCl3
There is another interesting example of formylation reaction called

Vilsmeier-Haack reaction. Activated aromatic compounds such as
phenols, aryl ethers and aryl amines can be formylated by a mixture of
N,N-dimethylformamide [HCON(CH3)2] and phosphorus oxychloride
(POCl3). The reaction involves electrophilic attack of a intermediate,
chloroiminium ion [(CH3)2N=CHCl], which is formed by the reaction of
N,N-dimethylformamide and phosphorus oxychloride. Hydrolysis of
dimethyl imine gives final product.
O
Cl
O O P Cl
+ O Cl
C P Cl - C +
H Cl Cl C + H N(CH3)2
N(CH3)2 Cl N(CH3)2
H
N(CH3)3
Cl
Cl
(CH3)3N CH
+ C + H N(CH3)3
H N(CH3)2
N(CH3)3
-H+
Cl + H2O
(CH3)3N CH
-
N(CH3)3 - Cl
CHO
v) By Rosenmund reduction and Stephens reaction
The Rosenmund reduction is controlled hydrogenation of acid halides in

presence of a catalyst poison, BaSO4 or quinoline/sulphur, which
prevents over reduction to alcohols. In the Stephens reaction, a nitrile 253
group is reduced by tin(II) chloride and HCl to imine salt which is
hydrolysed to give benzaldehyde.
O O
C C CN
Cl H /Pd +BaSO H SnCl2/HCl
2 4
Rosenmund reduction Stephens reaction
Acetophenone can be obtained by the following methods.
v) By the Friedel-Crafts Acylation Reaction
Aryl ketones can be prepared by Friedel-Crafts acylation reaction. For

example, acetophenone is prepared as follows:
O
O C
AlCl3 CH3
+ H C C Cl
3
Benzene Ethanoyl chloride Phenylethanone

(acetophenone)
Phenolic aromatic ketones can be prepared by Fries rearrangement

and Hoesch reaction or Houben–Hoesch reactions.
O OH
C OH O
O CH3
C
AlCl 3 CH3
D +
C
Fries rearrangement H3C O
Hoesch reaction or Houben–Hoesch reaction is variation of Gattermann-

Koch formylation. In this reaction, activated aromatic compounds such
as dihydric and trihydric phenols can be acylated by reaction with
acetonitrile in presence of a Lewis acid usually Zinc chloride and HCl.
This reaction proceeds via formation of an iminium salt, which is isolated
and subsequently hyrolysed.
OH OH OH
ZnCl2 HCl H2O

+ CH3CN
ether
HO OH HO OH
HO OH
C C
H3C NH H3C O
Houben-Hoesch reaction
Commercially benzaldehyde and acetophenone are preapared as

follows:
Benzaldhyde is prepared commercially by the oxidation of

254 methylbenzene. This is done either in the vapour phase or in the liquid
phase. In the vapour phase oxidation, methylbenezene (toluene)
vapours, mixed with air, are passéd over a catalyst, a mixture of oxides
of manganese, molybdenum, ziroconium etc., heated to 773 K:
O2/cat. O
C6H5CH3 + H2O
C
773 K
Ph H
Liquid phase oxidation uses manganese dioxide and 65% suplhuric acid
at 313 K.
Acetophenone is manufactured by the oxidation of ethylbenzene with air

in the presence of manganese ethanoate as catalyst at 399 K:
O
Mn(CH3COO)2/air
C6H5CH2CH3 C
399 K
Ph CH3
SAQ 1
Benzaldehyde is obtained by the hydrolysis of:
a) methyl benzoate
b) (chloromethyl)benzene
c) (dichloromethyl)benzene
SAQ 2
How will you prepare 2,6-dihydroxyacetophenone from benzene-1,3-diol?
19.3 REACTIONS OF ARYL ALDEHYDES AND

KETONES
The major differences between aromatic carbonyl compounds and most
aliphatic analogues are that i) the carbonyl group of former reacts with
nucleophile at a much slower rate ii) the aromatic ring of former also reacts
with electrophile at a slower rate and iii) those reactions depending upon the
presence of alpha hydrogen are not observed in the case of benzaldehyde.
The less reactivity of carbonyl group of aromatic aldehydes and ketones

towards nucleophilic attack can be attributed to the resonance interaction
between carbonyl group and aromatic ring.
- - - -
H3C H3C O HC O H3C O H3C O
O + 3
C C C C C
C C C C C
+ +
+
Resonating structures of acetophenone 255
The result of this resonance interaction is
i) a weakening of the positive charge on the carbonyl carbon atom through

dispersal of the charge into the ring, and
ii) deactivation of ring.
Because the carbon atom of carbonyl group attached to the ring is positively
charged due to the electrongativity of oxygen atom, thus carbonyl group
behaves as an electron withdrawing group and so it deactivates the ring
towards electrophilic substitution reactions. As illustrated above, ortho and
para positions have positive charges and the electron density at the meta
position is not much affected by the carbonyl group. Therefore, the
electrophiles preferably go to the meta position. Thus, both benzldehyde and
acetophenone will form major meta disubstituted products and attack of
electrophile will be slower than attack in benzene.
Formation of the major meta product can also be explained on the basis of the
stability of the cyclohexadienyl cation intermediates formed on attack of
electrophile. The intermediates for ortho and para substitution are particular
unstable because each has a resonance structure in which there is a positive
charge on the ring carbon that bears the electron-withdrawing substituent.
Such situation is not observed in case of meta attack.
d  d  d 
O d CH3 O d CH3 O d CH3
C C C
E
+ + +
H E
H
H E
Unstable because Positively charged atoms Unstable because
of adjacent positively not adjacent, of adjacent positively
charged atoms most stable intermrdiate charged atoms
With the above general ideas, it will be easier to understand the reactions of
aromatic aldehydes and ketones. Many of the reactions, which aliphatic
aldehydes and ketones undergo, are also shown by aromatic aldehydes and
ketones. In next sub-section, our focus mainly will be on the reactions, which
show exceptional behaviors.
SAQ 3
Why are aromatic aldehydes and ketones less reactive than alphatic
aldehydes and ketones for nucleophilic attack?
19.3.1 Benzaldehyde
Reactions of Aldehyde Group
Even though the carbonyl group of benzaldehyde is less reactive than

carbonyl group of aliphatic aldehydes, benzaldehyde gives many general
256 reactions of aldehydes as described in previous unit. Benzaldehyde forms
many useful intermediate products with a range of nitrogen nucleophiles.
Imines (Schiff bases) are formed with amines, hydrazones with hydrazines,
semicarbazones from semicabazide and oximes from hyroxylamine. These
products are of value in the synthesis of heterocycles.
Catalytic hydrogenation and chemical reduction convert benzaldehyde to

phenyl methanol (benzyl alcohol). On the other hand, Clemmension and Wolff-
Kishnner reduction converts it into methylbenzene (toluene).
O
C
H OH
H2/Ni
or NaBH4
O Phenylmethanol
C H CH3
Zn/Hg+ conc. HCl
or H2NNH2/NaOH
Methylbenzene (toluene)
Benzaldehyde reacts with zinc and hydrochloric acid or with sodium amalgam
and undergoes reductive dimerisation to give 1,2-diphenyl-1,2-ethanediol
(hydrobenzoin):
O H H
2[H]
C6H5 C H C6H5 C C C6H5
OH OH
Hydrobenzoin
However, it does not reduce Fehling’s solution but is easily oxidised by mild
oxidising agents such as ammoniacal silver nitrate (Tollens’ reagent). These
two reactions are used to differentiate benzaldehyde from aliphatic aldehydes
and ketones. Even atmospheric oxygen is enough to convert this to benzoic
acid. When benzaldehyde is exposed to air, it forms a peroxide, perbenzoic
acid, which oxidises another molecule of benzaldehyde as follows:
O O
O
C C OH
H O C
C6H5CHO OH
+ O2
Perbenzoic acid Benzoic acid
This type of oxidation, known as auto-oxidation, may be prevented by adding

small amount of any antioxidant such as hydroquinone.
Formation of cyanohydrin from aromatic aldehydes and ketones with hydrogen

cyanide is not a very useful reaction, but benzldehyde undergoes
condensation reaction on refluxing with aqueous ethanolic potassium cyanide
and forms benzoin. This condensation is known as benzoin condensation.
O OH O
KCN
2 C6H5 C H C6H5 CH C C6H5
Benzoin 257
The mechanism of this condensation reaction is as follows:
Ph OH Ph
Ph
- -
C O + CN H C O Ph C CN + C O
- H
H CN
- -
OH O O OH O OH
- CN-
Ph C C Ph Ph C C Ph Ph C C Ph
CN H CN H H
Benzoin
As mentioned above, benzadehyde does not have an alpha hydrogen.
Therefore, it cannot be enolised and therefore, enolate/carbanion cannot be
generated from it. However, benzaldehyde can react with enlolates/carbanions
generated from other aldehydes, ketones, esters, anhydrides, and so
undergoes wide range of condensation reactions.
We have seen earlier that benzaldehyde undergoes mixed aldol condensation

with aldehydes or ketones having -hydrogen in the presence of alkali to form
, -unsaturated carbonyl compounds. This reaction is also known as
Claisen-Schmidt reaction.
O O
OH-
C6H5 C H + H3C C H C6H5CH CHCHO
3-Phenylpropenal
(Cinnamaldehyde)
O O O
OH-
C6H5 C H + H3C C CH3 C6H5CH CH C CH3
Benzylidene acetophenone or
Benzal acetophenone
On treatment with ethanoic anhydride and sodium ethanoate, benzaldehyde

gives 3-phenylpropenoic acid (cinnamic acid). This condensation is known as
Perkin reaction.
1. CH3COO-Na+/NaOH
O O O 2. Acid workup
C 6H 5 C H + H3C C O C CH3 C6H5CH CHCOOH
3-Phenylpropenoic acid
(Cinnamic acid)
Benzaldehyde also gives 3-phenylpropenoic acid with propanedioic acid

(malonic acid) in the presence of pyridine. This reaction is known as
Knoevenagel condensation.
O
Pyridine
C6H5 C H + CH2(COOH)2 C6H5CH CHCOOH
(cinnamic acid)
Mechanistically, both the named reactions discussed above proceed by a

common pathway involving four steps:
258
Step 1
Generation of a carbanion: Carbonyl compounds having active α-hydrogen
generate the resonance-stabilised enolate anion on reaction with a base.
O O O-
C -HBase R - C R C
R
- C C C
Base: R R R
H H H
H
An enolate anion
Step 2
Making a new C−C bond between a nucleophile and an electrophile:
Nucleophilic addition of the enolate anion to the carbonyl carbon of
benzaldehyde gives addition intermediate, oxyanion.
-
O O
O O CH C
C C CH3
H R - C
C R R H
+
H
Step 3
Protonation of the oxyanion formed in the previous step: Reaction of the
oxyanion intermediate with a proton donor gives the aldol product and
generate a new base catalyst.
OH O
-
O O
C C
C -
:Base C CH3
C CH3 H
C + Hbase R H
H
R H
Step 4
Dehydration of the aldol product: In such aldol condensation reactions,
dehydration of the aldol product is rapid, which leads to formation of the more
thermodynamically sable α,β-unsaturated product and prevent the retroaldol
reaction from taking place.
O O
OH H
CH C C C
CH3 C CH3
Base
H R R
-H2O
Benzaldehyde undergoes Cannizzaro reaction as discussed with

formaldehyde, in which two molecules of benzaldehyde react to produce one
molecule of benzoic acid one molecule of benzyl alcohol as per scheme given
below: 259
- -
Ph O Ph O O
- slow
C O + OH Ph C OH + C O Ph C OH + Ph C H
H H H H
O OH
fast -
Ph C O + Ph C H
H
Condensation of benzaldehyde with phenols or tertiary aromatic amines in the
presence of dehydrating agents, H2SO4 or ZnCl2, gives triphenyl derivatives.
Oxidation with lead dioxide followed by treatment with hydrochloric acid gives
a dye, e.g.,
CH3
O N
CH3
H2SO4
C H + 2 N CH
CH3
CH3 CH3
N
CH3 CH3
CH3
N N
[O]
CH3 HCl CH3
C C
CH3
HO -
N Cl CH
+ 3
CH3 N
Malachite green
CH3
SAQ 4
How the following conversion can be carried out?
a) Benzoic acid from benzaldehyde
b) Benzyl alcohol from benzadehyde
c) toluene from benzaldehyde
19.3.2 Acetophenone
Acetophenone undergoes typical reactions of ketones, e.g., reduction with
sodium and ethanol gives phenylethanol, Clemensen’s reduction gives ethyl
benzene. It undergoes addition reaction with hydrogen cyanide,
hydroxylamine, etc. in the manner expected of a ketone, but because of low
reactivity of the carbonyl group, acetophenone does not react with saturated
aqueous sodium sulphate.
It is oxidised by cold potassium permanganate to give phenyl-2-oxoethanoic

acid (phenyl glyoxolic) acid which gets further oxidised to benzoic acid:
O O O O
[O] [O]
C6H5 C CH3 C6H5 C C OH C6H5 C OH
Phenyl-2-oxoethanoic acid Benzoic acid
(Phenyl glyoxalic acid)
260
Oxidation with selenium dioxide gives phenyl-2-oxoethanal:
O O O
SeO2
C6H5 C CH3 C6H5 C C H + Se + H2O
Phenyl-2-oxoethanal
(Phenyl glyoxal)
Acetophenone undergoes α-halogenation like aliphatic methyl ketones as

illustrated by acid catalysed bromination of acetophenone.
O O
C C Br
CH3 CH3COOH
+ Br2 + HBr
or AlCl3
Bromoacetophenone
(2-bromo-1-phenylethanone)
On treatment with bromine in ether at 273 K in the presence of aluminium

chloride, used as a catalyst, it also gives phenyl-1-bromo-2-ethanone 2-Chloro-1-
(phenacyl bromide): phenylethanone is used
as riot control agent (tear
Acetophenone also undergoes iodoform reaction with iodine. gas).
- +
C6H5COCH3 + NaOH+ 3I2 C6H5COO Na + CHI3 + 3NaI + 3H 2O
Iodoform
If we use one equivalent of aluminium chloride and bromine is added after the
formation of aluminum chloride complex with acetophenone, nuclear
bromination is taken place and major product will be 3'-bromoacetophenone.
The methyl group in acetophenone is adjacent to a carbonyl group. Therefore

it can form stable carbanion/enolate and takes part as nucleophile in addition
reaction and condensation reactions similar to aliphatic ketones.
NaOH
C6H5COCH3 + C6H5CHO C6H5COCH CHC6H5 + H O
2
1,3-Diphenyl-2-propenone
(Chalcone)
Two molecules of acetophenone can also condense together in the presence

of aluminium tert -butoxide to give 1,3 diphenyl-2-buten-1-one(dypnone):
O O CH3
(tert-Bu)3Al
2 C6H5 C CH3 C6H5 C CH CC6H5
1,3-Diphenyl-2-buten-1-one
(Dypnone)
Condensation in the presence of hydrochloric acid forms

1,3,5-triphenylbenzene:
O C6H5
CH 6 5
- 3H2O
3 C6H5 C CH3
C6 H 5 261
Acetophenone reacts with methanal (formaldehyde) and ammonia or a
primary or secondary amine (as hydrochloride) to give ketoamines called
Mannich bases. This reaction is called the Mannich reaction, e.g.,
O O
3 C6H5 C CH3 + H C H + (CH3)2NH:HCl

O
C 6 H5 C CH2 CH2 N(CH3)2:HCl
Mannic base
Mechanism of Mannich reaction:
Three steps are involved in the Mannich reaction: Step 1: formation of

Imminium ion, Step 2: formation of carbanion and Step 3: attack by carbanion.
Step 1: Formation of imminium ion
H H
H -H+ H3O+
(CH3)2N H + C O (CH3)2N C OH (CH3)2N C O+ H
+H+ H
H H H
+ H
(CH3)2N C + H2O
Imminium ion H
Step 2: Formation of carbanion
O O O-
Base -
C6H5 C CH3 C6H5 C CH2 C6H5 C CH2
Step 3: Attack by carbanion
O H + O
-
C6H5 C CH2 + C N(CH3)2 C6H5 C CH2 CH2 N(CH3)2
H Mannnich base
1, 3-Diketones are formed from acetophenone by condensation either with

ethyl ethanoate in the presence of sodium ethoxide or with ethanoic anhydride
in the presence of boron trifluoride:
O O O O
C2H5O-Na+
C6H5 C CH3 + H3C C OC2H5 C6 H5 C CH2 C CH3
1-Phenyl-1,3-butanedione
1,3-Diketone
O O O O
BF3
C6H5 C CH3 + ( H3C C O)2O C6H5 C CH2 C CH3 + CH3COOH
1,3-Diketone
By heating acetophenone with aqueous yellow ammonium polysuplhide,
phenylethanamide and ammonium phenylethanoate are obtained (Willgerodt
reaction):
O O O
262 C6 H5 C CH3 + (NH4)2Sx C6H5 CH2 C NH2 + C6H5 CH2 C ONH4

19.3.3 Reactions due to the Benzene Ring
As we mentioned earlier, the carbonyl group is a deactivated in electrophilic
aromatic substitution reactions and directs substitution to the meta positions.
Therefore, benzaldeyde and phenylethanone are less reactive towards
electrophilic substitution reactions than the benzene. Nitration and
sulphonation are possible, but care must be taken to avoid interaction with the
carbonyl group. Dilute nitric acid brings about oxidation of the –CHO group of
benzaldehyde. Strong concentrated nitric and sulphuric acids are normally
used in nitration reactions. As discussed above, ring halogenations depend on
the reaction condition used. Both benzadehyde and acetophenone do not
undergo Friedel-Craft reaction.
O R O R
O R
C C C
H2SO4 conc.HNO3/conc. H2SO4
O +
S N O
OH R = H or CH3 -
O O
Br2 Fe
O R
C
Br
SAQ 5
Complete the following reactions:
a) C6H5COCH3 + C6H5CHO NaOH
b) C6H5CHO + KCN
C2H5ONa
c) C6H5COCH3 + CH3COOC2H5
d) C6H5COCH3 + HCl
19.4 SUMMARY
In this unit we have described the chemistry of aromatic aldeydes and
ketones. We are summarising below what we have studied:
 Benzaldehyde can be prepared by the hydrolysis of (dichloromethyl)

benzene and by the oxidation of toluene with chromium trioxide in acetic
anhydride. It can also be prepared by direct formylation of benzene
usimg several methos such as Gattermann-Koch reaction, Gattermann
synthesis, Vilsmeier-Haack reaction, etc. Benzaldehyde can also be
obtained from benzoic acid using Stephens reaction and from benzoyl
chloride using Rosenmund reduction.
 Acetophenone can be prepared by the Friedel-Crafts acylation, Fries

rearrangement and Hoesch reaction. 263
 Because of the resonance effect necleophilic reactions of the carbonyl
group of benzaldehyde and acetophenone take place at a slower rate.
Carbonyl group being an electron withdrawing group, it deactivate the
benzene ring and the electrophile will preferably attack on meta
positions of the ring.
 Benzaldehyde undergoes several types of condensation reactions and

forms many useful synthetic intermediates, for example: Benzoin
condensation, Claisen-Schmidt reaction, Perkin reaction, and
Knoevenagel reaction.
 Acid catalysed bromination of acetophenone, brominates side chain.

With methanal (formaldehyde) and ammonia or a primary or secondary
amine (as hydrochloride), acetophenone undergoes Mannich reaction
and forms Mannich base.

1. Write the steps involved in Sommelet reaction.
2. Draw resonating structures for the resonance-stabilised cation

intermediates formed by attack of a nucleophile on ortho, para and meta
position to carbonyl group of benzaldehyde.
3. Explain why is carbonyl group is meta directing?
4. Propose a reasonable mechanism for the following conversion.

O
COOH
H O O 1. CH3COO-Na+
+ +
H3C O CH3 2. H3O
5. How will you bring about following conversions?
a) Benzaldehyde to cinnamaldehyde
b) Benzaldehyde to cinnamic acid
c) Acetophenone to dypnone
d) Acetophenone to 1,2,3-triphenylbenzene
e) Acetophenone to 1-Phenyl-1,3-butanedione
19.6 ANSWERS
1. c)
ZnCl2 HCl H2O

+ CH3CN
2. ether
HO OH HO OH
HO OH
HoubenHoesch reactions H3C O
H3C NH
264
3. A weakening of the positive charge on the carbonyl carbon atom through
dispersal of the charge into the ring through resonance effect is mainly
responsible for the lesser reactivity of aromatic aldehydes and ketones
than alphatic aldehydes and ketones for nucleophilic attack.
4. a) By oxidation methods. Benzaldehyde can easily be converted to

acid even with mild oxidizing agents.
b) By the catalytical hydrogenation or chemical reduction using Lithium

aluminium hydride or sodium borohydride.
c) By Clemmension reduction or Wolff-Kishner reduction method.
5. a) C 6H 5COCH 3 + C 6H5CHO C 6H5COCH 2 CHC 6H5
OH
b) C6H 5CHO + KCN C6H5CHCOC6H5
C2H5ONa
c) C 6H 5COCH3 + CH3COOC2H5 C6H5COCH2COCH3
-
d) C6H5COCH3 + HCl 1,3,5 triphenylbenzene
Terminal Questions
1. N N
X-
+
N N N N Ar ArCHO
Ar- X + N CHCl3 N H2O
d d d
CH3 O d CH3 d d d d CH
O O CH3 O 3
E E E
+ +
E
H H H
2. + +
ortho attack
d
d  d d CH d
O d CH3

O d CH3

O 3 O d CH3
meta attack + +
+
E
E + E E
H H H
d d  d d
O d CH3 O d CH3 
O d CH3

O d CH3
para attack +
+ +
E +
H E H E H E
3. The resonace structures drawn for the intermediates formed on ortho ,

para and meta attack of electophile, clearly indicate that the
intermediates for ortho and para substitutions are particular unstable 265
because each has a resonance structure in which there is a positive
charge on the carbon that bears the electron-withdrawing substituent.
Such situation is not observed in case of meta attack.
4. Five steps are involved in this reaction: Step 1: Formation of carbanion

Step 2: Attack by carbanion on the aromatic carbonyl compound to form
alkoxide, Step 3: protonation of the alkoxide ion to form an aldol type
compound. Step 4: dehydration, the hydroxyl group and neighbouring
hydrogen are removed as water and Step 5: hydration
H
O O O-
O C H
6 5 C
H2C C O
H3C C Base
O O + C6 H 5 C H H2C C
H3C C H2O O
H3C C H
O H O OH H3C C
C6H5 C
O O
C 6H 5 C
O H2O H CH C
HC C O
O
H3C C
H3C C O
H2O
O
O
-
C6H5 CH CH C OH + CH3COO
Cinnamic acid)
O O
OH-
5. a) C6H5 C H + H3C C H C6H5CH CHCHO
3-Phenylpropenal
(cinnamaldehyde)
O O O
b) C6H5 C H + H3C C O C CH3 C6H5CH CHCOOH

O (cinnamic acid)
Pyridine
C6H5 C H + CH2(COOH)2 C6H5CH CHCOOH
(cinnamic acid)
O O CH3
(tert-Bu)3Al
c) 2 C6H5 C CH3 C6H5 C CH CC6H5
Dypnone
O C6H5 C6H5
- 3H2O
d) 3 C6H5 C CH3
C 6H5
O O O O
C2H5O-Na+
e) C6H5 C CH3 + H3C C OC2H5 C6 H5 C CH2 C CH3
1-Phenyl-1,3-butanedione
1,3-Diketone
266
FURTHER READING
1. W. Graham Solomons: Organic Chemistry, John Wiley and Sons.
2. Peter Sykes: A Guide Book to Mechanism in Organic Chemistry, Orient Longman.
3. I.L. Finar: Organic Chemistry (Vol. I & II), E. L. B. S.
4. R. T. Morrison & R. N. Boyd: Organic Chemistry, Prentice Hall.
5. Arun Bahl and B. S. Bahl: Advanced Organic Chemistry, S. Chand.
6. J. C. Kotz, P. M. Treichel& J. R. Townsend: General Chemistry Cengage Lening India

Pvt. Ltd., New Delhi (2009).
7. B. H. Mahan: University Chemistry 3rd Ed. Narosa (1998).
 R. H. Petrucci: General Chemistry 5th Ed. Macmillan Publishing Co.: New York
(1985).
8. McMurry, J.E. Fundamentals of Organic Chemistry, 7th Ed. Cengage Learning India
Edition, 2013.
267
Notes
BCHCT-133 CHEMICAL ENERGETICS, EQUILIBRIA AND FUNCTIONAL ORGANIC CHEMISTRY-I Vol. 2
MPDD/IGNOU/P.O. 16.5K/December, 2019
ISBN : 978-93-89668-67-4

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BCHCT-133

Indira Gandhi National

FUNCTIONAL GROUP ORGANIC Vol. 2

Dr. Rakesh Kumar School of Sciences,

Dr. Toqueer Ahmad

Block Preparation Team

Expected Learning Outcomes

 describe the preparations of benzene;

 discuss the important reactions of benzene;

 classify and draw structures of simple halogen derivatives;

 outline the methods of preparation of aliphatic and aromatic halogen derivatives;

 describe reactions of aliphatic and aromatic halogen derivatives;

 explain the mechanism of nucleophilic substitution and elimination reactions of alkyl

 explain the mechanism of nucleophilic substitution reactions of aryl halides.

Expected Learning Outcomes

 explain the basic concept of aromatic hydrocarbons;

 explain Huckel’s rule;

 describe the structure of benzene;

 describe the physical properties of benzene;

 describe the carcinogenic nature of benzene; and

 Outline the methods of preparation of benzene and alkylbenzene.

10.2 AROMATIC HYDROCARBONS – AN

i) benzenoid compounds; and

ii) non-benzenoid compounds.

Before we proceed further, let us recall some important facts of aromatic

A hydrocarbon can be an aromatic compound if it follows the Huckel’s rule.

10.2.1 Huckle’s Rule

 The compound is a cyclic structure.

 The compound must contain (4n + 2)  electrons, where n is any number

 The compound must be co- planar.

4n + 2-electrons are required for aromacity. Cyclobutadiene has

Benzene is a typical example of an aromatic compound. Here, the Huckel’s

Cycloheptatrienyl cation and cycloheptatriene

In the above two compounds both have 6 elections but 1, 3, 5-

ii) Benzin was isolated from ----------- and lime.

iv) -------------- is a byproduct of the incomplete combustion of many

v) Today, major amount of benzene comes from ----------------.

10.4 STRUCTURE OF BENZENE

These structures are called resonance structures or contributors or canonical

Orbital picture of benzene

Benzene is visualised as a symmetrical, flat, planar molecule having a regular

(a) (b) (c)

Fig. 10.1: a)  Skeleton of benzene; b)  Bond formation in benzene;

10.5 PHYSICAL PROPERTIES OF BENZENE

Like other hydrocarbons, benzene is also non-polar in nature. Benzene is

10.6 USES OF BENZENE AND ITS DERIVATIVES

ethylbenzene, a precursor to styrene, benzene is used to make plastics,

Due to carcinogenic nature of benzene, in most of the industries, it is being

i) Benzene is a colorless or light yellow liquid at room temperature.

10.7 CARCINOGENIC NATURE OF BENZENE

10.8 PREPARATION OF BENZENE AND

10.8.1 Preparation of Benzene

Some important methods for preparation of benzene are summarised in

3. Decarboxylation of sodium benzoate

Sodium benzoate Benzene

5. Reduction of Benzenediazonium Salts

+ H3PO 2 + H2O + H3PO 3 + HCl + N 2

6. Hydrolysis of sulphonic acids:

Sulphonic acid Benzene

Let us study each method in detail.