CHM 203

COURSE
GUIDE
CHM 203
ORGANIC CHEMISTRY II
Course Team Prof. Femi Peters, Mr. Adakole Ikpe & Dr.
Makanjuola Oki (Course Developers) - NOUN
Prof. J. Amupitan (Course Editor) - NOUN
Prof. H.D. Aliyu (Course Reviewer) NOUN
NATIONAL OPEN UNIVERSITY OF NIGERIA

CHM 203 COURSE GUIDE
© 2020 by NOUN Press

National Open University of Nigeria
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All rights reserved. No part of this book may be reproduced, in any

form or by any means, without permission in writing from the publisher.
Printed 2009, 2021

Revised in February, 2021
ISBN: 978-058-798-5
ii
CONTENTS PAGE
Introduction……………………………………………...… iv
What You Will Learn in this Course……………………... iv
Course Aims………………………………………………. iv
Course Objectives…………………………………………. v
Contents …………………………………………………… v
Working through this Course……………………………… v
Course Materials…………………………………………... v
Course Guide……………………………………………..... vi
Study Units………………………………………………….. vi
Assignment Files……………………………………...….... vi
Presentation Schedule……………………………………… vii
iii
INTRODUCTION
Chemistry is the study of matter. Matter is studied under the three divisions
of chemistry, viz: Physical, Inorganic and Organic chemistry. While
inorganic and physical chemistry are detailed elsewhere, organic chemistry
which deals with hydrocarbons, their numerous derivatives in addition to
their physical and chemical properties will be studied in this text. This course
is coded CHM 203. It forms the second part of organic chemistry courses
you will encounter during the course of your programme in chemistry and
related programmes. CHM 203 is a two credit unit course. The course content
consists of 3 inter-related and interesting modules.
WHAT YOU WILL LEARN IN THIS COURSE
In this course, you will learn about the electronic concepts in organic
chemistry where we discussed the various factors affecting the structure and
physical properties of organic compounds, availability of electrons and
stereochemistry, the relationship between the structure of organic
compounds and their reactivity. Also this course describes Aromatic
hydrocarbons and their derivatives in addition to their physical and
chemical properties which determine their uses in the industry. You will find
several In-Text Questions (ITQs) and Self-Assessment Questions (SAQs),
with answers provided as well as activity exercise in each unit.
COURSE AIMS
The course aims at giving you an in-depth knowledge of the physical and
chemical properties of selected, important classes of organic compounds thus
giving you a solid foundation in organic compounds of industrial importance.
The aim of this course can be summarized as follows:
1. Discuss the Relationship between the structure and reactivity of

organic compounds.
2. Acquaint learners with Aromatic and polynuclear aromatic
compounds.
3. To study the determinants of the properties and identification of
selected classes of organic compounds.
4. To determine the importance of molecular architecture on physical
properties of organic compounds.
iv
COURSE OBJECTIVES
Each unit has its respective objective which you should always refer to in
your course of study so that derailment from set target will be avoided.
Always make a list of your attainment after each unit and compare them with
the objectives listed by the course developers. Thus the overall objective of
the course can be summarized as:
a) Familiarize ourselves with molecular structure of organic

compounds.
b) Note the characteristics of selected groups of organic compounds.
c) Describe how compounds of the same group can be identified.
d) Describe the importance and uses of organic compounds
CONTENTS
CHM 203 Organic Chemistry II consists of three modules which have been
painstakingly put together to take you through a unique, structured learning
experience.
WORKING THROUGH THIS COURSE
In order to be able to successfully complete this course, you are required to

carefully study each unit along with recommended textbooks and other
materials that may be provided by the National Open University. You may
also need to exploit other e-reading such as internet for further useful
information on the course.
Each unit contains SAQs and ITQs. At certain points in the course you would
be required to submit assignments for grading and recording purposes. You
are also to participate in the final examination at the end of the course. It is
recommended that you devote an abundant time for reading and
comprehension. It is highly necessary that you avail yourselves the
opportunity of attending the tutorial sessions where you will be able to
compare your understanding of the course contents with your colleagues.
COURSE MATERIALS
The course materials are made up of the following sections:
v
COURSE GUIDE
This describes how best to study this major aspect of organic chemistry and
it also spells out what constitute the course itself.
STUDY UNITS
Each study unit gives an overview of the content to be covered in this course.
This is sub-divided into sub-headings as introduction, objectives; that is what
to focus on, the content, conclusion, summary, references and a list of other
materials to be consulted in order to augment or facilitate the student’s
understanding and finally the tutor-marked assignments.
Module 1 Electronic Concept and Stereochemistry
Unit 1 Factors Affecting Structure and Physical Properties of

Organic Compounds
Unit 2 Factors Affecting Availability of Electrons
Unit 3 Stereochemistry
Module 2 Functional Groups and Reactivity in Organic Chemistry
Unit 1 Functional Group Chemistry of Main Class Organic

Compounds
Unit 2 Alkanes, Free Radical Substitution Reactions in Alkanes
and The Reactivity-Selectivity Principle
Unit 3 Various Organic Reactions
Unit 4 Nucleophilic Substitution and Elimination Reactions
Module 3 Aromatic Compounds
Unit 1 Benzene and other Aromatic Compounds

Unit 2 Reactions in Aromatic Compounds
ASSIGNMENT FILES
The files contain tutorial questions that cover the whole course. These will
enable you to assess your understanding of the course by the facilitator. The
marks scored for the assignments will be stored and will constitute 30% of
the final score at the end of the semester examination.
vi
PRESENTATION SCHEDULE
The method of operation, that is, self-tutored and face to face facilitation with
respect to the course will be available at the information desk at different
study centres nearest to you.
You are welcome to the study of CHM 203 - Organic Chemistry II, one of
the tripods on which the study of chemistry stands.
vii
MAIN
COURSE
CONTENTS PAGE
Module 1 Electronic Concept and Stereochemistry….. 1
Unit 1 Factors Affecting Structure and Physical

Properties of Organic Compounds……………. 1
Unit 2 Factors Affecting Availability of Electrons…… 21
Unit 3 Stereochemistry……………………………….. 59
Module 2 Functional Groups and Reactivity in

Organic Chemistry…………………………… 85
Unit 1 Functional Group Chemistry of Main Class

Organic Compounds…………………………... 85
Unit 2 Alkanes, Free Radical Substitution Reactions
in Alkanes and The Reactivity-Selectivity
Principle………………………………………..103
Unit 3 Various Organic Reactions…………………… 125
Unit 4 Nucleophilic Substitution and Elimination
Reactions………………………………………143
Module 3 Aromatic Compounds…………………………..175
Unit 1 Benzene and other Aromatic Compounds……...175

Unit 2 Reactions in Aromatic Compounds…………….197
CHM 203 MODULE 1
MODULE 1 ELECTRONIC CONCEPT AND

STEREOCHEMISTRY
INTRODUCTION
The study of organic chemistry involves the reactions and interactions of

molecules. Since molecules are composed of atoms, it is necessary to
study the structure of atoms and how they contribute to the properties of
molecules. In this module we will study the factors that affect the
structures and physical properties of organic compounds. This knowledge
will make learning about organic molecules a little easier. Because
organic chemistry is a study of compounds that contain carbon and to have
a better understanding of the properties of organic molecules, one has to
study their three-dimensional (3D) structure. Why is this important? Our
perception of smell and taste depends, in many instances, on the 3D
structure of molecules. Enzymes are very selective in the 3D structure of
the molecules they interact with. The effectiveness of drugs is highly
dependent on their 3D structure. Organic chemists need to be able to
determine the 3D structures (stereochemistry) of new and existing
molecules to relate 3D structure to reactivity. Hence, the following units
will be discussed in this module:
Unit 1 Effect of molecular architecture on physical properties of

organic compounds
Unit 2 Factors affecting availability of electrons in organic
compounds
Unit 3 Stereochemistry
UNIT 1 EFFECT OF MOLECULAR ARCHITECTURE

ON PHYSICAL PROPERTIES OF
ORGANIC COMPOUNDS
CONTENTS
1.0 Introduction
2.0 Learning Objectives
3.0 Main Content
3.1 Molecular Architecture and Factors Affecting Physical
Properties
3.1.1 Intermolecular Forces
3.1.2 Melting Point
3.1.3 Boiling Point
3.1.4 Solubility
4.0 Conclusion
5.0 Summary
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CHM 203 ORGANIC CHEMISTRY II
6.0 Tutor Mark Assignment

7.0 References/Further Readings
1.0 INTRODUCTION
In our previous knowledge in organic chemistry, we have learnt some of

the important aspects of bonding and the structures of organic molecules
in detail. But have you thought about how we establish the identity and
structure of a molecule? One answer to this question could be comparing
its physical and chemical properties with those of the known compounds.
Earlier methods of identification involved the determination of physical
properties such as melting point, boiling point, solubility and refractive
index. The chemical methods used for identification involved, however,
either the degradation of the molecule to simple compounds of known
structure or its synthesis from the simple compounds of known structure.
The structure and properties of organic compounds are considerably
influenced by the conditions under which they are formed most especially
bond type and temperature. In this unit, we will discuss the relationship
between molecular structure and physical properties. The study of
physical properties is also important in the purification of organic
compounds.
2.0 OBJECTIVES
By the end of this unit you should be able to:
 identify organic molecules using their physical properties such

as melting and boiling points, solubility and refractive index
 determine the relationship between molecular structure and
physical properties of organic compounds.
3.0 MAIN CONTENT
3.1 Molecular Architecture and Factors Affecting Physical

Properties of Compound
The bonding and structural features of a compound are manifested in its

physical properties. Thus, physical properties of a compound such as
melting point, boiling point, solubility, etc., often give valuable clues
about its structure. Conversely, if the structure of a compound is known,
its physical properties can be predicted.
The physical properties of a compound depend upon the number and

nature of atoms constituting its structural units and also on the nature of
forces holding these units together. You know that in case of ionic
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CHM 203 MODULE 1
compounds, the positive and negative ions are held together by strong
electrostatic forces. Contrary to this, in covalent compounds, the
molecules are held together by intermolecular forces. Let us now study
briefly what these intermolecular forces are. Then, you will learn how
these intermolecular forces affect the physical properties of the
compounds.
3.1.1 Intermolecular Forces
Forces between molecules are responsible for the magnitude of the melting
and boiling temperatures and for solubility characteristics of molecules.
The greater the attraction between molecules of a specific compound, the
higher the melting and boiling points are likely to be. Solubility
characteristics use the classic saying, like dissolves like. Polar molecules
are most soluble in polar solvents and nonpolar molecules are most soluble
in nonpolar solvents. The three important intermolecular forces are: (i)
dipole-dipole interactions, (ii) London forces and (iii) hydrogen bonding.
Let us now consider these intermolecular forces one by one.
(i) Dipole-Dipole Interactions: are defined as the interactions

between the different molecules of a compound having permanent
dipoles. Dipoles result from unequal sharing of electrons in bonds. If
molecules are close to each other, the negative pole of one molecule is
attracted to the positive pole of another molecule. Consider the example
of chloromethane which has a permanent dipole. The molecule of
chloromethane orient themselves in such a way that the positive end
of one dipole points towards, and is thus attracted by, the negative end
of the other dipole. These interactions, called dipole-dipole interaction are
depicted in Fig 1.1.
a) b)
Fig. 1.1: Intermolecular forces (“- - - - -” indicates interaction). a) A

polar hydrogen chloride molecule interacting with another hydrogen
chloride molecule b) Arrangement of chloromethane molecules
showing positive and negative poles of one molecule and the Dipole-
dipole interactions between chloromethane molecules.
The dipole-dipole interactions are weak interactions and are of the order
of 4 to 12 kJ mol-1 whereas the bond energy for an ordinary covalent
bond ranges from 125 to 420 kJ mol-1.
3
In-Text Question 1
When the positive end of a molecule attracts the negative end of another
molecule, the electrostatic forces that arise is named ________
A. Electrovalent bond B. Dipole-dipole forces C. Weak forces D.
Gaseous forces
In-Text Answer 1
Option B
(ii) London Forces: The intermolecular interactions exist between

non polar molecules also. At any given instant, the electrons surrounding
an atom or molecule are not uniformly distributed; that is, one side of
the atom may have a greater electron density than the other side. This
results in a momentary dipole within the atom. The dipole on one atom
may induce a dipole on another atom. The net result is an attraction
between atoms.
Consider two nonpolar molecules A and B in which the centre of positive
charge coincides with that of the negative charge.
When the molecules A and B approach each other, there is a distortion

in the distribution of the charge resulting in a small and momentary dipole
in one molecule. This small dipole can then create another dipole in the
second molecule which is called induced dipole. Thus, if the momentary
dipole of molecule A and B is as shown below;
Such a distribution of charge leads to mutual attraction between the

molecules. These induced dipole – induced dipole interaction are also
known as London forces (illustrated with … in Figure 1.2).
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CHM 203 MODULE 1
Fig. 1.2: London forces are induced-dipole–induced-dipole

interactions.
London forces are the only forces of attraction possible between nonpolar
molecules. These interactions are weaker than the dipole-dipole
interactions and are of the order of 4 kJ mol-1. These forces vary with the
distance between the molecules. If ‘r’ is the distance between the two
molecules, then the London forces are proportional to 1/r6. This explains
the interaction between helium atoms (Fig. 1.3), that are nonpolar, yet
they must have attraction for each other since they form liquids when
cooled sufficiently. All molecules exhibit dispersion forces.
Fig 1.3: London dispersion forces in two helium atoms
In-Text Question 2
1. Classify the following statement as true or false: London forces
are the only forces operating between polar molecules.
2. At 25oC, chlorine (Cl2) is a gas whereas bromine (Br2) is a liquid.
Why?
(iii) Hydrogen Bonding: This is a special type of dipole-dipole

interaction. It does not refer to an actual bond, but a strong interaction
between a covalently bonded hydrogen atom and a molecule containing
an atom with nonbonding electrons, such as oxygen, nitrogen, and the
halogens. The hydrogen atom undergoing hydrogen bonding must be
covalently bonded to an oxygen, a nitrogen, or a fluorine atom, resulting
in a highly polar covalent bond. This puts a large partial positive charge
(δ+) on the covalently bonded hydrogen atom and it seeks an electron pair
on another atom. Hydrogen bonds are stronger than most dipole-dipole
interactions but weaker than a covalent bond. An example is shown for
water in Fig 1.4.
Fig. 1.4: hydrogen bonding in water molecules
5
The strength of a hydrogen bond ranges from 10 to 40 kJ mol-1. Hydrogen

bonding has an important influence on physical properties such as melting
point, boiling point and solubility of substances. This will be illustrated
using examples in the following subsections.
The dipole-dipole, induced dipole-induced dipole etc. interactions are

collectively known as van der Waals forces. Some authors prefer to
give the name van der Waals forces only for London forces. Having
understood the intermolecular forces, let us now study how the variation
in molecular structure affects these intermolecular forces which in turn
is reflected in the physical properties of the molecules.
In-Text Question 3
Which response includes only those compounds that can exhibit hydrogen
bonding?
(a) AsH3, H2Te

(b) AsH3, CH3NH2
(c) CH4, AsH3, H2Te
(d) CH3NH2, HF
(e) HF, H2Te
3.1.2 Melting Point
The melting point (mp) is the temperature at which a solid is converted

into a liquid.
Pure crystalline solids have sharp melting points. Thus, melting point is
used as an important physical property both for the identification of
organic compounds and for making the general assessment of the purity
of these compounds. Pure crystalline solids have sharp melting points
and they melt over a temperature range of 1o or less. In contrast to this,
impure crystalline solids melt over wider ranges of temperatures. In a
crystalline solid, the constituent ions or molecules are arranged in an
orderly and rigid fashion. When such as solid is heated, the thermal
energy of the molecules increases. This finally leads to the
disintegration of the crystal structure and at the melting point a disorderly
and random arrangement of particles, characteristic of a liquid, is
obtained. Since the electrostatic forces holding the ions are very strong,
they can be overcome only at high temperatures. Therefore, the ionic
compounds generally have high melting points. For example, the melting
point of sodium chloride is 1074 K and that of sodium ethanoate is 595
K. But, the intermolecular forces are very weak as compared to the
interionic forces and hence, these can be overcome at lower temperatures
leading to lower melting points for covalent compounds. The melting
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CHM 203 MODULE 1
point of methane, a covalent compound, is only 90 K and the melting

point of methanol, another covalent compound, is 179 K.
Let us now study the effect of molecular weight on the melting point.
If you examine the melting points of the alkanes in Table 1.1, you will see
that the melting points increase (with a few exceptions) in a homologous
series as the molecular weight increases. The increase in melting point is
less regular than the increase in boiling point because packing influences
the melting point of a compound. Packing is a property that determines
how well the individual molecules in a solid fit together in a crystal lattice.
The tighter the fit, the more energy is required to break the lattice and
melt the compound.
In Figure 1.5, you can see that the melting points of alkanes with even
numbers of carbon atoms fall on a smooth curve (the red line). The
melting points of alkanes with odd numbers of carbon atoms also fall on
a smooth curve (the green line). The two curves do not overlap, however,
because alkanes with an odd number of carbon atoms pack less tightly
than alkanes with an even number of carbon atoms. Alkanes with an odd
number of carbon atoms pack less tightly because the methyl groups at
the ends of their chains can avoid those of another chain only by
increasing the distance between their chains. Consequently, alkane
7
molecules with odd numbers of carbon atoms have lower intermolecular

attractions and correspondingly lower melting points.
Fig. 1.5: Plot of melting points of straight-chain alkanes. Alkanes with

even numbers of carbon atoms fall on a melting-point curve that is
higher than the melting point curve for alkanes with odd numbers of
carbon atoms.
You can see in the figure that the melting point increases with the
increase in the molecular weight. This can also be explained due to
increase in the London forces between the larger molecules of higher
molecular weight. Thus, each additional methylene (-CH2) unit
contributes to the increase in melting point.
In a homologous series, the higher the molecular weight, the larger will
be the molecules and the greater will be the ‘area of contact’ between
the two molecules and hence the greater will be the London forces.
You must have noticed in Fig. 1.5, the alternating pattern of melting
points for the alkanes having odd and even number of carbon atoms. It is
also evident from the figure that the compounds having even number of
carbon atoms lie on a higher curve as compared to the compounds
having odd number of carbon atoms. This can be explained on the basis
that in solid state, the London forces among the molecules having odd
number of carbon atoms are weaker than those in the molecules having
even number of carbon atoms. This is because the molecules of alkanes
having odd number of carbon atoms do not fit well in the crystal lattice
as compare to those of the alkanes having even number of carbon atoms.
After studying the effect of molecular weight on melting point, let us
now see how the isomeric compounds having the same molecular weight,
show different melting points. The melting points of straight chain and
branched chain isomers of butane are given below:
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CHM 203 MODULE 1
The branching of the carbon chain interferes with the regular packing of
the molecules in the crystal; branched chain hydrocarbons tend to have
lower melting points than their straight chain isomers.
But, in case, the branched molecule has a substantial symmetry, then its
melting point is relatively high. This is clearly evident when we compare
the melting points of isomeric pentanes which are as given below:
The branching from pentane to 2-methylbutane lowers the melting point

but further branching in 2,2-dimethylpropane increases the melting point.
This can be explained by the fact that the symmetrical molecules fit
together more easily in the crystal lattice and hence have higher melting
points as compared to the less symmetrical molecules. Hence, higher
melting point for 2,2-dimethylpropane is justified.
This is also reflected when we analyse the melting points of cis- and
trans-isomers. The trans- isomer being more symmetrical, fits better in
the crystal lattice than the less symmetrical cis- isomer. Hence, the
trans- isomers generally have higher melting points.
The nature of the functional groups present in a molecule also affects its
physical properties. For example, when the functional group is such that
it introduces polarity, and hence leads to a permanent dipole moment in
the molecule; then, due to the dipole-dipole forces of attraction between
the polar molecules, they show higher melting points than the nonpolar
molecules of comparable molecular weights. For example, the melting
point of propanone, a polar molecule having molecular weight of 58, is
178 K. You can compare it with the melting points of isomers of nonpolar
butane (mol. Wt. = 58) you have just studied above. This leads to the
conclusion that the polar propanone has higher melting point than the
nonpolar isomeric butanes.
9
The effect of hydrogen bonding on melting point is small. But, the

hydrogen bonding has significant effect on the boiling point, about which
you will study in the next subsection.
In-Text Question 4
Which compound has the highest melting point? A. decane B. 2,2,3,3-
tetramethylbutane C. 2,2,3-trimethylpentane D. 4-methylnonane
3.1.3 Boiling Point
The boiling point of a substance is the temperature at which it changes

(vapourizes) from the liquid to the gaseous state. At the boiling point the
vapour pressure of a liquid is equal to the external pressure. Thus, the
boiling point depends on the external pressure and it increases with
increase in the external pressure. Hence, while reporting the boiling point
of a substance, external pressure must be specified.
Similar to the case of melting points, the boiling points are also used as
constants for identification and characterization of liquid substances.
The knowledge of boiling points is also important in the purification of
liquids.
Let us now study some of the factors affecting the boiling point.
The boiling point of a substance depends on its molecular structure. In

order for a compound to vapourize, the forces that hold the individual
molecules close to each other in the liquid must be overcome. This means
that the boiling point of a compound depends on the strength of the
attractive forces between the individual molecules. If the molecules are
held together by strong forces, it will take a lot of energy to pull the
molecules away from each other and the compound will have a high
boiling point. In contrast, if the molecules are held together by weak
forces, only a small amount of energy will be needed to pull the molecules
away from each other and the compound will have a low boiling point.
For example, relatively weak forces hold alkane molecules together.
Alkanes contain only carbon and hydrogen atoms. Because the
electronegativities of carbon and hydrogen are similar, the bonds in
alkanes are nonpolar. Consequently, there are no significant partial
charges on any of the atoms in an alkane.
The molecules of an alkane are held together by these induced-dipole–

induced-dipole interactions, which are known as van der Waals forces.
Van der Waals forces are the weakest of all the intermolecular attractions.
In order for an alkane to boil, the van der Waals forces must be overcome.
The magnitude of the van der Waals forces that hold alkane molecules
together depends on the area of contact between the molecules. The
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CHM 203 MODULE 1
greater the area of contact, the stronger are the van der Waals (London)
forces and the greater is the amount of energy needed to overcome those
forces. If you look at the homologous series of alkanes in Table 1.1, you
will see that the boiling points of alkanes increase as their size increases.
Generally, this increase in boiling point amounts to 20-30o for the
addition of each carbon atom in the molecule. This relationship holds
because each additional methylene group increases the area of contact
between the molecules. The four smallest alkanes have boiling points
below room temperature (room temperature is about 25 °C), so they exist
as gases at room temperature. Pentane (bp = 36.1oC) is the smallest alkane
that is a liquid at room temperature. The boiling points of the compounds
in any homologous series increase as their molecular weights increase
because of the increase in van der Waals forces. So the boiling points of
the compounds in a homologous series of ethers, alkyl halides, alcohols,
and amines increase with increasing molecular weight.
Among isomeric molecules, since the unbranched isomer is linear and

hence extended in shape, it has larger surface area as compared to the
branched isomers. Therefore, the London forces are stronger in the
unbranched isomer leading to higher boiling point for this isomer. Thus,
if two alkanes have the same molecular weight, the more highly branched
alkane will have a lower boiling point This is illustrated in the structures
below for the isomers of pentane.
The boiling points of these compounds, however, are also affected by the
polar character of the bond (where Z denotes N, O, F, Cl, or Br) because
nitrogen, oxygen, and the halogens are more electronegative than the
carbon to which they are attached.
The magnitude of the charge differential between the two bonded atoms is
indicated by the bond dipole moment. The dipole moment of a bond is
equal to the magnitude of the charge on one of the bonded atoms times the
distance between the bonded atoms.
When we compare molecules having the same shape and size, the more
polar molecule has the higher boiling point. Examples are:
11
Dipole moment 20.98 x 10-30cm -0

Boiling point 249.4 K 231 K
Molecular weight 46 44
Alcohols have much higher boiling points than alkanes or ethers of

comparable molecular weight (Table 1.2) because, in addition to London
forces and the dipole–dipole interactions of the bond, alcohols can form
hydrogen bonds. A hydrogen bond is a special kind of dipole–dipole
interaction that occurs between a hydrogen that is bonded to an oxygen,
a nitrogen, or a halogen and the lone-pair electrons of an oxygen,
nitrogen, or halogen in another molecule (see subsection 3.1.1 of this
unit). Thus, to vaporize such a compound, hydrogen bonds between the
molecules must be broken. This requires energy, which is manifested as
the unusually high boiling point for such compounds.
Table 1.2: Comparative Boiling Points (°C)

Alkanes Ethers Alcohols Amines
CH3CH2CH3 CH3OCH3 CH3CH2OH CH3CH2NH2
-42.1 -23.7 73 16.6
CH3CH2CH2CH3 CH3OCH2CH3 CH3CH2CH2OH CH3CH2CH2NH2
-0.5 10.8 97.4 47.8
CH3CH2CH2CH2 CH3CH2OCH2C CH3CH2CH2CH2 CH3CH2CH2CH2
36.1
CH3 34.5
H3 117.3
OH 77.8
NH2
The length of the covalent bond between oxygen and hydrogen is 0.96 Å.
The hydrogen bond between an oxygen of one molecule and a hydrogen
of another molecule is almost twice as long (1.69–1.79 Å), which means
that a hydrogen bond is not as strong as an O-H covalent bond. A
hydrogen bond, however, is stronger than other dipole–dipole
interactions. The strongest hydrogen bonds are linear—the two
electronegative atoms and the hydrogen between them lie on a straight
line. Although each individual hydrogen bond is weak—requiring about
21 kJ/mol (5 kcal/mol) to break—there are many such bonds holding
alcohol molecules together. The extra energy required to break these
hydrogen bonds is the reason alcohols have much higher boiling points
than either alkanes or ethers with similar molecular weights.
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CHM 203 MODULE 1
The boiling point of water illustrates the dramatic effect hydrogen

bonding has on boiling points. Water has a molecular weight of 18 and a
boiling point of 100 °C. The alkane nearest in size is methane, with a
molecular weight of 16. Methane boils at -167.7oC.
Primary and secondary amines also form hydrogen bonds, so these amines
have higher boiling points than alkanes with similar molecular weights.
Nitrogen is not as electronegative as oxygen, however, which means that
the hydrogen bonds between amine molecules are weaker than the
hydrogen bonds between alcohol molecules. An amine, therefore, has a
lower boiling point than an alcohol with a similar molecular weight (Table
1.2).
Because primary amines have two bonds, hydrogen bonding is more

significant in primary amines than in secondary amines. Tertiary amines
cannot form hydrogen bonds between their own molecules because they
do not have a hydrogen attached to the nitrogen. Consequently, if you
compare amines with the same molecular weight and similar structures,
you will find that primary amines have higher boiling points than
secondary amines and secondary amines have higher boiling points than
tertiary amines.
Hydrogen bonding is also important in other ways. As we shall see in

the next subsection, hydrogen bonding plays an important role in the
solubility of organic compounds.
In-Text Question 5
Which of the following alkanes will have the lowest boiling point?
13
3.1.4 Solubility
When any substance dissolves in a solvent, its constituent ions or

molecules get separated from each other and the space between them is
filled by solvent molecules. This is known a solvation and the amount of
substance dissolved in a certain amount of solvent is referred to as its
solubility in that solvent. Solubility thus depends on the interactions
between solute-solute, solute-solvent and solvent-solvent molecules. The
general rule that explains solubility on the basis of the polarity of
molecules is that “like dissolves like”. In other words, polar compounds
dissolve in polar solvents, and nonpolar compounds dissolve in nonpolar
solvents. This is because a polar solvent such as water has partial charges
that can interact with the partial charges on a polar compound. The
negative poles of the solvent molecules surround the positive pole of the
polar solute, and the positive poles of the solvent molecules surround the
negative pole of the polar solute. Clustering of the solvent molecules
around the solute molecules separates solute molecules from each other,
which is what makes them dissolve. Clearly strong solute-solvent
molecular interactions as compare to those of solute-solute or solvent –
solvent molecules will lead to dissolution of the solute.
Similar to the processes of melting or boiling, dissolution of a substance

also requires that the interionic or intermolecular forces of attraction
between the ions or molecules must be overcome. The strong electrostatic
14
CHM 203 MODULE 1
forces between the ions of an ionic compound can be overcome by the

solvents which have high dielectric constant. Thus, water which has a
high dielectric constant (є ) of 80, dissolves ionic compounds readily
whereas solvents like carbon tetrachloride (є =1.2) or ether (є = 4.4)
are extremely poor solvents for such compounds. Hence, ionic
compounds have greater solubility in polar solvents.
The dielectric constant є, of a solvent measures its ability to separate the

ions of the solute.
The term polar has double usage in organic chemistry. When we refer that
it has a significant dipole moment, µ. But, when we talk about a polar
solvent, we understand that it has a high dielectric constant, є. Thus, the
dipole moment is the property of individual molecules whereas solvent
polarity or dielectric constant is a property of many molecules acting
together.
In determining the solubility of covalent compounds, the rule of thumb

is like-dissolves-like. Since water is a polar compound, it is a good solvent
for polar compounds, but is a poor solvent for hydrocarbon which are
nonpolar in nature. Thus, the hydrocarbons readily dissolve in other
hydrocarbons or in nonpolar solvents such as benzene, ether or
tetrahydrofuran. This is because the van der Waals interactions between
solvent and solute molecules are about the same as between solvent–
solvent and solute–solute molecules.
Alkanes are nonpolar, which causes them to be soluble in nonpolar

solvents and insoluble in polar solvents such as water. The densities of
alkanes (Table 1.1) increase with increasing molecular weight, but even
a 30-carbon alkane such as triacontane (density at 20 oC = 0.8097 g/mL)
is less dense than water (density at 20 oC = 0.9982 g/mL). This means
that a mixture of an alkane and water will separate into two distinct
layers, with the less dense alkane floating on top.
An alcohol has both a nonpolar alkyl group and a polar OH group. So, is
an alcohol molecule nonpolar or polar? Is it soluble in a nonpolar solvent,
or is it soluble in water? The answer depends on the size of the alkyl
group. As the alkyl group increases in size, it becomes a more significant
fraction of the alcohol molecule and the compound becomes less and less
soluble in water. In other words, the molecule becomes more and more
like an alkane. Four carbons tend to be the dividing line at room
temperature. Alcohols with fewer than four carbons are soluble in water,
but alcohols with more than four carbons are insoluble in water. In other
words, an OH group can drag about three or four carbons into solution in
water.
15
The four-carbon dividing line is only an approximate guide because the

solubility of an alcohol also depends on the structure of the alkyl group.
Alcohols with branched alkyl groups are more soluble in water than
alcohols with non-branched alkyl groups with the same number of
carbons, because branching minimizes the contact surface of
the nonpolar portion of the molecule. So tert-butyl alcohol is more
soluble than n-butyl alcohol in water.
The solubility of organic compounds in water also depends on the extent

of hydrogen bonding possible between the solute and the solvent (water)
molecules. For example, the greater solubility of ether in water as
compared to that of pentane (in water can be accounted on the basis of
hydrogen bonding present in the former case.
Since the olefinic, acetylenic or benzenoid character does not affect the
polarity much, the solubility of unsaturated and aromatic hydrocarbons
in water is similar to that of alkanes. In compounds like ethers, esters,
aldehydes, ketones, alcohols, amides, acids and amines, solubility in
water depends on the length of the alkyl chain and the members
containing less than five carbon atoms in the molecules are soluble in
water.
Increase in the intermolecular forces in a solute, as a result of increase in

the molecular weight, is also reflected in the low solubility of compounds
having high molecular weight. For example, glucose is soluble in water
but its polymer, starch is insoluble in water. This is because polymers
have high molecular weight. Thus, in a homologous series, the solubility
of the members decreases with the increase in molecular weight.
However, branching of the carbon chain leads to a decrease in the
intermolecular forces. Hence, the branched chain isomer is more soluble
as compared to the straight chain isomer.
Apart from other factors discussed above, solubility of a compound in a

given solvent generally increases with temperature.
Sometimes high solubility of a compound is observed due to a chemical

reaction which acts as a driving force. One such category of reactions is
16
CHM 203 MODULE 1
acid-base reactions. For example, the higher solubility of aniline in

aqueous acid is due to the formation of anilinium ion.
Although determination of the physical properties such as those discussed

above helps in the identification of organic compounds, physical methods
involving the use of spectroscopy allow determination of the molecular
structure much more rapidly and nondestructively using small quantities
of material.
In-Text Question 6
Which of the following compounds is expected to have the greatest
solubility in water?
SELF ASSESSMENT EXERCISE
i. Which of the following compounds will form hydrogen bonds

between its molecules?
ii. Which of the compounds in SAQ 4.1 above will form hydrogen
bonds with a solvent such as ethanol?
iii. List the following compounds in order of decreasing boiling point:
iv Rank the following groups of compounds in order of decreasing

solubility in water:
17
v. In which of the following solvents would cyclohexane have the

lowest solubility: pentanol, diethyl ether, ethanol, or hexane?
vi. Rank the following compounds in order of increasing strength
of intermolecular forces: CH3CH2CH2CH2CH3 (pentane),
CH3CH2CH2CH2OH (1-butanol), and CH3CH2CH2CHO
(butanal).
 Pentane has only nonpolar C-C and C-H bonds, so its molecules
are held together by only van der Waals forces.
 1-Butanol is a polar bent molecule, so it can have dipole-dipole
interactions in addition to van der Waals forces. Because it has an
O-H bond, 1-butanol molecules are held together by
intermolecular hydrogen bonds as well.
 Butanal has a trigonal planar carbon with a polar C=O bond, so it
exhibits dipole-dipole interactions in addition to van der Waals
forces. There is no H atom bonded to O, so two butanal molecules
cannot hydrogen bond to each other.
vii Which compound in each pair has the higher boiling point?
viii Which compound is water soluble?
ix Which of the following molecules can hydrogen bond to another

molecule like itself?
 Which of the following molecules can hydrogen bond with
water?
18
CHM 203 MODULE 1
4.0 CONCLUSION
We can safely conclude that a good knowledge of the physical and

chemical properties of organic compounds is paramount in the
identification of such compounds.
5.0 SUMMARY
During the course of this unit, we have learnt about the relationship
between molecular architecture and physical properties of organic
compounds. We have also learnt about the interrelationship between
intermolecular forces, melting and boiling points and the solubility of
organic compounds. The greater the attractive forces between
molecules—London (van der Waals) forces, dipole–dipole interactions,
hydrogen bonds—the higher is the boiling point of the compound. A
hydrogen bond is an interaction between a hydrogen bonded to an O, N,
or F and the lone pair of an O, N, or F in another molecule. The boiling
point increases with increasing molecular weight of the homolog.
Branching lowers the boiling point. Polar compounds dissolve in polar
solvents, and nonpolar compounds dissolve in nonpolar solvents. The
interaction between a solvent and a molecule or an ion dissolved in that
solvent is called solvation. The oxygen of an alcohol or an ether can drag
about three or four carbons into solution in water.
6.0 TUTOR MARK ASSIGNMENT
7.0 REFERENCES/FURTHER READINGS
Bruice, P. Y. (2004). Organic Chemistry, 7th Edition. Pearson Education:

London.
Dewick, P. M. (2006). Essentials of organic chemistry: for students of

pharmacy, medicinal chemistry and biological chemistry. John
Wiley & Sons.
Morrison, R. T., & Boyd, R. N. (2007). Organic Chemistry text book, 6th
editions. Prentice-Hall of India Pvt. Ltd.
Brown, T. L. (2009). Chemistry: the central science. Pearson Education.
19
Mukherji, S. M., Singh, S. P., Kapoor, R. P., & Dass, R. (2010). Organic
Chemistry, vol. I. New Age International.
Okuyama, T., & Maskill, H. (2013). Organic Chemistry: a mechanistic

approach. Oxford University Press.
Ghatak, K. L. (2014). A Textbook of Organic Chemistry and Problem

Analysis. PHI Learning Pvt. Ltd.
Brown, W. H., & Poon, T. (2016). Introduction to organic chemistry.

John Wiley & Sons.
20
CHM 203 MODULE 1
UNIT 2 FACTORS AFFECTING AVAILABILITY

OF ELECTRONS
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 Factors Affecting Availability of Electrons in Organic
Compounds
3.1.1 Inductive Effect
3.1.2 Resonance (Mesomeric) Effect
3.1.3 Hyperconjugation
3.2 Application of Inductive Effect, Hyperconjugation and
Mesomeric Effect: Acidity and Basicity
3.2.1 Strengths of Acids and Bases
3.3 Steric Effect
3.4 Tautomerism
4.0 Conclusion
5.0 Summary
6.0 Tutor Mark Assigment
1.0 INTRODUCTION
In this unit, you will study about the factors that affect the availability of
electrons in organic compounds. These factors are known to affect the
reactivity of organic molecules. The reactivity of one substance towards
another is measured by the rate at which the two substances react and
the amount of the products formed. These effects which are associated
with the change in molecular structure are called structural effects
which includes: inductive effect, resonance effect and steric effect.
Not all molecules are equally reactive. But, what make some organic
molecules more reactive than others? To find an answer to this question,
we should have some idea of the nature of reactions that the organic
molecules undergo. A large number of reactions that the organic
molecules undergo can be readily understood as simple analogies of
acid-base reactions. Therefore, it is important for us to know the basic
features of acid-base reactions. We will familiarize ourselves with the
concept of acid-base equilibrium in this unit. Here, you will also study
that the position of the acid-base equilibrium is a measure of molecular
reactivity; further it is influenced by many factors. Although, the
functional groups present in a molecule are of key importance in
determining the molecular reactivity, it has been observed that various
compounds containing the same functional groups differ in their
21
reactivity. Thus, in addition to the presence of the functional groups,

structural effects vis-a-vis the nature and arrangement of atoms attached
to the functional groups also control the molecular reactivity. We will also
discuss solvent effects and hydrogen bonding which are also important
factors affecting the rate and the extent of such reactions. Finally, you will
study an interesting equilibrium involving a proton shift from one atom
of a molecule to another, called tautomerism.
2.0 OBJECTIVES
By the end of this unit, you should be able to:
 understand some of the factors affecting electron availability in

organic molecules, along with their consequences.
 apply these factors on organic substrates to locate electron
deficient and electron rich sites.
 define acids and bases and be able to classify given compounds as
acids or bases according to Bronsted – Lowry and Lewis
definitions.
 define pKa of an acid and predict the relative acidities and
basicities of compounds.
 explain the effect of structural changes on the acidic and basic
behaviour of organic molecules.
 define tautomerism and give examples of various kinds of
tautomerism.
3.0 MAIN CONTENT
3.1 Factors Affecting Availability of Electrons in Organic

Compounds
Electronic factors that influence organic reactions include the inductive

effect, electromeric effect, resonance (mesomeric) effects, and
hyperconjugation. These electronic factors involve organic molecules,
most of which are made from a combination of the following six elements:
carbon, hydrogen, nitrogen, oxygen, phosphorus, and sulfur (known
collectively as CHNOPS). Yet, the limited number of building blocks
does not prevent organic compounds from taking on diverse properties in
their physical characteristics and chemical reactivity. The subtle
differentiation of various compounds in organic chemistry is essential for
the biological functions of the molecules and creates a wide variety of
reactions. Let us now discuss these factors one after the other.
22
CHM 203 MODULE 1
3.1.1 Inductive Effect
We have seen that when carbon bonds to an electronegative element like

O, N, CI, or F, a bond polarization develops, making the C δ+ and the
heteroatom or halogen δ-. The phenomenon of withdrawing electrons
through sigma (σ) bonds to the more electronegative atom or group is
called an inductive effect. The inductive effect is a permanent state of
polarization. The electron density in a σ bond between two unlike atoms
is not uniform and denser toward the more electronegative of the two
atoms. The inductive effect is what gives rise to bond polarizations,
polarizations within molecules, and bond and molecular dipole moments.
Partial charges due to induction
The inductive effect is a distance-dependent phenomenon:
If the electronegative atom X is connected to a chain of carbon atoms,

then the positive charge is relayed to the other carbon atoms. C1, with its
positive δ charge, exerts a pull on the electrons of C2, but the pull is
weaker than it is between X on C1. The effect rapidly dies out and is
usually not significant after the 2nd carbon atom, or at most the 3rd.
There are two categories of inductive effects: the electron-withdrawing

(-I) effect and the electron-donating (+I) effect. In the figure above, X is
electron-withdrawing and Y is electron-donating.
These relative inductive effects are measured with reference to hydrogen:

The -I effect is seen around a more electronegative atom or group, and
electron density is higher there than elsewhere in the molecule. Electron-
withdrawing groups include halogen, nitro (−NO2), cyano (−CN),
carboxyl (−COOH), ester (−COOR), and aryloxy (−OAr). On the other
hand, the +I effect is observed among the less electronegative atoms of
the molecule by electron-releasing (or electron-donating) groups. The
alkyl groups are usually considered electron-releasing (or electron-
donating) groups.
Inductive effect generally influences both physical and chemical

properties of organic compounds as seen in the strength of organic acids
23
(to be discussed in later section of this unit), basic strength of amines and
amides, ease of substitution reactions of haloalkanes (dipole moment and
bond length), the ease of addition reactions of unsaturated hydrocarbons,
and so on.
In-Text Question 1
a. State whether the following statements or True or False? Explain
your choice: Inductive effect is the ability of an atom or a group of
atoms to cause polarization of electron density along the covalent
bond so that the atom of higher electronegativity becomes electron
deficient.
b. Explain the comparative stability of primary, secondary and
tertiary carbocations using Inductive effect.
3.1.2 Resonance (Mesomeric) Effect
Whilst inductive effects pull electrons through the σ-bond framework,

electrons can also move through the π-bond network. A π-bond can
stabilize a negative charge, a positive charge, a lone pair of electrons or
an adjacent bond by resonance (i.e. delocalisation or ‘spreading out’ of
the electrons). A resonance effect reflects the ability of an atom or group
of atoms to withdraw or donate electrons through π-bonds. This is also
sometimes referred to as a mesomeric effect.
In a normal π bond, the π electrons are localized between the constituent

atoms. However, if double and single bonds are present alternately in a
molecule, it is called conjugation e.g. in 1,3-butadiene, the double bonds
are conjugated.
Similarly, if the double, single and a lone pair are present, alternatively,
it is also called conjugation e.g. vinyl chloride.
The presence of conjugation alters the properties of the compound and

there is a difference in the actual and expected properties. The theory of
resonance explains the anomalous properties of such conjugated
compounds. This theory states that when a molecule can be represented
by two or more classical structural (or electronic) formula, all of which
can explain some but not all the properties, then the molecule has neither
of these structures (called contributing or canonical or limiting structures)
but is a hybrid of all these contributing structures. For example:
24
CHM 203 MODULE 1
Note that the π electrons are not necessarily present where one would
expect them, but are rather delocalised over the entire molecule which
gives it extra stability expressed in terms of delocalisation energy or
resonance energy. Also, normally, we find chlorine withdrawing electrons
towards itself by -I effect but here we find that the same chlorine has got
a positive charge and is involved in a double bond. Does this mean that
chlorine has lost its -I effect? No, this is not true as -I effect is a permanent
effect. In fact, in addition to the –I effect, it now also has an electron
donating mesomeric or resonance effect (called +M or +R effect).
Since the two effects are operating in opposite directions, one of them will
overwhelm the other. Remember there was no such possibility if halogen's
lone pair was not conjugated. For example, in the following case, the Cl
is not conjugated to the double bond and hence Cl is only exerting its –I
effect.
The atoms/groups like Cl in which lone pair (or electrons of negative

charge) is in conjugation with double or triple bond are electron donating
and gain a formal positive charge in the resonating structure in the process
and are known to exert +M/+R Effect.
Consider the case of –NO2 joined to a conjugated system, where the nitro
withdraws the conjugated electrons and gives rise to polarization as
shown below:
The atoms/groups like –NO2 which are in conjugation with double or

triple bond and are electron withdrawing and gain a formal negative
charge in the resonating structure in the process and are known to exert -
M/-R Effect.
The resonance effect also alters the electron density distribution in the
molecule significantly and its direction may be different from the normal
inductive effect. In case the two effects are operating in opposite
directions, the relative strengths of the two effects will determine which
will dominate. Mesomeric/resonance effect introduces total
25
delocalization of charges while inductive effect introduces partial

polarization, hence, in general M > I. But there are exceptions to it like
when halogens are attached to a conjugated system like benzene, -I > +R
(negative inductive effect is greater than resonance effect).
In neutral compounds, therewill always be a +M and –M group(s): One

group donates (+M) the electrons and the other group(s) accepts the
electrons (–M).
All resonance forms are not of the same energy. In phenol, for example,
the resonance form with the intact aromatic benzene ring is expected to
predominate.
As a rule of thumb, themore resonance structures an anion, cation or

neutral π-system can have, the more stable it is.
Key point about resonance:

(i) Resonating/canonical structure are maginary hypothetical, while
resonance hybrid is the true strucure.
(ii) Resonance involve the delocalization of lone pair and π-electrons.
(iii) Resonance is an intramolecular process.
(iv) Resonance must follow the Lewis octet rule, i.e. C-atom, N-atom
are never pentavalent and O-atom never tetravalent.
(v) In the resonating structure arrangement of atoms remain same,
they should differ only with respect to arrangement of electrons.
26
CHM 203 MODULE 1
(vi) The energy difference in between resonance hybrid and most

stable resonating structure is called resonance energy.
(vii) Resonance work only at ortho and para position with equal
intensity, it never work at meta position.
(viii) Resonance proceeds in the system via π-electrons.
Inductive versus mesomeric effects:

 Mesomeric effects are generally stronger than inductive effects.
A+M group is likely to stabilise an anion more effectively than a
+I group.
 Mesomeric effects can be effective over much longer distances
than inductive effects, provided that conjugation is present (i.e.
alternating single and double bonds).Whereas inductive effects are
determined by distance, mesomeric effects are determined by the
relative positions of +M and –M groups in a molecule.
In-Text Question 2
a. Mesomeric effect involves delocalisation of __________.
b. State whether the following statements or True or False? Explain
your choice: The –OH group cannot exhibit Inductive effect.
3.1.3 Hyperconjugation
A σ-bond can stabilize a neighbouring carbocation (or positively charged

carbon) by donating electrons to the vacant p-orbital. The positive charge
is delocalized or ‘spread out’, and this stabilizing effect is known as “no-
bond resonance”. Hyperconjugation helps explain the stability of alkyl
radicals. It involves the delocalization of σ-electrons belonging to the C-
H bond of the alkyl group attaching to an atom with an unshared p-orbital.
The more the hyperconjugative hydrogen, the more is the stability.
Why are more highly substituted alkenes more stable? One explanation
involves hyperconjugation: hyper meaning above/beyond and
conjugation meaning getting together. Figure 1.6 shows the overlapping
of the sp3-s orbitals of a C-H bond with an empty antibonding π orbital of
an adjacent alkene carbon atom. This overlapping of orbitals and sharing
of the C-H bonding electrons, called hyperconjugation, increases the
stability of the molecule.
27
Fig. 1.6: Hyperconjugation stabilization.
Hyperconjugation involves the conjugation of sigma-electrons with

adjacent pi electrons, as shown below:
This interaction is also known as conjugation. This type of delocalization

leads to a situation where there is no bond between the hydrogen and the
carbon atom of the molecule. Therefore, it is also known as hydrogen
no-bond resonance. Remember that the proton does not leave its
position and since the nuclei or the atoms do not change their positions,
therefore, the hyperconjugation becomes similar to resonance.
Hyperconjugation also results in the delocalization of charge, as you will
now study in case of carbocations. Hyperconjugation involving
hydrogens is the most common.
The stability of carbocations has been earlier explained on the basis of

inductive effect of the alkyl groups. Let us consider again a primary
carbocation, such as the one shown below in Fig. 1.7 below:
28
CHM 203 MODULE 1
Fig 1.7: the hyperconjugation in a carbocation
It is clear from the above structure that the electrons forming the -C–H
bond can overlap, into the empty p orbital of the carbon atom carrying the
positive charge. The C–H bond adjacent to the >C = C< or carbonation is
referred here as -C-H bond. The resulting hyperconjugation can be
represented as illustrated below:
Note that hyperconjugation produces some additional bonding between

the electron-deficient carbon and the adjacent carbon atom. Hence,
hyperconjugation results in the stabilization of carbocation by
delocalizing the positive charge. Obviously, the more the number -C–H
bonds which can participate in hyperconjugation, the more stable will be
the carbocation. You can see that in case of the primary carbocation
shown above, there are three such -C–H bonds. Let us now examine the
secondary and the tertiary carbocations.
For hyperconjugation to occur, the substituent next to the positively

charged carbon must have a filled σ-orbital available to overlap with
vacant p-orbital of the carbon atom carrying the positive charge.
29
The secondary carbocation has 6 -C–H bonds which can participate in

hyperconjugation whereas the tertiary carbocation has 9 -C–H bonds.
Certainly, more delocalization of charge is possible in case of a tertiary
carbocation than in a secondary carbocation which is in turn more
than the possibility in a primary carbocation. Therefore, the tertiary
carbocation is more stable than the secondary carbocation which is more
stable-than the primary carbocation. Highly alkyl substituted alkenes have
more opportunities to undergo hyperconjugation and therefore have
increased stability.
Hyperconjugation has therefore been used to explain the relative

stabilities of substituted alkenes. Consider the following order of stability
of some alkenes.
30
CHM 203 MODULE 1
You can see that in an alkene, the more the number of -C-H bonds which
can participate in hyperconjugation, the higher is its stability.
In spite of the fact that hyperconjugation can be used to explain many

otherwise unconnected phenomena, it is controversial as it involves the
formation of a weaker pi bond at the expense of a strong sigma bond.
In-Text Question 3
a. Hyperconjugation involves the delocalisation of __________
b. The larger the number of hyperconjugation structures, the stability
of free radicals will __________
3.2 Application of Inductive Effect, Hyperconjugation and

Mesomeric Effect: Acidity and Basicity
What are Acids and Bases?
There are various ways of defining acids and bases. According to

Arrhenius (1884), a Swedish chemist, an acid is a substance which
ionizes in aqueous solution to produce hydrogen ions (H+), also known
as protons. And, a base is a substance which ionizes to produce hydroxide
(OH) ions. Thus, Arrhenius theory assumes a simple dissociation such as,
Note that during dissociation, the covalent bond between H–A is broken
and the electrons forming this bond shift on A as shown by the curved
arrow.
Thus, HCl is an acid and NaOH is a base because on dissociation they

yield H + and OH- ions, respectively. Thus, the strength of these acids
and bases is related to the degree of their dissociation. The mineral acids
such as HCl, HI, HBr, H2SO4 and HNO3 are strong acids because they
31
are almost completely dissociated in aqueous solutions. Similarly, the

strength of a base will also depend upon its degree of dissociation.
An alternative theory of acids and bases was devised independently by

Bronsted and Lowry in 1922. According to the Bronsted-Lowry approach,
an acid is a proton donor and a base is a proton acceptor. Since under
ordinary reaction conditions a free proton cannot exist as a separate entity,
when an acid in the Bronsted-Lowry sense is considered, a base must be
present to accept the proton from the acid. The Bronsted acids are also
called protic acids because they react by the transfer of a proton. Consider
the following example,
Here, the ethanoic acid is an acid because it donates a proton to water

which is a base because it accepts the proton. Similarly, the ethanoate
ion, which is formed by the loss of a proton from ethanoic acid, functions
as a base because it can accept a proton to become ethanoic acid again.
Thus, ethanoate ion is called the conjugate base of ethanoic acid.
Similarly, the hydronium ion is the conjugate acid of the base, water. This
pair of a base and its conjugate acid or an acid and its conjugate base is
also called conjugate acid-base pair.
Let us now consider an acid-base reaction involving methylamine which

acts as a base and water which acts as an acid in this case, as shown below:
Note that water can act both as an acid as well as a base. It acts as an
acid by donating a proton to yield the OH- ion which is its conjugate base.
It can also act as a base by accepting a proton to yield a hydronium ion
which is its conjugate acid.
Although, we have illustrated both the above examples using water as one
of the components, the scope of Bronsted-Lowry definition of acids and
32
CHM 203 MODULE 1
bases is not limited to aqueous solutions as is the case in Arrhenius

definition. The Bronsted-Lowry concept of acids and bases is more
general and applies to any type of solvent.
Thus, according to this concept the general form of an acid-base reaction

can be written as;
where A1 – B1 and A2 – B2 are conjugate acid-base pairs.
The acid-base theory was further broadened by Lewis in 1934. He

proposed that the acids are the electron-pair acceptors and the bases
are the electron-pair donors.
Hence, according to this idea any molecule or ion which can

accommodate an electron pair is an acid. For example, a proton, H + , is a
Lewis acid because it can accept an electron pair.
A proton is only one of a large number of species that may act as a

Lewis acid. The electron deficient species such as AlCl3, BF3, BCl3,
ZnCl2, Mg2+ and carbocations are also Lewis acids. The electron deficient
atoms in these species accept the electrons to complete their valence shell
octets.
Similarly, any molecule or ion which has an unshared pair of electrons to

donate can act as a base. Thus, dimethyl ether acts as a Lewis base
towards boron trichloride which acts as a Lewis acid. This acid-base
reaction is represented below:
Note that the curved arrow shows the movement of a pair of electrons
from their source to their destination.
You will agree that the bases are much the same in both the Lewis and
the Bronsted-Lowry definitions because a Bronsted-Lowry base must
possess a pair of electrons in order to accept a proton.
33
Having identified a substance as an acid or a base according to the

above criteria, let us study how to determine the strength of an acid or a
base using the electronic factors discussed previously in section 3.1 of
this unit.
In-Text Question 4
Label the conjugate acid and the conjugate base in each of the following
reactions.
3.2.1 Strengths of Acids and Bases
It is not possible to determine the strength of an acid or a base in

absolute terms. Therefore, these strengths are always expressed in relative
terms. The relative strengths of acids are determined by the extent to
which they transfer a proton to a standard base. The standard base which
is commonly used for such comparisons is water. Hence, for an acid HA,
the proton transfer can be represented by the following equilibrium;
The equilibrium constant, Ka, for the above equilibrium can be written
as,
34
CHM 203 MODULE 1
where the quantities in square brackets are the molar concentrations

(expressed as moles dm-3) of the species at equilibrium. For dilute
solutions, the concentration of water is large and is almost constant.
The pKa value equals the pH of the acid when it is half dissociated. At
pH above the pKa the acid exists predominantly as the conjugate base in
water. At pH below the pKa, it exists predominantly as HA.
The pKa values are influenced by the solvent. Polar solvents will stabilize
cations and/or anions by solvation, in which the charge is delocalized over
the solvent (e.g. by hydrogen-bonding in water).
The dissociation of acid HA in solvents other than water can be

generalized as,
The more electronegative the atom bearing the negative charge, the more
stable the conjugate base (which is negatively charged).
Therefore, F- is more stable than H3C-.
The conjugate base can also be stabilised by –I and –M groups which can
delocalize the negative charge (the more spread out the negative charge,
the more stable it is). While the cation can be stabilised by +I and +M
groups, which can delocalize the positive charge. (The more ‘spread out’
the positive charge, the more stable it is).
–I and –M groups therefore lower the pKa, while +I and +M groups raise the pKa
On the other hand, basic compounds have high pKa values and are good
proton acceptors, as the cations (or conjugate acids), formed on
protonation, are relatively stable. Similar to acids, an equilibrium for bases
in water can be written as,
35
The strength of bases are usually described by the Ka and pKa values of
the conjugate acid.
Since the reaction is carried out in aqueous solution, water is acting both
as a solvent as well as an acid; hence, its concentration can be taken as
almost constant.
 If B is a strong base, then BH+ will be relatively stable and not

easily deprotonated. BH+ will therefore have a high pKa value.
 If B is a weak base, then BH will be relatively unstable and easily
deprotonated. BH+ will therefore have a low pKa value.
It is customary to express the strengths of organic bases not as Kb values

but in terms of the Ka and pKa values because it allows a single continuous
scale for both acids and bases. As has been stated above the stronger the
acid, the weaker will be its conjugate base and vice versa. In other words,
the stronger the acid, the lower the pKa, but, the stronger the base, the
higher is the pKa.
A comparison of the pKa values shows the following order of the basicities
for some of the bases.
Note that the organic compounds which act as bases can be regarded as
alkyl derivatives of either water or ammonia; for example, alcohols (R –
O – H), ethers (R – O – R-) and amines RNH2, R2NH and R3N. The basic
character of these compounds can be attributed to atoms such as nitrogen
and oxygen which contain at least one lone pair of electrons.
The strengths of acids and bases depend upon many factors. Apart from
the presence of functional groups; structural variations in molecules also
influence their acidic or basic properties. We will now focus our attention
on some effects which arise due to structural changes in the molecule. A
change in molecular structure can affect the reactivity of the molecule by
changing the electron distribution of the system, in which case it is called
an electronic effect. Another possibility is that two or more groups or
36
CHM 203 MODULE 1
atoms may come close enough in space so that the London interactions
between them become significant. The effects arising from such
interactions are called steric effects.
Before proceeding to the study of the lists which deals with these factors,
answer the following ITQ 5.
In-Text Question 5
An acid HA1 has pKa = 20 and another acid HA2 has pKa = 10.
1. Which of these two acids is stronger?

2. If Na+ A1 salt is added to acid HA2, does any acid-base reaction
take place? Explain.
a) Inductive effects in carboxylic acids and aliphatic (or alkyl)

amines:
The carboxylate anion is formed on deprotonation of carboxylic acids. The
anion is stabilised by resonance (i.e. the charge is spread over both oxygen
atoms) but can also be stablised by the R group if this has a –I effect.
Note that the inductive effect is a permanent effect.
Let us now analyse how inductive effect causes a change in the acidity
or basicity of a molecule. Let us take the example of ethanoic acid
whose structure is shown below:
If we substitute one of the hydrogen atoms on the C2 carbon atom with

a substituent X, then, the nature of the substituent group may affect
the electron density of the O–H bond resulting in a change in the acidity
of the molecule.
37
Depending upon whether the substituent X is electron-withdrawing or

electron donating, the electron density will decrease or increase,
respectively. If the electron density between the bond formed by O and
H atoms decreases, then, the loss of H as H+ ion is facilitated resulting
in the increased acidity of the molecule. On the other hand, an increase
in the election density at the bond between O and H atoms will make the
proton release difficult, thereby, decreasing the acidity.
The greater the -I effect, the more stable the carboxylate anion and the
more acidic is carboxylic acid.
(i) When the substitution X is electron withdrawing, it decreases the

electron density at H as shown below:
(ii) When the substituent X is electron donating, it increases the

electron density at H as represented below:
The effect of some of these substituents on the acidity of the substituted

acids in terms of their pKa values is shown in Table 1.3 below:
38
CHM 203 MODULE 1
Table 1.3: pKa values for some substituted acids determine in water
at 298 K.
Table 1.3 shows the decreased acidity for propanoic acid (larger pKa
value) as compared to the ethanoic acid. Note that the propanoic acid
has a methyl group in place of H in ethanoic acid. The methyl group is
electron-donating in nature and therefore, has a +I effect which results
in the decrease in the acidity. But the acidity increases when the electron-
withdrawing substituents such as F, Cl, Br and l are present. Note that the
increase in acidity is in accordance with the electronegativity of these
elements.
The inductive effect of these substituents is further enhanced with the

increase in the number of these substituents. This is represented in Table
1.4.
39
Table 1.4: Effect of increase in the number of chlorine substituents

on acidity of ethanoic acid
In monochloroethanoic acid, one of the three hydrogen atoms in ethanoic

acid has been replaced by an electron withdrawing chlorine atom. Hence,
the electron pair constituting the C–Cl bond is drawn closer to the
chlorine atom. This effect is transmitted through other atoms forming
σ-bonds to the OH bond of the group. This results in a shift

of the electrons constituting the O–H bond towards oxygen as shown
below:
Such an electron withdrawal by chlorine atom, thus, facilities the

department of the proton and hence, increases the acidic character of
monochloroethanoic acid as compared to ethanoic acids, the presence of
second and third chlorine.
In the di- and trichloroethanoic acids, the presence of second and third
chlorine.
40
CHM 203 MODULE 1
Atoms results in more electron withdrawal away from hydrogen of the

O–H bond and would, therefore, further increases the acidity of the
compounds as compared to ethanoic acid or chloroethanoic acid.
Therefore, we can arrange these acids in the increasing order of their
acidities as ethanoic acid < chloroethanoic acid < dichloroethanoic acid
< trichloroethanoic acid.
The position of electron-withdrawing substituents in a molecule also

influences its acidic character. This is shown by the pKa values of
isomeric monochlorobutanoic acids given in Table 1.5.
Table 1.5: Effect of position of substituent on acidity
It can be seen that although in each of these acids a chlorine atom has
replaced a hydrogen atom but they show different acidities. Note that as
the distance of the electron withdrawing chlorine atom from the reaction
site (i.e., O–H of the COOH group) increases, the acid strength decreases.
Thus, the influence of the inductive effect on acid strength is greatest
when the electron withdrawing chlorine atom is present on the carbon
next to the carboxylic group and it diminishes quickly with increase in the
distance. This effect is almost negligible after the fourth carbon atom in
the chain.
41
A similar electron withdrawal occurs when a positively charged group is

present in a molecule. A positive centre such as (CH3)3N+- (trimethyl
ammonium) or + NH3 (ammonium), eases the departure of proton by
withdrawing electrons and hence, increases the acid character of the
molecule. This is illustrated in the example given below:
Note that here also with the increase in the distance between the positively
charged group and the carboxyl group, the inductive effect decreases.
If the presence of a positively charged group increases the acidity of a
molecule, then a negatively charged group should decrease the acidity.
Consider the dissociation of propanedioic acid, as given below:
where Ka1 is the dissociation constant.
Here, a proton is lost from one of the two carboxyl groups of the molecule.
The dissociation constant for this dissociation is called the first
dissociation constant and is represented by Ka1. Further dissociation of
the anion obtained in the above dissociation is difficult because it involves
the removal of the proton from a negatively charged species. Therefore,
this step has a pKa value equal to 5.69. This is called pKa2 because Ka2
represents the second dissociation constant.
Always remember that Ka1 is larger than Ka2 for a dicarboxylic acid.
Therefore, for these acids pKa1 is lower than pKa2.
From the above discussion, we can say that the substituents having –I
effect increase the acidity while the substituents having +I effect
decrease the acidity.
In a similar way, since the substitution having +I effect decrease the

acidity, their presence should also increase the basicity. This is what is
actually observed when the hydrogen atoms of ammonia are successively
replaced by methyl groups to give methylamine and dimethylamine
whose basicities increase with the increase in the number of methyl
groups, as shown below by the pKa values of their conjugate acids.
42
CHM 203 MODULE 1
On protonation of amines, ammonium salts are formed.
The greater the +I effect of the R group, the greater the electron density
at nitrogen and the more basic the amine. The greater the +I effect, the
more stable the ammonium cation and the more basic the amine.
The pKa values should increase steadily as more +I alkyl groups are
introduced on nitrogen. However, the pKa values are determined in water,
and the more hydrogen atoms on the positively charged nitrogen, the
greater the extent of hydrogen-bonding between water and the cation.
This solvation leads to the stabilization of the cations containing N–H
bonds. However, in organic solvents (which cannot solvate the cation),
the order of pKas is expected to be as follows:
The presence of –I and /or –M groups on nitrogen reduces the basicity, and
hence, for example, amides are poor bases. Ethanamide has a pKa of –0.5.
43
At this stage, it would be helpful to answer the following ITQ.
In-Text Question 6
1. Arrange the following compounds in the decreasing order of their

acid strengths. Also, give reasons in support of your answer.
(i) CH3COOH, NCCH2COOH, NCCH2CH2CH2COOH

(ii) CH3NO2, CH2(NO2)2 CH(NO2)3
(iii) CH3COOH, HOOCCOOH, - OOCCOOH
2. Arrange the following compounds in the decreasing order of their

base strength. Support your answer with reasons.
(i) aniline, N-methylaniline, N, N-dimethylaniline
(ii) NH3, NH2CH3, NH2OH
The COOH group is –I type. Hence, it increases the acidity in case of

HOOCCOOH as compared to CH3COOH. But, in case of -OOCCOOH,
the removal of a proton is different because it is a negatively charged
species. Hence, it is less acidic as compared to CH3COOH.
i) The basicities decrease in the following order:
N,N-dimethylaniline > N-methylaniline > aniline
As the methyl group is electron donating, it increases the basicity in case

of N-methylaniline as compared to aniline. The basicity further increases
in N, N-dimethylaniline due to the increase in the number of methyl
groups.
ii) The decreasing order of basicities is as shown below: CH3NH2 >

NH3 > NH2OH
Since the methyl group has +I effect, it increases the basicity of CH3NH2
as compared to NH2. But, the substitution of an –OH group in NH3
decreases its basicity because it has –I effect.
b) Mesomeric effects in phenols and aryl (or aromatic) amines:
Mesomeric effects can also stabilise positive and negative charges. In this
case, The negative charge needs to be on adjacent carbon atom for a –M
group to stabilise it while the positive charge needs to be on adjacent
carbon atom for a +M group to stabilise it. On deprotonation of phenol the
44
CHM 203 MODULE 1
phenoxide anion is formed. This stabilised by delocalisation of the

negative charge at the 2-, 4- and 6-positions of the benzene ring.
Keynotes in mesomeric effects
 If –M groups are introduced at 2-, 4- and/or 6-positions, the anion

can be further stabilised by delocalization through the π-system, as
the negative charge can be spread onto the –M group. We can use
double-headed curly arrows to show this process.
 If –M groups are introduced at the 3- and/or 5-positions, the anion
cannot be stabilised by delocalization, as the negative charge
cannot be spread onto the –M group. There is no way of using curly
arrows to delocalize the charge onto the –M groups.
 If –I groups are introduced on the benzene ring, the effect will
depend on their distance from the negative charge. The closer the –
I group is to the negative charge, the greater will be the stabilising
effect. The order of –I stabilisation is therefore 2-position > 3-
position >4-position.
 The –M effects are much stronger than –I effects.
Example: The NO2 group is strongly electron-withdrawing; –I and –M.
45
The presence of groups such as OH, OMe, or halogen an electron-

withdrawing inductive effect, but an electron-donating mesomeric effect
when in the o- and p- positions, may, however, cause the p- substituted
acids to be weaker than the m- and, on occasion, weaker even than the
unsubstituted acid itself, e.g. p-hydroxybenzoic acid:
It will be noticed that this compensating effect becomes more pronounced

in going Cl ≈ Br → OH, i.e. in increasing order of readiness with which
the atom attached to the nucleus will part with its electron pairs. The
behaviour of o- substituted acids is, as seen above, often anomalous. Their
strength is sometimes found to be considerably greater than expected due
to direct interaction between the adjacent groups. Thus intramolecular
hydrogen bonding stabilises the anion (B) from o-hydroxybenzoic
(salicyclic) acid (A) by delocalising its charge, an advantage not shared by
its m- and p- isomers, nor by o- methoxy benzoic acid:
Intramolecular hydrogen bonding can, of course, operate in the

undissociated acid as well as in the anion, but it is likely to be considerably
more effective in the latter than in the former - with consequent relative
stabilisation - because the negative charge on oxygen in the anion will lead
to stronger hydrogen bonding. The effect is even more pronounced where
hydrogen bonding can occur with hydroxyl groups in both o-position, and
2, 6-dihydroxybenzoic acid is found to have pKa = 1.30. The below table
shows different carboxylic acids and their respective pKa values.
46
CHM 203 MODULE 1
Table 1.6: Different carboxylic acids and their respective pKa values
Acid pKa Acid pKa Value
Value
HCO2H 3.77 HO2CCO2H 1.23
CH3CO2H 4.76 HO2CCH2CO2H 2.83
CH3CH2CO 4.88 HO2CCH2CH2CO2 4.19
2H H
C6H5CO2H 4.17 HO2CC6H4CO2H o- 2.98; m- 3.46; p-
3.51
Similar to acidity, the basicity of compounds is also affected by the

resonance. For example, in case aminobenzene (aniline), the lone pair
of electrons on the nitrogen atom of the aminobenzene can be stabilized
by the delocalization of the electrons onto the 2-, 4-and 6-positions of the
benzene ring. Aromatic amines are therefore less basic than aliphatic
amines.
 If –M groups are introduced at the 2-, 4-and/or 6-positions (but not

at the 3- or 5-position), the anion can be further stabilised by
delocalization, as the negative charge can be spread onto the –M
group. This reduces the basicity of the amine.
 If –I groups are introduced on the benzene ring, the order of –I
stabilisation is 2-position > 3-position > 4-position. This reduces
the basicity of the amine.
 If +M group (e.g. OMe) are introduced at the 2-, 4- or 6-position of

aminobenzene, then the basicity is increased. This is because the
47
+M group donates electron density to the carbon atom bearing the

amine group.
This trend can be illustrated using the scheme below:
Resonance structures discussed in this section involve π - electrons and

in some cases non-bonded electrons. These resonance structures clearly
show that the nonbonding electrons of the nitrogen atom are delocalized
over the aromatic ring. Thus, the electron density at the nitrogen atom
increases which results in the higher basicity of p-substituted aniline.
You can test your knowledge of resonance by answering the following

ITQ.
In-Text Question vii
Draw resonance structures for the following species to rationalize the

facts given with them.
a. H2C = :O+–H is the conjugate acid of methanal (formaldehyde)

and has a substantial positive charge on carbon.
b. In acetonitrile oxide. H3C – C = N+–O: -, the inner carbon can

act as a Lewis acid.
So far we have been discussing factors that may influence the relative
availability of electrons in bonds, or at particular atoms, in a compound,
and hence affect that compound’s reactivity. The operation of these factors
48
CHM 203 MODULE 1
may, however, be modified or even be nullified by the influence of steric

factors; thus effective delocalization via π-orbitals can only take place if
the p or π-orbitals on the atoms involved in the delocalization, can become
parallel or fairly nearly so. If this is prevented, significant overlapping
cannot take place and delocalization may be inhibited. In the next section,
you will study the steric effect on molecular reactivity.
3.3 Steric Effect
The effect arising from the spatial interactions between the substituent
groups is called the steric effect. Resonance ability of an atom is lost if
it loses planarity with the other part of the system due to steric crowding
by bulky group in adjacent positions. In a way, you have already studied
the effect of such interactions on the stability of geometrical isomers
(where you studied that the trans-isomer is more stable than the cis-
isomers) and conformational isomers (where you studied that the
staggered conformation is more stable than the eclipsed conformation).
As the acid-base behaviour or the molecular reactivity is related to the
availability of the electrons, steric factors may also influence the
molecular reactivity. For example, they can inhibit the delocalization of
charge, as observed in case of N,N-dimethyl-o-toluidine. The
delocalization of the non-bonded electron pair on nitrogen, as shown in
the structure of N,N-dimethylaniline in Fig 1.8 (a).
Fig 1.8: (a) Delocalization of non-bonded electrons on nitrogen into

aromatic ring in N,N-dimethylaniline (b) Such a delocalization in not
possible in N,N-dimethyl-o-toluidine requires that the p-orbital of
nitrogen and those of the aromatic ring should be coplanar. Such
coplanarity is inhibited in the case N,N-dimethyl-o-toluidine due to the
presence of the ortho methyl group, as shown in Fig. 1.8 (b). Therefore,
in this molecule the electron pair is not delocalized but is available for
bonding with the proton which makes this molecule more basic than
49
N,N-dimethylaniline. This type of steric effect is known as steric,

inhibition of resonance.
The most common steric effect is, however, the steric hindrance where
the presence of the bulky groups makes the approach of the reagent to
the reaction site difficult. Such steric hindrance can account for the
lower basicity of tertiary amines as compared to secondary amines.
Remember that the steric hindrance affects the molecular reactivity not
by increasing or decreasing the electron availability but due to spatial
congestion. Therefore, it is different from electronic effects.
Let’s look at some other acid and base examples below:
In the above compounds, A and B have everything identical except

position of the two methyl group. It is expected that A should be stronger
base than B due to closeness of two electron donating methyl group to –
NH2. The fact is opposite to this. In compound B –NO2 is surrounded by
two bulky methyl group and they sterically repel the –NO2 group. In order
to minimize the steric repulsion by the two adjacent methyl group, the
nitro group loses planarity with the benzene ring. Therefore, –NO2 due to
lack of planarity-weigh ring is not able to resonate. This is known as steric
inhibition of resonance. Thus in B, –NO2 is not decreasing basic strength
by resonance. In A –NO2 lies in the plane of the ring, it is in resonance
50
CHM 203 MODULE 1
with the ring, decreases basic strength of –NH2 by resonance, hence

weaker base.
Using same analogy, we can explain the acidic strength of C and D. C is

stronger acid in spite of closeness of two electron donating methyl group
to –COOH.
Activity 3.1:
Make models of primary, secondary and tertiary amines and compare
the steric hindrance observed in these molecules.
Trimethylamine is thus least stabilized by solvation, leading to the lower

basicity of trimethylamine in water as compared to dimethylamine and
methylamine. However, in the gas phase or non-aqueous media, the
electron-donating inductive effect of a methyl group makes
trimethylamine the most basic among the methylamines.
Let us now study what is solvation and the role of solvent on the reactivity
of the molecules.
The presence of a solvent in acid-base reactions leads to the solvation of

the ionized species which are the conjugate acid and the conjugate base
when we are dealing with Bronsted acids and bases. Solvation refers to
the interaction of the dissolved species and solvent molecules wherein
several solvent molecules surround the dissolved species by forming a
solvent shell or solvent cage around it, as shown below:
51
The greater the solvation, the greater is the delocalization of the charge
on the species. Thus, increased solvation increases the dissociation of an
acid or a base by increasing the stability of the ions. These interactions
are particularly important when water is used as a solvent where the
hydrogen bonding plays an important role in solvating the anions. The
high dielectric constant of water also helps in the dissociation of the acids.
Thus, the ionization and the acidity of a substance increases with the
increase in the dielectric constant of the solvent. This is illustrated in
Table 1.7.
Table 1.7: Effect of solvent on pKa of ethanoic acid at 298 K

Solvent pKa
Benzene Almost unionized
82% Dioxane – 18% Water 10.14
Water 4.76
Thus, as the percentage of water in the solvent system increases, pKa

value of the acid decreases. Water is peculiar solvent as it can behave both
as an acid as well as a base. But its use has a limitation in the sense that
some organic compounds are not soluble in it.
Having discussed the various aspects of acids and bases, let us now
focus our attention on an internal acid-base process called tautomerism.
In-Text Question viii

What is a steric effect in organic chemistry?
52
CHM 203 MODULE 1
3.4 Tautomerism
The term tautomerism designates a rapid and reversible interconversion

of isomers which are related to each other with the actual movement of
electrons as well as of one or more atoms. Such isomers are called
tautomers. Thus, tautomerism is a chemical reaction and is to be
differentiated from resonance in which the nuclei do not move. It is,
therefore, represented by the equilibrium sign ( ) between the
tautomers. Tautomers which differ from each other only in the location
of a hydrogen atom and a double bond are called proton tautomers.
Table 1.8 shows some examples of proton tautomers. In contrast to
resonance structure, tautomers are real compounds and are capable of
independent existence.
Table 1.8: Some examples of proton tautomers
A particular example of tautomerism involving the ketones as carbonyl

compounds is called keto-enol tautomerism and is represented below:
53
The keto-enol tautorism is enormous importance as you will study later

in this course and also in the Organic Reactions Mechanism course. In
keto-enol tautomers, the keto form is usually the more stable form and,
therefore, it predominates at equilibrium.
The mechanism of enolisation involves solvent mediated proton transfer

steps rather than a direct intramolecular jump of the proton from carbon
to oxygen. Proton tautomerism in some cases leads to the formation of a
ring in one of the tautomers. Such a tautomerism is known as ring-chain
tautomerism and is illustrated below for 2-acetylbenzoic acid:
Another kind of tautomerism, known as valence tautomerism involves

a shift in interatomic distance within a molecule, without the separation
of any atom from the rest of the molecule, as an intermediate stage. This
kind of tautomerism occurs as a result of movement of valence electrons
of the molecule. An example of valence tautomerism is shown below:
54
CHM 203 MODULE 1
cyclooctatetraene
The valence tautomerism may appear similar to resonance but remember

that the two are different. The difference is that the valence tautomerism
involves making and breaking of σ and π electrons or the nonbonding
electrons shift and the σ framework of the molecule is not disturbed.
Some other differences between tautomerism and resonance are as
follows:
ii) Tautomerism may involve a change in the hybridization of

atoms which may result in a change in the shape of the molecule.
While in resonance there is no such change in the hybridization
and geometry of the molecule.
iii) The tautomers have a physical reality while the resonance
structures are imaginery.
iv) Tautomerism involves an equilibrium between two or more
tautomers. On the other hand, the resonance implies that the
actual structure of the molecule in the weighted averaged of
various resonance contributors and not a mixture on them.
i. Explain the acidic nature of 2,2,2-trifluoroethanol as compared

to ethanol.
ii. Explain the difference between pKa1 (4.16) and pKa2 (5.61)
of butanedioic acid.
iii. Draw resonance structures for the following:
i) chlorobenzene ii) acetonitrile iii) pyrrole
Pyrrole is less resonance stabilized than benzene, as can be seen from the
above resonance structure of pyrrole that in four out of the five structures
an electronegative nitrogen atom has a positive charge over it.
iv. Ethylamine and aniline react with aq. HCl. Write the equation
for these reactions.
v. Draw all the enol tautomers for each of the following ketones.
55
vi Which of the following alcoholic proton (OH) is expected to be

the most acidic?
vii Deduce the correct order of acidity among the following

compound I-IV.
viii Are the following pairs of compounds tautomers or resonance

forms?
56
CHM 203 MODULE 1
4.0 CONCLUSION
Electronic effects are the effects originating or present in the organic

molecules due to which the reactivity at one part of a molecule is affected
by electron attraction or repulsion originating in another part of a
molecule. These electronic effects are of three types mainly, inductive
effect, mesomeric (or resonance) effect, and hyperconjugative effect.
They are all permanent effects that stability and reactivity of organic
molecules and also determines the strength of an organic acid or base.
5.0 SUMMARY
In this unit, you studied that:
 Many reactions of organic compounds can be classified as acid-

base reactions. Therefore, the study of acids and bases is important
for understanding the organic reactions.
 According to Bronsted-Lowry definition, an acid is a proton donor
and a base is proton acceptor.
 Lewis definition classifies acids as electron pair acceptors and
bases as electric pair donors.
 The acidities of Bronsted acids can be expressed in terms of their
pKa values
 A strong acid has a weak conjugate base and a weak acid has a
strong conjugate base and vice versa.
 Structural changes can bring about marked differences in the acidic
and basic behaviour of a molecule which can be explained on the
basis of inductive, resonance and steric effects and on the basis of
hydrogen bonding.
 The inductive effects operate through sigma bonds and decrease
rapidly with increase in the distance between the substituent and
the reaction site. As a consequence of the fact that inductive effect
increases with the number of substituents present, a tertiary
carbocation is more stable than a secondary carbocation which is
more stable than a primary carbocation.
 Resonance stabilization of an anion (or the conjugate base) favours
dissociation of the acid.
 The steric effect operates due to the presence of the bulky groups
near the reaction site which prevent the approach of the reagent to
the reaction site. The steric requirements for Bronsted acids are
usually negligible because of the small size of the proton but are
important in case of Lewis acids.
57
 In addition to the structural changes mentioned above, the nature

of the solvent also plays an important role in the acid-base
equilibrium.

London.

Wiley & Sons.



John Wiley & Sons.
58
CHM 203 MODULE 1
UNIT 3 STEREOCHEMISTRY
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 Definition of Isomers
3.1.1 Constitutional Isomers (Structural Isomers)
3.1.2 Stereoisomers (Spatial Isomers)
3.1.3 Optical Isomerism
3.1.3.1 Chirality
3.1.3.2 Enantiomers
3.1.3.3 Optical Activity
3.1.3.4 Naming of Enantiomers: The R and S System of
Nomenclature
4.0 Conclusion
5.0 Summary
6.0 Tutur Mark Assignment
1.0 INTRODUCTION
Compounds that have the same molecular formula but are not identical in
structure are called isomers. Isomers fall into two main classes:
constitutional isomers and stereoisomers. Constitutional isomers differ in
the way their atoms are connected (revised your introduction to organic
chemistry course). For example, ethanol and dimethyl ether are
constitutional isomers because they have the same molecular formula,
C2H6O, but the atoms in each compound are connected differently. While
the oxygen in ethanol is bonded to a carbon and to a hydrogen, the oxygen
in dimethyl ether is bonded to two carbons.
Unlike the atoms in constitutional isomers, the atoms in stereoisomers are

connected in the same way. Stereoisomers (also called configurational
isomers) differ in the way their atoms are arranged in space.
Stereoisomers are different compounds that do not readily interconvert.
Therefore, they can be separated. There are two kinds of stereoisomers:
cis–trans isomers and isomers that contain chirality centers.
This unit is all about stereochemistry which deals with the arrangement
of atoms in space. Here, you will learn about the different kinds of
stereoisomers that are possible for organic compounds.
59
2.0 OBJECTIVES
At the end of this unit, you should be able to:
 Understand the concept of stereochemistry.

 differentiate chiral and achiral molecules.
 recognize and draw structural isomers (constitutional isomers),
stereoisomers including enantiomers and diastereomers and
racemic mixture.
 identify the stereocenters in a molecule and assign the
configuration as R or S.
 know the relationship between enantiomers and their specific
rotations.
3.0 MAIN CONTENT
3.1 Definition of Isomers
If two or more different compounds have the same molecular formula we

call them isomers. This is the general definition of isomer. Isomers are
the compounds with the same composition of elements, therefore their
relative molecular weights and general formulas are identical, but their
structures – including in the 3D arrangement – are different. There are
two major classes of isomers, and under these major classes there are
further classifications of isomers as in Fig 1.9.
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CHM 203 MODULE 1
Fig 1.9: Types of Isomers
Now let us look individually at the different types of isomer and see some
examples for each type.
3.1.1 Constitutional Isomers (Structural Isomers)
Different compounds that have the same molecular formula are called
isomers and when they have different connectivity (i.e. which atom is
bonded to which) we call them constitutional isomer or structural isomers.
Examples are as shown below:
This compound has a molecular formula of C2H6O. Now we can draw two
structures 1 & 2 for this molecular formula:
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Dimethyl ether 1 and Methanol 2 are constitutional isomers (or structural

isomers) because both of them have the same molecular formula C2H6O
but they have different structures due to the difference in the bond
connectivity of the atoms to each other. In 1 the bonds are C-O-C and
each C atom has 3 H atoms. In structure 2 the bonds are C-C-O and each
carbon has 2 H and there is a one H bonded to O atom.
Similarly, the molecular formula of butane is C4H10. Two structures can

be drawn for butane in order to obtain a saturated hydrocarbon with
molecular formula C4H10. The two structures have the same molecular
formula but they have different bond connectivity so they are
constitutional isomers. Note that structure 1 & 2 are completely two
different compounds, they have different physical (boiling and melting
point etc.) and chemical properties. The second example is however
chemically active and both isomer 3 & 4 can react with carboxylic acid
to form ester while 1 will not react.
Now if you try to convert 1 to 2 or vice versa, you will never be able to
do so without breaking the bonds and then re-building the molecules. The
same thing is applicable in the case of structures 3 & 4. We will never be
able to interconvert from one structural isomer to another by rotation
about bonds. We only can do that via only breaking bonds.
In-Text Question 1
a. Draw three constitutional isomers with molecular formula
C3H8O.
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CHM 203 MODULE 1
b. How many constitutional isomers can you draw for C4H10O?
3.1.2 Stereoisomers (Spatial Isomers)
In stereoisomers (spatial isomers), different compounds that have the

same molecular formula and the same bonds connectivity but they have
different arranging (orientation) in the space. There are two types of
stereoisomers which are:
Conformational isomers
1) Configurational isomers
Both types are stereoisomers that have the same molecular formula and
the same connectivity and both of them have different arrangement in the
space. However, in Conformational isomers we can convert from one
isomer to another isomer by just rotation about a C-C bond. Ethane is
good and simple example on conformational isomers. Let us look at the
most two important conformations of ethane staggered and eclipsed
conformations.
Now apply the definition of stereoisomers on the two isomers and see
what you will find out?
The two structures have the same molecular formula that means they are
isomers, they have the same bond connectivity that mean they are
stereoisomers, they have different bonds arrangement in the space and so
they may be either conformational isomers or configurational isomers.
For sure now we can say they are conformational isomers because we can
convert from staggered conformation to the eclipsed one via rotation
about the C-C bonds. Let us look at, respectively, the chair conformers
and Newman projection representation of the same example.
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Hence, conformational isomers are stereoisomers that can be converted

from one isomer to other isomers by rotation about C-C bond. The
conformations of propane, butane and all other conformations have the
same property as the ethane so they all are conformational isomers.
In-Text Question 2
Using Newman projections, draw the most stable conformer for the
following:
a. 3-methylpentane, considering rotation about the bond
b. 3-methylhexane, considering rotation about the bond
c. 3,3-dimethylhexane, considering rotation about the bond
Now let us look at the second type of stereoisomers; Configurational

isomers.
In the Configurational isomers we cannot convert from one isomer to

other isomers by rotation about bonds. We can only convert from one
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CHM 203 MODULE 1
isomer to other isomers via bond breaking. There are two major types of
Configurational isomers which are:
1) Geometrical isomers
2) Optical isomers
Geometrical isomers (cis-trans isomers) are isomers that have the same
molecular formula, the same bond connectivity but the atoms are in
different non-equivalent positions to one another. Geometrical isomers
occur as a result of restricted rotation about a carbon-carbon bond.
Restricted rotation about C-C bond can arise in two different situations:
(a) In a double bond

(b) In a cyclic compound
That means geometrical isomers can arise only if we have a double bonds
and/or cyclic structures.
As a result of the restricted rotation about a carbon–carbon double bond,

an alkene such as 2-pentene can exist as cis and trans isomers. The cis
isomer has the hydrogens on the same side of the double bond, whereas
the trans isomer has the
hydrogens on opposite sides of the double bond.
Cyclic compounds can also have cis and trans isomers. The cis isomer has
the hydrogens on the same side of the ring, whereas the trans isomer has
the hydrogens on opposite sides of the ring.
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In-Text Question 3
Draw the cis and trans isomers for the following compounds:
a. 3-hexene c. 1-bromo-4-chlorocyclohexane
b. 3-methyl-2-pentene d. 1-ethyl-3-methylcyclobutane
Now we will study the second type of configurational isomers which is

the optical isomers.
3.1.3 Optical Isomerism
Optical isomerism is one form of stereoisomerism. In optical isomerism

there is presence of a tetrahedral center. By tetrahedral center we mean
that a C atom is attached to four other atoms or group with single bonds
(sp3 hybridization). We have the name optical isomers because of their
effect on plane polarized light (reacts with light) as we will see later.
There are two major types of optical isomers

1) Enantiomers
2) Diastereomers
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CHM 203 MODULE 1
Before we start studying the optical isomers in details we need to learn

some definition of terms related to the stereochemistry.
3.1.3.1 Chirality
Chirality means "handedness". Chiral objects (molecules) are those

objects (molecules) which are not superimposable on (cannot be made to
coincide with) their mirror image. In other words, its mirror image is not
the same as itself. A hand is chiral because if you look at your left hand
in a mirror, you do not see your left hand; you see your right hand (Figure
1.10). In contrast, a chair is not chiral—it looks the same in the mirror.
Objects that are not chiral are said to be achiral. An achiral object has a
superimposable mirror image. Some other achiral objects would be a
table, a fork, and a glass.
Figure 1.10: Using a mirror to test for chirality. A chiral object, right
hand, is not the same as its mirror image - they are non-
superimposable. An achiral object, chair, is the same as its mirror
image - they are superimposable.
An object will exhibit handedness if it has no plane of symmetry. Plane

of symmetry is a position where an object can be cut in half and each half
is identical. In other words, a plane of symmetry bisects a molecule into
two mirror images halves.
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Not only objects can be chiral, molecules can be chiral, too. The feature
that most often is the cause of chirality in a molecule is an asymmetric
carbon.
An asymmetric carbon is a carbon atom that is bonded to four different

groups. The asymmetric carbon in each of the following compounds is
indicated by an asterisk. For example, the starred carbon in 4-octanol is
an asymmetric carbon because it is bonded to four different groups (H,
OH, CH2CH2CH3 and CH2CH2CH2CH3). The starred carbon in 2,4-
dimethylhexane is an asymmetric carbon because it is bonded to four
different groups—methyl, ethyl, isobutyl, and hydrogen.
An asymmetric carbon is also known as a chirality center. The

hybridization on the chiral carbon must be sp3. Examples:
An sp3 hybridized carbon with 1, 2, or 3 different atoms or groups

attached can be superimposed on its mirror image and is, therefore achiral.
None of the following three compounds (a, b, c) is chiral because they do
not have 4 different atoms or groups on the sp3 central C atom. Each of
them are superimpose on its mirror image.
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CHM 203 MODULE 1
Now it is important to learn how to draw the mirror image of the structure.
All what you need to do is to imagine that you have a mirror and draw
what you will see. Let us take 3-methylhexane for example:
Another example using 2-chlorobutane can be shown as,
In-Text Question 4
a. Name five capital letters that are chiral.
b. Name five capital letters that are achiral.
3.1.3.2 Enantiomers
Molecules that are not superimposable on their mirror images are chiral.
The existence of chirality is necessary and sufficient condition for the
existence of enantiomers i.e. if a compound is chiral; it can exist as
enantiomers and if it is achiral it cannot exist as enantiomers.
69
Enantiomers (from the Greek enantion, which means “opposite”) are

stereoisomers that are mirror image of each other and they are non-
superimposable on their mirror images. In other words, two isomers (the
original molecule and its mirror image) have a different spatial
arrangement, and so cannot be superimposed on each other. All
enantiomers are chiral (we will study them in more details soon).
2-bromobutane can also be presented in a similar manner.
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CHM 203 MODULE 1
The two stereoisomers of 2-bromobutane are enantiomers. A molecule

that has a non-superimposable mirror image, like an object that has a non-
superimposable mirror image, is chiral. Each of the enantiomers is chiral.
A molecule that has a superimposable mirror image, like an object that
has a superimposable mirror image, is achiral.
To see that the achiral molecule is superimposable on its mirror image

(i.e., they are identical molecules), mentally rotate the achiral molecule
clockwise.
Now let us look at how chemists draw Enantiomers.
Chemists draw enantiomers using either perspective formulas or Fischer

projections.
Perspective formulas show two of the bonds to the asymmetric carbon

in the plane of the paper, one bond as a solid wedge protruding out of the
paper, and the fourth bond as a hatched wedge extending behind the paper.
You can draw the first enantiomer by putting the four groups bonded to
71
the asymmetric carbon in any order. Draw the second enantiomer by

drawing the mirror image of the first enantiomer.
A shortcut—called a Fischer projection—for showing the three-

dimensional arrangement of groups bonded to an asymmetric carbon was
devised in the late 1800s by Emil Fischer. A Fischer projection represents
an asymmetric carbon as the point of intersection of two perpendicular
lines; horizontal lines represent the bonds that project out of the plane of
the paper toward the viewer, and vertical lines represent the bonds that
extend back from the plane of the paper away from the viewer. The carbon
chain always is drawn vertically with C-1 at the top of the chain.
To draw enantiomers using a Fischer projection, draw the first enantiomer

by arranging the four atoms or groups bonded to the asymmetric carbon
in any order. Draw the second enantiomer by interchanging two of the
atoms or groups. It does not matter which two you interchange. It is best
to interchange the groups on the two horizontal bonds because the
enantiomers then look like mirror images on paper.
Physical properties including melting point, boiling point, colour,

hardness, density, etc. All physical properties of pair of enantiomers are
the same except for one propriety which is optical activity (we will discuss
this in the next subsection). However, enantiomers have identical
chemical properties, except toward chiral substances where they will
behave differently. That mean a pair of enantiomers react in different way
with external chiral molecule.
In-Text Question 5
Using Fischer projections, draw enantiomers for each of the following
compounds:
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CHM 203 MODULE 1
In-Text Answer 5
3.1.3.3 Optical Activity
Enantiomers share many of the same properties—they have the same

boiling points, the same melting points, and the same solubility. In fact,
all the physical properties of enantiomers are the same except those that
stem from how groups bonded to the asymmetric carbon are arranged in
space. One of the properties that enantiomers do not share is the way they
interact with polarized light.
What is polarized light? Normal light consists of electromagnetic waves

that oscillate in all directions. Plane-polarized light (or simply polarized
light), in contrast, oscillates only in a single plane passing through the
path of propagation. Polarized light is produced by passing normal light
through a polarizer such as a polarized lens or a Nicol prism or other
polarizing medium so that all of the vibrations are in the same plane.
73
However, when polarized light passes through a solution of a chiral

compound, the light emerges with its plane of polarization changed. Thus,
a chiral compound rotates the plane of polarization. A chiral compound
will rotate the plane of polarization clockwise or counterclockwise. If one
enantiomer rotates the plane of polarization clockwise, its mirror image
will rotate the plane of polarization exactly the same amount
counterclockwise. Therefore, enantiomers rotate a plane polarized light in
different direction.
A compound that rotates the plane of polarization is said to be optically

active. In
other words, chiral compounds are optically active and achiral
compounds are optically inactive. If an optically active compound rotates
the plane of polarization clockwise, it is called dextrorotatory, indicated
by (+). If an optically active compound rotates the plane of polarization
counterclockwise, it is called levorotatory, indicated by (-). Dextro and
levo are Latin prefixes for “to the right” and “to the left,” respectively.
Sometimes lowercase d and l are used instead of (+) and (-). The degree
to which an optically active compound rotates the plane of polarization
can be measured with an instrument called a polarimeter.
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CHM 203 MODULE 1
Fig 1.11: Schematic representation of polarimeter
Now when a polarized light pass through a sample in the polarimeter there
are two possibilities:
1) The polarized light will pass straight without any reflection, that
means either the substance in the polarimeter is achiral.
OR
The substance in the polarimeter is an equal mixture of two enantiomers.
In this cases we say the substance is optically inactive. Optically inactive
substances are those substances which do not rotate the polarized light.
An equal mixture of enantiomers is called Racemic mixture. This is a
mixture containing equal quantities of enantiomers (50:50) (i.e. a chiral
molecule and its mirror image). The racemic mixture is optically inactive
because one molecule will rotate the
polarized light for example by 50o to the right, the other enantiomers will
rotate the polarized light by 50o to the left so they cancel each other and
the resultant rotation is zero.
2) The second possibility is when the polarized light of a polarimeter

pass through a sample and there is a rotation of the polarized light either
to the left or to the right depending on the nature of the substance. If such
a rotation takes place, we say the substance is optically active. For a
substance to be optically active it must be chiral and it should be either
single enantiomers or unequal mixture of enantiomers (one of them
present in excess).
The amount of rotation is called the observed optical rotation, α, this value
is obtained directly from the polarimeter and it depends on:
1. Concentration
2. length of the cell
3. the wavelength
4. solvent
5. temperature
To compare samples, a quantity called the specific rotation, [α], is

measured. The specific rotation is the number of degrees of rotation
caused by a solution of 1.0 g of the compound per mL of solution in a
sample tube 1.0 dm long at a specified temperature and wavelength. The
specific rotation can be calculated from the observed rotation using the
following formula:
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Where, [α] = specific rotation

T = temperature in °C
λ = wavelength
α = observed rotation
l = length of sample container in
decimeters
c = concentration in g/mL
Example: The observed rotation of 2.0 g of a compound in 50 mL of

solution in a polarimeter tube 20-cm long is +13.4o. What is the specific
rotation of the compound?
l in decimeter = 20/10 = 2 dm (10cm = 1 dm)
c in g/mL = 2/ 50 = 0.04 g/mL

.
Therefore, specific rotation, [α]T = = +167.5
.
For example, one enantiomer of 2-methyl-1-butanol has been found to

have a specific rotation of +5.75o. Because its mirror image rotates the
plane of polarization the same amount but in the opposite direction, the
specific rotation of the other enantiomer must be -5.75o.
Note: when the sodium D-line is used, is indicated as D.
3.1.3.4 Naming of Enantiomers: The R and S System of

Nomenclature
We need a way to name the individual stereoisomers of a compound such

as 2-bromobutane so that we know which stereoisomer we are talking
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CHM 203 MODULE 1
about. In other words, we need a system of nomenclature that indicates

the configuration (arrangement) of the atoms or groups about the
asymmetric carbon. Chemists use the letters R and S to indicate the
configuration about an asymmetric carbon. For any pair of enantiomers
with one asymmetric carbon, one will have the R configuration and the
other will have the S configuration. The R,S system was devised by Cahn,
Ingold, and Prelog.
Let us now look at the Cahn-Ingold-Prelog (CIP) sequence rules in

naming enantiomers.
1. Rank the groups (or atoms) bonded to the asymmetric carbon in

order of priority. The atomic numbers of the atoms directly attached to
the asymmetric carbon determine the relative priorities. The higher the
atomic number, the higher the priority.
2. Orient the molecule so that the group (or atom) with the lowest
priority (4) is directed away from you. Then draw an imaginary arrow
from the group (or atom) with the highest priority (1) to the group (or
atom) with the next highest priority (2). If the arrow points clockwise, the
asymmetric carbon has the R configuration (R is for rectus, which is Latin
for “right”). If the arrow points counterclockwise, the asymmetric carbon
has the S configuration (S is for sinister, which is Latin for “left”).
As an example, we will determine which of the enantiomers of 2-

bromobutane has the R configuration and which has the S configuration.
77
From step 1 above, we have:
From step 2, if the group (or atom) with the lowest priority is bonded by
a hatched wedge, draw an arrow from the group (or atom) with the highest
priority (1) to the group (or atom) with the second highest priority (2). If
the arrow points clockwise, the compound has the R configuration, and if
it points counterclockwise, the compound has the S configuration.
If the group with the lowest priority (4) is not bonded by a hatched wedge,
then switch two groups so group 4 is bonded by a hatched wedge. Then
proceed as in step 2 (above): Draw an arrow from the group (or atom)
with the highest priority (1) to the group (or atom) with the second highest
priority (2). So if the arrow for the enantiomer with the switched groups
points clockwise, the molecule has the R configuration. This means the
original molecule before the switch has the S configuration. In contrast,
if the arrow points counterclockwise, the enantiomer (with the switched
groups) has the S configuration, which means the original molecule has
the R configuration.
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CHM 203 MODULE 1
3. In drawing the arrow from group 1 to group 2, you can draw past
the group with the lowest priority (4), but never draw past the group with
the next lowest priority (3).
Now let’s see how to determine the configuration of a compound drawn

as a Fischer projection.
1. Rank the groups (or atoms) that are bonded to the asymmetric
carbon in order of priority.
2. Draw an arrow from the group (or atom) with the highest priority
(1) to the group (or atom) with the next highest priority (2). If the arrow
points clockwise, the enantiomer has the R configuration; if it points
counterclockwise, the enantiomer has the S configuration, provided that
the group with the lowest priority (4) is on a vertical bond.
3. If the group (or atom) with the lowest priority is on a horizontal

bond, the answer you get from the direction of the arrow will be the
opposite of the correct answer. For example, if the arrow points
clockwise, suggesting that the asymmetric carbon has the R configuration,
it actually has the S configuration; if the arrow points counterclockwise,
suggesting that the asymmetric carbon has the S configuration, it actually
has the R configuration. In the following example, the group with the
lowest priority is on a horizontal bond, so clockwise signifies the S
configuration, not the R configuration.
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4. In drawing the arrow from group 1 to group 2, you can draw past
the group (or atom) with the lowest priority (4), but never draw past the
group (or atom) with the next lowest priority (3).
Knowing whether a chiral molecule has the R or the S configuration does

not tell us the direction the compound rotates the plane of polarization,
because some compounds with the R configuration rotate the plane to the
right (+) and some rotate the plane to the left (-). We can tell by looking
at the structure of a compound whether it has the R or the S configuration,
but the only way we can tell whether a compound is dextrorotatory (+) or
levorotatory (-) is to put the compound in a polarimeter. For example, (S)-
lactic acid and (S)-sodium lactate have the same configuration, but (S)-
lactic acid is dextrorotatory whereas (S)-sodium lactate is levorotatory.
When we know the direction an optically active compound rotates the
plane of polarization, we can incorporate (+) or (-) into its name.
Note: When comparing two Fischer projections to see if they are the same
or different, never rotate one 90° or turn one over, because this is a quick
way to get a wrong answer. A Fischer projection can be rotated 180° in
the plane of the paper, but this is the only way to move it without risking
an incorrect answer.
Now answer the following ITQ to check your understanding.
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CHM 203 MODULE 1
In-Text Question 6
Indicate whether each of the following structures has the R or the S
configuration:
i. 20 mg mandelic acid was dissolved in 1 cm3 of ethanol and the

solution placed in a 10 cm long polarimeter cell. An optical
rotation of –4.35ºC was measured (that is, 4.35º to the left) at
20ºC with light of wavelength 589 nm. What is the specific
rotation of the acid?
ii. Neglecting stereoisomers, give the structures of all compounds
with molecular formula C5H10. Which ones can exist as cis-
trans isomers?
iii. The relationship between the following two structures is:
(A) enantiomers (B) diastereomers (C) structural isomers (D) identical

iv The specific rotation of pure (R)-2-butanol is -13.5°. What % of a
mixture of the two enantiomeric forms is (S)-2-butanol if the specific
rotation of this mixture is -5.4°? (A) 40%(B) 30%(C) 60%(D) 70%(E)
None of the above
v Which of the following objects are chiral?
a. A mug with DAD written on one side of the handle.

b. A mug with MOM written on one side of the handle.
c. A mug with DAD written opposite the handle.
d. A mug with MOM written opposite the handle.
e. A wheelbarrow.
f. A remote control device.
g. A nail.
h. A screw.
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vi Do the following structures represent identical molecules or a pair

of enantiomers?
SAQ 4.7
Name each of the following compounds using R,S and E,Z designations
where necessary:
4.0 CONCLUSION
The excitement that chemists feel for the area of stereochemistry has
hopefully rubbed off during your reading of this unit. From simple
structural isomers to geometric isomers and then optical isomers where
we mentioned enantiomers and diastereomers, stereochemistry continues
to challenge organic chemists to create molecules of increasing
complexity, which inevitably leads to molecules with intriguing
properties and simple aesthetic beauty. Furthermore, stereochemical
concepts shed important light on the study of reaction mechanisms. It is
this topic that we still need to develop further. In our analyses of reaction
mechanisms, we will rely heavily upon the concepts and terminology
introduced in this unit. All introductory organic chemistry courses teach
the fundamentals of stereoisomerism, and we have only briefly review
that information here.
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CHM 203 MODULE 1
5.0 SUMMARY
 Stereochemistry is the field of chemistry that deals with the

structures of molecules in three dimensions.
 Compounds that have the same molecular formula but are not
identical are called isomers; they fall into two classes:
constitutional isomers and stereoisomers. Constitutional isomers
differ in the way their atoms are connected. Stereoisomers differ
in the way their atoms are arranged in space. There are two kinds
of stereoisomers: cis–trans isomers and isomers that contain
chirality centers.
 A chiral molecule has a nonsuperimposable mirror image. An
achiral molecule has a superimposable mirror image. The feature
that is most often the cause of chirality is an asymmetric carbon.
 Nonsuperimposable mirror-image molecules are called
enantiomers. Diastereomers are stereoisomers that are not
enantiomers.
 The letters R and S indicate the configuration about an asymmetric
carbon. If one molecule has the R and the other has the S
configuration, they are enantiomers; if they both have the R or both
have the S configuration, they are identical.
 Chiral compounds are optically active-they rotate the plane of
polarized light; achiral compounds are optically inactive. If one
enantiomer rotates the plane of polarization clockwise (+), its
mirror image will rotate the plane of polarization the same amount
counterclockwise (-).
 A racemic mixture (recemate) is optically inactive.
6.0 TUTOR MARK ASSIGMENT

London.

Wiley & Sons.
83



John Wiley & Sons.
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CHM 203 MODULE 2
MODULE 2 FUNCTIONAL GROUPS AND

REACTIVITY IN ORGANIC CHEMISTRY
INTRODUCTION
The main classes of compounds you will study in organic chemistry are
alkanes, alkenes, alkynes, alkyl halides, ethers, alcohols, and amines. As
you learn various properties and reactivity of compounds, you will need
to be able to refer to them by name. So you will begin your study of this
module by learning how to identify and name some of these main classes
of organic compounds. First you will learn how to name alkanes and the
way they react because they form the basis for the names of almost all
organic compounds. Subsequently you will study the various organic
reactions. It is important that you are conversant with the names and
formula of at least the first 10 members of each functional group in
organic chemistry. The following units will be discussed in this module:
Unit 1 Functional group chemistry of main class organic

compounds
Unit 2 Alkanes, free radical substitution reactions in alkanes and
the reactivity - selectivity principle
Unit 3 Electrophilic and nucleophilic substitution reaction
Unit 4 Various organic reactions e.g. addition free radicals,
elimination reaction etc.
UNIT 1 FUNCTIONAL GROUP CHEMISTRY OF MAIN

CLASS ORGANIC COMPOUNDS
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 Functional Groups in Organic Chemistry
3.2 An Overview of Functional Groups
3.2.1 Hydrocarbons
3.2.2 Compounds Containing C-Z σ Bonds
3.2.3 Compounds Containing C=O Group
3.2.4 Alcohols
3.2.5 Amines
3.2.6 Thiol
3.3 Functional Groups and Reactivity
4.0 Conclusion
5.0 Summary
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1.0 NTRODUCTION
Chemists have learned through years of experience that organic

compounds can be classified into families according to their structural
features and that the members of a given family often have similar
chemical behaviour. Instead of 40 million compounds with random
reactivity, there are a few dozen families of organic compounds whose
chemistry is reasonably predictable. We’ll study the chemistry of the
specific families throughout much of this unit, beginning in this module
with a look at the simplest family, the hydrocarbons.
The structural features that make it possible to classify compounds into

families are called functional groups. A functional group is a group of
atoms within a molecule that has a characteristic chemical behaviour.
Chemically, a given functional group behaves in nearly the same way in
every molecule it is a part of. For example, compare ethylene, a plant
hormone that causes fruit to ripen, with menthene, a much more
complicated molecule found in peppermint oil. Both substances contain a
carbon–carbon double-bond functional group, and both therefore react
with Br2 in the same way to give a product in which a Br atom has added
to each of the double-bond carbons. This example is typical: the chemistry
of every organic molecule, regardless of size and complexity, is
determined by the functional groups it contains.
2.0 OBJECTIVES
When you have studied this unit, you should be able to:
 know the major classes of organic compounds and identify

important functional groups.
 understand the factors that determine the properties of organic
compounds.
 have a better understanding of functional groups and reactivity of
organic compounds.
 describe the importance and purpose of functional groups in
organic reactions.
3.0 MAIN CONTENT
3.1 Functional Groups in Organic Chemistry
What are the characteristic features of an organic compound? Most

organic molecules have C-C and C-H σ bonds. These bonds are strong,
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CHM 203 MODULE 2
nonpolar, and are not readily broken. Organic molecules may have the
following structural features as well:
• Heteroatoms - atoms other than carbon or hydrogen. Common

heteroatoms are nitrogen, oxygen, sulfur, phosphorus, and the
halogens.
• π Bonds. The most common π bonds occur in C-C and C-O double
bonds.
These structural features distinguish one organic molecule from another.

They determine a molecule’s geometry, physical properties, and
reactivity, and comprise what is called a functional group.
• A functional group is an atom or a group of atoms with

characteristic chemical and physical properties. It is the
reactive part of the molecule.
Why do heteroatoms and π bonds confer reactivity on a particular

molecule?
• Heteroatoms have lone pairs and create electron-deficient sites on

carbon.
• π Bonds are easily broken in chemical reactions. A π bond makes

a molecule a base and a nucleophile.
Don’t think, though, that the C-C and C-H σ bonds are unimportant. They
form the carbon backbone or skeleton to which the functional groups
are bonded. A functional group usually behaves the same whether it is
bonded to a carbon skeleton having as few as two or as many as 20
carbons. For this reason, we often abbreviate the carbon and hydrogen
portion of the molecule by a capital letter R, and draw the R bonded to a
particular functional group.
Ethane, for example, has only C-C and C-H σ bonds, so it has no
functional group. Ethane has no polar bonds, no lone pairs, and no π
bonds, so it has no reactive sites. Because of this, ethane and molecules
like it are very unreactive.
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Ethanol, on the other hand, has two carbons and five hydrogens in its
carbon backbone, as well as an OH group, a functional group called a
hydroxyl group. Ethanol has lone pairs and polar bonds that makes it
reactive with a variety of reagents, including the acids and bases.
The hydroxyl group makes the properties of ethanol very different from
the properties of ethane. Moreover, any organic molecule containing a
hydroxyl group has properties similar to ethanol.
Ethane
All C-C and C-H σ bonds Polar C-O and O-H bonds
No functional group Two lone pairs
Most organic compounds can be grouped into a relatively small number

of categories, based on the structure of their functional group. Ethane, for
example, is an alkane, whereas ethanol is a simple alcohol.
3.2 An Overview of Functional Groups
We can subdivide the most common functional groups into several types.
• Hydrocarbons
• Compounds containing a C-Z σ bond where Z = an electronegative
element
• Compounds containing a C=O group
• Others.
In-Text Question 1
What is a functional group? Give at least two examples of functional
groups.
3.2.1 Hydrocarbons
Hydrocarbons are compounds made up of only the elements carbon and

hydrogen. They may be aliphatic or aromatic.
1. Aliphatic hydrocarbons can be divided into three subgroups.
• Alkanes have only C-C σ bonds and no functional group. Ethane,

CH3CH3, is a simple alkane.
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CHM 203 MODULE 2
• Alkenes are hydrocarbons that contain one or more double bonds

between neighboring carbon atoms. They have a C-C double bond as a
functional group. Ethylene, CH2=CH2, is a simple alkene.
• Alkynes contain one or more triple bonds between neighboring

carbon atoms. They have a C-C triple bond as a functional group.
Acetylene, HC≡CH, is a simple alkyne.
2. Aromatic hydrocarbons. The additional functional group that

contains only carbon and hydrogen is an aromatic ring which is a six-
carbon ring with alternating double bonds. The aromatic ring can also be
shown as a ring with a circle in the middle representing the double bonds.
Aromatic rings are found in many compounds including steroids and
medications. This class of hydrocarbons was so named because many of
the earliest known aromatic compounds had strong, characteristic odours.
The simplest aromatic hydrocarbon is benzene. The six-membered ring

and three π bonds of benzene comprise a single functional group.
When a benzene ring is bonded to another group, it is called a phenyl

group. In phenylcyclohexane, for example, a phenyl group is bonded to
the six-membered cyclohexane ring.
Alkanes, which have no functional groups, are notoriously unreactive

except under very drastic conditions. For example, polyethylene is a
synthetic plastic and high molecular weight alkane, consisting of chains
of –CH2– groups bonded together, hundreds or even thousands of atoms
long. Because it is an alkane with no reactive sites, it is a very stable
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compound that does not readily degrade and thus persists for years in
landfills.
In-Text Question 2
a. Identify the type of hydrocarbon in each structure.
b. Give the systematic name of the following compound:
3.2.2 Compounds Containing C-Z σ Bonds
The electronegative heteroatom Z creates a polar bond, making carbon

electron deficient. The lone pairs on Z are available for reaction with
protons and other electrophiles, especially when Z = N or O.
Several simple compounds in this category are widely used.
1. Alkyl halides: The haloalkanes, also known as alkyl halides, are a

group of chemical compounds that comprised of an alkane with one or
more hydrogens replaced by a halogen atom (Group 17 atom). There is a
fairly large distinction between the structural and physical properties of
haloalkanes and the structural and physical properties of alkanes.
As an example, chloroethane (CH3CH2Cl, commonly called ethyl

chloride) is an alkyl halide used as a local anesthetic. Chloroethane
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CHM 203 MODULE 2
quickly evaporates when sprayed on a wound, causing a cooling sensation

that numbs the site of an injury.
Haloalkanes are found in fire extinguishers, refrigerants, propellants,

solvents, and medications. They are also a significant source of pollution
and their use has been reduced or eliminated in some products.
Chlorofluorocarbons (CFCs) were used as refrigerants in air-conditioners
but were found to be a major cause of the depletion of the ozone layer.
Research and development of alternatives began in the 1970s.
Hydrochlorofluorocarbons (HCFCs) have been used for many years since
they cause less damage to the ozone layer, but many countries agreed to
eliminate HCFCs by the year 2020.
2. Ethers: The ether functional group consists of an oxygen atom that

forms single bonds with two carbon atoms. Molecules containing these
functional groups may be simple or very complex.
Diethyl ether, the first common general anesthetic, is a simple ether

because it contains a single O atom, depicted in red, bonded to two C
atoms. Hemibrevetoxin B, on the other hand, contains four ether groups,
in addition to other functional groups.
Diethyl ether
Although ethers themselves are relatively unreactive, they can be

converted to peroxides after prolonged exposure to oxygen. Peroxides are
very reactive and are often explosive at elevated temperatures. Many
commercially available ethers come with a small amount of a peroxide
scavenger dissolved in them to help prevent this type of safety hazard.
In-Text Question 3
Determine the molecular formula of a 5-carbon hydrocarbon with one
bond and one ring
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3.2.3 Compounds Containing C=O Group
Many different types of functional groups possess a C-O double bond (a

carbonyl group). The polar C-O bond makes the carbonyl carbon an
electrophile, while the lone pairs on O allow it to react as a nucleophile
and base. The carbonyl group also contains a π bond that is more easily
broken than a C-O σ bond.
Reactive features of a carbonyl group
1. Aldehyde: A very common structural component of organic

structures is the carbonyl, which is simply a carbon atom and an oxygen
atom connected by a double bond. The reactivity of carbonyls is primarily
dictated by the polarization of the C=O bond, but the surrounding atoms
also play a role in its specific reaction pathways.
The other group attached to the carbonyl may be an R-group or a

hydrogen atom. Because the hydrogen atom is so small, the partial
positive charge on the carbonyl carbon is very easy for other molecules to
approach, making aldehydes a particularly reactive type of carbonyl.
Aldehydes are versatile reactants for a wide variety of organic syntheses.

Many aldehydes also have distinctive flavours and aromas. For example,
the flavour of cinnamon is primarily due to the molecule cinnamaldehyde,
and vanillin is the Aldehyde most responsible for the smell and taste of
vanilla extract.
A special aldehyde is the molecule in which the carbonyl is bonded to two

hydrogen atoms. This molecule, called formaldehyde, has a wide variety
of uses. By itself, it can be used as a tissue preservative or as a very harsh
disinfectant. It is also used as a precursor to various materials, including
plastics, resins, and other polymers.
2. Ketone: A ketone involves a carbonyl in which the carbon atom

makes single bonds with two R-groups. Ketones undergo most of the
same reactions as aldehydes, but they tend to be slightly less reactive. The
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CHM 203 MODULE 2
simplest ketone is acetone, in which the carbonyl carbon is bonded to two

CH2 groups. This ketone is commonly used to remove fingernail polish
and serves as an industrial solvent. Methyl ethyl ketone is used as a paint
stripper and a solvent. Ketones are also used in the production of various
polymers, either as a building block or as a solvent. The R-group in a
ketone can be the same or different as seen in the example.
3. Carboxylic acids: are another carbonyl-containing functional

group, in which the carbon atom is bonded to a hydroxyl group on one
side and either a carbon or hydrogen atom on the other.
As the name implies, carboxylic acids are weak acids. An OH group that
is directly connected to a carbonyl will ionize to a small extent when
dissolved in water. The reason for this is the relative stability of the
resulting anion. A carboxylate ion, in which the negative charge is spread
over two different oxygen atoms through resonance structures, is more
stable than an isolated oxygen-centered anion. The carboxylic acid and
carboxylate ion are interchangeable. Carboxylate ions are often present in
amino acids.
Carboxylate ion
4. Ester: An ester is similar to a carboxylic acid, in that it contains a

carbonyl where the carbon is bonded to one additional oxygen atom and
one carbon or hydrogen atom. However, the second oxygen atom is
bonded to another carbon instead of to an acidic hydrogen atom.
Structurally, carboxylic acids and esters are related to one another in the
same way as alcohols and ethers.
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Esters can be formed by heating carboxylic acids and alcohols in the

presence of an acid catalyst. This process is reversible, and the starting
materials can be regenerated by reacting an ester with water in the
presence of a weak base.
Some esters have very pleasant odours, so they are used in the
manufacture of many perfumes. Propyl acetate contributes to the odour of
pears, while isoamyl acetate gives bananas their smell. This ester also
serves as an alarm signal for honeybees. Esters are employed in the
manufacture of fabrics (polyesters) and Plexiglass. Anesthetics such as
procaine and benzocaine also contain esters.
5. Amides: An amide is a carbonyl in which the carbon is attached to

one nitrogen atom and one carbon or hydrogen atom. Alternatively, we
could define an amide as an amine in which one of the carbon atoms
attached to the nitrogen is part of a carbonyl.
An amide can be formed by combining a carboxylic acid and an amine.

Only primary and secondary amines can be sued to form amides, since
they have a hydrogen that can be replaced with the carbonyl carbon;
tertiary amines will not form amides.
Amides are used as colouring agents in crayons, pencils, and ink. They
are employed in the paper, plastic, and rubber industries. Polyacrylamide
is a very widely used amide; it is involved in the treatment of drinking
water and sewage, and in plastics manufacture. The amide Kevlar is
widely employed for the production of body armor, and nylon is another
type of amide-based polymer.
Atenolol and donepezil are examples of useful drugs that contain a variety
of functional groups. Atenolol is a β blocker, a group of drugs used to
treat hypertension. Donepezil, sold under the trade name Aricept, is used
to treat mild to moderate dementia associated with Alzheimer's disease.
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CHM 203 MODULE 2
3.2.4 Alcohols
The alcohol functional group involves an oxygen atom that is bonded to

one hydrogen atom and one carbon atom. The carbon atom will be part of
a larger organic structure. One way to indicate a generic alcohol would be
with the formula R-OH. R represents any organic fragment in which a
carbon atom is directly bonded to the explicitly indicated functional group
(in this case, OH). The R group is typically a chain of carbon atoms.
Alcohols can be classified as primary, secondary, or tertiary based on the

characteristics of the carbon to which it is attached. In a primary alcohol,
the carbon bonded directly to the oxygen atom is also bonded to exactly
one carbon atom, with the other bonds generally going to hydrogen atoms.
In a secondary alcohol, the carbon is attached to two other carbon atoms,
and in a tertiary alcohol, the carbon is bonded to three other carbon atoms.
The type of alcohol being used will determine the product of certain
reactions.
We are already familiar with several common alcohols. For example,

ethanol is the alcohol present in alcoholic beverages. It is also widely used
in the industrial manufacture of other chemicals. Methanol is used as a
gasoline additive or alternative. Additionally, methanol can be used to
manufacture formaldehyde, which is employed in the production of
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plastics, paints, and other useful substances. Isopropanol is commonly

known as rubbing alcohol. In addition to its industrial uses, isopropanol
is used to clean various surfaces, including computer monitors,
whiteboards, and even skin (e.g., before getting blood drawn).
3.2.5 Amines
An amine consists of a nitrogen atom bonded to some combination of

carbons and hydrogens.
Like alcohols, amines can be classified as primary, secondary, or tertiary.

However, the rules for assigning these categories are slightly different. In
an alcohol, the oxygen atom is always bonded to exactly one carbon atom,
so we look at the branching on the adjacent carbon, not the oxygen atom
itself. In a neutral amine, the nitrogen can be bonded to one, two, or three
carbon atoms, and this is how we decide whether it is called a primary,
secondary, or tertiary amine.
Neutral amines are weak bases, because the lone pair on nitrogen can act
as a proton acceptor. Many smaller amines have very strong and offensive
odors. For example, the aptly-named compounds cadaverine and
putrescine are foul-smelling amines, formed as a part of the decay process
after death.
Amines serve a wide variety of uses. Diphenylamine acts as a stabilizer

for certain types of explosives. Amines are found as components in some
lubricating materials, in developers, and are a part of waterproofing
textiles. Some amines, such as Novocain, are used as anesthetics. Many
pharmaceutical compounds contain amines, including 8 of the 10 most
prescribed medications in 2012.
In-Text Question 4
1. The general formula for amines is __________.
A. R-CH2 B. R2CH C. R-NH2 D. R-COOH
2. Glutamic acid is the parent compound of monosodium glutamate
(known as MSG), which is used as a flavor enhancer. Glutamic
acid has the following structure:
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CHM 203 MODULE 2
Name the functional groups you recognize in this molecule. Do you think
there are other groups of atoms in this molecule that might qualify as
functional groups?
3.2.6 Thiol
The thiol functional group contains a sulphur atom bonded to a hydrogen

atom. It is very similar to an alcohol functional group with the sulphur
replacing the O.
Thiols are also called mercaptans which are derived from the Latin phrase
for "capturing mercury" because of the strong bonds it forms with
mercury-containing compounds. Some thiol compounds have a
distinctive smell similar to rotten eggs. They are often added to natural
gas, which itself has no odor, as a way to detect leaks since its odor can
be detected by humans in very small amounts. A thiol group is also
present in the amino acid cysteine.
3.3 Functional Groups and Reactivity
A functional group also determines reactivity. What type of reaction does

a particular kind of organic compound undergo? Begin by recalling two
fundamental concepts.
 Functional groups create reactive sites in molecules.

 Electron-rich sites react with electron-poor sites.
All functional groups contain a heteroatom, a π bond, or both, and

these features make electron-deficient (or electrophilic) sites and
electron-rich (or nucleophilic) sites in a molecule. Molecules react at
these sites. To predict reactivity, first locate the functional group and then
determine the resulting electron-rich or electron-deficient sites it creates.
Keep three guidelines in mind.
97
• An electronegative heteroatom like N, O, or halogens makes a

carbon atom electrophilic.
• A lone pair on a heteroatom makes it basic and nucleophilic.
• π Bonds create nucleophilic sites and are more easily broken than
r bonds.
By identifying the nucleophilic and electrophilic sites in a compound you

can begin to understand how it will react. In general, electron-rich sites
react with electron-deficient sites:
• An electron-deficient carbon atom reacts with a nucleophile,

symbolized as :Nu–.
• An electron-rich carbon reacts with an electrophile, symbolized as

E+.
At this point we don’t know enough organic chemistry to draw the

products of many reactions with confidence. We do know enough,
however, to begin to predict if two compounds might react together based
solely on electron density arguments, and at what atoms that reaction is
most likely to occur.
For example, alkenes contain an electron-rich C–C double bond and so

they react with electrophiles, E+. On the other hand, alkyl halides possess
an electrophilic carbon atom, so they react with electron-rich
nucleophiles.
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CHM 203 MODULE 2
In-Text Question 5
1. Why are alkanes sometimes called paraffins?
2. What is the principal difference in properties between alkenes and
alkanes? How are they alike?
4.0 CONCLUSION
Propose structures for simple molecules that contain the following

functional groups:
(a) Alcohol
(b) Aromatic ring
(c) Carboxylic acid
(d) Amine
(e) Both ketone and amine
(f) Two double bonds
SAQ 4.2
Identify the functional groups in each of the following molecules:
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SAQ 4.3
Propose structures for two isomers with the formula C2H7N.
There are two isomeric structures. One has the connection C-C-N,
and the other has the connection C-N-C.
SAQ 4.4
The correct IUPAC name for the following structure is.
CH3CH2CHCH2CH CH2
OH
(A) 5-hexen-3-ol (B) 1-hexen-4-ol

(C) 3-hydroxy-5-hexene (D) Isohexen-3-ol
(E) 4-hydroxy-1-hexene
SAQ 4.5
Write a structure for each of the following compounds:
a. isopropyl alcohol d. neopentyl chloride
b. isopentyl fluoride e. tert-butylamine
c. sec-butyl iodide f. n-octyl bromide
4.0 CONCLUSION
In this unit, we have been able to classify the numerous organic

compounds into several major categories based on the functional groups
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CHM 203 MODULE 2
they contain. We also explained how functional groups present in organic

molecules determine the chemical reactivity of those molecules.
5.0 SUMMARY
With over twenty million known organic compounds in existence, it

would be very challenging to memorize chemical reactions for each one.
Fortunately, molecules with similar functional groups tend to undergo
similar reactions. A functional group is defined as an atom or group of
atoms within a molecule that has similar chemical properties whenever it
appears in various compounds. Even if other parts of the molecule are
quite different, certain functional groups tend to react in certain ways.
Organic molecules vary greatly in size and when focusing on functional

groups, we direct our attention to the atoms involved in the functional
group. As a result, the abbreviation R is used in some examples. The letter
R is used in molecular structures to represent the “Rest of the molecule”.
It consists of a group of carbon and hydrogen atoms of any size. It is used
as an abbreviation since a group of carbon and hydrogen atoms does not
affect the functionality of the compound. In some molecules, you will see
R, R’, or R’’ which indicates that the R groups in the molecule can be
different from one another. For example, R might be –CH2CH3 while R’
is –CH2CH2CH2CH3.

London.

Wiley & Sons.

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John Wiley & Sons.
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CHM 203 MODULE 2
UNIT 2 ALKANES, FREE RADICAL SUBSTITUTION

REACTIONS IN ALKANES AND THE
REACTIVITY-SELECTIVITY PRINCIPLE
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 Physical Properties of Alkanes
3.2 Chemical Reactions of Alkanes
3.2.1 Combustion of Alkanes
3.2.2 Halogenation of Alkanes (Free Radical Substitution
Reaction)
3.2.2.1 Factors that Determine Product Distribution
3.2.2.2 The Reactivity–Selectivity Principle
4.0 Self-Assessment Questions (SAQs)
5.0 Conclusion
6.0 Summary
1.0 INTRODUCTION
It will be well to reiterate what an alkane is, lest you be confused as to the
difference between alkanes and alkenes. Alkanes are compounds of
carbon and hydrogen only, without double bonds, triple bonds, or rings.
They all conform to the general formula CnH2n+2 and sometimes are called
paraffin hydrocarbons, open-chain saturated hydrocarbons, or acyclic
hydrocarbons. The nomenclature of alkanes has been discussed in the
previous units, and you may find it well to review Module 1-unit 1 and
Module 2-unit 1 before proceeding.
This unit is concerned with the chemistry of only one class of compounds,
saturated hydrocarbons or alkanes, several fundamental reaction
principles are developed that we shall discussed extensively in later units.
The study of some of these principles such as activation energy of a
reaction has been associated traditionally more with physical chemistry
than with organic chemistry. We include them here because they provide
a sound basis for understanding the key questions concerning the practical
use of organic reactions. Is the equilibrium point of a given reaction far
enough toward the desired products to be useful? Can conditions be found
in which the reaction will take place at a practical rate? How can
unwanted side reactions be suppressed?
Initially, we will be concerned with the physical properties of alkanes and

how these properties can be correlated by the important concept of
103
homology. This will be followed by a brief survey of the occurrence and

uses of hydrocarbons, with special reference to the petroleum industry.
Chemical reactions of alkanes then will be discussed, with special
emphasis on free radical substitution reaction. These reactions are
employed to illustrate how we can predict and use energy changes-
particularly ∆H, the heat evolved or absorbed by a reacting system, which
often can be estimated from bond energies. Then we consider some of the
problems involved in predicting reaction rates in the context of a specific
reaction, the chlorination of methane. The example is complex, but it has
the virtue that we are able to break the overall reaction into quite simple
steps.
2.0 LEARNING OBJECTIVES
By the end of this unit, you should be able to:
 understand the chemistry of alkanes.

 know the characteristic physical properties of alkanes.
 describe the chemical reactions alkanes undergo.
 understand the concept of free radical substitution reactions in
alkanes.
 use the reactivity-selectivity principle and activation energy to
predict expected products yield in a radical substitution reaction.
3.0 MAIN CONTENT
3.1 Physical Properties of Alkanes
The series of straight-chain alkanes, in which n is the number of carbons

in the chain, shows a remarkably smooth gradation of physical properties
(see Table 2.1). As n increases, each additional CH2 group contributes a
fairly constant increment to the boiling point and density, and to a lesser
extent to the melting point. This makes it possible to estimate the
properties of an unknown member of the series from those of its
neighbors. For example, the boiling points of hexane and heptane are 69o
and 98o, respectively. Thus a difference in structure of one CH2 group for
these compounds makes a difference in boiling point of 29o; we would
predict the boiling point of the next higher member, octane, to be 98o +
29o = 127o, which is close to the actual boiling point of 126o.
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CHM 203 MODULE 2
Table 2.1: Physical Properties of Alkanes, CH3(CH2)n-1 H
a
At the boiling point. bUnder pressure. cFor the supercooled liquid.
Members of a group of compounds, such as the alkanes, that have similar

chemical structures and graded physical properties, and which differ from
one another by the number of atoms in the structural backbone, are said
to constitute a homologous series. When used to forecast the properties
of unknown members of the series, the concept of homology works most
satisfactorily for the higher-molecular-weight members because the
introduction of additional CH2 groups makes a smaller relative change in
the overall composition of such molecules.
Branched-chain alkanes do not exhibit the same smooth gradation of

physical properties as do the continuous-chain alkanes. Usually there is
too great a variation in molecular structure for regularities to be apparent.
Nevertheless, in any one set of isomeric hydrocarbons, volatility increases
with increased branching. This can be seen from the data in Table 2.2 and
Figure 2.1, which lists the physical properties of the five hexane isomers.
The most striking feature of the data is the 19o difference between the
boiling points of hexane and 2,2-dimethylbutane.
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Table 2.2: Physical Properties of Hexane Isomers
Activity 3.1
Use the data of Tables 2.1 and 2.2 to estimate the boiling points of
tetradecane, heptadecane, 2-methylhexane, and 2,2-dimethylpentane.
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CHM 203 MODULE 2
Fig 2.1: Graph of Boiling Points of Alkanes
Straight chain alkanes have a higher boiling point than branched alkanes
due to the greater surface area in contact and therefore greater van der
Waals interactions.
Since alkanes are hydrocarbons and there is no significant difference in

electronegativity between carbon and hydrogen, they are nonpolar. In
being nonpolar, alkanes dissolve in nonpolar solvents because the van der
Waals interactions between nonpolar alkane molecules and nonpolar
solvent molecules are similar to the alkane-alkane and nonpolar solvent-
nonpolar solvent molecule interactions.
Alkanes are thus soluble in nonpolar solvents (i.e. other alkanes) and
insoluble in polar solvents (such as water). The liquid alkanes are
therefore good solvents for
nonpolar covalent compounds.
In-Text Question 1
For each of the following pairs of compounds, select the substance you
expect to have the higher boiling point.
1. octane and nonane.
2. octane and 2,2,3,3‑tetramethylbutane.
Note: The actual boiling points are nonane = 150.8°C, octane = 125.7°C,
2,2,3,3‑tetramethylbutane = 106.5°C
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3.3 Chemical Reactions of Alkanes
Alkanes have only strong σ bonds. Because the carbon and hydrogen
atoms of an alkane have approximately the same electronegativity, the
electrons in the C-H and C-C σ bonds are shared equally by the bonding
atoms. Consequently, none of the atoms in an alkane have any significant
charge. This means that neither nucleophiles (electron pair donors) nor
electrophiles (electron pair acceptors) are attracted to them. Alkanes,
therefore, are relatively unreactive compounds. Their failure to undergo
reactions prompted early organic chemists to call them paraffins, from the
Latin parum affinis, which means “little affinity” (for other compounds).
Thus none of the C-H or C-C bonds in a typical saturated hydrocarbon,
for example ethane, are attacked at ordinary temperatures by a strong acid,
such as sulfuric acid (H2SO4), or by an oxidizing agent, such as bromine
(in the dark), oxygen, or potassium permanganate (KMnO4). Under
ordinary conditions, ethane is similarly stable to reducing agents such as
hydrogen, even in the presence of catalysts such as platinum, palladium,
or nickel.
However, all saturated hydrocarbons are attacked by oxygen at elevated

temperatures and, if oxygen is in excess, complete combustion to carbon
dioxide and water occurs.
Vast quantities of hydrocarbons from petroleum are utilized as fuels for

the production of heat and power by combustion. Natural gas consists of
about 75% methane. The remaining 25% is composed of small alkanes
such as ethane, propane, and butane.
Petroleum is a complex mixture of alkanes and cycloalkanes that can be

separated into fractions by distillation. The fraction that boils at the lowest
temperature (hydrocarbons containing three and four carbons) is natural
gas that can be liquefied under pressure. This gas is used as a fuel for
cigarette lighters, camp stoves, and barbecues. The fraction that boils at
somewhat higher temperatures (hydrocarbons containing 5 to 11 carbons)
is gasoline; the next fraction (9 to 16 carbons) includes kerosene and jet
fuel. The fraction with 15 to 25 carbons is used for heating oil and diesel
oil, and the highest-boiling fraction is used for lubricants and greases. The
nonpolar nature of these compounds is what gives them their oily feel.
After distillation, a nonvolatile residue called asphalt or tar is left behind.
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CHM 203 MODULE 2
Fig 2.2: Different fractions of petroleum
Alkanes (the most basic of all organic compounds) undergo very few
reactions. The two reactions of more importance are combustion and
halogenation (i.e., substitution of a single hydrogen on the alkane for a
single halogen to form a haloalkane). The halogen reaction is very
important in organic chemistry because it opens a gateway to further
chemical reactions.
In-Text Question 2
1. Liquefied petroleum gas is mainly composed of _____________
a) Methane and ethane b) Ethane and propane c) Propane
and butane
d) Butane and hexane
2. If you drop a lighted match onto some petrol (gasoline), it ignites
almost explosively. If you drop a lighted match onto some tar on
the road, almost certainly nothing will happen. Both contain
alkanes, Explain the difference.
3.3.6 Combustion of Alkanes
In general, the formula for complete combustion of alkanes is:
When there is sufficient oxygen, alkanes will burn and form water and
carbon dioxide as products:
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It is quite important that you can write properly balanced equations for
these reactions, because they often come up as a part of thermochemistry
calculations. Some are easier than others. For example, with alkanes, the
ones with an even number of carbon atoms are marginally harder than
those with an odd number.
For example, with propane (C3H8), you can balance the carbons and
hydrogens as you write the equation down. Your first draft would be:
C3H8 + O2 → 3CO2 + 4H2O
Counting the oxygens leads directly to the final version:
With butane (C4H10), you can again balance the carbons and hydrogens
as you write the equation down.
C4H10 + O2 → 4CO2 + 5H2O
Counting the oxygens leads to a slight problem - with 13 on the right-

hand side. The simple trick is to allow yourself to have "six-and-a-half"
O molecules on the left.
If you are not comfortable with that, double everything:
The hydrocarbons become harder to ignite as the molecules get bigger.

This is because the bigger molecules do not vaporize so easily - the
reaction is much better if the oxygen and the hydrocarbon are well mixed
as gases. If the liquid is not very volatile, only those molecules on the
surface can react with the oxygen. Bigger molecules have greater Van der
Waals attractions which makes it more difficult for them to break away
from their neighbors and turn to a gas.
Provided the combustion is complete, all the hydrocarbons will burn with
a blue flame. However, combustion tends to be less complete as the
number of carbon atoms in the molecules rises. That means that the bigger
the hydrocarbon, the more likely you are to get a yellow, smoky flame.
Incomplete combustion (where there is not enough oxygen present) can
lead to the formation of carbon or carbon monoxide. As a simple way of
thinking about it, the hydrogen in the hydrocarbon gets the first chance at
the oxygen, and the carbon gets whatever is left over. The presence of
glowing carbon particles in a flame turns it yellow, and black carbon is
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CHM 203 MODULE 2
often visible in the smoke. Carbon monoxide is produced as a colourless

poisonous gas.
For example, incomplete combustion of octane can be represented as:
Note: Why is carbon monoxide said to be poisonous?

Oxygen is carried around the blood by haemoglobin. Carbon monoxide unfortunately binds to
exactly the same site on the haemoglobin that oxygen does. The difference is that carbon
monoxide binds irreversibly (or very strongly) - making that particular molecule of haemoglobin
useless for carrying oxygen. Hence, if you breath in enough carbon monoxide you will die from
a sort of internal suffocation.
In-Text Question 3
Write equations for the complete combustion of
a) pentane, C5H12 b) ethane, C2H6 c) decane, C10H22 d)
cyclohexane, C6H12
3.2.2 Halogenation of Alkanes (Free Radical Substitution Reaction)
Alkanes do react with chlorine (Cl2) or bromine (Br2) to form alkyl

chlorides or alkyl bromides. These halogenation reactions take place only
at high temperatures or in the presence of light (symbolized by hv). They
are the only reactions that alkanes undergo—with the exception of
combustion (burning), a reaction with oxygen. Unlike the complex
transformations of combustion, the halogenation of an alkane appears to
be a simple substitution reaction in which a C-H bond is broken and a
new C-X bond is formed.
When a bond breaks so that both of its electrons stay with one of the
atoms, the process is called heterolytic bond cleavage or heterolysis.
When a bond breaks so that each of the atoms retains one of the bonding
electrons, the process is called homolytic bond cleavage or homolysis.
The mechanism for the halogenation of an alkane is well understood. The

high temperature (or light) supplies the energy required to break the or
bond homolytically. Homolytic bond cleavage is the initiation step of the
111
reaction because it creates the radical that is used in the first propagation
step.
A radical (often called a free radical) is a species containing an atom with

an unpaired electron. A radical is highly reactive because it wants to
acquire an electron to complete its octet. As an example, in the mechanism
for the monochlorination of methane, the chlorine radical formed in the
initiation step abstracts a hydrogen atom from methane, forming HCl and
a methyl radical. The methyl radical abstracts a chlorine atom from Cl2,
forming methyl chloride and another chlorine radical, which can abstract
a hydrogen atom from another molecule of methane. These two steps are
called propagation steps because the radical created in the first
propagation step reacts in the second propagation step to produce a radical
that can repeat the first propagation step. Thus, the two propagation steps
are repeated over and over. The first propagation step is the rate-
determining step of the overall reaction. Because the reaction has radical
intermediates and repeating propagation steps, it is called a radical chain
reaction.
Any two radicals in the reaction mixture can combine to form a molecule
in which all the electrons are paired. The combination of two radicals is
called a termination step because it helps bring the reaction to an end by
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CHM 203 MODULE 2
decreasing the number of radicals available to propagate the reaction. Any

two radicals present in the reaction mixture can combine in a termination
step, so radical reactions produce a mixture of products.
The radical chlorination of alkanes other than methane follows the same
mechanism. The reaction of an alkane with chlorine or bromine to form
an alkyl halide is called a radical substitution reaction because radicals
are involved as intermediates and the end result is the substitution of a
halogen atom for one of the hydrogen atoms of the alkane.
In order to maximize the amount of monohalogenated product obtained,

a radical substitution reaction should be carried out in the presence of
excess alkane. Excess alkane in the reaction mixture increases the
probability that the halogen radical will collide with a molecule of alkane
rather than with a molecule of alkyl halide —even toward the end of the
reaction, by which time a considerable amount of alkyl halide will have
been formed. If the halogen radical abstracts a hydrogen from a molecule
of alkyl halide rather than from a molecule of alkane, a dihalogenated
product will be obtained.
Bromination of alkanes follows the same mechanism as chlorination.
3.2.2.1 Factors that Determine Product Distribution
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The distribution of products depends on probability and reactivity. Two

different alkyl halides are obtained from the monochlorination of butane.
Substitution of a hydrogen bonded to one of the terminal carbons
produces 1-chlorobutane, whereas substitution of a hydrogen bonded to
one of the internal carbons forms 2-chlorobutane.
The expected (statistical) distribution of products is 60% 1-chlorobutane

and 40% 2-chlorobutane because six of butane’s 10 hydrogens can be
substituted to form 1-chlorobutane, whereas only four can be substituted
to form 2-chlorobutane. This assumes, however, that all of the bonds in
butane are equally easy to break. Then, the relative amounts of the two
products would depend only on the probability of a chlorine radical
colliding with a primary hydrogen, compared with its colliding with a
secondary hydrogen. When we carry out the reaction in the laboratory and
analyze the product, however, we find that it is 29% 1-chlorobutane and
71% 2-chlorobutane.
Therefore, probability alone does not explain the regioselectivity of the

reaction. Because more 2-chlorobutane is obtained than expected and the
rate-determining step of the overall reaction is hydrogen atom abstraction,
we conclude that it must be easier to abstract a hydrogen atom from a
secondary carbon than from a primary carbon.
Alkyl radicals have different stabilities, and the more stable the radical,
the more easily it is formed because the stability of the radical is reflected
in the stability of the transition state leading to its formation.
Consequently, it is easier to remove a hydrogen atom from a secondary
carbon to form a secondary radical than it is to remove a hydrogen atom
from a primary carbon to form a primary radical.
When a chlorine radical reacts with butane, it can abstract a hydrogen

atom from an internal carbon, thereby forming a secondary alkyl radical,
or it can abstract a hydrogen atom from a terminal carbon, thereby
forming a primary alkyl radical. Because it is easier to form the more
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CHM 203 MODULE 2
stable secondary alkyl radical, 2-chlorobutane is formed faster than 1-

chlorobutane.
After experimentally determining the amount of each chlorination

product obtained from various hydrocarbons, chemists were able to
conclude that at room temperature it is 5.0 times easier for a chlorine
radical to abstract a hydrogen atom from a tertiary carbon than from a
primary carbon, and it is 3.8 times easier to abstract a hydrogen atom from
a secondary carbon than from a primary carbon. The precise ratios differ
at different temperatures.
To determine the relative amounts of products obtained from radical

chlorination of an alkane, both probability (the number of hydrogens that
can be abstracted that will lead to the formation of the particular product)
and reactivity (the relative rate at which a particular hydrogen is
abstracted) must be taken into account. When both factors are considered,
the calculated amounts of 1-chlorobutane and 2-chlorobutane agree with
the amounts obtained experimentally.
The percent yield of each alkyl halide is calculated by dividing the relative
amount of the particular product by the sum of the relative amounts of all
the alkyl halide products (16 + 15 = 21).
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Radical monochlorination of 2,2,5-trimethylhexane results in the

formation of five monochlorination products. Because the relative
amounts of the five alkyl halides total 35 (19.0 + 7.6 + 7.6 + 5.0 + 6.0 =
35), the percent yield of each product can be
calculated as follows:
Because radical chlorination of an alkane can yield several different

monosubstitution products as well as products that contain more than one
chlorine atom, it is not the best method for synthesizing an alkyl halide.
Addition of a hydrogen halide to an alkene or conversion of an alcohol to
an alkyl halide is a much better way to make an alkyl halide. Radical
halogenation of an alkane is nevertheless still a useful reaction because it
is the only way to convert an unreactive alkane into a reactive compound.
Once the halogen is introduced into the alkane, it can be replaced by a
variety of other substituents.
In-Text Question 4
How many alkyl halides can be obtained from monochlorination of the

following alkanes? Neglect stereoisomers.
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CHM 203 MODULE 2
The relative rates of radical formation when a bromine radical abstracts a

hydrogen atom are different from the relative rates of radical formation
when a chlorine radical abstracts a hydrogen atom. At 125 °C, a bromine
radical abstracts a hydrogen atom from a tertiary carbon 1600 times faster
than from a primary carbon and abstracts a hydrogen atom from a
secondary carbon 82 times faster than from a primary carbon.
When a bromine radical is the hydrogen-abstracting agent, the differences

in reactivity are so great that the reactivity factor is vastly more important
than the probability factor. For example, radical bromination of butane
gives a 98% yield of 2-bromobutane, compared with the 71% yield of 2-
chlorobutane obtained when butane is chlorinated. A bromine radical is
less reactive and more selective than a chlorine radical. In other words,
bromination is more highly regioselective than chlorination.
Similarly, bromination of 2,2,5-trimethylhexane gives an 82% yield of the

product in which bromine replaces the tertiary hydrogen. Chlorination of
the same alkane results in a 14% yield of the tertiary alkyl chloride.
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In-Text Question 5
Calculate the percent yield of each product obtained in Problems 1a and
b above if chlorination is carried out in the presence of light at room
temperature.
3.2.2.2 The Reactivity–Selectivity Principle
Why are the relative rates of radical formation so different when a

bromine radical rather than a chlorine radical is used as the hydrogen-
abstracting reagent? To answer this question, we must compare the ∆H o
values for the formation of primary, secondary, and tertiary radicals when
a chlorine radical is used, as opposed to when a bromine radical is used.
These ∆H o values can be calculated using the bond dissociation energies
in Table 2.3 below. Remember that ∆Ho is equal to the energy of the bond
being broken minus the energy of the bond being formed.
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CHM 203 MODULE 2
Table 2.3: Homolytic Bond Dissociation Energies Y-Z → Y∙ + Z∙
We must also be aware that bromination is a much slower reaction than

chlorination. The activation energy for abstraction of a hydrogen atom by
a bromine radical has been found experimentally to be about 4.5 times
greater than that for abstraction of a hydrogen atom by a chlorine radical.
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Using the calculated values and the experimental activation energies, we

can draw reaction coordinate diagrams for the formation of primary,
secondary, and tertiary radicals by chlorine radical abstraction
(Figure 2.3a) and by bromine radical abstraction (Figure 2.3b).
Figure 2.3: (a) Reaction coordinate diagrams for the formation of

primary, secondary, and tertiary alkyl radicals as a result of
abstraction of a hydrogen atom by a chlorine radical. The transition
states have relatively little radical character because they resemble
the reactants. (b) Reaction coordinate diagrams for the formation of
primary, secondary, and tertiary alkyl radicals as a result of
abstraction of a hydrogen atom by a bromine radical. The transition
states have a relatively high degree of radical character because they
resemble the products.
Because the reaction of a chlorine radical with an alkane to form a

primary, secondary, or tertiary radical is exothermic, the transition states
resemble the reactants more than they resemble the products. The
reactants all have approximately the same energy, so there will be only a
small difference in the activation energies for removal of a hydrogen atom
from a primary, secondary, or tertiary carbon. In contrast, the reaction of
a bromine radical with an alkane is endothermic, so the transition states
resemble the products more than they resemble the reactants. Because
there is a significant difference in the energies of the product radicals—
depending on whether they are primary, secondary, or tertiary—there is a
significant difference in the activation energies. Therefore, a chlorine
radical makes primary, secondary, and tertiary radicals with almost equal
ease, whereas a bromine radical has a clear preference for formation of
the easiest-to-form tertiary radical (Figure 2.3). In other words, because a
bromine radical is relatively unreactive, it is highly selective about which
hydrogen atom it abstracts. In contrast, the much more reactive chlorine
radical is considerably less selective. These observations illustrate the
reactivity–selectivity principle, which states that the greater the
reactivity of a species, the less selective it will be.
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CHM 203 MODULE 2
Because chlorination is relatively nonselective, it is a useful reaction only

when there is just one kind of hydrogen in the molecule.
By comparing the values for the sum of the two propagating steps for the
monohalogenation of methane, we can understand why alkanes undergo
chlorination
and bromination but not iodination and why fluorination is too violent a
reaction to be useful. The fluorine radical is the most reactive of the
halogen radicals, and it reacts violently with alkanes (∆Ho = -31
kcal/mol). In contrast, the iodine radical is the least reactive of the halogen
radicals. In fact, it is so unreactive (∆H o = 34 kcal/mol) that it is unable to
abstract a hydrogen atom from an alkane. Consequently, it reacts with
another iodine radical and reforms I2.
In-Text Question 6
Carry out the calculations that predict that
a. 2-bromobutane will be obtained in 98% yield.
b. 2-bromo-2,5,5,-trimethylhexane will be obtained in 82% yield.
SELF-ASSESSMENT EXERCISE
i. Explain why chlorination or bromination of methylcyclohexane

will produce a greater yield of 1-halo-1-methylcyclohexane.
a. Would chlorination or bromination produce a greater yield of 1-
halo-2,3 dimethylbutane?
b. Would chlorination or bromination produce a greater yield of 2-
halo-2,3-dimethylbutane?
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c. Would chlorination or bromination be a better way to make 1-halo-

2,2-dimethylpropane?
ii Iodine does not react with ethane even though I2 is more easily
cleaved homolytically than the other halogens. Explain.
iii When 2-methylpropane is monochlorinated in the presence of light

at room temperature, 36% of the product is 2-chloro-2-methylpropane and
64% is 1-chloro-2-methylpropane. From these data, calculate how much
easier it is to abstract a hydrogen atom from a tertiary carbon than from a
primary carbon under these conditions.
Let total amount of product = 100

The relative amount of 1-chloro-2-methylpropane = number of primary
hydrogen x ease of the primary hydrogen removal (X)
i.e. 64 = 9 x X
X = 7.11
Similarly,
The relative amount of 2-chloro-2-methylpropane = number of tertiary
hydrogen x ease of the tertiary hydrogen removal (Y)
i.e. 36 = 1 x Y
Y = 36
Relative ease of removal of hydrogen atom from a tertiary carbon than
from a primary carbon are Y : X i.e. 36 : 7.11
=5:1
Hence, it is five times easier to abstract a hydrogen atom from a tertiary
carbon than from a primary carbon under the given conditions.
iv If 2-methylpropane is brominated at 125 °C in the presence of
light, what percent of the product will be 2-bromo-2-methylpropane?
Compare your answer with the percent given in Problem 2 above for
chlorination.
v. a) Why does a bunsen burner with the air-hole closed produce
a yellow flame?
b) Explain why carbon monoxide, formed by incomplete
combustion of hydrocarbons, is poisonous.
4.0 CONCLUSION
Alkanes (the most basic of all organic compounds) undergo very few
reactions. The two reactions of more importance are combustion and
halogenation. Halogenation is the replacement of one or more hydrogen
atoms in an organic compound by a halogen (fluorine, chlorine, bromine
or iodine). Unlike the complex transformations of combustion, the
halogenation of an alkane appears to be a simple substitution reaction in
which a C-H bond is broken and a new C-X bond is formed.
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CHM 203 MODULE 2
5.0 SUMMARY
 Alkanes are called saturated hydrocarbons because they do not

contain any double or triple bonds. Since they also have only
strong σ bonds and atoms with no partial charges, alkanes are very
unreactive.
 Alkanes do undergo radical substitution reactions with chlorine
(Cl2) or bromine (Br2) at high temperatures or in the presence of
light, to form alkyl chlorides or alkyl bromides. The substitution
reaction is a radical chain reaction with initiation, propagation, and
termination steps.
 Unwanted radical reactions are prevented by radical inhibitors—
compounds that destroy reactive radicals by creating unreactive
radicals or compounds with only paired electrons.
 The rate-determining step of the radical substitution reaction is
hydrogen atom abstraction to form a radical.
 The relative rates of radical formation are 3o > 2o > 1o > methyl.
 To determine the relative amounts of products obtained from the
radical halogenation of an alkane, both probability and the relative
rate at which a particular hydrogen is abstracted must be taken into
account.
 The reactivity–selectivity principle states that the more reactive a
species is, the less selective it will be.
 A bromine radical is less reactive than a chlorine radical, so a
bromine radical is more selective about which hydrogen atom it
abstracts.
 Fluorine radicals (F∙) are the most reactive of all of the halogen
atoms and iodine radicals (I∙) are the least reactive. I∙ is so
unreactive that it does not abstract H from most alkanes. The
overall reactivity trend for halogen atoms is F > Cl > Br > I and
this is the same order as they appear in the next to the last column
of a periodic table.

London.
123

Wiley & Sons.



John Wiley & Sons.
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CHM 203 MODULE 2
UNIT 3 VARIOUS ORGANIC REACTIONS
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 Writing Equations for Organic Reactions
3.2 Reaction Mechanism
3.2.1 Bond Cleavage
3.2.2 Radicals, Carbocations, and Carbonions
3.2.3 Bond Formation
3.2.4 Kinds of Arrows
3.3 Various Organic Reactions
3.3.1 Substitution Reactions
3.3.2 Elimination Reactions
3.3.3 Addition Reactions
3.3.4 Redox Reactions
3.3.5 Rearrangement Reactions
3.3.6 Pericyclic Reactions
3.3.7 Free Radical Reactions
3.4 Types of Reagents
4.0 Conclusion
5.0 Summary
1.0 INTRODUCTION
An understanding of chemical processes has made possible the

conversion of natural substances into new compounds with different, and
sometimes superior, properties. Aspirin, ibuprofen, nylon, and
polyethylene are all products of chemical reactions between substances
derived from petroleum.
Reactions are difficult to learn when each reaction is considered a unique
and isolated event.
Virtually all chemical reactions are woven together by a few basic themes.
In this unit, we shall be looking at the equations for organic reactions,
reaction mechanisms, various organic reactions, how a reaction occurs,
and types of reagents. Understanding the details of an organic reaction
allows us to determine when it might be used in preparing interesting and
useful organic compounds.
A chemical reaction is the transformation of one chemical or collection of
chemicals into another chemical or collection of chemicals. This involves
the making of new chemical bonds and the breaking of old chemical
bonds. Organic reactions are the chemical reactions that are undergone by
125
organic compounds. Reactions of organic compounds can be organized

broadly by the types of reactions and how these reactions occur. The types
of reactions organic compounds undergo are divided into substitution
reactions, elimination reactions, addition reactions, redox reactions,
rearrangement reactions, pericyclic reactions and free radical reactions.
2.0 OBJECTIVES
When you have studied this unit, you should be able to:
 understand how equations for organic reactions are written.

 have a better understanding of reaction mechanisms.
 become familiar with the various classes of organic reactions.
3.0 MAIN CONTENT
3.1 Writing Equations for Organic Reactions
Like other reactions, equations for organic reactions are usually drawn
with a single reaction arrow (→) between the starting material and
product, but other conventions make these equations look different from
those encountered in general chemistry.
The reagent, the chemical substance with which an organic compound

reacts, is sometimes drawn on the left side of the equation with the other
reactants. At other times, the reagent is drawn above the reaction arrow
itself, to focus attention on the organic starting material by itself on the
left side. The solvent and temperature of a reaction may be added above
or below the arrow. The symbols “hv” and “Δ” are used for reactions
that require light or heat, respectively. Figure 3.1 presents an organic
reaction in different ways.
When two sequential reactions are carried out without drawing any
intermediate compound, the steps are usually numbered above or below
the reaction arrow. This convention signifies that the first step occurs
before the second, and the reagents are added in sequence, not at the same
time.
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CHM 203 MODULE 2
In this equation only the organic product is drawn on the right side of the
arrow. Although the reagent CH3MgBr contains both Mg and Br, these
elements do not appear in the organic product, and they are often omitted
on the product side of the equation. These elements have not disappeared.
They are part of an inorganic by-product (HOMgBr in this case), and are
often of little interest to an organic chemist.
Figure 2.4: Different ways of writing organic reactions
3.2 Reaction Mechanisms
Having now learned how to write and identify some common kinds of
organic reactions, we can turn to a discussion of reaction mechanism.
Due to the unique properties of carbon, namely, its ability to catenate,
form chains and rings, and form multiple bonds with itself or other atoms,
an enormous number of organic compounds are possible. Moreover, an
organic compound can undergo many different reactions. For example,
ethanol may react to form acetaldehyde, acetic acid, ethylene, formic acid,
carbon dioxide, and so on. So, it may appear that studying organic
reactions should be a very difficult and almost futile exercise. But,
127
fortunately, closer studies have revealed that the reactions of enormously

large number of organic compounds actually take place in such ways that
these may be classified into a few groups of reactions. In most cases, the
organic reactions are brought about with inorganic compounds like acids,
bases, oxidizing agents, reducing agents and so on. The inorganic
compounds that bring about the organic reactions are termed as reagents,
and the organic compounds undergoing the chemical transformations are
termed as substrates.
A reaction mechanism is a detailed description of how bonds are

broken and formed as a starting material is converted to a product.
A reaction mechanism describes the relative order and rate of bond
cleavage and formation. It explains all the known facts about a reaction
and accounts for all products formed, and it is subject to modification or
refinement as new details are discovered.
A reaction can occur either in one step or in a series of steps.

A one-step reaction is called a concerted reaction. No matter how many
bonds are broken or formed, a starting material is converted directly to a
product.
A→B
A stepwise reaction involves more than one step. A starting material is

first converted to an unstable intermediate, called a reactive intermediate,
which then goes on to form the product.
A → reactive intermediate → B
3.2.1 Bond Cleavage
Bonds are broken and formed in all chemical reactions. No matter how
many steps there are in the reaction, however, there are only two ways to
break (cleave) a bond: the electrons in the bond can be divided equally or
unequally between the two atoms of the bond.
• Breaking a bond by equally dividing the electrons between the two

atoms in the bond is called homolysis or homolytic cleavage.
Homolysis or homolytic cleavage
• Breaking a bond by unequally dividing the electrons between the

two atoms in the bond is called heterolysis or heterolytic cleavage.
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CHM 203 MODULE 2
Heterolysis of a bond between A and B can give either A or B the two

electrons in the bond. When A and B have different electronegativities,
the electrons normally end up on the more electronegative atom.
Heterolysis or heterolytic cleavage
Homolysis and heterolysis require energy. Both processes generate

reactive intermediates, but the products are different in each case.
 Homolysis generates uncharged reactive intermediates with

unpaired electrons.
 Heterolysis generates charged intermediates.
Each of these reactive intermediates has a very short lifetime, and each
reacts quickly to form a stable organic product.
3.2.2 Radicals, Carbocations, and Carbanions
The curved arrow notation works fine for heterolytic bond cleavage
because it illustrates the movement of an electron pair. For homolytic
cleavage, however, one electron moves to one atom in the bond and one
electron moves to the other, so a different kind of curved arrow is needed.
• To illustrate the movement of a single electron, use a half-headed
curved arrow, sometimes called a fishhook.
Homolysis
Two half-headed curved arrows are needed for two single electrons.
Heterolysis
One full-headed curved arrow is needed for one electron pair.
A full-headed curved arrow shows the movement of an electron pair. A

half headed curved arrow shows the movement of a single electron.
Homolysis of the C–Z bond generates two uncharged products with

unpaired electrons.
129
• A reactive intermediate with a single unpaired electron is called a

radical.
Most radicals are highly unstable because they contain an atom that does
not have an octet of electrons. Radicals typically have no charge. They
are intermediates in a group of reactions called radical reactions.
Heterolysis of the C–Z bond can generate a carbocation or a carbanion.
 Giving two electrons to Z and none to carbon generates a

positively charged carbon intermediate called a carbocation.
 Giving two electrons to C and none to Z generates a negatively

charged carbon species called a carbanion.
Both carbocations and carbanions are unstable reactive intermediates: A

carbocation contains a carbon atom surrounded by only six electrons. A
carbanion has a negative charge on carbon, which is not a very
electronegative atom. Carbocations (electrophiles) and carbanions
(nucleophiles) can be intermediates in polar reactions - reactions in
which a nucleophile reacts with an electrophile.
Figure 2.5: Three reactive intermediates resulting from homolysis

and heterolysis of a C–Z bond
Thus, homolysis and heterolysis generate radicals, carbocations, and

carbanions, the three most common reactive intermediates in organic
chemistry.
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CHM 203 MODULE 2
• Radicals and carbocations are electrophiles because they contain

an electron-deficient carbon.
• Carbanions are nucleophiles because they contain a carbon with

a lone pair.
In-Text Question 1
1. Select the correct statement on carbanion from the following
option.
a) Carbanion is an intermediate compound

b) In carbanion, central carbon atom carries negative charge
c) It possess an unshared pair of electron
d) All of the mentioned
2. Carbonium ions are the intermediates in which the positive charge
is carried by the carbon atom with ___________ electrons in the
valence shell.
a) 6 b) 5 c) 4 d) 3
3.2.3 Bond Formation
Like bond cleavage, bond formation occurs in two different ways. Two
radicals can each donate one electron to form a two-electron bond.
Alternatively, two ions with unlike charges can come together, with the
negatively charged ion donating both electrons to form the resulting two
electron bond. Bond formation always releases energy.
131
3.2.4 Kinds of Arrows
Table 3.1 below summarizes the many kinds of arrows used in describing
organic reactions. Curved arrows are especially important because they
explicitly show what electrons are involved in a reaction, how these
electrons move in forming and breaking bonds, and if a reaction proceeds
via a radical or polar pathway.
Table 2.4: A Summary of Arrow Types in Chemical Reactions
Arrow Name Use

Reactive arrow Drawn between the
starting materials
and products in an
equation
Double reaction Drawn between the
arrows starting materials
(equilibrium and products in an
arrows) equilibrium
equation
Double-headed Drawn between
arrow resonance
structures
Full-headed Shows movement
curved arrow of an electron pair
Half-headed Shows movement
curved arrow of a single electron
(fishhook)
In-Text Question 2
Use full-headed or half-headed curved arrows to show the movement of

electrons in the following equations.
In-Text Answer 2
a. In this reaction, the C–O bond is broken heterolytically. Because

only one electron pair is involved, one full-headed curved arrow is
needed.
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CHM 203 MODULE 2
b. This reaction involves radicals, so half-headed curved arrows are

needed to show the movement of single electrons. One new two-electron
bond is formed between H and Cl, and an unpaired electron is left on C.
Because a total of three electrons are involved, three half headed curved
arrows are needed.
3.3 Various Organic Reactions
Like other compounds, organic molecules undergo the following

reactions:
3.3.1 Substitution Reactions
A substitution reaction is that in which an atom or a group of atoms is

replaced by another atom or group of atoms.
A general substitution reaction:
(Z = H or heteroatom).
In a general substitution reaction, Y replaces Z on a carbon atom.
Substitution reactions involve σ bonds: one σ bond breaks and
another form at the same carbon atom. The most common examples of
substitution occur when Z is hydrogen or a heteroatom that is more
electronegative than carbon.
Examples:
133
3.3.2 Elimination Reactions
An elimination reaction is one in which elements of the starting material

are “lost” and a π bond is formed.
A general elimination reaction can be represented as below:
In an elimination reaction, two groups X and Y are removed from a

starting material. Two σ bonds are broken, and a π bond is formed
between adjacent atoms. The most common examples of elimination
occur when X=H and Y is a heteroatom more electronegative than carbon.
Examples:
3.3.3 Addition Reactions
Addition reactions occur when one or two molecules of the reagent are
added to a multiple bond or a small ring of the substrate. The two starting
materials add together to form only one product with no atoms left over.
A + B → A-B
In an addition all parts of the adding reagent appear in the product; two
molecules become one.
When you take an alkene (or alkyne) and add certain types of reagents to
them, you get results like this. In this reaction, − − are
broken and − − bonds are formed.
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CHM 203 MODULE 2
A typical addition reaction:
All addition reactions follow the same pattern (break a π bond, form two
single bonds). However, these do not always proceed through the same
mechanism. One of the challenges with learning addition reactions is in
keeping track of which kinds of reagents lead to “regioisomers” (i.e.
constitutional isomers) and which lead to “stereoisomers” as some even
lead to both!
3.3.4 Redox Reactions
In these reactions, the reagents bring about a change in the oxidation

number of the C-atom of the substrate molecule. A reduction reaction is
that in which the oxidation number of the C-atom in the molecule
decreases to form the product, while in an oxidation reaction, oxidation
number increases. For example,
It is a reduction reaction as the oxidation number of the C1-atom of the

substrate decreases from 0 to -2.
It is an oxidation reaction as the oxidation number of the C1-atom of the

substrate increases from -2 to +2.
3.3.5 Rearrangement Reactions
In these reactions, the bond connectivity within the molecule changes to

give a different compound having same molecular formula. Such a change
in the bond connectivity takes place due to the migration of an atom or a
group from one location to a new location within the molecule. Such a
migration of an atom or a group may take place within the same molecule
in Intramolecular processes or may involve two different molecules of the
same species in intermolecular processes. For example,
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In-Text Question 3
Classify each reaction as addition, elimination, substitution, or
rearrangement.
(a) CH3CH2Br + LiOH → CH3CH2OH + LiBr
(b) CH3CH2CH2Cl → CH3CH=CH2 + HCl
(c) CH3CH=CH2 + H2 → CH3CH2CH3
3.3.6 Pericyclic Reactions
In these reactions, the electron reorganization of the substrate molecule

takes place through a cyclic transition state in a single-step reaction,
giving stereo specific products under the influence of either heat or light.
For example,
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CHM 203 MODULE 2
In these reactions, the products that are obtained by heating the substrate
cannot be formed by irradiation with light and vice versa. The mechanism
of a reaction of any one of the above types consists of everything that
happens as the starting materials are converted to the products.
The reactions may take place in a single step or in a multiple step. In a
multiple-step reaction, the product of a step that takes part in the
successive step is considered as an intermediate in the overall reaction.
For example,
B and C are intermediates for the overall reaction:
The reactions take place due to electron reorganization in the reactant

molecule.
3.3.7 Free Radical Reactions
As discussed earlier in unit 2 of this module, free radicals are chemical

species having one or more unpaired electrons in their valence shells.
Homolytic bond fission leads to the formation of free radicals. Thus, free
radicals are odd electron molecules, e.g. •CH3, •C2H5, •C6H5, (C6H5)3•C,
etc., and are highly reactive. Free radicals are paramagnetic, that is, they
possess a small permanent magnetic moment, due to the presence of
unpaired electron(s). This property is used for the detection of the
presence of free radicals.
Formation of Free Radicals

Free radicals are formed by homolytic fission of a covalent bond, when a
molecule is supplied with sufficient energy – thermal or photochemical.
(i) Thermal Cleavage – Most of the covalent bonds are thermally

stable up to a temperature of 200℃ . However, there are a few
group of compounds (peroxy and azo) which undergo homolytic
cleavage at temperatures below 200℃. These are designated as
initiators.
137
(ii) Photochemical Cleavage – A second general method of obtaining

radicals is through irradiation with either UV or visible light. The
energy transferred to the molecule by the interaction must be of
the order of bond dissociation energy or grater to produce
homolysis.
Alkanes undergo substitution reaction with halogens. The hydrogen atom

of the alkane is substituted with a halogen atom to give an alkyl halide in
the presence of light or heating at 250℃ - 400℃.
This free radical reaction is less vigorous in bromine and more

discriminatory. Bromine radical will prefer secondary carbon to the
primary.
This reaction proceeds via a free radical mechanism.
Mechanism of Free Radical Reaction
(i) Chain Initiation Step: This is the step in which energy is absorbed
and reactive particles are generated. Here the chlorine molecule is broken
into chlorine radicals. This cleavage is homolytic.
(ii) Chain Propagation Step: Here, a reactive particle (free radical)

is consumed and another reactive particle is generated.
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CHM 203 MODULE 2
(iii) Chain Termination Step: Here, the reactive particles are consumed
but no new particles are generated.
In-Text Question 4
Radical chlorination of alkanes is not generally useful because mixtures
of products often result when more than one kind of C-H bond is present
in the substrate. Draw and name all mono-chloro substitution products
C6H13Cl you might obtain by reaction of 2-methylpentane with Cl2.
3.4 Types of Reagents
Many reagents that bring about numerous organic reactions can be

classified into two main groups. This classification is done on the basis of
the ability of the reagents to accept or donate electrons to the substrate
molecule.
The reagent that accept electrons are termed as Electrophiles (philic

meaning loving, that is, electron loving) and often abbreviated by the
symbol E ⊕ . The reagents that donate electrons to the electron-deficient
species are called Nucleophiles (nucleus or positive centre loving) and
often abbreviated by the symbolNu⊖ .
Electrophiles are electron-deficient species. All positively charged
species are electrophilic in nature, for example, H ⊕ , CH⊕ , •
Cl⊕ , NO⊕ , and so on.
Neutral molecules or species where the central atom is unsaturated with

respect to electrons also behave as electrophiles. For example, AlCl ,
BF , and C̈H , where the central atom contains the sextet of electrons.
Other neutral molecules where the central atom can expand its octet to
decet or dodecet also behave as electrophiles. For instance, SF can form
species like SF , and SiCl and form SiCl ⊖ ,so, SF and SiCl behave as
electrophiles. Transition metal compounds that act as Lewis acids due to
the ability of the metal ions to accommodate electrons in the d-AOs also
behave as electrophile, for example, ZnCl , SnCl , FeCl , and so on. Odd
electron species like free radicals where the unpaired electron is
accommodated in a low energy. Singly Occupied Molecular Orbital
(SOMO) also act as electrophiles, for example, CH O.
Nucleophiles, on the other hand, are electron-rich species.
139
All negatively charged species by nature are Nucleophilic, for example,

H ⊖ , CH ⊖ , Cl⊖ , HO⊖ , HS ⊖ , and so on. Neutral species that have loosely
held electrons as in π-bonds, act as nucleophiles. For example, alkenes,
alkynes, and so on, are Nucleophilic in nature. Neutral molecules that
have one or more lone pairs on an atom, usually a heteroatom, behave as
the nucleophiles. For example, H Ö: , N̈H , and so on.
Odd electron species where the unpaired electron is accommodated in a

high-energy SOMO also behave as nucleophiles, for example, ĊH .
In-Text Question 5
1. Which of the following is not an electrophile?
a) (CH3)4N+ b) Cl2 c) HBr d) Br2
2. Which reagent is a good nucleophile?
a) NH3 b) BH3 c) Br2 d) HBr
i. Classify each of the following reactions as an addition,

elimination, substitution, or rearrangement:
(a) CH3Br + KOH → CH3OH + KBr

(b) CH3CH2Br → H2C=CH2 + HBr
(c) H2C=CH2 + H2 → CH3CH3
ii Which of the following species are likely to be nucleophiles and

which electrophiles? Which might be both?
iii What product would you expect from reaction of cyclohexene with
HBr? With HCl?
iv Add curved arrows to the following polar reaction to show the flow
of electrons:
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CHM 203 MODULE 2
v. Add curved arrows to the following polar reactions to indicate the

flow of electrons in each:
4.0 CONCLUSION
We have been able to explain how equations for organic reaction are
written; the reaction mechanism involving bond cleavage, radicals,
carbocation and carbonions, bond formation and kind of arrows. Also the
various types of organic reactions with examples and lastly the types of
reagents used in organic reactions.
5.0 SUMMARY
There are common patterns to how organic reactions occur. In a

substitution reaction, one atom or a group of atoms in a substance is
replaced by another atom or group of atoms from another substance.
Bulky groups that prevent attack cause the reaction to be sterically
hindered. In an elimination reaction, adjacent atoms are removed with
subsequent formation of a multiple bond and a small molecule. An
addition reaction is the reverse of an elimination reaction. Radical
reactions are not very selective and occur in three stages: initiation,
propagation, and termination. Oxidation-reduction reactions in organic
chemistry are identified by the change in the number of oxygen in the
hydrocarbon skeleton or the number of bonds between carbon and oxygen
or carbon and nitrogen.

London.
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Wiley & Sons.



John Wiley & Sons.
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CHM 203 MODULE 2
UNIT 4 NUCLEOPHILIC SUBSTITUTION AND

ELIMINATION REACTIONS
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 The Discovery of Nucleophilic Substitution Reactions
3.2 The SN2 Reaction
3.3 Characteristics of the SN2 Reaction
3.3.1 The Substrate: Steric Effects in the SN2 Reaction
3.3.2 The Nucleophile
3.3.3 The Leaving Group
3.3.4 The Solvent
3.5 Characteristics of SN1 Reaction
3.5.1 The Substrate
3.5.4 The Solvent
3.6 Biological Substitution Reactions
3.7 Elimination Reactions
3.8 The E2 Reaction and the Deuterium Isotope Effect
3.9 The E2 Reaction and Cyclohexane Conformation
3.10 The E1 and E1CB Reactions
3.10.1 The E1 Reaction
3.10.2 The E1CB Reactions
3.11 Biological Elimination Reactions
4.0 Self-Assessment Questions (SAQs)
5.0 Conclusion
6.0 Summary
1.0 INTRODUCTION
The carbon-halogen bond in an alkyl halide is polar and the carbon atom
is electron-poor. Thus, alkyl halides are electrophiles, and much of their
chemistry involves polar reactions with nucleophiles and bases. Alkyl
halides do one of two things when they react with a nucleophile/base, such
as hydroxide ion: either they undergo substitution of the X group by the
nucleophile, or they undergo elimination of HX to yield an alkene.
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Substitution
Elimination
Nucleophilic substitution and base-induced elimination are two of the

most widely occurring and versatile reaction types in organic chemistry,
both in the laboratory and in biological pathways. We’ll look at them
closely in this unit to see how they occur, what their characteristics are,
and how they can be used. We’ll begin with nucleophilic substitution
reactions.
2.0 OBJECTIVES
By the end of this session, you should be able to:
 have a better understanding of nucleophilic substitution and

elimination reactions.
 have a better understanding of the types of nucleophilic
substitution and elimination reactions.
 understand the characteristics of nucleophilic substitution and
elimination reactions.
 become familiar with biological nucleophilic substitution and
elimination reactions
3.0 MAIN CONTENT
3.1 The Discovery of Nucleophilic Substitution Reactions
The discovery of the nucleophilic substitution reaction of alkyl halides

dates back to work carried out in 1896 by the German chemist Paul
Walden. Walden found that the pure enantiomeric (+)- and (-)-malic acids
could be interconverted through a series of simple substitution reactions.
When Walden treated (-)-malic acid with PCl5, he isolated (+)-
chlorosuccinic acid. This, on treatment with wet Ag2O, gave (+)-malic
acid. Similarly, reaction of (+)-malic acid with PCl5 gave (-)-
chlorosuccinic acid, which was converted into (-)-malic acid when treated
with wet Ag2O. The full cycle of reactions is shown in Figure 2.6 below.
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CHM 203 MODULE 2
Figure 2.6: Walden’s cycle of reactions interconverting (+)- and (-)-

malic acids.
At the time, the results were astonishing. The eminent chemist Emil
Fischer called Walden’s discovery “the most remarkable observation
made in the field of optical activity since the fundamental observations of
Pasteur.” Because (-)-malic acid was converted into (+)-malic acid, some
reactions in the cycle must have occurred with a change, or inversion, in
configuration at the chirality center.
Today, we refer to the transformations taking place in Walden’s cycle as

nucleophilic substitution reactions because each step involves the
substitution of one nucleophile (chloride ion, Cl-, or hydroxide ion, HO-)
by another. Nucleophilic substitution reactions are one of the most
common and versatile reaction types in organic chemistry.
Following the work of Walden, further investigations were undertaken

during the 1920s and 1930s to clarify the mechanism of nucleophilic
substitution reactions and to find out how inversions of configuration
occur. Among the first series studied was one that interconverted the two
enantiomers of 1-phenyl-2-propanol (Figure 2.7). Although this
particular series of reactions involves nucleophilic substitution of an alkyl
p-toluenesulfonate (called a tosylate) rather than an alkyl halide, exactly
the same type of reaction is involved as that studied by Walden. For all
practical purposes, the entire tosylate group acts as if it were simply a
halogen substituent. (In fact, when you see a tosylate substituent in a
molecule, do a mental substitution and tell yourself that you’re dealing
with an alkyl halide.)
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Figure 2.7: A Walden cycle interconverting (+) and (-) enantiomers

of 1-phenyl-2-propanol.
In the three-step reaction sequence shown in Figure 2.7, (+)-1-phenyl-2-

propanol is interconverted with its (-) enantiomer, so at least one of the
three steps must involve an inversion of configuration at the chirality
center. Step 1, formation of a tosylate, occurs by breaking the O-H bond
of the alcohol rather than the C-O bond to the chiral carbon, so the
configuration around carbon is unchanged. Similarly, step 3, hydroxide-
ion cleavage of the acetate, takes place without breaking the C-O bond at
the chirality center. The inversion of stereo chemical configuration must
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CHM 203 MODULE 2
therefore take place in step 2, the nucleophilic substitution of tosylate ion

by acetate ion.
From this and nearly a dozen other series of similar reactions, workers
concluded that the nucleophilic substitution reaction of a primary or
secondary alkyl halide or tosylate always proceeds with inversion of
configuration.
In-Text Question 1
What product would you expect from a nucleophilic substitution reaction

of (R)-1-bromo-1-phenylethane with cyanide ion, − ≡ , as
nucleophile? Show the stereochemistry of both reactant and product,
assuming that inversion of configuration occurs.
≡
?
In every chemical reaction, there is a direct relationship between the rate

at which the reaction occurs and the concentrations of the reactants. When
we measure this relationship, we measure the kinetics of the reaction. For
example, let’s look at the kinetics of a simple nucleophilic substitution—
the reaction of CH3Br with OH- to yield CH3OH plus Br-.
At a given temperature, solvent, and concentration of reactants, the

substitution occurs at a certain rate. If we double the concentration of OH-
, the frequency of encounter between the reaction partners doubles and
we find that the reaction rate also doubles. Similarly, if we double the
concentration of CH3Br, the reaction rate again doubles. We call such a
reaction, in which the rate is linearly dependent on the concentrations of
two species, a second-order reaction. Mathematically, we can express this
second-order dependence of the nucleophilic substitution reaction by
setting up a rate equation. As either [RX] or [-OH] changes, the rate of
the reaction changes proportionately.
Reaction rate = Rate of disappearance of reactant
147
= k x [RX] x [-OH]
Where [RX] = CH3Br concentration in molarity
[-OH] = -OH concentration in molarity
k = A Constant value (the rate constant).
The essential feature of the SN2 mechanism is that it takes place in a single
step without intermediates when the incoming nucleophile reacts with the
alkyl halide or tosylate (the substrate) from a direction opposite the group
that is displaced (the leaving group). As the nucleophile comes in on one
side of the substrate and bonds to the carbon, the halide or tosylate departs
from the other side, thereby inverting the stereo chemical configuration.
The process is shown in Figure 2.8 for the reaction of (S)-2-bromobutane
with HO- to give (R)-2-butanol.
Mechanism
The mechanism of the SN2 reaction takes place in a single step when the
incoming nucleophile approaches from a direction 180° away from the
leaving halide ion, thereby inverting the stereochemistry at carbon.
Step 1: The nucleophile –OH uses its lone-pair electrons to attack the
alkyl halide carbon 180° away from the departing halogen. This leads to
a transition state with a partially formed C–OH bond and a partially
broken C–Br bond.
Step 2: The stereochemistry at carbon is inverted as the C–OH bond forms

fully and the bromide ion departs with the electron pair from the former
C–Br bond.
Figure 2.8: Mechanism of SN2 reaction
As shown in the mechanism above, the SN2 reaction occurs when an

electron pair on the nucleophile Nu:- forces out the group X:-, which takes
with it the electron pair from the former C-X bond. This occurs through a
transition state in which the new Nu-C bond is partially forming at the
same time that the old C-X bond is partially breaking and in which the
negative charge is shared by both the incoming nucleophile and the
outgoing halide ion. The transition state for this inversion has the
remaining three bonds to carbon in a planar arrangement (Figure 2.9).
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CHM 203 MODULE 2
Figure 2.9: The transition state of an SN2 reaction has a planar

arrangement of the carbon atom and the remaining three groups.
Electrostatic potential maps show that negative charge is delocalized
in the transition state.
The mechanism proposed by Hughes and Ingold is fully consistent with

experimental results, explaining both stereo chemical and kinetic data.
Thus, the requirement for backside approach of the entering nucleophile
from a direction 180° away from the departing X group causes the
stereochemistry of the substrate to invert, much like an umbrella turning
inside out in the wind. The Hughes–Ingold mechanism also explains why
second-order kinetics are found: the SN2 reaction occurs in a single step
that involves both alkyl halide and nucleophile. Two molecules are
involved in the step whose rate is measured.
Now that we know how SN2 reactions occur, we need to see how they can
be used and what variables affect them. Some SN2 reactions are fast, and
some are slow; some take place in high yield and others in low yield.
Understanding the factors involved can be of tremendous value. Let’s
begin by recalling a few things about reaction rates in general.
The rate of a chemical reaction is determined by the activation energy
∆G‡, the energy difference between reactant ground state and transition
state. A change in reaction conditions can affect ∆G‡ either by changing
the reactant energy level or by changing the transition-state energy level.
Lowering the reactant energy or raising the transition-state energy
increases ∆G‡ and decreases the reaction rate; raising the reactant energy
or decreasing the transition-state energy decreases ∆G‡ and increases the
reaction rate (Figure 2.10). We’ll see examples of all these effects as we
look at SN2 reaction variables.
149
Figure 2.10: The effects of changes in reactant and transition-state

energy levels on reaction rate. (a) A higher reactant energy level (red
curve) corresponds to a faster reaction (smaller ∆G‡). (b) A higher
transition state energy level (red curve) corresponds to a slower
reaction (larger ∆G‡).
3.3.1 The Substrate: Steric Effects in the SN2 Reaction
The first SN2 reaction variable to look at is the structure of the substrate.
Because the SN2 transition state involves partial bond formation between
the incoming nucleophile and the alkyl halide carbon atom, it seems
reasonable that a hindered, bulky substrate should prevent easy approach
of the nucleophile, making bond formation difficult. In other words, the
transition state for reaction of a sterically hindered substrate, whose
carbon atom is “shielded” from approach of the incoming nucleophile, is
higher in energy and forms more slowly than the corresponding transition
state for a less hindered substrate (Figure 2.11).
Figure 2.11: Steric hindrance to the SN2 reaction. As the models

indicate, the carbon atom in (a) bromomethane is readily accessible,
resulting in a fast SN2 reaction. The carbon atoms in (b) bromoethane
(primary), (c) 2-bromopropane (secondary), and (d) 2-bromo-2-
methylpropane (tertiary) are successively more hindered, resulting in
successively slower SN2 reactions.
As Figure 2.11 shows, the difficulty of nucleophile approach increases as

the three substituents bonded to the halo-substituted carbon atom increase
in size. Methyl halides are by far the most reactive substrates in SN2
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CHM 203 MODULE 2
reactions, followed by primary alkyl halides such as ethyl and propyl.

Alkyl branching at the reacting center, as in isopropyl halides (2°), slows
the reaction greatly, and further branching, as in tert-butyl halides (3°),
effectively halts the reaction. Even branching one carbon removed from
the reacting center, as in 2,2-dimethylpropyl (neopentyl) halides, greatly
slows nucleophilic displacement. As a result, SN2 reactions occur only at
relatively unhindered sites and are normally useful only with methyl
halides, primary halides, and a few simple secondary halides. Relative
reactivities for some different substrates are as follows:
Vinylic halides (R2C=CRX) and aryl halides are not shown on this
reactivity list because they are unreactive toward SN2 displacement. This
lack of reactivity is due to steric factors: the incoming nucleophile would
have to approach in the plane of the carbon–carbon double bond and
burrow through part of the molecule to carry out a backside displacement.
151
Another variable that has a major effect on the SN2 reaction is the nature
of the nucleophile. Any species, either neutral or negatively charged, can
act as a nucleophile as long as it has an unshared pair of electrons; that is,
as long as it is a Lewis base. If the nucleophile is negatively charged, the
product is neutral; if the nucleophile is neutral, the product is positively
charged.
A wide array of substances can be prepared using nucleophilic

substitution reactions.
Table 2.5 lists some nucleophiles in the order of their reactivity, shows
the products of their reactions with bromomethane, and gives the relative
rates of their reactions. Clearly, there are large differences in the rates at
which various nucleophiles react.
What are the reasons for the reactivity differences observed in Table 2.5?
Why do some reactants appear to be much more “nucleophilic” than
others? The answers to these questions aren’t straightforward. Part of the
problem is that the term nucleophilicity is imprecise. The term is usually
taken to be a measure of the affinity of a nucleophile for a carbon atom in
the SN2 reaction, but the reactivity of a given nucleophile can change from
one reaction to the next. The exact nucleophilicity of a species in a given
reaction depends on the substrate, the solvent, and even the reactant
concentrations. Detailed explanations for the observed nucleophilicities
aren’t always simple, but some trends can be detected in the data of Table
2.5.
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CHM 203 MODULE 2
Table 2.5: Some SN2 Reactions with Bromomethane
• Nucleophilicity roughly parallels basicity when comparing

nucleophiles that have the same reacting atom. Thus, OH- is both
more basic and more nucleophilic than acetate ion, CH3CO2-,
which in turn is more basic and more nucleophilic than H2O. Since
“nucleophilicity” is usually taken as the affinity of a Lewis base
for a carbon atom in the SN2 reaction and “basicity” is the affinity
of a base for a proton, it’s easy to see why there might be a
correlation between the two kinds of behavior.
• Nucleophilicity usually increases going down a column of the
periodic table. Thus, HS- is more nucleophilic than HO-, and the
halide reactivity order is I-. Br-. Cl-. Going down the periodic table,
elements have their valence electrons in successively larger shells
where they are successively farther from the nucleus, less tightly
held, and consequently more reactive. The matter is complex,
though, and the nucleophilicity order can change depending on the
solvent.
• Negatively charged nucleophiles are usually more reactive than
neutral ones. As a result, SN2 reactions are often carried out under
basic conditions rather than neutral or acidic conditions.
Still another variable that can affect the SN2 reaction is the nature of the
group displaced by the incoming nucleophile. Because the leaving group
is expelled with a negative charge in most SN2 reactions, the best leaving
groups are those that best stabilize the negative charge in the transition
state. The greater the extent of charge stabilization by the leaving group,
the lower the energy of the transition state and the more rapid the reaction.
153
Thus, weak bases such as Cl-, Br-, and tosylate ion make good leaving
groups, while strong bases such as OH- and NH2- make poor leaving
groups.
It’s just as important to know which are poor leaving groups as to know
which are good, and the preceding data clearly indicate that F-, HO-, RO-
, and H2N- are not displaced by nucleophiles. In other words, alkyl
fluorides, alcohols, ethers, and amines do not typically undergo SN2
reactions. To carry out an SN2 reaction with an alcohol, it’s necessary to
convert the -OH into a better leaving group. This, in fact, is just what
happens when a primary or secondary alcohol is converted into either an
alkyl chloride by reaction with SOCl2 or an alkyl bromide by reaction
with PBr3.
Alternatively, an alcohol can be made more reactive toward nucleophilic

substitution by treating it with para-toluenesulfonyl chloride to form a
tosylate. As noted previously, tosylates are even more reactive than
halides in nucleophilic substitutions. Note that tosylate formation does not
change the configuration of the oxygen-bearing carbon because the C-O
bond is not broken.
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CHM 203 MODULE 2
The one general exception to the rule that ethers don’t typically undergo
SN2 reactions occurs with epoxides and the three-membered cyclic ethers.
Epoxides, because of the angle strain in the three membered rings, are
much more reactive than other ethers. They react with aqueous acid to
give 1,2-diols, and they react readily with many other nucleophiles as
well. Propene oxide, for instance, reacts with HCl to give 1-chloro-2-
propanol by SN2 backside attack on the less hindered primary carbon
atom.
3.3.4 The Solvent
The rates of SN2 reactions are strongly affected by the solvent. Protic
solvents—those that contain an -OH or -NH group - are generally the
worst for SN2 reactions, while polar aprotic solvents, which are polar but
don’t have an –OH or -NH group, are the best.
Protic solvents, such as methanol and ethanol, slow down SN2 reactions
by solvation of the reactant nucleophile. The solvent molecules hydrogen
bond to the nucleophile and form a cage around it, thereby lowering its
energy and reactivity.
A solvated anion (reduced nucleophilicity due to enhanced ground-state

stability).
In contrast with protic solvents, which decrease the rates of SN2 reactions
by lowering the ground-state energy of the nucleophile, polar aprotic
solvents increase the rates of SN2 reactions by raising the ground-state
energy of the nucleophile. Acetonitrile (CH3CN), dimethylformamide
[(CH3)2NCHO, abbreviated DMF], dimethyl sulfoxide [(CH3)2SO,
abbreviated DMSO], and hexamethylphosphoramide {[(CH3)2N]3PO,
abbreviated HMPA} are particularly useful. These solvents can dissolve
many salts because of their high polarity, but they tend to solvate metal
cations rather than nucleophilic anions. As a result, the bare unsolvated
anions have a greater nucleophilicity and SN2 reactions take place at
155
correspondingly faster rates. For instance, a rate increase of 200,000 has

been observed on changing from methanol to HMPA for the reaction of
azide ion with 1-bromobutane.
Most nucleophilic substitutions take place by the SN2 pathway just

discussed. The reaction is favoured when carried out with an unhindered
substrate and a negatively charged nucleophile in a polar aprotic solvent,
but is disfavoured when carried out with a hindered substrate and a neutral
nucleophile in a protic solvent. You might therefore expect the reaction
of a tertiary substrate (hindered) with water (neutral, protic) to be among
the slowest of substitution reactions. Remarkably, however, the opposite
is true. The reaction of the tertiary halide (CH3)3CBr with H2O to give the
alcohol 2-methyl-2-propanol is more than 1 million times as fast as the
corresponding reaction of CH3Br to give methanol.
A nucleophilic substitution reaction is occurring - a halogen is replacing

a hydroxyl group - yet the reactivity order seems backward. These
reactions can’t be taking place by the SN2 mechanism we’ve been
discussing, and we must therefore conclude that they are occurring by an
alternative substitution mechanism. This alternative mechanism is called
the SN1 reaction, for substitution, nucleophilic, unimolecular.
In contrast to the SN2 reaction of CH3Br with OH-, the SN1 reaction of
(CH3)3CBr with H2O has a rate that depends only on the alkyl halide
concentration and is independent of the H2O concentration. In other
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CHM 203 MODULE 2
words, the reaction is a first-order process; the concentration of the

nucleophile does not appear in the rate equation.
Reaction rate = Rate of disappearance of alkyl halide

= k x [RX]
Many organic reactions occur in several steps, one of which usually has a
higher-energy transition state than the others and is therefore slower. We
call this step with the highest transition-state energy the rate-limiting step,
or rate determining step. No reaction can proceed faster than its rate-
limiting step, which acts as a kind of traffic jam, or bottleneck. In the SN1
reaction of (CH3)3CBr with H2O, the fact that the nucleophile
concentration does not appear in the first-order rate equation means that
it is not involved in the rate limiting step and must therefore be involved
in some other, non–rate-limiting step.
Mechanism
Step 1: Spontaneous dissociation of the alkyl bromide occurs in a slow,
rate-limiting step to generate a carbocation intermediate plus bromide ion.
Step 2: The carbocation intermediate reacts with water as nucleophile in

a fast step to yield protonated alcohol as product.
Step 3: Loss of a proton from the protonated alcohol intermediate then

gives the neutral alcohol product.
157
The mechanism of the SN1 reaction of 2-bromo-2-methylpropane with

H2O involves three steps. Step - the spontaneous, unimolecular
dissociation of the alkyl bromide to yield a carbocation - is rate-limiting.
Unlike what happens in an SN2 reaction, where the leaving group is
displaced at the same time the incoming nucleophile approaches, an SN1
reaction takes place by loss of the leaving group before the nucleophile
approaches. 2-Bromo-2-methylpropane spontaneously dissociates to the
tert-butyl carbocation plus Br- in a slow rate-limiting step, and the
intermediate carbocation is then immediately trapped by the nucleophile
water in a faster second step. Water is not a reactant in the step whose rate
is measured. The energy diagram is shown in Figure 2.12.
Figure 2.12: An energy diagram for an SN1 reaction. The rate-

limiting step is the spontaneous dissociation of the alkyl halide to give
a carbocation intermediate. Reaction of the carbocation with a
nucleophile then occurs in a second, faster step
Because an SN1 reaction occurs through a carbocation intermediate, its

stereo chemical outcome is different from that of an SN2 reaction.
Carbocations, as we’ve seen, are planar, sp2-hybridized, and achiral.
Thus, if we carry out an SN1 reaction on one enantiomer of a chiral
reactant and go through an achiral carbocation intermediate, the product
must lose its optically activity. That is, the symmetrical intermediate
carbocation can react with a nucleophile equally well from either side,
leading to a racemic, 50;50 mixture of enantiomers.
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The conclusion that SN1 reactions on enantiomerically pure substrates

should give racemic products is nearly, but not exactly, what is found. In
fact, few SN1 displacements occur with complete racemization. Most give
a minor (0–20%) excess of inversion. The reaction of (R)-6-chloro-2,6-
dimethyloctane with H2O, for example, leads to an alcohol product that is
approximately 80% racemized and 20% inverted (80% R,S+20% S is
equivalent to 40% R+60% S).
This lack of complete racemization in SN1 reactions is due to the fact that
ion pairs are involved. If a certain amount of substitution occurs before
the two ions fully diffuse apart, then a net inversion of configuration will
be observed.
Just as the SN2 reaction is strongly influenced by the structure of the

substrate, the leaving group, the nucleophile, and the solvent, the SN1
reaction is similarly influenced. Factors that lower ∆G‡, either by
lowering the energy level of the transition state or by raising the energy
level of the ground state, favor faster SN1 reactions. Conversely, factors
that raise ∆G‡, either by raising the energy level of the transition state or
by lowering the energy level of the reactant, slow down the SN1 reaction.
3.5.1 The Substrate
According to the Hammond postulate, any factor that stabilizes a high-

energy intermediate also stabilizes the transition state leading to that
intermediate. Since the rate-limiting step in an SN1 reaction is the
spontaneous, unimolecular dissociation of the substrate to yield a
carbocation, the reaction is favored whenever a stabilized carbocation
intermediate is formed. The more stable the carbocation intermediate, the
faster the SN1 reaction.
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The stability order of alkyl carbocations is 3° > 2° > 1° > -CH3. To this
list we must also add the resonance-stabilized allyl and benzyl cations.
Just as allylic radicals are unusually stable because the unpaired electron
can be delocalized over an extended p orbital system, so allylic and
benzylic carbocations are unusually stable. An allylic cation has two
resonance forms. In one form the double bond is on the “left”; in the other
form it’s on the “right.” A benzylic cation has five resonance forms, all
of which contribute to the overall resonance hybrid.
Figure 2.13: Resonance forms of allylic and benzylic carbocations.

The positive charge is delocalized over the p system in both
Because of resonance stabilization, a primary allylic or benzylic

carbocation is about as stable as a secondary alkyl carbocation and a
secondary allylic or benzylic carbocation is about as stable as a tertiary
alkyl carbocation. This stability order of carbocations is the same as the
order of SN1 reactivity for alkyl halides and tosylates.
We said during the discussion of SN2 reactivity that the best leaving
groups are those that are most stable; that is, those that are the conjugate
bases of strong acids. An identical reactivity order is found for the SN1
reaction because the leaving group is directly involved in the rate-limiting
step. Thus, the SN1 reactivity order is
Note that in the SN1 reaction, which is often carried out under acidic
conditions, neutral water is sometimes the leaving group. This occurs, for
example, when an alkyl halide is prepared from a tertiary alcohol by
reaction with HBr or HCl. The alcohol is first protonated and then
spontaneously loses H2O to generate a carbocation, which reacts with
halide ion to give the alkyl halide. Knowing that an SN1 reaction is
involved in the conversion of alcohols to alkyl halides explains why the
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reaction works well only for tertiary alcohols. Tertiary alcohols react
fastest because they give the most stable carbocation intermediates.
Mechanism
Step 1: The –OH group is first protonated by HBr.
Step 2: Spontaneous dissociation of the protonated alcohol occurs in a

slow, rate limiting step to yield a carbocation intermediate plus water.
Step 3: The carbocation intermediate reacts with bromide ion in a fast

step to yield the neutral substitution product.
Figure 2.14: The mechanism of the SN1 reaction of a tertiary alcohol

with HBr to yield an alkyl halide. Neutral water is the leaving group
(step).
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The nature of the nucleophile plays a major role in the SN2 reaction but
does not affect an SN1 reaction. Because the SN1 reaction occurs through
a rate-limiting step in which the added nucleophile has no part, the
nucleophile can’t affect the reaction rate. The reaction of 2-methyl-2-
propanol with HX, for instance, occurs at the same rate regardless of
whether X is Cl, Br, or I. Furthermore, neutral nucleophiles are just as
effective as negatively charged ones, so SN1 reactions frequently occur
under neutral or acidic conditions.
3.5.4 The Solvent
What about the solvent? Do solvents have the same effect in SN1 reactions
that they have in SN2 reactions? The answer is both yes and no. Yes,
solvents have a large effect on SN1 reactions, but no, the reasons for the
effects on SN1 and SN2 reactions are not the same. Solvent effects in the
SN2 reaction are due largely to stabilization or destabilization of the
nucleophile reactant, while solvent effects in the SN1 reaction are due
largely to stabilization or destabilization of the transition state.
The properties of a solvent that contribute to its ability to stabilize ions by

solvation are related to the solvent’s polarity. SN1 reactions take place
much more rapidly in strongly polar solvents, such as water and methanol,
than in less polar solvents, such as ether and chloroform. In the reaction
of 2-chloro-2-methylpropane, for example, a rate increase of 100,000 is
observed on going from ethanol (less polar) to water (more polar). The
rate increases on going from a hydrocarbon solvent to water are so large
they can’t be measured accurately.
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Both the SN1 and the SN2 reaction show solvent effects, but they do so for
different reasons. SN2 reactions are disfavoured in protic solvents because
the ground-state energy of the nucleophile is lowered by solvation. SN1
reactions are favoured in protic solvents because the transition-state
energy leading to carbocation intermediate is lowered by solvation.
In-Text Question 2
Predict whether each of the following substitution reactions is likely to be

SN1 or SN2:
3.6 Biological Substitution Reactions
Both SN1 and SN2 reactions are well-known in biological chemistry,

particularly in the pathways for biosynthesis of the many thousands of
plant-derived substances called terpenoids. Unlike what typically
happens in the laboratory, however, the substrate in a biological
substitution reaction is usually an organodiphosphate rather than an alkyl
halide. Thus, the leaving group is the diphosphate ion, abbreviated PPi,
rather than a halide ion. In fact, it’s useful to think of the diphosphate
group as the “biological equivalent” of a halogen. The dissociation of an
organodiphosphate in a biological reaction is typically assisted by
complexation to a divalent metal cation such as Mg2+ to help neutralize
charge and make the diphosphate a better leaving group.
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3.7 Elimination Reactions: Zaitsev’s Rule
We said at the beginning of this unit that two kinds of reactions can take
place when a nucleophile/Lewis base reacts with an alkyl halide. The
nucleophile can either substitute for the halide by reaction at carbon or
can cause elimination of HX by reaction at neighbouring hydrogen.
Elimination reactions are more complex than substitution reactions for
several reasons. One is the problem of regiochemistry. What products
result by loss of HX from an unsymmetrical halide? In fact, elimination
reactions almost always give mixtures of alkene products, and the best we
can usually do is to predict which will be the major product.
According to Zaitsev’s rule, formulated in 1875 by the Russian chemist

Alexander Zaitsev, base-induced elimination reactions generally
(although not always) give the more stable alkene product - that is, the
alkene with more alkyl substituents on the double-bond carbons. In the
following two cases, for example, the more highly substituted alkene
product predominates.
Zaitsev’s Rule
In the elimination of HX from an alkyl halide, the more highly substituted
alkene product predominates.
Another factor that complicates a study of elimination reactions is that

they can take place by different mechanisms, just as substitutions can.
We’ll consider three of the most common mechanisms - the E1, E2, and
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CHM 203 MODULE 2
E1cB reactions - which differ in the timing of C-H and C-X bond-
breaking.
In the E1 reaction, the C-X bond breaks first to give a carbocation

intermediate that undergoes subsequent base abstraction of H+ to yield the
alkene. In the E2 reaction, base-induced C-H bond cleavage is
simultaneous with C-X bond cleavage, giving the alkene in a single step.
In the E1cB reaction (cB for “conjugate base”), base abstraction of the
proton occurs first, giving a carbanion (R:-) intermediate. This anion, the
conjugate base of the reactant “acid,” then undergoes loss of X- in a
subsequent step to give the alkene. All three mechanisms occur frequently
in the laboratory, but the E1cB mechanism predominates in biological
pathways.
E1 Reaction: C–X bond breaks first to give a carbocation intermediate,

followed by base removal of a proton to yield the alkene.
E2 Reaction: C–H and C–X bonds break simultaneously, giving the

alkene in a single step without intermediates.
E1cB Reaction: C–H bond breaks first, giving a carbanion intermediate

that loses X– to form the alkene.
In-Text Question 3
What product would you expect from reaction of 1-chloro-1-
methylcyclohexane with KOH in ethanol?
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3.8 The E2 Reaction and the Deuterium Isotope Effect
The E2 reaction (for elimination, bimolecular) occurs when an alkyl

halide is treated with a strong base, such as hydroxide ion or alkoxide ion
(RO-). It is the most commonly occurring pathway for elimination.
Mechanism
Step 1: Base (B:) attacks a neighboring hydrogen and begins to remove
the H at the same time as the alkene double bond starts to form and the X
group starts to leave.
Step 2: Neutral alkene is produced when the C–H bond is fully broken
and the X group has departed with the C–X bond electron pair.
Figure 2.15: Mechanism of the E2 reaction of an alkyl halide. The

reaction takes place in a single step through a transition state in
which the double bond begins to form at the same time the H and X
groups are leaving.
Like the SN2 reaction, the E2 reaction takes place in one step without
intermediates. As the base begins to abstract H+ from a carbon next to the
leaving group, the C-H bond begins to break, a C=C bond begins to form,
and the leaving group begins to depart, taking with it the electron pair
from the C-X bond. Among the pieces of evidence supporting this
mechanism is that E2 reactions show second-order kinetics and follow the
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CHM 203 MODULE 2
rate law: rate = k x [RX] x [Base]. That is, both base and alkyl halide takes
part in the rate-limiting step.
A second piece of evidence in support of the E2 mechanism is provided

by a phenomenon known as the deuterium isotope effect. For reasons that
we won’t go into, a carbon–hydrogen bond is weaker by about 5 kJ/mol
(1.2 kcal/mol) than the corresponding carbon–deuterium bond. Thus, a C-
H bond is more easily broken than an equivalent C-D bond, and the rate
of C-H bond cleavage is faster. For instance, the base-induced elimination
of HBr from 1-bromo-2-phenylethane proceeds 7.11 times as fast as the
corresponding elimination of DBr from 1-bromo-2,2-dideuterio-2-
phenylethane. This result tells us that the C-H (or C-D) bond is broken in
the rate-limiting step, consistent with our picture of the E2 reaction as a
one-step process. If it were otherwise, we couldn’t measure a rate
difference.
Yet a third piece of mechanistic evidence involves the stereochemistry of

E2 eliminations. As shown by a large number of experiments, E2
reactions occur with periplanar geometry, meaning that all four reacting
atoms—the hydrogen, the two carbons, and the leaving group—lie in the
same plane. Two such geometries are possible: syn periplanar geometry,
in which the H and the X are on the same side of the molecule, and anti
periplanar geometry, in which the H and the X are on opposite sides of
the molecule. Of the two, anti periplanar geometry is energetically
preferred because it allows the substituents on the two carbons to adopt a
staggered relationship, whereas syn geometry requires that the
substituents be eclipsed.
In-Text Question 4
What stereochemistry do you expect for the alkene obtained by E2

elimination of (1S,2S)-1,2-dibromo-1,2-diphenylethane?
3.9 The E2 Reaction and Cyclohexane Conformation
Anti periplanar geometry for E2 reactions is particularly important in

cyclohexane rings, where chair geometry forces a rigid relationship
between the substituents on neighboring carbon atoms. The anti
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periplanar requirement for E2 reactions overrides Zaitsev’s rule and can

be met in cyclohexanes only if the hydrogen and the leaving group are
trans diaxial. If either the leaving group or the hydrogen is equatorial, E2
elimination can’t occur.
The difference in reactivity between the isomeric methyl chlorides is due

to the difference in their conformations. Neomethyl chloride has a
conformation with the methyl and isopropyl groups equatorial and the
chlorine axial - a perfect geometry for E2 elimination. Loss of the
hydrogen atom at C4 occurs easily to yield the more substituted alkene
product, 3-menthene, as predicted by Zaitsev’s rule.
Methyl chloride, by contrast, has a conformation in which all three

substituents are equatorial. To achieve the necessary geometry for
elimination, methyl chloride must first ring-flip to a higher-energy chair
conformation, in which all three substituents are axial. E2 elimination
then occurs with loss of the only trans-diaxial hydrogen available, leading
to the non-Zaitsev product 2-methene. The net effect of the simple change
in chlorine stereochemistry is a 200-fold change in reaction rate and a
complete change of product. The chemistry of the molecule is controlled
by its conformation.
3.10 The E1 and E1cB Reactions
3.10.1 The E1 Reaction
Just as the E2 reaction is analogous to the SN2 reaction, the SN1 reaction
has a close analog called the E1 reaction (for elimination, unimolecular).
The E1 reaction can be formulated for the elimination of HCl from 2-
chloro-2-methylpropane.
Mechanism
Step 1: Spontaneous dissociation of the tertiary alkyl chloride yields an

intermediate carbocation in a slow, rate-limiting step.
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CHM 203 MODULE 2
Step 2: Loss of a neighboring H+ in a fast step yields the neutral alkene

product. The electron pair from the C–H bond goes to form the alkene π
bond.
Figure 2.16: Mechanism of the E1 reaction. Two steps are involved,

the first of which is rate-limiting, and a carbocation intermediate is
present.
E1 eliminations begin with the same unimolecular dissociation to give a

carbocation that we saw in the SN1 reaction, but the dissociation is
followed by loss of H+ from the adjacent carbon rather than by
substitution. In fact, the E1 and SN1 reactions normally occur together
whenever an alkyl halide is treated in a protic solvent with a nonbasic
nucleophile. Thus, the best E1 substrates are also the best SN1 substrates,
and mixtures of substitution and elimination products are usually
obtained. For example, when 2-chloro-2-methylpropane is warmed to
65°C in 80% aqueous ethanol, a 64;36 mixture of 2-methyl-2-propanol
(SN1) and 2-methylpropene (E1) results.
Much evidence has been obtained in support of the E1 mechanism. For

example, E1 reactions show first-order kinetics, consistent with a rate-
169
limiting, unimolecular dissociation process. Furthermore, E1 reactions

show no deuterium isotope effect because rupture of the C-H (or C-D)
bond occurs after the rate-limiting step rather than during it. Thus, we
can’t measure a rate difference between a deuterated and nondeuterated
substrate.
A final piece of evidence involves the stereochemistry of elimination.

Unlike the E2 reaction, where anti periplanar geometry is required, there
is no geometric requirement on the E1 reaction because the halide and the
hydrogen are lost in separate steps. We might therefore expect to obtain
the more stable (Zaitsev’s rule) product from E1 reaction, which is just
what we find. To return to a familiar example, methyl chloride loses HCl
under E1 conditions in a polar solvent to give a mixture of alkenes in
which the Zaitsev product, 3-menthene, predominates.
3.10.2The E1cB Reaction
In contrast to the E1 reaction, which involves a carbocation intermediate,

the E1cB reaction takes place through a carbanion intermediate. Base-
induced abstraction of a proton in a slow, rate-limiting step gives an anion,
which expels a leaving group on the adjacent carbon. The reaction is
particularly common in substrates that have a poor leaving group, such as
-OH, two carbons removed from a carbonyl group, HO-C-CH-C=O. The
poor leaving group disfavors the alternative E1 and E2 possibilities, and
the carbonyl group makes the adjacent hydrogen unusually acidic by
resonance stabilization of the anion intermediate.
3.11 Biological Elimination Reactions
All three elimination reactions - E2, E1, and E1cB - occur in biological
pathways, but the E1cB mechanism is particularly common. The substrate
is usually an alcohol rather than an alkyl halide, and the H atom removed
is usually adjacent to a carbonyl group, just as in laboratory reactions.
Thus, 3-hydroxy carbonyl compounds are frequently converted to
unsaturated carbonyl compounds by elimination reactions. A typical
example occurs during the biosynthesis of fats when a 3-hydroxybutyryl
thioester is dehydrated to the corresponding unsaturated (crotonyl)
thioester. The base in this reaction is a histidine amino acid in the enzyme,
and loss of the -OH group is assisted by simultaneous protonation.
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CHM 203 MODULE 2
In-Text Question 5
Tell whether each of the following reactions is likely to be SN1, SN2, E1,
E1cB, or E2, and predict the product of each:
i. What product would you expect to obtain from a nucleophilic

substitution reaction of (S)-2-bromohexane with acetate ion,
CH3CO2-?
ii. What product would you expect to obtain from SN2 reaction of OH-
with (R)-2-bromobutane? Show the stereochemistry of both
reactant and product.
iii What product would you expect from SN2 reaction of 1-
bromobutane with each of the following?
(a) NaI (b) KOH (c) H − C ≡ C − Li (d) NH3
171
iv Which substance in each of the following pairs is more reactive as

a nucleophile? Explain.
(a) (CH3)2N- or (CH3)2NH (b) (CH3)3B or (CH3)3N (c) H2O or H2S
v. Rank the following compounds in order of their expected reactivity

toward SN2 reaction: CH3Br, CH3OTos, (CH3)3CCl, (CH3)2CHCl
vi What product(s) would you expect from reaction of (S)-3-chloro-
3-methyloctane with acetic acid? Show the stereochemistry of both
reactant and product.
Vii Rank the following substances in order of their expected SN1
reactivity:
4.0 CONCLUSION
In this unit, we have succeeded in explaining that nucleophilic

substitution and base-induced elimination are two of the most widely
occurring and versatile reaction types in organic chemistry, both in the
laboratory and in biological pathways.
5.0 SUMMARY
The effects on SN1 reactions of the four variables - substrate, leaving

group, nucleophile, and solvent - are summarized in the following
statements:
Substrate: The best substrates yield the most stable carbocations. As a

result, SN1 reactions are best for tertiary, allylic, and benzylic halides.
Leaving group: Good leaving groups increase the reaction rate by

lowering the energy level of the transition state for carbocation formation.
Nucleophile: The nucleophile must be nonbasic to prevent a competitive

elimination of HX, but otherwise does not affect the reaction rate. Neutral
nucleophiles work well.
Solvent: Polar solvents stabilize the carbocation intermediate by

solvation, thereby increasing the reaction rate.
SN1, SN2, E1, E1cB, E2—how can you keep it all straight and predict
what will happen in any given case? Will substitution or elimination
occur? Will the reaction be bimolecular or unimolecular? There are no
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CHM 203 MODULE 2
rigid answers to these questions, but it’s possible to recognize some trends
and make some generalizations.
• Primary alkyl halides: SN2 substitution occurs if a good

nucleophile is used, E2 elimination occurs if a strong, sterically
hindered base is used, and E1cB elimination occurs if the leaving
group is two carbons away from a carbonyl group.
• Secondary alkyl halides: SN2 substitution occurs if a weakly basic

nucleophile is used in a polar aprotic solvent, E2 elimination
predominates if a strong base is used, and E1cB elimination takes
place if the leaving group is two carbons away from a carbonyl
group. Secondary allylic and benzylic alkyl halides can also
undergo SN1 and E1 reactions if a weakly basic nucleophile is used
in a protic solvent.
• Tertiary alkyl halides: E2 elimination occurs when a base is used,

but SN1 substitution and E1 elimination occur together under
neutral conditions, such as in pure ethanol or water. E1cB
elimination takes place if the leaving group is two carbons away
from a carbonyl group.

London.

Wiley & Sons.


173

John Wiley & Sons.
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MODULE 3 AROMATIC COMPOUNDS
INTRODUCTION
Compounds which have relatively few hydrogens in relation to the number

of carbons, such as benzene, are typically found in oils produced by trees and
other plants. Early chemists called such compounds aromatic compounds
because of their pleasing fragrances. In this way, they were distinguished
from aliphatic compounds, with higher hydrogen-to-carbon ratios, that were
obtained from the chemical degradation of fats. The chemical meaning of the
word “aromatic” now signifies certain kinds of chemical structures. This
module will lead us to the discussion of two units where we will examine the
criteria that a compound must satisfy to be classified as aromatic and their
reaction types. These units are:
Unit 1 Benzene and other Aromatic Compounds

Unit 2 Reactions in Aromatic Compounds
UNIT 1 BENZENE AND OTHER AROMATIC

COMPOUNDS
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 Isolation of Benzene
3.2 The Structure of Benzene
3.2.1 Resonance
3.2.2 Hybridization and Orbitals
3.3 Nomenclature of Benzene Derivatives
3.3.1 Monosubstituted Benzenes
3.3.2 Disubstituted Benzenes
3.3.3 Polysubstituted Benzenes
3.3.4 Naming Aromatic Rings as Substituents
3.4 Interesting Aromatic Compounds
3.5 Stability of Benzene
3.6 The Criteria for Aromaticity - Hückel’s Rule
3.7 Examples of Aromatic Compounds
3.7.1 Aromatic Compounds with a Single Ring
3.7.2 Aromatic Compounds with More Than One Ring
3.7.3 Aromatic Heterocycles
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CHM 203 MODULE 3
3.7.4 Charged Aromatic Compounds

3.8 Basis of Hückel’s Rule
3.8.1 Bonding and Antibonding Orbitals
3.8.2 Molecular Orbitals Formed When More Than Two p Orbitals
Combine
4.0 Conclusion
5.0 Summary
6.0 Tutor Mark Assignemt
1.0 INTRODUCTION
Benzene (C6H6) is the simplest aromatic hydrocarbon (or arene). Since its
isolation by Michael Faraday from the oily residue remaining in the
illuminating gas lines in London in 1825, it has been recognized as an
unusual compound. Benzene has four degrees of unsaturation, making it a
highly unsaturated hydrocarbon. But, whereas unsaturated hydrocarbons
such as alkenes, alkynes, and dienes readily undergo addition reactions,
benzene does not. For example, bromine adds to ethylene to form a
dibromide, but benzene is inert under similar conditions.
Ethylene addition product
Benzene
Benzene does react with bromine, but only in the presence of FeBr3 (a Lewis
acid), and the reaction is a substitution, not an addition.
Substitution: Br replaces H
Thus, any structure proposed for benzene must account for its high degree of
unsaturation and its lack of reactivity towards electrophilic addition.
176
For 6C’s, the maximum number of H’s = 2n + 2 = 2(6) + 2 = 14. Because

benzene contains only 6H’s, it has 14 – 6 = 8 H’s fewer than the maximum
’
number. This corresponds to for each degree of unsaturation = four
’
degrees of unsaturation in benzene.
In the last half of the nineteenth century August Kekulé proposed structures
that were close to the modern description of benzene. In the Kekulé model,
benzene was thought to be a rapidly equilibrating mixture of two compounds,
each containing a six-membered ring with three alternating π bonds. These
structures are now called Kekulé structures. In the Kekulé description, the
bond between any two carbon atoms is sometimes a single bond and
sometimes a double bond.
Kekulé description: An equilibrium
Although benzene is still drawn as a six-membered ring with three alternating

π bonds, in reality there is no equilibrium between two different kinds of
benzene molecules. Instead, current descriptions of benzene are based on
resonance and electron delocalization due to orbital overlap.
In the nineteenth century, many other compounds having properties similar

to those of benzene were isolated from natural sources. Because these
compounds possessed strong and characteristic odours, they were called
aromatic compounds. It is their chemical properties, though, not their odour
that make these compounds special.
• Aromatic compounds resemble benzene - they are unsaturated

compounds that do not undergo the addition reactions characteristic of
alkenes.
2.0 OBJECTIVES
When you have studied this session, you should be able to:
 understand the processes of benzene isolation.

 get acquainted with the nomenclature of benzene and benzene
derivatives.
 understand the stability of benzene and the criteria for Aromaticity.
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CHM 203 MODULE 3
3.0 MAIN CONTENT
3.1 Isolation of Benzene
Benzene and other arenes can be obtained by distilling coal. This is a

particular messy process in the laboratory, and requires a lengthy business of
separating the products from one another. However, in industry it is an
economic way of isolating benzene. There is strong demand for coke, which
is produced by heating coal in the absence of air. For every tone of coal
turned into coal, about 70 dm3 of coal tar is made. This is an oily liquid,
which contains a variety of products. If the coal tar is separated by fractional
distillation, around 30 dm3 of benzene can be collected. Methylbenzene,
naphthalene and anthracene are also obtained in smaller quantities.
In the laboratory a quicker way to make benzene is to heat the calcium salt
of benzoic acid, (C6H5COOH)2Ca, with soda lime (soda lime contains
calcium hydroxide together with sodium hydroxide):
(C6H5COO)2Ca(s) + Ca(OH)2(s) → 2C6H6(l) + 2CaCO3(s)
3.2 The Structure of Benzene
Any structure for benzene must account for the following:
• It contains a six-membered ring and three additional degrees of

unsaturation.
• It is planar.
• All C - C bond lengths are equal.
Although the Kekulé structures satisfy the first two criteria, they break down
with the third, because having three alternating π bonds means that benzene
should have three short double bonds alternating with three longer single
bonds.
3.2.1 Resonance
Benzene is conjugated, so we must use resonance and orbitals to describe its

structure. The resonance description of benzene consists of two equivalent
178
Lewis structures, each with three double bonds that alternate with three
single bonds.
The resonance description of benzene matches the Kekulé description with

one important exception. The two Kekulé representations are not in
equilibrium with each other. Instead, the true structure of benzene is a
resonance hybrid of the two Lewis structures, with the dashed lines of the
hybrid indicating the position of the π bonds.
The resonance hybrid of benzene explains why all C – C bond lengths are
the same. Each C– C bond is single in one resonance structure and double in
the other, so the actual bond length (139 pm) is intermediate between a
carbon–carbon single bond (153 pm) and a carbon– carbon double bond (134
pm).
The C–C bonds in benzene are equal and intermediate in length.
3.2.2 Hybridization and Orbitals
Each carbon atom in a benzene ring is surrounded by three atoms and no lone
pairs of electrons, making it sp2 hybridized and trigonal planar with all bond
angles 120°. Each carbon also has a p orbital with one electron that extends
above and below the plane of the molecule.
The six adjacent p orbitals overlap, delocalizing the six electrons over the six
atoms of the ring and making benzene a conjugated molecule. Because each
p orbital has two lobes, one above and one below the plane of the benzene
ring, the overlap of the p orbitals creates two “doughnuts” of electron density.
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• Benzene’s six π electrons make it electron rich and so it readily reacts

with electrophiles.
In-Text Question 1
In principle, which of the following is true regarding benzene and 1,3,5-
cyclohexatriene?
a. Theoretically they are the same molecules

b. Both have same length of all their C-C bonds
c. Both have same enthalpy of hydrogenation
d. Cyclohexatriene has three different C-C bond lengths while benzene
has only one type of C-C bond length whose value is between those
of cyclohexatriene
3.3 Nomenclature of Benzene Derivatives
Many organic molecules contain a benzene ring with one or more

substituents, so we must learn how to name them. Many common names are
recognized by the IUPAC system, however, so this complicates the
nomenclature of benzene derivatives somewhat.
3.3.1 Monosubstituted Benzenes
To name a benzene ring with one substituent, name the substituent and add
the word benzene. Carbon substituents are named as alkyl groups.
Many monosubstituted benzenes, such as those with methyl (CH3–), hydroxy

(–OH), and amino (–NH2) groups, have common names.
In-Text Question 2
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Draw the structure of each of the following compounds:

a. 2-phenylhexane
b. benzyl alcohol
c. 3-benzylpentane
d. bromomethylbenzene
3.3.2 Disubstituted Benzenes
There are three different ways that two groups can be attached to a benzene
ring, so a prefix - ortho, meta, or para - can be used to designate the relative
position of the two substituents. Ortho, meta, and para are also abbreviated
as o, m, and p, respectively.
If the two groups on the benzene ring are different, alphabetize the names of
the substituents preceding the word benzene. If one of the substituents is part
of a common root, name the molecule as a derivative of that monosubstituted
benzene.
Alphabetize two different substituent names:
Use a common root name:
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3.3.3 Polysubstituted Benzenes
For three or more substituents on a benzene ring:

 Number to give the lowest possible numbers around the ring.
 Alphabetize the substituent names.
 When substituents are part of common roots, name the molecule as a

derivative of that monosubstituted benzene. The substituent that
comprises the common root is located at C1.
Examples of naming polysubstituted benzenes
4-chloro-1-ethyl-2-propylbenzene
 Assign the lowest set of numbers.
 Alphabetize the names of all the substituents.
2,5-dichloroaniline
 Name the molecule as a derivative of the common root aniline.
 Designate the position of the NH2 group as “1” and then assign the
lowest possible set of numbers to the other substituents.
In-Text Question 3
Tell whether the following compounds are ortho-, meta-, or para-
disubstituted:
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3.3.4 Naming Aromatic Rings as Substituents
A benzene substituent (C6H5–) is called a phenyl group, and it can be

abbreviated in a structure as Ph–.
• A phenyl group (C6H5–) is formed by removing one hydrogen from

benzene (C6H6).
Benzene, therefore, can be represented as PhH, and phenol would be PhOH.
The benzyl group, another common substituent that contains a benzene ring,
differs from a phenyl group.
Finally, substituents derived from other substituted aromatic rings are

collectively called aryl groups.
Examples of aryl groups:
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3.4 Interesting Aromatic Compounds
Benzene and toluene, the simplest aromatic hydrocarbons obtained from

petroleum refining, are useful starting materials for synthetic polymers. They
are two components of the aromatic compound mixture added to gasoline to
boost octane ratings.
Polycyclic aromatic hydrocarbons (PAHs). Naphthalene, the simplest

PAH, is the active ingredient in mothballs.
Benzo[a]pyrene, a more complicated PAH is formed by the incomplete

combustion of organic materials. It is found in cigarette smoke, automobile
exhaust, and the fumes from charcoal grills. When ingested or inhaled,
benzo[a]pyrene and other similar PAHs are oxidized to carcinogenic
products.
Helicene and twistoflex are two synthetic PAHs. Helicene consists of six
benzene rings. Because the rings at both ends are not bonded to each other,
all of the rings twist slightly, creating a rigid helical shape that prevents the
hydrogen atoms on both ends from crashing into each other. Similarly, to
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reduce steric hindrance between the hydrogen atoms on nearby benzene

rings, twistoflex is also nonplanar.
• Benzo[a]pyrene, produced by the incomplete oxidation of organic

compounds in tobacco, is found in cigarette smoke.
3.5 Stability of Benzene
Considering benzene as the hybrid of two resonance structures adequately

explains its equal C-C bond lengths, but does not account for its unusual
stability and lack of reactivity towards addition.
Heats of hydrogenation, used to show that conjugated dienes are more stable
than isolated dienes, can also be used to estimate the stability of benzene.
Equations (1) - (3) compare the heats of hydrogenation of cyclohexene, 1,3-
cyclohexadiene, and benzene, all of which give cyclohexane when treated
with excess hydrogen in the presence of a metal catalyst.
The addition of one mole of H2 to cyclohexene releases -120 kJ/mol of

energy. If each double bond is worth -120 kJ/mol of energy, then the addition
of two moles of H2 to 1,3-cyclohexadiene should release 2 × -120 kJ/mol = -
240 kJ/mol of energy. The observed value, however, is -232 kJ/mol. This is
slightly smaller than expected because 1,3-cyclohexadiene is a conjugated
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diene, and conjugated dienes are more stable than two isolated carbon-carbon
double bonds.
The hydrogenations of cyclohexene and 1,3-cyclohexadiene occur readily at

room temperature, but benzene can be hydrogenated only under forcing
conditions, and even then the reaction is extremely slow. If each double bond
is worth -120 kJ/mol of energy, then the addition of three moles of H2 to
benzene should release 3 × -120 kJ/mol = -360 kJ/mol of energy. In fact, the
observed heat of hydrogenation is only -208 kJ/mol, which is 152 kJ/mol less
than predicted and even lower than the observed value for 1,3-
cyclohexadiene.
The huge difference between the hypothetical and observed heats of

hydrogenation for benzene cannot be explained solely on the basis of
resonance and conjugation.
• The low heat of hydrogenation of benzene means that benzene is
especially stable, even more so than the conjugated. This unusual stability is
characteristic of aromatic compounds.
Benzene’s unusual behaviour in chemical reactions is not limited to

hydrogenation. Benzene does not undergo addition reactions typical of other
highly unsaturated compounds, including conjugated dienes. Benzene does
not react with Br2 to yield an addition product. Instead, in the presence of a
Lewis acid, bromine substitutes for a hydrogen atom, thus yielding a product
that retains the benzene ring.
Addition does not occur. An addition product would no longer contain a

benzene ring.
Addition occurs. A substitution product still contains a benzene ring
This behavior is characteristic of aromatic compounds.
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3.6 The Criteria for Aromaticity - Hückel’s Rule
Four structural criteria must be satisfied for a compound to be aromatic:

A molecule must be cyclic.
• To be aromatic, each p orbital must overlap with p orbitals on two

adjacent atoms.
The p orbitals on all six carbons of benzene continuously overlap, so
benzene is aromatic. 1,3,5-Hexatriene has six p orbitals, too, but the
two on the terminal carbons cannot overlap with each other, so 1,3,5-
hexatriene is not aromatic.
A molecule must be planar.
• All adjacent p orbitals must be aligned so that the o electron density

can be delocalized.
For example, cyclooctatetraene resembles benzene in that it is a cyclic

molecule with alternating double and single bonds. Cyclooctatetraene is tub
shaped, however, not planar, so overlap between adjacent π bonds is
impossible. Cyclooctatetraene, therefore, is not aromatic, so it undergoes
addition reactions like those of other alkenes.
A molecule must be completely conjugated.
Both 1,3-cyclohexadiene and 1,3,5-cycloheptatriene contain at least one

carbon atom that does not have a p orbital, and so they are not completely
conjugated and therefore not aromatic.
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CHM 203 MODULE 3
A molecule must satisfy Hückel’s rule, and contain a particular number

of π electrons.
Some compounds satisfy the first three criteria for aromaticity, but still they
show none of the stability typical of aromatic compounds. For example,
cyclobutadiene is so highly reactive that it can only be prepared at extremely
low temperatures.
• Aromatic compounds must have a p orbital on every atom.
It turns out that in addition to being cyclic, planar, and completely

conjugated; a compound needs a particular number of π electrons to be
aromatic. Erich Hückel first recognized in 1931 that the following criterion,
expressed in two parts and now known as Hückel’s rule, had to be satisfied,
as well:
• An aromatic compound must contain 4n + 2 π electrons (n = 0, 1, 2,

and so forth).
• Cyclic, planar, and completely conjugated compounds that contain 4n
π electrons are especially unstable, and are said to be antiaromatic.
Thus, compounds that contain 2, 6, 10, 14, 18, and so forth π electrons are
aromatic. Benzene is aromatic and especially stable because it contains 6 π
electrons. Cyclobutadiene is antiaromatic and especially unstable because it
contains 4 π electrons.
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Table 3.1: The Number of π Electrons That Satisfy Hückel’s Rule
Considering aromaticity, all compounds can be classified in one of three

ways:
Aromatic - A cyclic, planar, completely conjugated compound with 4n + 2
π electrons.
Antiaromatic - A cyclic, planar, completely conjugated compound with 4n
π electrons.
Not aromatic - A compound that lacks one (or more) of the four
requirements (or nonaromatic) to be aromatic or antiaromatic.
Note:
• An aromatic compound is more stable than a similar acyclic
compound having the same number of π electrons. Benzene is more
stable than 1,3,5-hexatriene.
• An antiaromatic compound is less stable than an acyclic compound
having the same number of π electrons. Cyclobutadiene is less stable
than 1,3-butadiene.
• A compound that is not aromatic is similar in stability to an acyclic
compound having the same number of π electrons. 1,3-
Cyclohexadiene is similar in stability to cis, cis-2,4- hexadiene, so it
is not aromatic.
In-Text Question 4
a. What is the value of n in Hückel’s rule when a compound has nine
pairs of π-electrons?
b. Is such a compound aromatic?
3.7 Examples of Aromatic Compounds
3.7.1 Aromatic Compounds with a Single Ring
Benzene is the most common aromatic compound having a single ring.

Completely conjugated rings larger than benzene are also aromatic if they
are planar and have 4n + 2 π electrons.
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CHM 203 MODULE 3
• Hydrocarbons containing a single ring with alternating double and

single bonds are called annulenes.
To name an annulene, indicate the number of atoms in the ring in brackets
and add the word annulene. Thus, benzene is [6]-annulene. Both [14]-
annulene and [18]-annulene are cyclic, planar, completely conjugated
molecules that follow Hückel’s rule, and so they are aromatic.
[10]-Annulene has 10 π electrons, which satisfies Hückel’s rule, but a planar

molecule would place the two H atoms inside the ring too close to each other,
so the ring puckers to relieve this strain. Because [10]-annulene is not
planar, the 10 π electrons can’t delocalize over the entire ring and it is not
aromatic.
3.7.2 Aromatic Compounds with More Than One Ring
Hückel’s rule for determining aromaticity can be applied only to monocyclic

systems, but many aromatic compounds containing several benzene rings
joined together are also known. Two or more six-membered rings with
alternating double and single bonds can be fused together to form polycyclic
aromatic hydrocarbons (PAHs). Joining two benzene rings together forms
naphthalene. There are two different ways to join three rings together;
forming anthracene and phenanthrene, and many more complex
hydrocarbons are known.
As the number of fused benzene rings increases, the number of resonance

structures increases as well. Although two resonance structures can be drawn
for benzene, naphthalene is a hybrid of three resonance structures.
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Three resonance structures for naphthalene
3.7.3 Aromatic Heterocycles
Heterocycles containing oxygen, nitrogen, or sulphur - atoms that also have

at least one lone pair of electrons - can also be aromatic. With heteroatoms,
we must always determine whether the lone pair is localized on the
heteroatom or part of the delocalized π system. Two examples, pyridine and
pyrrole, illustrate these different possibilities.
3.7.4 Charged Aromatic Compounds
Both negatively and positively charged ions can also be aromatic if they
possess all the necessary elements. These charged aromatic compounds
include: cyclopentadienyl anion and tropylium cation.
In-Text Question 5
Which of the following compounds are aromatic?
3.8 Basis of Hückel’s Rule?
Why does the number of π electrons determine whether a compound is

aromatic? Cyclobutadiene is cyclic, planar, and completely conjugated, just
like benzene, but why is benzene aromatic and cyclobutadiene antiaromatic?
A complete explanation is beyond the scope of an introductory organic

chemistry text, but nevertheless, you can better understand the basis of
aromaticity by learning more about orbitals and bonding.
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CHM 203 MODULE 3
3.8.1 Bonding and Antibonding Orbitals
So far we have used the following basic concepts to describe how bonds are
formed:
• Hydrogen uses its 1s orbital to form σ bonds with other elements.

• Second-row elements use hybrid orbitals (sp, sp2, or sp3) to form σ
bonds.
• Second-row elements use p orbitals to form π bonds.
This description of bonding is called valence bond theory. In valence bond

theory, a covalent bond is formed by the overlap of two atomic orbitals, and
the electron pair in the resulting bond is shared by both atoms. Thus, a
carbon–carbon double bond consists of a σ bond, formed by overlap of two
sp2 hybrid orbitals, each containing one electron, and a π bond, formed by
overlap of two p orbitals, each containing one electron.
This description of bonding works well for most of the organic molecules we
have encountered thus far. Unfortunately, it is inadequate for describing
systems with many adjacent p orbitals that overlap, as there are in aromatic
compounds. To more fully explain the bonding in these systems, we must
utilize molecular orbital (MO) theory.
MO theory describes bonds as the mathematical combination of atomic

orbitals that form a new set of orbitals called molecular orbitals (MOs). A
molecular orbital occupies a region of space in a molecule where electrons
are likely to be found. When forming molecular orbitals from atomic orbitals,
keep in mind:
• A set of n atomic orbitals forms n molecular orbitals.

• When two p orbitals of similar phase overlap side-by-side, a π
bonding molecular orbital results.
• When two p orbitals of opposite phase overlap side-by-side, a π*
antibonding molecular orbital results.
A π bonding MO is lower in energy than the two atomic p orbitals from which
it is formed because a stable bonding interaction results when orbitals of
similar phase combine. A bonding interaction holds nuclei together.
Similarly, a π* antibonding MO is higher in energy because a destabilizing
node results when orbitals of opposite phase combine. A destabilizing
interaction pushes nuclei apart.
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If two atomic p orbitals each have one electron and then combine to form
MOs, the two electrons will occupy the lower energy π bonding MO.
3.8.2 Molecular Orbitals Formed When More Than Two p

Orbitals Combine
The molecular orbital description of benzene is much more complex than the
two MOs formed. Because each of the six carbon atoms of benzene has a p
orbital, six atomic p orbitals combine to form six π molecular orbitals. A
description of the exact appearance and energies of these six MOs requires
more sophisticated mathematics and understanding of MO theory than is
presented in this unit. Nevertheless, note that the six MOs are labeled 1–
6, with ψ1 being the lowest in energy and ψ6 the highest.
The most important features of the six benzene MOs are as follows:
• The larger the number of bonding interactions, the lower in energy the
MO. The lowest energy molecular orbital (ψ1) has all bonding
interactions between the p orbitals.
• The larger the number of nodes, the higher in energy the MO. The
highest energy MO (ψ6*) has all nodes between the p orbitals.
• Three MOs are lower in energy than the starting p orbitals, making
them bonding MOs (ψ1, ψ2, ψ3), whereas three MOs are higher in
energy than the starting p orbitals, making them antibonding MOs
(ψ4*, ψ5*, ψ6*).
• The two pairs of MOs (ψ2 and ψ3; ψ4* and ψ5*) with the same energy
are called degenerate orbitals.
• The highest energy orbital that contains electrons is called the highest
occupied molecular orbital (HOMO). For benzene, the degenerate
orbitals ψ2 and ψ3 are the HOMOs.
• The lowest energy orbital that does not contain electrons is called the
lowest unoccupied molecular orbital (LUMO). For benzene, the
degenerate orbitals ψ4* and ψ5* are the LUMOs.
To fill the MOs, the six electrons are added, two to an orbital, beginning with
the lowest energy orbital. As a result, the six electrons completely fill the
bonding MOs, leaving the antibonding MOs empty. This is what gives
benzene and other aromatic compounds their special stability and this is why
six π electrons satisfy Hückel’s 4n + 2 rule.
• All bonding MOs (and HOMOs) are completely filled in aromatic

compounds. No π electrons occupy antibonding MOs.
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CHM 203 MODULE 3
• Depicted in this diagram are the interactions of the six atomic p

orbitals of benzene, which form six molecular orbitals. When orbitals
of like phase combine, a bonding interaction results. When orbitals of
opposite phase combine, a destabilizing node results.
i. Give IUPAC names for the following compounds:
ii. Azulene, a beautiful blue hydrocarbon, is an isomer of naphthalene.

Is azulene aromatic? Draw a second resonance form of azulene in
addition to that shown.
iii. How many electrons does each of the four nitrogen atoms in purine
contribute to the aromatic p system?
iv The [10]- and [12]-annulenes have been synthesized, and neither has
been found to be aromatic. Explain.
194
v. How many bonding, nonbonding, and antibonding molecular orbitals

does cyclobutadiene have? In which molecular orbitals are the electrons?
4.0 CONCLUSION
In this unit, we have been able to explain the concept of aromaticity, isolation
of benzene, structure of benzene, nomenclature of benzene and spectroscopic
properties of aromatic compounds. Also, we were able to give examples of
aromatic compound, explain why benzene is exceptionally stable, and
criteria and basis for Hückel’s rule.
5.0 SUMMARY
Aromatic rings are a common part of many biological structures and are
particularly important in nucleic acid chemistry and in the chemistry of
several amino acids. In this unit, we’ve seen how and why aromatic
compounds are different from such apparently related compounds as
cycloalkenes.
The word aromatic is used for historical reasons to refer to the class of
compounds related structurally to benzene. Aromatic compounds are
systematically named according to IUPAC rules, but many common names
are also used. Disubstituted benzenes are named as ortho (1,2 disubstituted),
meta (1,3 disubstituted), or para (1,4 disubstituted) derivatives. The C6H5-
unit itself is referred to as a phenyl group, and the C6H5CH2- unit is a benzyl
group.
Benzene is described by valence-bond theory as a resonance hybrid of two

equivalent structures and is described by molecular orbital theory as a planar,
cyclic, conjugated molecule with six π electrons. According to the Hückel
rule, a molecule must have 4n + 2 π electrons, where n = 0, 1, 2, 3, and so
on, to be aromatic. Planar, cyclic, conjugated molecules with other numbers
of π electrons are antiaromatic.
Other kinds of substances besides benzene-like compounds can also be

aromatic. The cyclopentadienyl anion and the cycloheptatrienyl cation, for
instance, are aromatic ions. Pyridine and pyrimidine are six-membered,
nitrogen-containing, aromatic heterocycles. Pyrrole and imidazole are five-
membered, nitrogen-containing heterocycles. Naphthalene, quinoline,
indole, and many others are polycyclic aromatic compounds.
Aromatic compounds have the following characteristics:

• Aromatic compounds are cyclic, planar, and conjugated.
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CHM 203 MODULE 3
• Aromatic compounds are unusually stable. Benzene, for instance, has

a heat of hydrogenation 150 kJ/mol less than we might expect for a
cyclic triene.
• Aromatic compounds react with electrophiles to give substitution
products, in which cyclic conjugation is retained, rather than addition
products, in which conjugation is destroyed.
• Aromatic compounds have 4n + 2 π electrons, which are delocalized
over the ring.

London.

pharmacy, medicinal chemistry and biological chemistry. John Wiley
& Sons.


Brown, W. H., & Poon, T. (2016). Introduction to organic chemistry. John

Wiley & Sons.
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UNIT 2 REACTIONS OF AROMATIC COMPOUNDS
CONTENTS
1.0 Introduction
3.0 Main Content
3.1 Electrophilic Aromatic Substitution
3.1.1 The General Mechanism
3.2 Halogenation
3.3 Nitration and Sulphonation
3.4 Friedel-Crafts Alkylation and Friedel-Crafts Acylation
3.4.1 General Features
3.4.2 Other Facts about Friedel-Crafts Alkylation
3.4.3 Intramolecular Friedel-Crafts Reaction
3.5 Substituted Benzenes
3.5.1 Inductive Effects
3.5.2 Resonance Effects
3.6 Electrophilic Aromatic Substitution of Substituted Benzenes
3.7 Activation and Deactivation of Benzene Ring
3.8 Orientation Effects in Substituted Benzenes
3.8.1 The CH3 Group – An ortho, para Director
3.8.2 The NH2 Group – An ortho, para Director
3.8.3 The NO2 Group – A meta Director
4.0 Conclusion
5.0 Summary
1.0 INTRODUCTION
In this unit, we shall look at the chemical reactions of benzene and other
aromatic compounds. Although aromatic rings are unusually stable, benzene
acts as a nucleophile with certain electrophiles, yielding substitution products
with an intact aromatic ring.
We begin this unit with the basic features and mechanism of electrophilic
aromatic substitution, the basic reaction of benzene. Next, we will discuss
the electrophilic aromatic substitution of substituted benzenes, and conclude
with other useful reactions of benzene derivatives. The ability to interconvert
resonance structures and evaluate their relative stabilities is crucial to
understanding this unit.
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CHM 203 MODULE 3
2.0 OBJECTIVES
By the end of this session, you should be able to:
 understand the concept of electrophilic aromatic substitution reaction.

 understand the general mechanism of electrophilic aromatic
substitution reaction.
 get acquainted with the chemistry of substituted benzenes and their
electrophilic substitution reaction.
 understand how benzene can be activated and deactivated.
 understand the orientation effects in substituted benzene.
3.0 MAIN CONTENT
3.1 Electrophilic Aromatic Substitution
Based on its structure and properties, what kinds of reactions should benzene
undergo? Are any of its bonds particularly weak? Does it have electron-rich
or electron-deficient atoms?
Benzene has six o electrons delocalized in six p orbitals that overlap above
and below the plane of the ring. These loosely held π electrons make the
benzene ring electron rich, and so it reacts with electrophiles.
Because benzene’s six π electrons satisfy Hückel’s rule, benzene is especially

stable.
Reactions that keep the aromatic ring intact are therefore favored.
As a result, the characteristic reaction of benzene is electrophilic aromatic
substitution - a hydrogen atom is replaced by an electrophile.
Benzene does not undergo addition reactions like other unsaturated

hydrocarbons, because addition would yield a product that is not aromatic.
Substitution of hydrogen, on the other hand, keeps the aromatic ring intact.
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Addition (The product is not aromatic)
Substitution (The product is aromatic)
3.1.1 The General Mechanism
No matter what electrophile is used, all electrophilic aromatic substitution

reactions occur via a two-step mechanism: addition of the electrophile E+
to form a resonance-stabilized carbocation, followed by deprotonation with
base, as shown in the mechanism below.
1. Halogenation - Replacement of H by X (Cl or Br).
2. Nitration - Replacement of H by NO2.
3. Sulfonation - Replacement of H by SO3H
4. Friedel - Crafts alkylation - Replacement of H by R
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CHM 203 MODULE 3
5. Friedel - Crafts acylation - Replacement of H by RCO
Mechanism
General Mechanism of Electrophilic Aromatic Substitution
Step 1: Addition of the electrophile (E+) to form a carbocation.
Resonance-stabilized carbocation
• Addition of the electrophile (E+) forms a new C - E bond using two π

electrons from the benzene ring, and generating a carbocation. This
carbocation intermediate is not aromatic, but it is resonance stabilized
- three resonance structures can be drawn.
• Step 1 is rate-determining because the aromaticity of the benzene ring

is lost.
Step 2: Loss of a proton to re-form the aromatic ring.
• In Step 2, a base (B:) removes the proton from the carbon bearing the
electrophile, thus re-forming the aromatic ring. This step is fast
because the aromaticity of the benzene ring is restored.
• Any of the three resonance structures of the carbocation intermediate

can be used to draw the product. The choice of resonance structure
affects how curved arrows are drawn, but not the identity of the
product.
The first step in electrophilic aromatic substitution forms a carbocation, for

which three resonance structures can be drawn.
200
This two-step mechanism for electrophilic aromatic substitution applies to

all electrophiles. The net result of addition of an electrophile (E+) followed
by elimination of a proton (H+) is substitution of E for H.
3.2 Halogenation
The general mechanism outlined above can now be applied to each of the
five specific examples of electrophilic aromatic substitution. For each
mechanism we must learn how to generate a specific electrophile. This step
is different with each electrophile. Then, the electrophile reacts with benzene
by the two-step process of the mechanism outlined above. These two steps
are the same for all five reactions.
Figure 3.1: Energy diagram for electrophilic aromatic substitution:

PhH + E+ → PhE + H+
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CHM 203 MODULE 3
• The mechanism has two steps, so there are two energy barriers.
• Step 1 is rate-determining; its transition state is at higher energy.
In halogenation, benzene reacts with Cl2 or Br2 in the presence of a Lewis

acid catalyst, such as FeCl3 or FeBr3, to give the aryl halides chlorobenzene
or bromobenzene, respectively. Analogous reactions with I2 and F2 are not
synthetically useful because I2 is too unreactive and F2 reacts too violently.
Chlorination
Bromination
In bromination, the Lewis acid FeBr3 reacts with Br2 to form a Lewis acid -
base complex that weakens and polarizes the Br–Br bond, making it more
electrophilic. This reaction is Step 1 of the mechanism for the bromination
of benzene. The remaining two steps follow directly from the general
mechanism for electrophilic aromatic substitution: addition of the
electrophile (Br+ in this case) forms a resonance-stabilized carbocation, and
loss of a proton regenerates the aromatic ring.
Mechanism for the Bromination of Benzene
Step 1: Generation of the electrophiles
• Lewis acid–base reaction of Br2 with FeBr3 forms a species with a

weakened and polarized Br – Br bond. This adduct serves as a source of Br+
in the next step.
202
Step 2: Addition of the electrophile to form a carbocation
• Addition of the electrophile forms a new C-Br bond and generates a

carbocation. This carbocation intermediate is resonance stabilized -
three resonance structures can be drawn.
• The FeBr4 – also formed in this reaction is the base used in Step 3.
Step 3: Loss of a proton to re-form the aromatic ring.
• FeBr4 – removes the proton from the carbon bearing the Br, thus re-
forming the aromatic ring.
• FeBr3, a catalyst, is also regenerated for another reaction cycle.
Chlorination proceeds by a similar mechanism. Reactions that introduce a

halogen substituent on a benzene ring are widely used, and many halogenated
aromatic compounds with a range of biological activity have been
synthesized, as shown in Figure 3.2.
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CHM 203 MODULE 3
Figure 3.2: Examples of biologically active aryl chlorides
3.3 Nitration and Sulphonation
Nitration and sulphonation of benzene introduce two different functional

groups on an aromatic ring. Nitration is an especially useful reaction because
a nitro group can then be reduced to an NH2 group, a common benzene
substituent.
Generation of the electrophile in both nitration and sulphonation requires

strong acid. In nitration, the electrophile is +NO2 (the nitronium ion),
formed by protonation of HNO3 followed by loss of water.
Mechanism for Formation of the Nitronium Ion (+NO2) for Nitration.
In sulphonation, protonation of sulfur trioxide, SO3, forms a positively

charged sulfur species (+SO3H) that acts as an electrophile.
204
These steps illustrate how to generate the electrophile E+ for nitration and
sulphonation, the process that begins any mechanism for electrophilic
aromatic substitution. To complete either of these mechanisms, you must
replace the electrophile E+ by either +NO2 or +SO3H in the general
mechanism. Thus, the two-step sequence that replaces H by E is the same
regardless of E+.
In-Text Question 1
Draw a stepwise mechanism for the nitration of a benzene ring.
3.4 Friedel - Crafts Alkylation and Friedel - Crafts Acylation
Friedel - Crafts alkylation and Friedel - Crafts acylation form new carbon-
carbon bonds.
3.4.1 General Features
In Friedel - Crafts alkylation, treatment of benzene with an alkyl halide and

a Lewis acid (AlCl3) forms an alkyl benzene. This reaction is an alkylation
because it results in transfer of an alkyl group from one atom to another (from
Cl to benzene).
Friedel-Crafts alkylation – General reaction
205
CHM 203 MODULE 3
Examples of Friedel-Crafts alkylation
In Friedel - Crafts acylation, a benzene ring is treated with an acid chloride

(RCOCl) and AlCl3 to form a ketone. Because the new group bonded to the
benzene ring is called an acyl group, the transfer of an acyl group from one
atom to another is an acylation.
Acid chlorides are also called acyl chlorides.
Mechanism
The mechanisms of alkylation and acylation proceed in a manner analogous
to those for halogenation, nitration, and sulphonation. The unique feature in
each reaction is how the electrophile is generated.
In Friedel–Crafts alkylation, the Lewis acid AlCl3 reacts with the alkyl
chloride to form a Lewis acid–base complex, illustrated with CH3CH2Cl and
(CH3)3CCl as alkyl chlorides. The identity of the alkyl chloride determines
the exact course of the reaction.
206
• For CH3Cl and 1° RCl, the Lewis acid–base complex itself serves as
the electrophile for electrophilic aromatic substitution.
• With 2° and 3° RCl, the Lewis acid–base complex reacts further to
give a 2° or 3° carbocation, which serves as the electrophile.
Carbocation formation occurs only with 2° and 3° alkyl chlorides,
because they afford more stable carbocations.
In either case, the electrophile goes on to react with benzene in the two-step
mechanism characteristic of electrophilic aromatic substitution, illustrated in
Mechanism 18.6 using the 3° carbocation, (CH3)3C+.
Mechanism of Friedel - Crafts Alkylation Using a 3° Carbocation.
• Addition of the electrophile (a 3° carbocation) forms a new carbon–

carbon bond in Step (1).
• AlCl4– removes a proton on the carbon bearing the new substituent,

thus re-forming the aromatic ring in Step (2).
In Friedel - Crafts acylation, the Lewis acid AlCl3 ionizes the carbon -
halogen bond of the acid chloride, thus forming a positively charged carbon
electrophile called an acylium ion, which is resonance stabilized. The
positively charged carbon atom of the acylium ion then goes on to react with
benzene in the two-step mechanism of Electrophilic aromatic substitution.
207
CHM 203 MODULE 3
To complete the mechanism for acylation, insert the electrophile into the
general mechanism and draw the last two steps, as illustrated in the ITQ 2
below.
In-Text Question 2
Draw a stepwise mechanism for the following Friedel–Crafts acylation.
3.4.2 Other Facts about Friedel - Crafts Alkylation
Three additional facts about Friedel - Crafts alkylations must be kept in mind.
1. Vinyl halides and aryl halides do not react in Friedel–Crafts

alkylation
Most Friedel - Crafts reactions involve carbocation electrophiles. Because

the carbocations derived from vinyl halides and aryl halides are highly
unstable and do not readily form, these organic halides do not undergo
Friedel–Crafts alkylation.
2. Rearrangements can occur
The Friedel - Crafts reaction can yield products having rearranged carbon
skeletons when 1° and 2° alkyl halides are used as starting materials, as
shown in Equations (1) and (2). In both reactions, the carbon atom bonded to
the halogen in the starting material (labeled in red) is not bonded to the
benzene ring in the product, thus indicating that a rearrangement has
occurred.
208
The result in Equation (1) is explained by a carbocation rearrangement

involving a 1,2-hydride shift: the less stable 2° carbocation (formed from
the 2° halide) rearranges to a more stable 3° carbocation, as illustrated
below.
Steps (1) and (2) Formation of a 2° carbocation
• Reaction of the alkyl chloride with AlCl3 forms a complex that

decomposes in Step (2) to form a 2° carbocation.
Step [3] Carbocation rearrangement
• 1,2-Hydride shift converts the less stable 2° carbocation to a more

stable 3° carbocation.
Steps (4) and (5) Addition of the carbocation and loss of a proton
209
CHM 203 MODULE 3
• Friedel–Crafts alkylation occurs by the usual two-step process:

addition of the carbocation followed by loss of a proton to form the
alkylated product.
A Rearrangement Reaction Beginning with a 1° Alkyl Chloride
Other functional groups that form carbocations can also be used as

starting materials
Although Friedel - Crafts alkylation works well with alkyl halides, any
compound that readily forms a carbocation can be used instead. The two most
common alternatives are alkenes and alcohols, both of which afford
carbocations in the presence of strong acid.
• Protonation of an alkene forms a carbocation, which can then act as

an electrophile in a Friedel - Crafts alkylation.
• Protonation of an alcohol, followed by loss of water, likewise forms a

carbocation.
210
Each carbocation can then go on to react with benzene to form a product of

electrophilic aromatic substitution. For example:
3.4.3 Intramolecular Friedel–Crafts Reactions
All of the Friedel–Crafts reactions discussed thus far have resulted from
intermolecular reaction of a benzene ring with an electrophile. Starting
materials that contain both units are capable of intramolecular reaction, and
this forms a new ring. For example, treatment of compound A, which
contains both a benzene ring and an acid chloride, with AlCl3, forms α-
tetralone by an intramolecular Friedel - Crafts acylation reaction.
3.5 Substituted Benzenes
Many substituted benzene rings undergo electrophilic aromatic substitution.

Common substituents include halogens, OH, NH2, alkyl, and many
functional groups that contain a carbonyl. Each substituent either increases
or decreases the electron density in the benzene ring, and this affects the
course of electrophilic aromatic substitution.
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CHM 203 MODULE 3
What makes a substituent on a benzene ring electron donating or electron

withdrawing? The answer is inductive effects and resonance effects, both
of which can add or remove electron density.
3.5.1 Inductive Effects
Inductive effects stem from the electronegativity of the atoms in the

substituent and the polarizability of the substituent group.
• Atoms more electronegative than carbon - including N, O, and X -

pull electron density away from carbon and thus exhibit an electron-
withdrawing inductive effect.
• Polarizable alkyl groups donate electron density, and thus exhibit an
electron-donating inductive effect.
Considering inductive effects only, an NH2 group withdraws electron
density and CH3 donates electron density.
Electron-withdrawing inductive effect

 N is more electronegative than C.
 N inductively withdraws electron density.
Electron-donating inductive effect

 Alkyl groups are Polarizable, making them electron-donating groups.
3.5.2 Resonance Effects
Resonance effects can either donate or withdraw electron density, depending

on whether they place a positive or negative charge on the benzene ring.
• A resonance effect is electron donating when resonance structures

place a negative charge on carbons of the benzene ring.
• A resonance effect is electron withdrawing when resonance structures
place a positive charge on carbons of the benzene ring.
212
An electron-donating resonance effect is observed whenever an atom Z

having a lone pair of electrons is directly bonded to a benzene ring (general
structure - C6H5–Z:). Common examples of Z include N, O, and halogen. For
example, five resonance structures can be drawn for aniline (C6H5NH2).
Because three of them place a negative charge on a carbon atom of the
benzene ring, an NH2 group donates electron density to a benzene ring by a
resonance effect.
Three resonance structures A, B, and C place a (-) charge on atoms in the

ring.
In contrast, an electron-withdrawing resonance effect is observed in

substituted benzenes having the general structure C6H5–Y=Z, where Z is
more electronegative than Y.
In-Text Question 3
Classify each substituent as electron donating or electron withdrawing.
3.6 Electrophilic Aromatic Substitution of Substituted Benzenes
Electrophilic aromatic substitution is a general reaction of all aromatic

compounds, including polycyclic aromatic hydrocarbons, heterocycles, and
substituted benzene derivatives. A substituent affects two aspects of
electrophilic aromatic substitution:
• The rate of reaction: A substituted benzene reacts faster or slower

than benzene itself.
• The orientation: The new group is located either ortho, meta, or para
to the existing substituent. The identity of the first substituent
determines the position of the second substituent.
213
CHM 203 MODULE 3
Toluene (C6H5CH3) and nitrobenzene (C6H5NO2) illustrate two possible

outcomes.
1. Toluene
Toluene reacts faster than benzene in all substitution reactions. Thus, its
electron-donating CH3 group activates the benzene ring to electrophilic
attack. Although three products are possible, compounds with the new group
ortho or para to the CH3 group predominate. The CH3 group is therefore
called an ortho, para director.
2. Nitrobenzene
Nitrobenzene reacts more slowly than benzene in all substitution reactions.
Thus, its electron withdrawing NO2 group deactivates the benzene ring to
electrophilic attack. Although three products are possible, the compound
with the new group meta to the NO2 group predominates. The NO2 group is
called a meta director.
Substituents either activate or deactivate a benzene ring towards

electrophiles, and direct selective substitution at specific sites on the ring. All
substituents can be divided into three general types.
Ortho, para directors and activators

• Substituents that activate a benzene ring and direct substitution ortho
and para.
214
General structure
Ortho, para deactivators
• Substituents that deactivate a benzene ring and direct substitution

ortho and para.
Meta directors
• Substituents that direct substitution meta.
• All meta directors deactivate the ring.
General structure –Y(δ+ or +)

In-Text Question 4
Draw the products of each reaction and state whether the reaction is faster or
slower than a similar reaction with benzene.
3.7 Activation and Deactivation of Benzene Ring
• Why do substituents activate or deactivate a benzene ring?
215
CHM 203 MODULE 3
• Why are particular orientation effects observed? Why are some

groups ortho, para directors and some groups meta directors?
To understand why some substituents make a benzene ring react faster than
benzene itself (activators), whereas others make it react slower
(deactivators), we must evaluate the rate-determining step (the first step) of
the mechanism. Recall the first step in Electrophilic aromatic substitution is
the addition of an electrophile (E+) to form a resonance-stabilized
carbocation. The Hammond postulate makes it possible to predict the relative
rate of the reaction by looking at the stability of the carbocation intermediate.
• The more stable the carbocation, the lower in energy the transition
state that forms it, and the faster the reaction.
The principles of inductive effects and resonance effects can now be used to
predict carbocation stability.
• Electron-donating groups stabilize the carbocation and activate a

benzene ring towards electrophilic attack.
• Electron-withdrawing groups destabilize the carbocation and
deactivate a benzene ring towards electrophilic attack.
The energy diagrams in Figure 3.3 illustrate the effect of electron-donating

and electron withdrawing groups on the energy of the transition state of the
rate-determining step in Electrophilic aromatic substitution.
• All activators are either R groups or they have an N or O atom with a

lone pair bonded directly to the benzene ring.
216
Figures 3.3: Energy diagrams comparing the rate of electrophilic

aromatic substitution of substituted benzenes
• Electron-donor groups D stabilize the carbocation intermediate, lower

the energy of the transition state, and increase the rate of reaction.
217
CHM 203 MODULE 3
• Electron-withdrawing groups W destabilize the carbocation

intermediate, raise the energy of the transition state, and decrease the
rate of reaction.
• All deactivators are either halogens or they have an atom with a partial
or full positive charge bonded directly to the benzene ring.
3.8 Orientation Effects in Substituted Benzenes
To understand why particular orientation effects arise, you must keep in mind
the general structures for ortho, para directors and for meta directors. There
are two general types of ortho, para directors and one general type of meta
director:
• All ortho, para directors are R groups or have a nonbonded electron

pair on the atom bonded to the benzene ring.
• All meta directors have a full or partial positive charge on the atom
bonded to the benzene ring.
To evaluate the directing effects of a given substituent, we can follow a
stepwise procedure.
How to Determine the Directing Effects of a Particular Substituent
Step 1: Draw all resonance structures for the carbocation formed from attack
of an electrophile E+ at the ortho, meta, and para positions of a
substituted benzene (C6H5-A).
• There are at least three resonance structures for each site of reaction.
218
• Each resonance structure places a positive charge ortho or para to the

new C–E bond.
Step 2: Evaluate the stability of the intermediate resonance structures. The

electrophile attacks at those positions that give the most stable carbocation.
3.8.1 The CH3 Group - An ortho, para Director
To determine why a CH3 group directs electrophilic aromatic substitution to

the ortho and para positions, first draw all resonance structures that result
from electrophilic attack at the ortho, meta, and para positions to the CH3
group.
To evaluate the stability of the resonance structures, determine whether any

are especially stable or unstable. In this example, attack ortho or para to CH3
generates a resonance structure that places a positive charge on a carbon atom
with the CH3 group. The electron-donating CH3 group stabilizes the adjacent
positive charge. In contrast, attack meta to the CH3 group does not generate
any resonance structure stabilized by electron donation. Other alkyl groups
are ortho, para directors for the same reason.
The CH3 group directs electrophilic attack ortho and para to itself because an
electron-donating inductive effect stabilizes the carbocation intermediate.
219
CHM 203 MODULE 3
3.8.2 The NH2 Group - An ortho, para Director
To determine why an amino group (NH2) directs electrophilic aromatic

substitution to the ortho and para positions, follow the same procedure.
Attack at the meta position generates the usual three resonance structures.
Because of the lone pair on the N atom, attack at the ortho and para positions
generates a fourth resonance structure, which is stabilized because every
atom has an octet of electrons. This additional resonance structure can be
drawn for all substituents that have an N, O, or halogen atom bonded directly
to the benzene ring.
The NH2 group directs electrophilic attack ortho and para to itself because
the carbocation intermediate has additional resonance stabilization.
3.8.3 The NO2 Group - A meta Director
To determine why a nitro group (NO2) directs electrophilic aromatic

substitution to the meta position, follow the same procedure.
220
Attack at each position generates three resonance structures. One resonance

structure resulting from attack at the ortho and para positions is especially
destabilized, because it contains a positive charge on two adjacent atoms.
Attack at the meta position does not generate any particularly unstable
resonance structures.
With the NO2 group (and all meta directors), meta attack occurs because
attack at the ortho or para position gives a destabilized carbocation
intermediate.
In-Text Question 5
The Friedel - Crafts reaction of benzene with 2-chloro-3-methylbutane in the
presence of AlCl3 occurs with a carbocation rearrangement. What is the
structure of the product?
SELF-ASSESSMENT EXERCISE)
i. Predict the major product of the sulphonation of toluene.

ii Rank the compounds in each of the following groups in order of their
reactivity to electrophilic substitution:
(a) Nitrobenzene, phenol, toluene, benzene

(b) Phenol, benzene, chlorobenzene, benzoic acid
(c) Benzene, bromobenzene, benzaldehyde, aniline
iii Predict the major products of the following reactions:
(a) Nitration of bromobenzene

(b) Bromination of nitrobenzene
221
CHM 203 MODULE 3
(c) Chlorination of phenol

(d) Bromination of aniline
iv Draw resonance structures for the intermediates from reaction of an

electrophile at the ortho, meta, and para positions of nitrobenzene.
Which intermediates are most stable?
v. What product would you expect from bromination of p-

methylbenzoic acid?
vi At what position would you expect electrophilic substitution to occur

in each of the following substances?
4.0 CONCLUSION
In this unit, we looked at some of the unique reactions that aromatic

molecules undergo and their mechanisms. These reactions include
halogenation, nitration and sulphonation, Friedel-Crafts Alkylation and
Friedel-Crafts Acylation. We also looked at the chemistry of
substituted benzene, activation and deactivation of benzene and lastly
orientation effects in substituted benzenes.
5.0 SUMMARY
In the preceding chapter, we looked at aromaticity - the stability associated

with benzene and related compounds that contain a cyclic conjugated system
of 4n + 2 π electrons.
The most common reaction of aromatic compounds is electrophilic aromatic

substitution, in which an electrophile (E+) reacts with an aromatic ring and
substitutes for one of the hydrogens. The reaction is characteristic of all
aromatic rings, not just benzene and substituted benzenes. In fact, the ability
222
of a compound to undergo electrophilic substitution is a good test of

aromaticity.
Many different substituents can be introduced onto an aromatic ring through

electrophilic substitution reactions. To list some possibilities, an aromatic
ring can be substituted by a halogen (-Cl, -Br, I), a nitro group (-NO2), a
sulphonic acid group (-SO3H), a hydroxyl group (-OH), an alkyl group (-R),
or an acyl group (-COR). Starting from only a few simple materials, it’s
possible to prepare many thousands of substituted aromatic compounds.

London.

pharmacy, medicinal chemistry and biological chemistry. John Wiley
& Sons.


223
CHM 203 MODULE 3
Brown, W. H., & Poon, T. (2016). Introduction to organic chemistry. John

Wiley & Sons.
224

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COURSE

NATIONAL OPEN UNIVERSITY OF NIGERIA

© 2020 by NOUN Press

All rights reserved. No part of this book may be reproduced, in any

Printed 2009, 2021

WHAT YOU WILL LEARN IN THIS COURSE

1. Discuss the Relationship between the structure and reactivity of

a) Familiarize ourselves with molecular structure of organic

WORKING THROUGH THIS COURSE

In order to be able to successfully complete this course, you are required to

The course materials are made up of the following sections:

Module 1 Electronic Concept and Stereochemistry

Unit 1 Factors Affecting Structure and Physical Properties of

Module 2 Functional Groups and Reactivity in Organic Chemistry

Unit 1 Functional Group Chemistry of Main Class Organic

Module 3 Aromatic Compounds

Unit 1 Benzene and other Aromatic Compounds

Module 1 Electronic Concept and Stereochemistry….. 1

Unit 1 Factors Affecting Structure and Physical

Module 2 Functional Groups and Reactivity in

Unit 1 Functional Group Chemistry of Main Class

Module 3 Aromatic Compounds…………………………..175

Unit 1 Benzene and other Aromatic Compounds……...175

MODULE 1 ELECTRONIC CONCEPT AND

The study of organic chemistry involves the reactions and interactions of

Unit 1 Effect of molecular architecture on physical properties of

UNIT 1 EFFECT OF MOLECULAR ARCHITECTURE

6.0 Tutor Mark Assignment

In our previous knowledge in organic chemistry, we have learnt some of

By the end of this unit you should be able to:

 identify organic molecules using their physical properties such

3.0 MAIN CONTENT

3.1 Molecular Architecture and Factors Affecting Physical

The bonding and structural features of a compound are manifested in its

The physical properties of a compound depend upon the number and

3.1.1 Intermolecular Forces

(i) Dipole-Dipole Interactions: are defined as the interactions

Fig. 1.1: Intermolecular forces (“- - - - -” indicates interaction). a) A

(ii) London Forces: The intermolecular interactions exist between

When the molecules A and B approach each other, there is a distortion

Such a distribution of charge leads to mutual attraction between the

Fig. 1.2: London forces are induced-dipole–induced-dipole

Fig 1.3: London dispersion forces in two helium atoms

(iii) Hydrogen Bonding: This is a special type of dipole-dipole

Fig. 1.4: hydrogen bonding in water molecules

The strength of a hydrogen bond ranges from 10 to 40 kJ mol-1. Hydrogen

The dipole-dipole, induced dipole-induced dipole etc. interactions are

(a) AsH3, H2Te

3.1.2 Melting Point

The melting point (mp) is the temperature at which a solid is converted

point of methane, a covalent compound, is only 90 K and the melting

molecules with odd numbers of carbon atoms have lower intermolecular

Fig. 1.5: Plot of melting points of straight-chain alkanes. Alkanes with

The branching from pentane to 2-methylbutane lowers the melting point

The effect of hydrogen bonding on melting point is small. But, the

3.1.3 Boiling Point

The boiling point of a substance is the temperature at which it changes

The boiling point of a substance depends on its molecular structure. In

The molecules of an alkane are held together by these induced-dipole–

Among isomeric molecules, since the unbranched isomer is linear and