NATIONAL OPEN UNIVERSITY OF NIGERIA

SCHOOL OF SCIENCE AND TECHNOLOGY

COURSE CODE: CHM 102

COURSE TITLE: INTRODUCTORY ORGANIC

CHEMISTRY
ii

COURSE
GUIDE

CHM 102
INTRODUCTORY ORGANIC CHEMISTRY I

Course Team Prof. Femi Peters, Mr. Adakole Ikpe & Dr.
Makanjuola Oki (Course Developers/Writers) –
NOUN
Prof. J. Amupitan (Course Editor) – NOUN
Dr. Makanjuola Oki (Programme Leader) –
NOUN

NATIONAL OPEN UNIVERSITY OF NIGERIA

ii
CHM 102
COURSE GUIDE

National Open University of Nigeria

Headquarters
14/16 Ahmadu Bello Way
Victoria Island, Lagos

Abuja Office
5 Dar es Salaam Street
Off Aminu Kano Crescent
Wuse II, Abuja

e-mail: centralinfo@nou.edu.ng
URL: www.nou.edu.ng

Published by
National Open University of Nigeria

Printed 2009

Reprinted 2014

ISBN: 978-058-594-X

All Rights Reserved

iii
iv

CONTENTS PAGE

Introduction…………………………………………….. iv
The Course…………………………………………….. iv
Course Aims…………………………………………… iv
Course Objectives……………………………………… iv
Working through this Course………………………….. v
The Course Material…………………………………… v
Study Units….…………………………………………. v
Assessment…………………………………………….. v
Tutor-Marked Assignment…………………………..… v
Final Examination and Grading……………………… vi
Summary……………………………………………….. vi

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CHM 102 MODULE 1

INTRODUCTION

Chemistry is an experimental science. Indeed, experiments have played

a vital role in the development of Chemistry. On the one hand,
experiments have provided evidences for testing theories; on the other,
their results have thrown up new questions and puzzles, which required
new insights, giving rise to new theories.

THE COURSE

CHM 102 Introductory Organic Chemistry I (2 Units)

We have divided this course into four units. The first unit provides you
an introduction to bonding in organic molecules, their functional
groups, classification and nomenclature. In Unit 2, we acquaint you
with the basic properties, methods of preparation of the group of
compounds called the alkanes. In the remaining units, we discussed the
chemistry of alkenes (Unit 3), and in Unit 4 we have explained the
importance of the alkynes as well as their preparations and properties.

The guiding theme in the development of these materials is a brief

description of the general properties, the underlying principles of the
preparation and observed trends in the properties of organic
compounds.

COURSE AIMS

The aim of this course is to give you a general introduction to organic

chemistry, giving explanations to observed physical and chemical
properties of organic compounds.

COURSE OBJECTIVES

After studying this course, you should be able to:

 Describe the general features of a covalent bond,

 Define bond length, bond angle and bond energy,
 Explain various types of hybridization of carbon compounds,
 Identify the functional groups present in a molecule,
 Give IUPAC names of various compounds belonging to different
classes, and
 Write the correct structure of a compound from its name.
 Describe the composition and fractionation of petroleum,
 Define octane number and cetane number,
 Discuss the physical properties of alkanes,

1
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

 List the characteristic spectral peaks of alkanes in uv, ir, nmr and
mass spectra
 List the methods for preparation of alkanes and cycloalkanes,
 Discuss the important chemical reactions of alkanes and
cycloalkanes.

WORKING THROUGH THIS COURSE

This course is very important for any student intending to study

Chemistry at any level, as it provides the basic ideas about the guiding
principles for the preparation, classification of organic compounds..
You are, therefore, expected to put some effort in understanding this
course, as some of the knowledge available in this course might not be
so easy to pick up later in your study of Chemistry.

THE COURSE MATERIAL

You will be provided with the following materials:

STUDY UNITS

The following study units are contained in this course:

Module 1

Unit 1 Bonding, Functional Groups, Classification and

Nomenclature of Organic Compounds
Unit 2 Alkanes
Unit 3 Alkenes
Unit 4 Alkynes

ASSESSMENT

There are two components of assessment for this course. The Tutor-
Marked Assignment (TMA) and the end of course examination.

TUTOR-MARKED ASSIGNMENT

The TMA is the continuous assessment component of your course. It

accounts for 30% of the total score. You will be given 4 TMA's to
answer. Three of these must be answered before you are allowed to sit
for the end of course examination. The TMA's would be given to you by
your facilitator and returned after they have been graded.

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CHM 102 MODULE 1

FINAL EXAMINATION AND GRADING

This examination concludes the assessment for the course. It constitutes

70% of the whole course. You will be informed of the time for the
examination. It may or may not coincide with the university semester
examination.

SUMMARY

This course intends to give you an introduction to the study of organic

chemistry on topics ranging from bonding to physical and chemical
properties of organic compounds. At the end of this course, you will be
able to answer questions of this nature.

To prepare basic organic compounds, explain observable trends in the

physical and chemical properties of compounds within a given group,
the relationship in properties of compounds among groups of
compounds, predict the properties of organic compounds after
identification.

We wish you success.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

MAIN
COURSE

CONTENTS PAGE

Module 1 ……………………………………………………… 1

Unit 1 Bonding, Functional Groups, Classification

and Nomenclature…………………………….…… 1
Unit 2 Alkanes…………………………………….……… 43
Unit 3 Alkenes…………………………………….……… 67
Unit 4 Alkynes…………………………………….……… 92

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CHM 102 MODULE 1

MODULE 1

Unit 1 Bonding, Functional Groups, Classification and

Nomenclature
Unit 2 Alkanes
Unit 3 Alkenes
Unit 4 Alkynes

UNIT 1 BONDING, FUNCTIONAL GROUP

CLASSIFICATION AND NOMENCLATURE

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 The Covalent Bond
3.2 Structural Formulas
3.3 Orbital Hybridization
3.3.1 sp3-Hybridisation
3.3.2 sp2-Hybridisation
3.3.3 sp-Hybridisation
3.4 Functional Group Classification
3.5 Nomenclature of Organic Compounds
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Readings

1.0 INTRODUCTION

Organic Chemistry is a highly organized discipline. It is the study of the

relationship between the structures of molecules and their reactions. We
will begin our study with the type of bonding and structural aspects of
the molecules. You are already familiar with the fact that compounds
can be broadly divided into two classes, ionic and covalent. Ionic
compounds are composed of positively and negatively charged ions
which are held together by electrostatic forces. Since ions can be
regarded as spheres having symmetrical distribution of charge, no
particular direction can be assigned to such type of bonding. For
example, in NaCl lattice, Na + and C1 ions are held together by
electrostatic forces; no Na + ion can be regarded as bonded to a
particular C1 ion. In other words, there is no such entity which can be
called as NaC1 molecule. In fact, the electrostatic forces operate
between a particular ion (Na+) and all its neighbouring ions (C1) of
5
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

opposite charge. On the other hand, in covalent compounds, molecules

are the structural units. In contrast to the ionic compounds, in covalent
compounds, the molecules are formed by the sharing of electron pair(s)
between the constituent atoms. The bonds formed by sharing of pair(s)
of electrons are called covalent bonds. Since in organic compounds, the
bonds formed by carbon atom are covalent in nature, we will study some
features of the covalent bonding in detail. We will then explain shapes
of molecules using the concept of hybridization. We shall also learn
various types of functional groups present in organic compounds and
classify these compounds into various classes on the basis of the
functional groups. Finally, we will study, how to name the compounds
belonging to various classes.

2.0 OBJECTIVES
After studying this unit, you should be able to:

 describe the general features of a covalent bond

 define bond length, bond angle and bond energy
 explain various types of hybridization of carbon compounds
 identify the functional groups present in a molecule
 give IUPAC names of various compounds belonging to different
classes
 write the correct structure of a compound from its name.

3.0 MAIN CONTENT

3.1 The Covalent Bond

The sharing of electrons to form a covalent bond leads to an increase in
electron density in between the nuclei. In such an arrangement, the
arrangement, the forces holding the atoms together are also electrostatic
in nature; but this time the forces operate between the electrons of one
atom and the nucleus of the other. Such a system has lower energy and
is more stable as compared to the energy of isolated atoms. It is so
because each electron is now attracted by two nuclei. As a result, the
formation of the bond is accompanied by the release of the energy. The
same amount of energy has to be supplied to break that particular bond.
The amount of energy required to break a particular bond (expressed in
terms of kJ mo1-1) is called its bond dissociation energy. You should
not confuse bond dissociation energy with another term bond energy
which is an average value for a particular bond. The difference in these
two energies can be illustrated by taking the example of methane, CH4.
If the C – H bonds are successively broken as shown below, then the
bond dissociation energy for each step is as indicated on the right hand
side.

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CHM 102 MODULE 1

Bond Dissociation Energy

CH4 
 H.  .CH3 427 kJ mo1-1
CH3 
 H. : CH2 460 kJ mol-1
CH2  H . : CH 435 kJ mo1-1
CH  H . : C. 339 kJ mo1-1

You can see from these values that the dissociation energies are different
for each C-H bond breakage. On the other hand, bond energy is a single
average value which can be obtained as,

Bond energy of the C-H bond = 427 + 460 + 435 + 339 kJ mo1-1
4

= 1661 kJ mo1-1 = 415.25 kJ mol-l

4
Thus, the C-H bond energy in methane is one-fourth of the energy
required for the following change.
.
. .
CH4 C. + 4 H.

Clearly, if the molecule is diatomic, then bond dissociation energy and

bond energy are the same. Generally, bond dissociation energy values
are more useful.

Table 1.1: Lists the bond energies and bond dissociation energies for
some bonds in kJ mol-l (at 298 K and 1 atm, pressure).

Table 1.1: Bond Energy and Bond Dissociation Energy Values in kJ

mol-l

Bond Bond Bond Bond Bond Bond Bond Bond

Energy Energy Energy Energy Dissociation Dissociation
H-H 436 N-N 163 CH3-H 427 Ph-OH 341
F-F 158 N=N 409 CH3CH2-H 418 Ph-NH2 381
Cl-Cl 242 N≡N 945 CH2CH2CH2-H 410 Ph-F 485
Br-Br 193 O-H 463 (CH3)2CH-H 395.5 Ph-Cl 406
l-l 151 0=0 497 CH3-CH3 368 Ph-l 272

H-Cl 424.8 C-O 334.7 CH3-F 451

H-Br 364 C=O 94.5 CH3-Cl 349
H-l 297.1 O=C=O 803.3 CH3-Br 293
C-H 414 C-N 284.5 CH3-l 234
C-F 484 C=N 15.l HO-H 498
C-Cl 338 C=N 64.1 CH3O-H 427
C-Br 276 N-H 89.1 CH3-0H 383
C-1 238 N-O 00.8 Ph-H 431
C-C 348 N=O 04.7 PhCH2-H 356
C=C 612 S-H 347.3 Ph-CH3 389
C≡C 813 S-S 25.9 PhO-H 356
S=O 97.9

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

There are two more parameters associated with a covalent bond which
determine the shape of a molecule and are known as bond length and
bond angle. Bond length can be defined as the average distance between
the nuclei of the atoms which are covalently bound together. Bond angle
can be defined as the angle between the atoms, forming the bonds to the
same atom. Table 1.2 gives the bond lengths for some of the bonds.

Table 1.2: Bond lengths for some of the bonds

Bond Bond length/pm Bond Bond length/pm

H-H 74 C-F 142
C-H 112 C-Cl 177
C-C 154 C-Br 191
C=C 134 C-l 213
C≡C 120 C-O 143
F-F 144 C=O 120
Cl-Cl 198 N-H 103
Br-Br 228 N-N 147
l-l 266 N=N 130
C-C in C6H6 139 C=N 130
O-H 97 C≡N 110

1 pm =1 picometer = 10-12m

From these values of bond lengths, we can conclude that:

(i) bond length decreases with the increase in multiplicity of the

bond. Thus, the decreasing – order for bond lengths for
carbon – carbon bonds is
C-C > C = C > C≡C.
(ii) bond lengths increase with the increasing size of the bonded
atoms, i.e., the increasing order of bond lengths is C-H < C-F <
C-Cl < C-Br < C-l.

We will study more about bond lengths and bond angles later in Sec.
1.4, when we discuss hybridization. You will see in the later units in this
course how important these parameters of a bond are in deciding the
chemical reactivity of a compound.

Before proceeding further, let us study something about how the

structures for organic compounds are written.

3.2 Structural Formulas

The structural formula of a compound is its Lewis structure, which
shows how various atoms are connected to each other. You are already
familiar with Lewis structures of some of the compounds. Some
examples are:

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CHM 102 MODULE 1

H H H H

H–C– C–H C =C H–C=C-H

H H H H
ethane ethylene acetylene

To save space and time, these structures are represented by condensed

formulas which do not show the bonds. For example, the condensed
formula for ethane can be written as CH3CH3.

Similarly, we can write condensed structural formula for

H H

H – C – C - Cl as CH3CH2Cl

H H
ethyl chloride

N.B. Remember that all the representations of the formulas are in two
dimensions but actually molecules are three-dimensional in nature.

and for

Repeating units such as (- CH2 -) in the structural formula can be

enclosed in brackets and hence hexane.

can be written as CH3(CH2)4CH3.

Condensed formulas for compounds having multiple bounds can be
written as show below:

H2C =CH2 HC = CH
ethylene acetylene

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

For simple compounds, it is easy to write the condensed formulas. But,

when the molecules are complex, these formulas look rather awkward
and can be further abbreviated. These representations are called line or
skeletal structures. Here, the Hydrogens are not shown and each end
and bends represents the carbon atoms as shown below for some cases:

Compound Line structure

The skeletal structures
or line structures show
only the carbon-
carbon bonds

CH3CH2CH2CH2CH3
pentane

Having understood the above representations, answer the following

SAQ.

SELF ASSESSMENT EXERCISE 1

Write the condensed formulas for the following compounds:

1.

Bonding, Functional Group

10 Classification
CHM 102 MODULE 1

2.

3.3 Orbital Hybridisation

Properties and chemical reactions of most organic molecules can be

easily explained by considering the molecules to be formed by sharing
of electron pairs between the atoms. Another approach to formation of
molecules is the molecular orbital method. Organic chemists have for
many years employed a bonding model that combines elements of
molecular orbital theory with Lewis model of formation of covalent
bond by electron sharing. This model was proposed by Pauling in 1930
and is based on the concept of orbital hybridization. This model uses the
terminology of molecular orbital theory but treats the bonds between the
atoms as though they are localized, as in the case of diatomic molecules.
In other words, it is a sort of localized molecular orbital treatment of
the bond.

You have already studied that various types of orbital hybridization is

possible depending upon the number and nature of the orbitals involved.
In this unit, we will restrict our discussion to the hybridization involving
s and p orbitals. Let us now study each type of hybridization involving s
and p orbitals, in detail, to understand this concept and its use in
explaining the formation of molecules.

Recall that: Hybridization is a theoretical concept which enables as

realistic medelling of molecular structure as possible.

The orbitals which undergo hybridization should not be energetically

much different.

The number of hybrid orbitals generated is always equal to the number

of atomic orbitals combined

Sp3 is pronounced as s-p-three and not sp cube.

The hybrid orbitals are obtained by mathematical combinations of

atomic orbitals.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.3.1 sp3-Hybridisation

Let us consider the simplest organic compound, methane, having the

molecular formula CH4. You can recall that carbon has the electron
configuration 1s2 2s2 2px1 2py1. Since only two unpaired electrons are
there, one may expect that it should form only two bonds with two
hydrogen atoms to form CH2. But actually it forms four bonds with four
hydrogen atoms to give CH4. Pauling proposed that this could be
explained by using orbital hybridization. In this method, atomic orbitals
are mixed to yield the new hybrid orbitals. In this case, in the first step
on of the 2s electrons is promoted to the 2pz orbital, electron
configuration can then be written as 251 2px1 2y1 2pz1. Bond formation
with these pure atomic orbitals would lead to the situation where the
bond formed by one 2s electron will be different from the bonds formed
by three 2p electrons. But, in methane molecule, all the four bonds are
equivalent. In order to explain this, the idea of orbital hybridisation was
invoked. In this process, one 2s and three 2p and three 2p orbitals on
hybridization yield a set of four new equivalent orbitals. These new
orbitals are called hybrid orbitals. Since they are formed by combining
one s and three p orbitals, they are called sp3 hybrid orbitals. All the four
sp3 hybrid orbitals are of equal energy and each one of them has 25% s
character and 75% p character.

These sp3 hybrid orbitals are shown in Fig. 1.1. You can see in Fig. 1.1
(a) that the

Carbon Carbon in methane

atom

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CHM 102 MODULE 1

Fig. 1.1: a) Hybridisation of one 2s and three 2p orbitals to yield four sp3 hybrid
orbitals. b) Four sp3 hybrid orbitals directed towards the corners of a
tetrahedron: small back lobes are not shown. c) Formation of methane molecule.

Sp3 hybrid orbital has two lobes of unequal size separated from each
other by a node. This situation is similar to a p orbital but with the
difference that here one lobe is very small and the other is very large. In
other words, in sp3 hybrid orbitals, the electron density is concentrated
in one direction which leads to greater overlap as compared to pure
atomic orbitals. Hence, the bonds formed by such orbitals will be
stronger and more stable in comparison to those formed by using pure
atomic orbital. The spatial orientation of these orbitals is obtained by
mathematical calculations and is shown in Fig. 1.1 (b). This is in
accordance with the VSEPR theory which you had studied. You can see
in the figure that these orbitals are directed towards the corners of a
tetrahedron and the bond angle between any two sp3 hybrid orbitals is
109.5o. In methane molecule, each of the four sp3 hybrid orbitals
overlaps with 1s orbital of four hydrogens as shown in Fig. 1.1 (c).

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Note that the bonds so formed, i.e: the C – H bonds, are  (sigma)
bonds. If instead of combining with hydrogens, the hybrid orbital forms
a bond with the similar hybrid orbital of another carbon atom, then a C –
C bond will result instead of the C – H bond. The C-C has a bond length
of 154 pm and a bond energy of 348 kJ mol-1. You will study more
about the compounds involving sp3 hybridisation in the latter part of this
course.

3.3.2 Sp2-Hybridisation
In a molecule like ethylene, where there are not enough hydrogen in the
molecule to form six C - H bonds, another type of hybridization has to
be thought of.

In this type of hybridization, as the name indicates, the 2s orbital of the

carbon is hybridized with only two of the three available 2p orbitals, as
shown below.

Since three orbitals are hybridized, three equivalent sp2 hybrid orbitals
are obtained. We shall now explain sp2 hybridisation using ethylene as
an example.

According to the VSEPR theory, these orbitals are oriented in space

making an angle of 120o with each other as shown in Fig. 1.2(a). Note
that the three sp2 hybrid orbitals are in one plane. The third p orbital
which is not utilized for hybridization is perpendicular to the sp2 hybrid
orbitals and is show in red colour in Fig. 1.2(a).

When two such sp2 hybridised carbon atoms form a bond, the C – C
bond formed is again a  bond. If the rest of the sp2 hybrid orbitals on
each carbon atom overlap with 1 s orbital of the two hydrogen atoms,
then as shown in Fig. 1.2 (b) the two unhybridised p orbitals on the two
carbon atoms are parallel to each other. These p orbitals can overlap
sideways to yield a second bond, known as  (pi) bond which is shown
in Fig. 1.2(c). The C = C bond length for ethylene molecule so obtained
is 134 pm. You can compare this value with C – C single bond length as

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CHM 102 MODULE 1

given before in case of ethane. You will study in detail, the compounds
having sp2 hybridised carbon atoms such as alkenes and dienes.

(a) You are aware that:

(i)  bonds are formed by the edge-on overlap of pure (s and p) or

hybrid orbitals. The electron density in  bonds is maximum
along the internuclear axis.
(ii)  bonds are formed by sideways overlap of p orbitals.  bonds
have maximum electron density above and below the
internuclear axis.

(a)

(b)

(c)
Fig. 1.2: (a) sp2 hybrid orbitals. (b) Formation of C – C δ bond. (c) Formation of
a π bond in ethylene molecule.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Activity

Make a model of ethylene molecule and convince yourself that it is flat

in shape with the two carbons and their substituent hydrogens lying in
one plane. However, the  bond is at right angles to this plane.

SELF ASSESSMENT EXERCISE 2

Predict the percentage of s and p character in sp2 hybrid orbitals.

3.3.3 Sp-Hybridisation

Let us now consider the third type of hybridization involving s and p

orbitals in cases where a triple bond is stipulated. In carbon atom when
2s and only one of the three 2 p orbitals hybridise as shown below, the
hybridization is known as sp- hybridization. This leads to two new
equivalent sp hybrid orbitails as shown in fig 1.3(a)

(c)

Fig. 1.3: (a) two sp hybrid orbitals. (b) Formation of one  (sigma) bond.
(c) Formation of two  bonds.

Acetylene is a linear molecule having cylindrically symmetrical 

electron density about the internuclear axis.

These two orbitals are oriented in space at an angle of 180o according to

the VSEPR theory. Let us study sp-hybridisation using acetylene as an
example. When one of the two sp hybrid orbitals on each carbon atom

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CHM 102 MODULE 1

combines with another, a C – C sigma bond is formed. The second sp

hybrid orbital on each carbon forms a sigma bond with 1s orbitals of
two hydrogens, as shown in Fig. 1.3 (b). This leaves two p orbitals on
each carbon atom which are not used in sp hybridization. These p
orbitals are perpendicular to each other and also to the sigma bond.
These p orbitals can overlap laterally to give rise to two  bonds. Such
a bond is called a triple bond and we get the acetylene molecule, as
shown in Fig. 1.3 (c) The C = C bond in acetylene has a bond length of
120 pm and the H – C – C angle is 180o which shows that it is linear.
Compounds having triple bond are called alkynes and will be dealt with
in detail in Unit 5 of module 2. We can sum up the above information as
shown in Table 1.3

Table 1.3: Bond characteristics and hybridization of carbon in

simple molecules

Compound Hybridisation Bond length Bond Nature of carbon-

of carbon atom in pm angle carbon bonds

Ethane Sp3 154 190.5o Single

Ethylene Sp2 134 120o Double

Acetylene Sp 120 180o Triple

From the data given in the Table 1.3 we can conclude that

(i) in the hybrid orbitals, as the s character increases, bond length

decreases.
(ii) as the bond order increases, the bond length decreases
Before proceeding to the next section, answer the following SAQ.

SELF ASSESSMENT EXERCISE 3

Indicate the type of hybridization for each of the carbon atoms in the
following compounds:

1. CH3  C  C CH 2  CH3

H
|
2. H–C=O

3. H2C=C=CH– CH3

4. CH3-C≡C-C≡C-CH3

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.4 Functional Group Classification

A systematic study of chemistry or for that matter any other branch of

science, is not possible without arranging the subject matter in a logical
manner when sufficient data has accumulated. In case of inorganic
chemistry, formulation of the periodic table stimulated not only the
search for missing elements but also led to the understanding of the
periodic behaviour. In organic chemistry, as the number of known
organic compounds runs into millions, it is very difficult to study each
and every compound individually. Thus, by grouping similar
compounds together in a class or a family, it is easier to understand their
properties, reactions etc. One way of such classification is based on the
functional groups. A functional group can be defined as an atom or a
group of atoms in a molecule which exhibits characteristic chemical
properties. Such chemical properties exhibited by the functional group
are more or less constant for various transformation of the functional
group and do not affect the rest of the molecule. The advantage of such a
classification based on functional groups is that in addition to logically
systematizing the organic compounds, the properties of the compounds
can be predicted just by looking at their structures, i.e., by knowing the
type of functional group present. Table 1.4 lists a number of important
functional groups. You will study each class of compounds in detail in
the forthcoming blocks of this course.

Table 1.4: Functional Groups

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CHM 102 MODULE 1

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

 Here, X stands for halogens (F, Cl, Br and 1), R stands for the
alkyl group and Ar stands for the aryl group.
 The names given in Column 4 are common names.
 At this stage, you should not worry about the last column of the
table. We will refer back to this column while studying
nomenclature of organic compounds in the next section.

The compounds which are listed in the first category in Table 1.4 are the
compounds which contain only carbon and hydrogen. These compounds
are also called hydrocarbons. The hydrocarbons can be classified as
aliphatic, alicylic or aromatic. In the aliphatic hydrocarbons, the
carbon atoms are linked to each other to form chains (straight of
branched). The aliphatic hydrocarbons can be further classified as
saturated or unsaturated. The saturated hydrocarbons contain the carbon
and hydrogen atoms linked to each other by single bonds and are called
alkanes. The unsaturated hydrocarbons are of two types: the one
containing double bond as the functional group are named as alkenes;
the other containing a triple bond as the functional group are known as
alkynes.

In the alicylic hydrocarbons, the carbon atoms are arranged in rings to

yield cyclic structures. These compounds are also known as
cycloalkanes.

The aromatic hydrocarbons include benzene and those compounds

which resemble benzene in their properties.

In fact, the hydrocarbons provide a backbone to which various

functional groups may be attached to yield an enormous variety of
organic compounds.

The alkyl groups, generally represented by R, are derived from alkanes

by removing one hydrogen. The simplest alkyl group is methyl group
(CH3-C) which is derived alkane, methane (CH4). Common alkyl
groups are listed in Table 1.7, Similarly, aryl groups denoted by Ar, are
obtained from benzene and its derivatives by removing on hydrogen.
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CHM 102 MODULE 1

The simplest aryl group is phenyl group (C6H5- and is

abbreviated as Ph. In general, aryl halide (Ar-X) can refer to any of the
following:

Let us now study about the structural features of some classes of

aliphatic compounds. The compounds in which the carbon and oxygen
atoms are linked by a single bond can be classified as alcohols or
ethers, depending upon the number of alkyl groups attached to oxygen.
In alcohols, oxygen is linked to only one alkyl group and one hydrogen;
but in ethers, oxygen has two alkyl groups attached to it. The
compounds containing carbon and oxygen linked by a double bond
(i.e C = O, which is called carbonyl group, can be classified as
aldehydes or ketones, depending on whether the number of alkyl
groups attached to carbonyl carbon is one or two, respectively. If
instead of an alkyl group, one hydroxyl (-OH) group is attached to the
carbonyl group, a class of compounds known as carboxylic acids.

O
||
(R – C – OH) is obtained. A number of carboxylic acid derivatives are
obtained by

O
||
replacing the hydroxyl group by halogens, - NH2 – O – C - R or – OR
groups.
O
||
Accordingly, these compounds are called acid halides (R – C – X),
amides

O O O O
|| || || ||
(R – C – NH2), anhydrides (R – C –O– C – R) and esters (R – C- OR).
They are also called functional derivatives of carboxylic acids, as they
are obtained by the changes in the functional group.

21
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

In a similar manner, compounds having carbon-nitrogen single bond are

called amines. The amines can be of three types: primary, secondary
and tertiary amines depending upon whether the number of alkyl
groups attached to nitrogen is one, two or three. The carbon-nitrogen
double bond is characteristic of the class of compounds known as
imines while compounds having carbon-nitrogen triple bond are called
nitriles. Then we have alkyl halides which have their unique
importance in the transformation of functional groups which you will
realize when you study their reactions in the following blocks. The
sulphur analogs of alcohols and carboxylic acids are known as thiols
and suphonic acids, respectively.

Parallel to the classes discussed above for aliphatic compounds, we

have aromatic compounds in which benzene forms the backbone to
which various functional groups mentioned above can be attached to
yield similar classes of aromatic compounds, like aryl halides,
arylamines, phenols, aromatic carbonyl compounds, aromatic acids and
their derivatives, etc. As you have seen in Table 1.4, R is generally used
to represent an alkyl group; the corresponding aromatic compounds are
obtained by replacing R by Ar which denotes an aryl group; this is
shown in Table 1.4 in case of alcohol and phenol. In the next section, we
well study about the nomenclature of these compounds. Before that
attempt the following SAQ to check your understanding about the
functional groups.

SELF ASSESSMENT EXERCISE 4

Encircle and name the functional groups present in the following

compounds:

1. CH3 – CH = CH – CH2OH

2. CH3COCH2CH2 – O – CH3

O
CH3
3. CH2- N –CH3

O O

4. OHCCH2CH – C – O – C – CH2CH3

CH3

22
CHM 102 MODULE 1

3.5 Nomenclature of Organic Compounds

The earliest attempts to name organic compounds were based either on

their origin or on their properties. For example, citric acid was named so
because of its occurrence in citrus fruits. The aromatic compounds were
called so because of their characteristic odour (Greek: aroma, fragrant
smell). Examples are oil of wintergreen and vanillin (a constituent of
vanilla also used as a flavouring agent) which were called aromatic due
to their characteristic fragrance. With the advancement and growth in
the knowledge of chemistry, the number of known organic compounds
has increased rapidly. Also, with the increase in the number of carbon
atoms, the number of possible isomers for hydrocarbons (without any
functional group) becomes very large (see Table 1.5).

Isomers are the compounds that have identical molecular formulas but
differ in the ways in which the atoms are bonded to each other. For
example, four carbons in a hydrocarbon having molecular formula
C4H10 can be arranged in the two different ways:

Straight chain H3C – CH2 – CH2 – Ch3

Common name; normal butane or n-butane Branched chain

CH3
|
H3C – CH – CH3 with a common name 150 – butane.

Thus, n-butane and isobutene are isomers.

Table 1.5: Possible Number of Isomers for Hydrocarbons

Number of carbon
Atoms in the
Hydrocarbon 4 5 6 7 8 9 10 12 15 20
Number of possible
Isomers 2 3 5 9 18 35 75 355 4,347 366,319

Having learned about the variety of functional groups, you can imagine
that the nature and position of functional groups present can raise these
numbers many fold. Under such a situation, it is next to impossible to
learn the names randomly assigned to the compounds, especially when
there is no correlation of the name to the structure of the compound.
This necessitated the need to have a systematic nomenclature for
which the International Committee of Chemists met at Geneva in 1892.
The work was carried on by the International Union of Chemists
(I.U.C.) which gave its report in 1931, known as the I.U.C. system of
nomenclature. As the nomenclature is always undergoing modifications
and revisions, the latest rules which are widely accepted were

23
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

recommended by the Commission on Nomenclature of Organic

Chemistry of the International Union of Pure and Applied Chemistry
(I.U.P.A.C.). We will now study this system in detail.

Since the nomenclature of other classes of compounds is based on the

nomenclature of alkanes, let us start the study of nomenclature with the
alkanes. Alkanes are represented by the general formula CnH2n+2 where
n can be 1,2,3,4… etc. The first four alkanes retain their original or
nonsystematic names. The names of alkanes higher than these start with
a prefix (Greek or Latin words) which indicates the number of carbon
atoms in the chain and end with suffix-ane. The IUPAC names for
various alkanes having different chain lengths are given in Table 1.4.
The unbranched alkanes have their common names as normal alkanes or
n-alkanes.

Compounds that differ from each other in their molecular formulas by

the unit – CH2- are called members of a homologous series. Thus, the
compounds listed in Table 1.6 belong to a homologous series.

Table 1.6: IUPAC Names of straight chain alkanes having general

formula CnH2n+2

n. Formula Name n. Formula Name

1 CH4 methane 11 CH3(CH2)CH3 undecane
2 CH3CH3 ethane 12 CH3(CH2)10CH3 dodecane
3 CH3CH2CH3 propane 13 CH3(CH2)11CH3 tridecane
4 CH3(CH2)2CH3 butane 14 CH3(CH2)12CH3 tetradecane
5 CH3(CH2)3CH3 pentane 15 CH3(CH2)13CH3 pentadecane
*
6 CH3(CH2)4CH3 hexane 20 CH3(CH2)18CH3 icosane
7 CH3(CH2)4CH3 heptane 30 CH3(CH2)28CH3 triacontane
8 CH3(CH2)6CH3 octane 40 CH3(CH2)38CH3 tetracontan
9 CH3(CH2)7CH3 nonane 50 CH3(CH2)48CH3 pentacontane
10 CH3(CH2)6CH3 decane 100 CH3(CH2)98CH3 hectane

* Prior to 1979 version of IUPAC rules, icosane was spelled as eicosane.

The branched chain alkanes are named by using the following steps:

1. The longest continuous chain of carbon atoms is taken as the

parent hydrocarbon. For example, in the compound shown below,
the parent hydrocarbon is heptane and not the hexane.

2. Identify the substituent alkyl groups attached to the parent chain.

24
CHM 102 MODULE 1

Some common alkyl groups are listed in Table 1.7. You can locate that
both the substituents in the example cited above are methyl groups.

Table 1.7: Common Alkyl groups

The IUPAC system of nomenclature has retained some of the older

names for branched alkyl groups such as isopropyl, isobutyl, sec-butyl,
and neopentyl.

Note that the numbering of carbon atoms is from the point of attachment
of the group to the parent chain.

3. The parent carbon chain is then numbered in such a way that the
substituents get the lowest possible numbers. The carbon atoms
in the above compound can be numbered as;

Can you guess which of the two numbering systems is correct: The first
possibility locates the methyl groups at carbons 4 and 5 and the second,
at carbons 3 and 4. Certainly, the second way of numbering the carbon
chain is correct.

25
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

4. Perfixes di, tri, tetra, penta etc, are used when the substituents
occur more that once. Since in the above compound the methyl
substituent is occurring twice, the name is prefixed with di for the
above compound.

5. The name of the compound is written by writing the location and

name of the substituents followed by the name of the parent
alkane. Thus, the above compound can be named as 3,
4-dimethylheptane. Note that a comma is used to separate the two
numbers and the numbers are separated from names of groups by
a hyphen. Also note that there is no blank space between the
name of the last substituent and the parent alkane.

6. When more than one type of alkyl groups are present, then they
are cited in the name in the alphabetical order, regardless of their
location in the principal chain.

The numerical prefixes di, tri, tetra, etc. and hyphenated prefixes such
as sec-tert – are not considered in determining the alphabetical order but
prefixes iso, neo, cyclo are considered for alphabetizing. To understand
it, let us consider the examples given below:

Note that here ethyl is cited before methyl, in spite of its higher location
number.

Similarly, the compound shown below,

can be named as 4-isopropyl-5,5-dimethylnonane or 4-(1-methylethy1)-

5, 5-dimethylnonane.

26
CHM 102 MODULE 1

7. The branched chain substituents, such as 1-methylethyl shown in

step 6, are numbered starting from the carbon attached directly to
the parent chain. Table 1.7 shows the numbering for the branched
substituents listed there. The longest carbon chain is selected and
the substituents are named according to the rules listed above for
compounds having unbranched substituents. Note that the name
and numbering of branched substituent is written in brackets in
order to separate it from the numbering of the main chain.

8. The alkyl substituents can be further classified as primary,

secondary or tertiary. An alkyl group is called a primary alkyl
group if the carbon atom at the point of attachment is bonded to
only one other carbon. For example, R – CH2 – is a primary alkyl
group. Similarly, a secondary alkyl group has two alkyl groups
bonded to the carbon atom taken as the point of attachment to the
main chain. Thus, a secondary alkyl group can be written as
shown below:

R
|
R – C -
| point of attachment
H
secondary alkyl group

Similarly, a tertiary alkyl group has three carbon atoms bonded to the
carbon atom taken as point of attachment. Thus, a tertiary alkyl group
can be represented as shown below:

R
|
R – C -
| point of attachment
R
Tertiary alkyl group

9. When more than one carbon chains of equal length are available,
the numbering is done considering the following points:

(a) The principal chain should have the greatest number of

side chains. For example, in the compound shown below;

27
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

The chain having numbering in red colour has four side chains while the
chain marked with numbers in black colour has three side chains. So the
principal chain is the one which is marked in the red colour. Hence, the
name is 3-ethyl-2,5,6-trimethyloctane

(b) The chain having the lowest number for substituents is chosen as
the principal chain. In the compound shown below;

If the numbering is done as shown in black colour, the name would have
substituents at positions 3,4 and 5. But, if the carbon chain numbered in
red colour is taken as the principal chain, then the substituents get the
numbers 2, 3 and 4, which is obviously the correct choice.

Till now we were studying the nomenclature of alkanes. Let us now

study how various compounds having different functional groups are
named. In case of compounds which have a functional group, the
functional group gets precedence over the alkyl substituents. At this
stage, you refer back to Table 1.4 where IUPAC prefixes and suffixes
for various classes of compounds are given.

Alkenes: The suffix ane of the parent hydrocarbon is changed to ene and
the functional group (a double bond in this case) is given the lowest
possible number.

Some examples are:

CH2=CH2 CH3CH=CH2
ethene propene
(common name: ethylene)

4 3 2 1 1 2 3 4 5
CH3 CH2 CH=CH2 CH3 – CH = CH – CH2 – CH3
but-l-ene pent-2-ene

Alkynes: In this case suffix ane of the parent hydrocarbon is changed to

yne. As expected, here also the functional group is given the lowest
number.

28
CHM 102 MODULE 1

When both double and triple bonds are present, then the double bond
gets the lower number. Thus, for the compound show below;

1 2 3 4 5
CH2 = CH – CH2 – C ≡ CH
The correct name is pent – l-ene-4-yne

Alkyl halides: The alkyl halides are the halogen derivatives of alkanes.
The halogens present are usually F, Cl, Br and 1. The common names
are arrived at by writing the name of alkyl group followed by the name
of the halide. Examples are shown below:

In the IUPAC system of nomenclature, prefix halo- (i.e., fluoro, chloro-,

bromo or iodo-) is used to give the lowest number to the carbon atom to
which the halogen is attached. For example, some halogen compounds
are named below:

When more than one type of halogen atoms are present, their names are
arranged in alphabetical order as shown in the next example,

5-bromo-1-chloro-2-iodo-4-methylpentane

29
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Alcohols: Alcohols are the compounds having hydroxyl (-OH) group

attached to the alkyl chain. The common names of the alcohols are
written by specifying the alkyl group followed by the word alcohol, e.g.

In the IUPAC nomenclature, suffix ol is used instead of final e of the

parent hydrocarbon. The position of the hydroxyl group is given by
assigning the lowest possible number to the carbon atom carrying it.
Some examples are:

Ethers: The common names for ethers are derived by naming the two
alkyl groups in alphabetical order followed by the word ether. This is
illustrated in the examples given below:

CH3OCH3 CH3OCH2CH3
dimethyl ether ethyl methyl ether

In the IUPAC system, ethers are named as alkoxyalkanes. The larger of

the two alkyl groups is chosen as the hydrocarbon chain. For example,
the compound,

1 2
CH3 OCH2 CH3

is named as 1-methoxyethane and not as ethoxymethane. Similarly, the

compound,

has the name 1-ethoxy-2-methylpropane.

30
CHM 102 MODULE 1

Aldehydes: Lower members of this class are commonly named after the
acids that they form on oxidation. For example, HCHO, formaldehyde is
named so because it forms formic acid (HCOOH) on oxidation.

In theIUPAC system of nomenclature, they are named as alkanals. The

simplest aldehyde is methanol. Since the aldehyde group – CHO) is
always at the end of the chain, it is always numbered as C – 1 in the
chain, but this number is not specified in the name, i.e. the compound.

is named as 3, 3-dimethylbutanal.

Ketones: The common names for ketones are written similar to ethers,
i.e. the two alkyl groups are written alphabetically followed by the word
ketone. For example, the compound,

O
||
CH3 – C – CH2CH3
is commonly known as ethyl methyl ketone.

O
||
Thus, acetone, CH3CCH3 is also known as dimethyl ketone. The IUPAC
names for ketones are derived by using the suffix one instead of final e
of the parent hydrocarbon. As usual, the position of the carbonyl group
is indicated by the lowest possible number. A few examples are,

Carboxylic acids: Nowhere else in organic chemistry, the common

names are so prevalent as they are among carboxylic acids. Some
examples are listed in Table 1.8 along with both their common and
IUPAC names. For monocarboxylic acids,
31
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

O
||
[i.e. acids having one carboxy (- C – OH) group], the IUPAC names are
derived by replacing e ending of the alkane by oic acid. As for
aldehydes, the carboxyl carbon is numbered 1. However, in case of the
dicarboxylic acids, the final e of the hydrocarbon is not dropped.

Table 1.8: Some Carboxylic Acids

Structure Common Name IUPAC Name

O
||
HCOH Formic acid Methanoic acid

O
||
CH3 – C – OH Acetic acid Ethanoic acid

OH O
| ||
CH3CHCOH Lactic acid 2-hydroxypropanoic acid

CH3(CH2)16COOH Stearic acid Octadecanoic acid

HO2C – CO2H Oxalic acid ethanedioic acid

HO2C(CH2)4CO2H Adipic acid Hexanedioic acid

O
|| Acrylic acid Propenoic acid
CH2 = CHCOH

OH
|
HOOC–CH–CH – COOH
| Tartaric acid 2,3-dihydroxybutanedioic
OH acid

Acyl halides: Acyl halides are commonly named by placing the names
of the halide after the name of the acyl group. The acyl group is obtained
from the carboxylic acid by removal

O O
|| ||
of its hydroxyl portion, i.e. R – C – OH leads to R–C – acyl group. The
acyl group is named by using yl as the ending instead of ending icin the
carboxylic acid. Some examples are:

32
CHM 102 MODULE 1

IUPAC names for acyl groups use the ending oyl instead offending e in
the name of the corresponding hydrocarbon. The acetyl chloride has the
IUPAC name

O
CH3 ||
ethanoyl chloride. Another example is CHC – C1 which is named as
2-methylpropanoyl chloride 2 1
3CH3

Acid amides: The common names for acid amides are derived by
replacing the suffix ic or oic of the carboxylic acid by the suffix amide
as shown below:

O
||
CH3C – NH2
(acetic - acetamide)

The IUPAC name for an amide is derived by appending the suffix amide
to the parent hydrocarbon with the final e dropped. Thus, acetamide has
the IUPAC name ethanamide. Having done this, can you give common
and IUPAC names for

O
||
HC – NH2? These are formamide and methanamide, respectively.

Acid anhydrides: A symmetrical anhydride is named as anhydride of

the parent
O O
|| ||
acid. Thus, CH3 – C – O - C – CH3, the anhydride which is obtained
from ethanic acid (common name: acetic acid) is commonly known as
acetic anhydride. The IUPAC name for this anhydride is ethanoic
anhydride.

For mixed anhydrides, both the parent carboxylic acids are cited in
alphabetical order, followed by the word anhydride, as illustrated below:

33
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

O O
|| ||
H – C – O - C – CH3
ethanoic methanoic anhydride
(common name: acetic formic anhydride)

Ethers: As the ethers contain alkyl and alkanoyl (acyl) groups, they are
named as alkyl alkanoates. The alkyl group is cited first, followed by the
name of the alkanoyl (acyl) portion which is named by replacing the ic
ending of the carboxylic acid by the suffix ate.

methyl ethanoate ethyl ethanoate methylpropanoate

Amines: There are two systems of naming amines. One method names
them as alkylamines and the other calls them as alkanamines. The
alkanamine naming system was introduced by Chemical Abstracts and
is easier to use as compared to the earlier IUPAC system of alkylamine
names. The latest revision of IUPAC rules accepts both systems and
examples below are named in both ways.

Bonding, Functional Group Classification and Nomenclature

(Note that the numbering starts at the carbon and not at the nitrogen of
the amine part).

Primary diamines are named by using the suffix diamine after the name
of the hydrocarbon.

1,4-butanediamine 1,2-pentanediamine

For the secondary and the tertiary amines, the longest alkyl group
present is considered as the parent chain. The remaining alkyl groups are
named as substituents attached to the nitrogen and a prefix N- is used
with the name of the alkyl group.

34
CHM 102 MODULE 1

When used as a substituent, the – NH2 group is named as amino and is

prefixed with a number indicating the carbon atom to which it is
attached.

Nitro compounds: The nitro compounds are named as nitroderivatives

of the corresponding hydrocarbons.

Examples being,

Nitriles: Nitriles are named in the IUPAC system by using the suffix –
nitrile to the name of the hydrocarbon corresponding to the longest
carbon chain. Note that here the carbon of the nitrile group is included in
the numbering of carbon chain and is numbered as position 1. Some
examples are given below:

35
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

When named as a substituent, the – CH group is called a cyano group.

For example, the compound.

O
||
CH3 – C – OCH2CN

is named as cyanomethyl ethanoate.

Thiols: In naming thiols, an ending thiol is used as a suffix to the name

of the corresponding hydrocarbon; for example,

Sulphonic acids: The names of sulphonic acids use the suffix sulphonic
acid with the name of the corresponding hydrocarbon.

Till now, you have studied about the nomenclature of monofunctional

compounds, i.e. the compounds which contain only one functional
group. In polyfuctional compounds were more than one functional
groups are present, one group is identified as the principal functional
group and this principal functional group is used as a suffix in the name
of the compound. The priorities for seletion of principal functional
group are given below in the order of decreasing precedence. The order
is carboxylic acid, sulphonic acid, ester, acid anhydride, acyl halide,
amide, nitrile, aldehyde, ketone, alcohol, thiol, amine, alkyne, alkene,
ethers, halides, nitro.

The order of priority for various functional groups is decided by

considering the following points:

(i) Functional groups that have an IUPAC suffix and terminate a

carbon chain, have .0highest priority, e.g. carboxylic acids and
their derivatives.

36
CHM 102 MODULE 1

(ii) Next are the groups that have a suffix and can be located at any
position in the molecule, e.g. hydroxyl and amino groups.
(iii) Groups having no suffix and which are named as substituents, are
given the lowest priority, Example being the halogens.

Let us study the examples given below which illustrate the nomenclature
of polyfunctional compounds.

Example 1

Here, the functional groups present are a hydroxyl group (- OH) and a
double bond. As per the order given above, the hydroxyl group is the
principal functional group and hence the compound should be named as
an alcohol (an not as an alkene). Hence, its name is pent-4-ene-l-ol.

Example 2

Now, in this case the carbonyl group or more specifically the aldehyde
functional group (- CHO is to be given priority over the hydroxyl group.
Hence, this compound is named as 4-hydroxybutanal.

Example 3

The principal functional group is the keto group. Hence, as shown in the
structure, the numbering of the carbon chain will be done so as to give
this function the lowest number. Thus, the name of name of this
compound will be 4-hydroxy-5-methyl-2-hexanone.

Let us now study the nomenclature of aromatic compounds. The

aromatic compounds can have any of the following types of basic
skeletons:

37
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

(a) Compounds Containing One Aromatic Ring

This class includes benzene and its derivatives. The derivatives of

benzene include the compounds which can have any of the functional
groups discussed before attached to the benzene ring.

(b) Compounds Containing Two Aromatic Rings

Examples being naphthalene and biphenyl.

(c) Compounds Having More Than Two Aromatic Rings

Examples are:

(d) Heterocyclic Compounds

Aromatic compounds containing heteroatoms such as O, N or S in the

aromatic ring are called heterocyclic compounds. Some heterocyclic
compounds are shown below:

38
CHM 102 MODULE 1

At this stage we will study in detail the nomenclature of benzene and its
derivatives only. Although the carbon skeletons for the type of
compounds shown in the categories (b), (c) and (d) are numbered here,
their nomenclature will be dealt at appropriate places in later units of
this course.

(a) Benzene and its Derivatives

A number of monosubstituted benzene derivatives are known by their

special names. These names are in common use for long and hence are
approved by IUPAC. Some examples of these compounds are given
below along with their common and IUPAC names (in brackets).

For disubstituted benzene derivatives, the following three arrangements

of the substituents are possible.

39
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

These arrangements are named using the Greek prefixes ortho-, meta-
and para which are abbreviated as o-, m- and p-. The substituents are
then named in the alphabetical order. This is illustrated in the examples
below:

Dimethyl derivatives of benzene are known as xylenes. The three

xylenes are;

When one substituent is such that it corresponds to the monosubstituted

benzene that has a special name, then this substituent is called the
principal functionality and the compound is named as a derivative of
that parent functionality. For example,

40
CHM 102 MODULE 1

The polysubstituted benzenes are named by identifying the principal

functions and then numbering is done such as to keep the principal
function as number. The other substituents are then given the lowest
possible numbers. This is illustrated in the following examples.

Having studied the nomenclature in detail, attempt the following SAQs

to check your understanding about it.

SELF ASSESSMENT EXERCISE 5

Name the following compounds according to the I.U.P.A.C. system of

nomenclature.

1.

2.

3.

41
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

4.

5.

6.

7.

8.

SELF ASSESSMENT EXERCISE 6

Given below are the names of some compounds. Write their structures

(1) 3-ethyl-3-petanol
(2) 3-methyl-2-buten-1-ol
(3) 2-bromo-4-nitrotoluene
(4) 5-hexyn-2-one
(5) benzoic anhydride
(6) ethyl formate

4.0 CONCLUSION
We have studied the general features of bonds and defined bond lengths,
angles and energy. In addition, the functional groups in molecules have
been identified.

42
CHM 102 MODULE 1

5.0 SUMMARY
In this unit you have studied about the basic features of the covalent
bond which is the bond occurring in all the compounds of carbon and is
responsible for the formation of organic compounds. The formation of
simple organic compounds is explained by using the concept of
hybridization. As these organic compounds are conveniently studied by
grouping the similar compounds together in a class, classification of
organic compounds has been dealt with in detail. The nomenclature of
various classes of the organic compounds is also discussed using simple
examples.

ANSWER TO SELF ASSESSMENT EXERCISE 1

ANSWER TO SELF ASSESSMENT EXERCISE 2

An sp2 hybrid orbital has 33.33% s character and 64.67% p character.

ANSWER TO SELF ASSESSMENT EXERCISE 3

43
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

ANSWER TO SELF ASSESSMENT EXERCISE 4

ANSWER TO SELF ASSESSMENT EXERCISE 5

(a) 3,3-dimethylbutanol
(b) 4-chloro-3-hexanol
(c) 3-hydroxyhexanedioic acid
(d) 2-chloropentanoyl chloride
(e) 2,2,2-trichloroethanal
(f) 4-hydroxy-3-methoxybenzaldehyde
(g) 1,1,1,3,3,3,-hexafluoro-2,2-propanediol
(h) 4-amino-3,5-dibromobenzenecarboxylic acid

6.0 TUTOR-MARKED ASSIGNMENT

1. Expand the following line structures.

44
CHM 102 MODULE 1

2. The structural formula for alene is shown below; illustrate the

formation of bonds in allene by showing the overlap of the
orbitals using a diagram.

H2C = C = CH2
allene

3. Many compounds isolated from natural sources often show more

than one functional group, given below are some such
compounds. Identify the functional groups present in these
compounds.

a substance produced by a beetle to help it float on water.

d)

a metabolite of a seaweed that is poisonous to fish

4. For compounds having molecular formula, C3H5Cl3, write

structural formulas for all possible isomers and name them.

45
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

5. Write the structural formulas and IUPAC names for the following
compounds:

(a) butanolic acid

(b) and its

(i) acid chloride

(ii) acid anhydride
(iii) acid amide
(iv) methyl ester

7.0 REFERENCES/FURTHER READING

R.T. Morrison and R.N. Boyd, Organic Chemistry, (6th Ed.), India:
Prentice-Hall Pvt. Ltd.

Lloyd N. Ferguson, Textbook of Organic Chemistry, (2nd Ed.), Affiliated

East-West Press Pvt. Ltd.

S.M. Mukherji, S.P. Singh and R.P Kapoor, Organic Chemistry, Vol. I
and II Wiley Eastern Ltd.

P.L. Soni and H.M. Chawla, Textbook of Organic Chemistry, (24th Ed.),
Sultan Chand and Sons.

46
CHM 102 MODULE 1

UNIT 2 ALKANES

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Petroleum: A Source of Alkanes
3.1.1 Composition
3.1.2 Fractionation of Petroleum
3.1.3 Synthetic Petroleum
3.1.4 Octane Number
3.1.5 Cetane Number
3.2 Physical Properties
3.3 Spectral Properties
3.4 Preparation of Alkanes and Cycloalkanes
3.4.1 Wurtz Reaction
3.4.2 Kolbe’s Electrolytic Method
3.4.3 Hydrogenation of Unsaturated Hydrocarbon
3.4.4 Reduction of Alkyl Halides
3.4.5 Decarboxylation of the Carboxylic Acid
3.4.6 Preparation of Cycloalkanes
3.5 Reactions of Alkanes
3.5.1 Halogenation
3.5.2 Nitration
3.5.3 Isomerization
3.5.4 Aromatisation
3.5.5 Pyrolysis
3.5.6 Combustion
3.5.7 Reactions of Small Ring Compounds
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

Alkanes are saturated aliphatic hydrocarbons. You have already learnt in

your previous classes that the saturated aliphatic hydrocarbons have the
general formula, CnH2n+2, Because of their zig-zag patterns due to the
tetrahedral geometry of sp3 hybridized carbon, carbon atoms which are
close together often join up with expulsion of two hydrogen atoms to
form a ring. Such ring compounds are referred to as cyclic aliphatic
hydrocarbons, also called alicyclic hydrocarbons or cycloalkanes which
have the general formula, CnH2n.

47
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Alkanes are also known as paraffins. The name paraffin comes from
two Latins words, “Paraum and affinis”, which mean “little affinity”.
This name was suggested because these hydrocarbons were apparently
unreactive. It is observed that, under ordinary conditions, alkanes are
inert toward reagents such as acids, alkanes, oxidizing and reducing
agents, halogenation, pyrolysis, aromatization, etc. Many of these
reactions proceed through the formation of highly reactive free radicals.

In this unit, first we shall discuss composition and fractionation of

petroleum, as it is the main source of alkanes. Then we shall discuss the
preparation, physical properties and spectral properties of alkenes.
Finally, we shall study some chemical reactions of alkanes and
cycloalkanes.

2.0 OBJECTIVES

After studying this unit, you should be able to:

 describe the composition and fractionation of petroleum

 define octane number and cetane number
 discuss the physical properties of alkanes,
 list the characteristic spectral peaks of alkanes in uv, ir, nmr and
mass spectra
 list the methods for preparation of alkanes and cycloalkanes
 discuss the important chemical reactions of alkanes and
cycloalkanes.

3.0 MAIN CONTENT

3.1 Petroleum: A Source of Alkanes

Petroleum is the chief of source of many acyclic as well as cyclic

alkanes. This complex mixture of alkanes occurs abundantly in various
natural deposits in the earth.

Petroleum is an oily, thick inflammable and usually dark coloured

liquid. The origi of the word petroleum is from the Latin words petra
(rock) and oleum (oil), as it is found in abundance near the surface of the
earth trapped by rock structure.

The biggest oil-producing country of the world is the USA. The other
major oil producing countries are Russia, Venezucla, Iran, Gulf
countries, Romania, Nyammar, Pakistan, India and Nigeria.

48
CHM 102 MODULE 1

Petroleum industry in Nigeria has made headway only after

independence. In the last 30 years, petroleum production and refining
levels have increased by more than 100 times whereas the consumption
has increased by around 15 times. It is worth mentioning that even with
this increased productivity, only a small percentage.

Petroleum can be separated into various fractions known as gasoline,

naphtha, kerosene, etc. In the following section, we will study the
composition of petroleum in detail.

3.1.1 Composition
The composition of petroleum varies with the locality of its occurrence
but all samples contain mixtures of alkanes ranging in size from
methane with only one carbon atom to long chain hydrocarbon
containing upto 40 carbon atoms. Cyclohexane, nephthalenes and other
aromatic hydrocarbons are also present in small amounts. In addition to
hydrocarbons, oxygen, nitrogen and sulphur containing compounds as
well as metallic constituents may also be present. In fact, as many as 500
compounds have sometimes been detected in a single of petroleum.
Liquefied petroleum gas (LPG) contains a mixture of propane and
butane.

Natural gas is found along with petroleum whose major components are
methane (80%) and ethane (10%). The remaining 10% being a mixture
of higher hydrocarbons. Besides hydrocarbons, natural gas also contains
carbon dioxide and nitrogen.

Fig. 2.1 Fractionation of Petroleum

49
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

The petroleum obtained directly from the ground is not readily usable,
since it is a mixture of many compounds. Separating the crude
petroleum into useful components is called refining. The first step in
refining is fractional distillation.

3.1.2 Fractionation of Petroleum

The first step in the refining of petroleum involves its separation into
fractions of different boiling ranges by fractional distillation. Crude
petroleum is heated in a furnace at 650 K and the hot liquid is then
passed through a flash chamber where the low boiling fractions are
volatilized by lowering the pressure. The vapours are then passed
through a tall bubble tower. This tower is filled with horizontal stainless
steel trays. Each tray is provided with chimneys covered with a loose
cap called bell cap (Fig.2.1). As the vapours ascend, they become
gradually cooler and, therefore, various fractions condense at different
heights. The higher boiling fractions condense in the lower portion of
the of the tower. This permits the separation of crude petroleum vapours
into a number of fractions, each condensing within a definite
temperature range. Each fraction is a mixture of different hydrocarbons.
Therefore, it has to be purified prior to use.

The important petroleum fractions along with their boiling ranges and
chief uses are given in Table2.1.

Table 2.1: Fractionation of Petroleum

Name B.P. (K) Approximate Uses

Composition
Natural gas 293-373 C1 – C4 Refinery and domestic fuel
Light petrol 343-363 C5 – C7 Solvent
Benzene 353-393 C6 – C7 Dry cleaning
Ligroin 343-473 C6-C8 Solvent
Petrol (gasoline) 473-573 C6-C11 Motor fuel
Kerosene (paraffin oil) above 573 C12-C16 Lighting
Gas oil (heavy oil) above 573 C13-C18 Fuel oil
Lubricating oil (mineral oil) above 573 C16-C20 Lubricants
Greases, Vaseline, Petroleum above 573 C18 –C22 Pharmaceutical preparations
Paraffin wax (hard wax) above 573 C20-C30 Candles, waxed paper, etc.
Residue (asphaltic bitumen) C30-C40 Asphalt tar, petroleum coke

3.1.3 Synthetic Petroleum

With the development of civilization and the growth of industry, the

demand of gasoline and petroleum products is increasing day by day.
The natural resources are limited and it is feared that they will soon be
exhausted. Keeping this in mind, the chemists have tried different
methods of manufacturing synthetic fuels. Following processes have
shown some promise.

50
CHM 102 MODULE 1

Bergius Process: In this process, finely powdered coal is hydrogenated

in presence of catalysts, such as tin and lead to give a mixture of liquid
hydrocarbons. During this process, the carbon rings in coal undergo
fission to give smaller fragments which are then hydrogenated to open
chain and cyclic hydrocarbons. Gasoline (bp up to 473) and kerosene
(bp up to 573 K) are obtained on fractional distillation of hydrogenation
products.

Fischer-Tropsch Process: This method was developed in 1923 by two

German chemists, Franz Fischer and Has Tropsch. Water gas, which is a
mixture of carbon monoxide and hydrogen, is obtained by the reaction
of steam with red hot coke. The water gas is mixed with half its volume
of hydrogen and the catalyst used in the process is a mixture of cobalt
(100 parts), thoria (5 parts), magnesia (8 parts) and kieselguar (100
parts). This water gas when hydrogenated and passed over a catalyst at
470-870 K under 1-10 atm pressure yields crude petroleum.

nCO + mH2 
 Mixture of hydrocarbons + H2O

The crude oil obtained is refined by the fractional distillation process as

described earlier.

3.1.4 Octane Number

The most commonly used fuel for automobiles is gasoline. Not all fuel
are equally good. Let us see how we can differentiate between good
quality fuels. This can be done by comparing their octane numbers.
Octane number is a measure of the quality of gasoline: the higher the
octane number, the better the fuel.

Thus 2, 2, 4-trimethylpentane (iso-octane), which is considered a good

fuel, is given an octane number of 100 whereas n-heptane, a very poor
fuel, is given an octane number of zero. Mixtures of these two
compounds are used to define octane numbers between 0 and 100.
Octane number is the percentage of 2, 2, 4-trimethylpentane present in a
mixture of 2, 2, 4-trimethylpentane and n-heptane which has similar
ignition properties as the fuel under examination. For example, a fuel
that performs as well as 1: 1 mixture of 2, 2, 4-trimethylpentane and n-
heptane has an octane number 50. Commercial gasoline has octane
number 81, 74 and 65 for the premium, regular and third grade gasoline.
Good quality motor fuels used in modern automobiles have octane
number in the 87-95 range.

51
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

It has been observed that:

 branching of the hydrocarbon chain increases octane number

 octane number decreases as the chain length increases
 unsaturated hydrocarbons have higher octane number than
saturated hydrocarbons
 cycloalkanes have higher octane number than the corresponding
acyclic alkanes.

Various additives, such as tetraethyllead, (C2H5)4 Pb and tert-butyl

methyl ether, (CH3)3COCH3, are used to boost the octane number of
gasoline. The use of tetraethyllead is being curtailed for environmental
reasons.

3.1.5 Cetane Number

The working of diesel engine differs from that of gasoline engine. In

diesel engines, fuels having a lower octane number are much more
useful than those having a higher octane number. In other words, the
straight chain hydrocarbons constitute a superior fuel than the branch
chain hydrocarbons. Quality of diesel fuel is expressed in terms of a
number called cetane number.

The hexadecane (cetane, C16C34), considered a good fuel, is given a

cetane number 100 whereas -methylnahthalene, a very poor fuel, is
given a cetane number zero. Cetane number is defined as the percentage
of hexadecane in a mixture of hexadecane and -methylnaphthalene
which has similar ignition properties as the fuel under examination.
Good quality diesel fuel required for modern diesel engine has cetane
number greater than 45.

SELF ASSESSMENT EXERCISE 1

State which compound has best octane rating in each of the following
pairs.

1) CH3(CH2)4CH3 ; CH3CH2CH2CH3

CH3
|
2) CH3CHCHCH3 ; CH3 (CH2)4CH3
|
CH3

52
CHM 102 MODULE 1

3) CH2 = CHCH2CH3 ; CH3CH2CH2CH3

CH3 CH3
| |
4) CH3C = CHCHCH3 ; CH3CHCH2CHCH3

3.2 Physical Properties

Covalent bonds of an alkane molecule are either carbon-carbon bonds or

bonds between carbon and hydrogen atoms that differ very little in
electronegativity. Therefore, the alkane molecule is the nonpolar or very
weakly polar. Their physical constants like boiling points densities, etc.,
increase with increase in the number of carbon atoms. Expect for the
few members, the boiling point increases by 20 to 30 degrees for each
CH2 unit that is added to the chain. Boiling point of a covalent substance
depends upon the intermolecular forces.

Intermolecular forces, in turn, depend upon the number of electrons,

surface area of the molecule and its dipole moment. The intermolecular
forces increase with the increase in the number of electrons or in the
value of the dipole moment and surface, area. The stronger in
intermolecular forces, the higher the boiling point. In a particular series,
with the increase in the number of carbon atoms, the surface area
increases and hence, the intermolecular forces and boiling points also
increase. Branching in a chain.

CH3CH2CH2CH3 CH3(CH2)3CH3
butane pentane

BP (K) 273 309

CH3 CH3
| |
CH3CHCH3 CH3CHCH2CH3 ; CH3CCH3
| |
CH3 CH3
2-methyl propane 2-methyl butane 2,2-dimethyl propane

BP 261 245 274.5

Unlike boiling point, the melting points of alkanes do not show a regular
increase. It has been found tat molecules with an odd number of carbon
atoms have lower melting point than those with an even number of
carbon atoms. A possible explanation in given here. The carbon atoms in
alkanes are sp3 hybridised state with a bond angle of 109o28. The
terminal carbon atoms in a carbon chain with an odd number of carbon

53
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

atoms lie on the same side, whereas those in a carbon chain with an even
number of carbon atoms lie on the opposite site. This means that the
packing efficiency and the interaction between the molecules in the solid
state is less in alkanes containing an odd number of carbon atoms as
compared to those with an even number of carbon atoms. This is
reflected in the lower melting points of alkanes with odd number of
carbon atoms. The maximum density of alkane is about 0.8, thus, all
alkanes are lighter than water. Alkanes are soluble in nonpolar solvents
but insoluble in polar solvents.

SELF ASSESSMENT EXERCISE 2

Fill in the blanks:

1. Alkane molecules are very weakly polar or nonpolar because

there is very little -------------------difference between the carbon
and hydrogen atoms.
2. Boiling point of alkanes ---------- with the increase in the length
of the carbon chain
3. Branching in the carbon chain ---------------- the boiling point.
4. Alkanes are soluble in ----------------- solvents.

3.3 Spectral Properties

UV spectroscopy is not of much help in the characterization of alkanes,

since the alkanes do not show any absorption band above 200 nm.

In the infrared (ir) spectra of alkanes, the position of C-H stretching

band depends on whether the hydrogen atom is attached to a primary,
secondary or tertiary carbon atom. Thus, we have the following regions:

-CH3 2975-2950 AND 2885-2860 CM-1

|
-CH2 2940-2915 AND 280-2845 CM -1
|
-CH 2900-2880 CM-1
|
Some C – H deformation absorption frequencies are – CH3, 1435 and
1385-1370 cm-1 and >CH2, 14801440 cm-1. Two useful skeletal
vibrations are: (CH3)2CH-, 1175-1165 cm and (CH3)3C-, 1255-1245
cm-l, it is thus possible to detect the presence of these groups in a
molecule.
The nmr spectra of alkanes give characteristic signals at,  0.9 (CH3),
 1.4 (-CH2) and |  1.5 (-CH).

54
CHM 102 MODULE 1

Let us now examine the mass spectra of alkanes. The stability of the
radical ions can also be presumed in the order tert > sec >p, hence, the
fission of bonds in alkanes occurs preferentially at the branched carbon
atom. When alternative fissions can occur, it is the heaviest side chain
that is eliminated preferentially. Since alkyl radical ions are formed, all
those with 1H and 12C will give peaks of odd masses in their mass
spectra. In particular, alkanes give a series of peaks separated by 14
mass units (CH2). The relative abundances of there peaks is usually the
greatest for C3H7+ (43), C4H9+(57) and C5H11+(71), and decreases fairly
regularly for the larger masses.

3.4 Preparation of Alkanes and Cycloalkanes

Alkanes are generally obtained from natural sources: petroleum and

natural gas. However, synthetic methods are more practical when a pure
alkane is required. Alkanes can be prepared from: (a) alkenes or a
alkynes, (b) alkyl halides, and (c) carboxylic acids. You have already
studied about the preparation of alkanes and cycloalkanes in your earlier
classes. Here we recall only the important methods. General methods for
the preparation of alkanes and cycloakanes are summarized in Table 2.2.

Table 2.2 Reactions for the preparation of alkanes and

cyclokanes

ALKANES
Wurtz reaction
2RX + 2Na 
 RR + 2naX
Kolbe’s electrolytic method

R’COOK + RCOOK 
 R’R + 2CQ2 + H2 + 2KOH1
at anode at cathode

Hydrogenation of unsaturated hydrocarbons

RCH = CHR + H2 catalyst

 RCH2CH2R
Reduction of alkyl halides

RX reducing
 
agent RH
Decomposition of Grignard’s Reagent


RX + RMgX 
H
RH + Mg(OH)X
H2O

Decarboxvlation of Carboxylic acids

RCOONa + NaOH RH + Na2CO3

55
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.4.1 Wurtz Reaction

In the Wurtz reaction, an alkyl halide is treated with sodium in the

presence of dry ether. The result is the joining of the two alkyl groups
from two molecules of alkyl halide with the loss of halogens.

2RX + 2Na RR + 2NaX

This reaction is useful only when two identical alkyl halide molecules
are used. When a mixture of two different alkyl halides is used, a
mixture of three different alkane is obtained. For example, if you take a
mixture of bromomethane and bromoethane, you will get three different
products, viz.

CH3Br + C2H5Br + 2Na  CH3-C2H5 + 2NaBr

CH3Br + CH3Br + 2Na   CH3-CH2 + 2NaBr
C2H5Br + C2H5Br + 2Na 
 C2H5-C2H5 + 2NaBr

The separation of such a mixture into individual alkane is quite difficult.

Thus, the Wurtz reaction between two different alkyl halides is normally
useless in practice. When a single alkyl halide is used, the synthesized
hydrocarbon contains an even number of carbon atoms. In other words,
we can say that Wurtz reaction is suitable for the preparation of only
those alkanes which contain an even number of carbon atoms. As show
above, the main difficulty with the Wurtz reactions is the formation of
many side products when an alkane with odd number of carbon atoms is
desired.

3.4.2 Kolbe’s Electrolytic Method

When a concentrated solution of sodium or potassium salt of a

carboxylic acid is electrolysed, an alkane is formed. The method is
known as Kolbe’s electrolytic method.

RCOOK + RCOOK + H2O 

 RR + 2CO2 + H2 + 2KOH
at anode at cathode

The following mechanistic pathway illustrates this method:


 CH3COO +K
- +
CH3COOK
at cathode

56
CHM 102 MODULE 1

In case a mixture of salts of two carboxylic acids is electrolysed, a

mixture of alkanes is formed:

RR
RCOOK + RCOOK 
 RR + CO2 + H2 + KOH
RR

This reaction has limited synthetic applications because of the formation

of many side products as a result of other reactions of the free radicals
formed.

2.4.3 Hydrogenation of Unsaturated Hydrocarbons

Alkanes or cycloalknes can be prepared by hydrogenation of unsaturated

hydrocarbons using platinum or palladium as a catalysts. The general
reaction to the reduction of alkene is:

Pt or Pd
RCH=CHR + H2   
 R CH2CH2R’
alkane alkane

Pt or Pd
RCCR + 2H2   
 RCH2CH2R
alkyne alkene

Hydrogenation of an alkene can also be carried out by using nickel

catalyst but relatively higher temperature and pressure are required for
this reaction. This reaction is called Sabatier Senderen’s reaction. An
example is given below:

Ni
CH2CH=CH2 + H2 
 CH3CH2CH3
l-propene propane

This is a very useful synthetic method and the yield is nearly 100%.
57
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.4.4 Reduction of Alkyl Halides

Alkanes can also be prepared by the reduction of alkyl halides by

various methods. Reducing agents like zinc and acetic acid and
zinc-copper couple give good yields of alkanes.

reducing
RX    zRH
agent

Lithium aluminium hydride, LiAlA4, is an excellent reducting agent.

Thought it reduces many unsaturated functional groups, such as CO3,
C=N, etc, it does not attack isolated double bond or triple bond. Dry
ether is the commonly used solvent. For example,

Alkyl halide in ether reacts with magnesium to form alkylmagnesium

halide (Grignard reagent) which, on treatment with water or dilute acid,
decomposes to give alkanes. We will take up the preparation and
properties of Grignard reagents in Unit 11 of this course.

Hydrogenation of an alkene can also be carried out by using nickel

catalyst but relatively higher temperature and pressure are required for
this reaction. This reaction is called Sabatier-Senderen’s reaction. An
example is given below:

Ni
CH2CH=CH2 + H2 
 CH3CH2CH3
l-propene propane

This is a very useful synthetic method and the yield is nearly 100%.

3.4.5 Decarboxylation of the Carboxylic Acids

Alkanes may be prepared through decarboxylation of carboxylic acids

by heating a mixture of the sodium salt of a carboxylic acid with soda
lime. Soda lime is a mixture of NaOH and CaO. The active ingredient is
NaOH, CaO helps in keeping the reaction mixture porous.

RCOONa + NaOH RH + Na2CO3

58
CHM 102 MODULE 1

This process of eliminating CO2 from a carboxylic acid is known as

decarboxylation. The alkanes so produced contain one carbon atom less
than the original acid. The new hydrogen atom in the product is derived
from soda lime.

Although methane is obtained from ethanoic acid in good yield, other

acids give only 10-20% of the corresponding hydrocarbon.

Sometimes decarboxylation of the acid itself is more effective than that

of its salt. The direct decarboxylation of a carboxylic acid can be carried
out by heating it with an organic base, such as pyridine using copper
chromite (CuO.Cr2O3) as catalyst

CuO . CR 2 O 3
CH3CH2COOH + C5H5N      CH3CH3 + CO2
Propanoic pyridine ethane
acid

Next we discuss two methods of preparation of cycloalkanes.

3.4.6 Preparation of Cycloalkanes

(i) When 1,5 –dihalogen derivatives of alkanes are treated with
sodium or zinc, the corresponding cycloalkane is formed, e.g. 1,
5-dibromopentane would form the cyclopentane.

(ii) When the calcium or barium salt of a dicarboxylic acid is

distilled, a cyclic ketone is formed, e.g., barium adipate gives
cyclopentanone

Salt of dicarboxylic acid cyclopentanone

59
CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

A cyclic ketone can be reduced into the corresponding cycloalkane

using zinc amalgam and concentrated hydrochloric acid (Clemmenson
reduction).

SELF ASSESSMENT EXERCISE 3

Write the equation showing synthesis of the following alkanes from the
starting materials indicated. Write your answer in the space given below:

1. Cyclohexane from cyclohexene

……………………………………………………………………
……………………………………………………………………
……………………………………………………………………

2. Undecane from the sodium salt of dodecanoic acid,

CH3(CH2)10COOH
……………………………………………………………………
……………………………………………………………………
…………………………………….………………………………

3. Cyclopropane from 1, 3-dibromopropane

……………………………………………………………………
……………………………………………………………………
…………………………………………………………….……....

4. Butane from 1-chlorobutane

……………………………………………………………………
……………………………………………………………………
……………………………….……………………………………

3.5 Reactions of Alkanes

Alkanes are relatively unreactive to most of the common reagents. It is

difficult to define the terms “reactive” and “unreactive”, since a
compound may be reactive under one set of conditions and unreactive
under another. This reactivity or unreactivity may be explained by
considering the nature of C – C and C – H bonds present in their
molecules. Since the electronegativities of carbon and hydrogen do not
differ appreciably, the bonded electrons in C – H are more or less
equally shared between them. Thus, C – H bonds encountered in alkanes
60
CHM 102 MODULE 1

are almost nonpolar and the same is true of C – C bonds. Thus, polar
and ionic reagents find no sites to attack an alkane molecule. Alkanes
undergo mainly substitution reactions, which can be explained using
free radical chain mechanism. These reactions take place in the presence
of UV light or at a high temperature or in the presence of certain free
radical initiators such as peroxide. The chemical reactions which take
place in the presence of light are called photochemical reactions. In
substitution reactions, one or more of the H atom(s) of alkanes are
substituted by halogen or some other groups. Some important reactions
of alkanes are given in Table 2.3

Table 2.3: Reactions of Alkanes

Let us discuss these reactions in detail.

3.5.1 Halogenation

Halogenation of alkane is one of the most important reactions of

alkanes. It is defined as the replacement of hydrogen atom(s), from an
alkane molecule, by halogen atom(s)

 /hv
RH + X2  
 RX + HX

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

The reaction does not take place in dark but a vigorous reaction occurs
when the mixture of alkane and halogen is exposed to light or heated to
a high temperature. But in most cases, the reaction is of limited synthetic
value because a mixture of products is obtained. Multiple substitutions
may occur. For example, chlorination of methane produces a mixture of
chloromethane, dichloromethane, trichloromethane and
tetrachloromethane.

hv
CH4 + Cl2 
 CH3Cl
chloromethane

hv
CH3Cl + Cl2 
 CH2Cl2
dichloromethane

hv
CHCl2 + Cl2 
 CHCl3
Trichloromethan

hv
CHCl3- + Cl2 
 CCl4
tetra chloromethane

The yield of the monosubstituted product may increase by using an

excess of alkane.

Similarly, a cycloalkane reacts with halogen to give halocyclalkane, e.g.

The mechanism of halogenation is supposed to involve the following

steps:

In the first step, the halogen molecule undergoes homolysis forming free
radicals. This step it called chain initiation:

hv/Δ
(i) X2   2X

In the next step, the halogen atom abstracts a hydrogen atom from the
alkane molecule thereby producing an alkyl radical.

(ii) RH + X 
 HX + R

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CHM 102 MODULE 1

The alkyl radical on collision with another molecule of halogen abstracts

a halogen atom from it generating a molecule of the alkyl halide and a
halogen atom. These two steps are called propagation. They are repeated
in sequence till the reactants are consumed.

(iii) X2 + R  RX + X
Finally, the above chain may be terminated by coupling of any two
radicals. This step is known as termination.

(iv) X + X 
 XX
R + X  RX
R + R  RR
The order of reactivity of halogen in halogenation of alkanes is:

F2 > Cl2 > Br >12

However, the fluorination reaction is too violent to be practical, and

iodine actually does not react at all.

3.5.2 Nitration
Alkanes especially the higher member, can be nitrated with nitric acid at
a temperature of 675-775 K. Like halogenation, it is also a free radical
reaction.

RH + HNO3 
 RNO2 + H2O

In this reaction, the product it usually a mixture of nitroalkanes

including those with smaller carbon chain than the parent alkane.
NO 2
HNO |
3  CH CH CH NO + CH CHCH + CH CH NO + CH NO
CH3CH2CH3   3 2 2 2 2 3 3 2 2 3 2
propane l-nitropropane 2-nitropropane nitroethane nitromethane

3.5.3 Isomerisation

The molecular rearrangement of one compound into another compound

or into more than one compound is called isomerisation. The straight
chain alkanes are converted into branched chain isomers in the presence
of aluminium chloride and hydrogen chloride.

CH3
AlCl HCl |
CH3CH2CH2CH3  3  CH3CHCH3
butane 2-methylpropane

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Similarly, other less branched alkanes isomerise to more branched ones.

Thus:
CH3 CH3 CH3
| | |
 CH3CH – CH3CHCH3
CH3CHCH2CH2CH3 
2-methylpentane 2, 3-methylpropane

Isomerization is used to increase the branched chain content of lower

alkanes produced by cracking; you have studied in subsec 2.2.4 that
branched chain alkanes are more valuable than straight chain alkanes as
motor fuel.

3.5.4 Aromatization

This is a process of converting aliphatic or acyclic compounds to

aromatic hydrocarbons. Alkanes with six or more carbon atoms, when
heated strongly under pressure in the presence of a catalyst, give
aromatic hydrocarbons. This process involves cyclisation, isomerization
and dehydrogenation. Aromatization of gasoline increases their octane
number from 40 to 95 because unsaturated hydrocarbons are better fuels.

Catalytic aromatization in the presence of platinum is sometimes

referred to as platforming or hydroforming. This process also constitutes
a value method for commercial production of these hydrocarbons.

3.5.5 Pyrolysis

This is a process of decomposing an organic substance by heating it to

high temperature in the absence of oxygen. The word pyrolysis is taken
from the Greek words pyro (fire) and lysis (disintegration). The
pyrolysis of alkanes, particularly where petroleum is concerned, is
known as cracking. When an alkane is heated to about 775-875 K, it

64
CHM 102 MODULE 1

decomposes into smaller molecules. For example, on cracking propane,

the possible products are:

CH3CH = CH2 + H2 
 CH3CH2CH3 
 CH4 + CH2 = CH2
propene propane methane ethane

Large quantities of high boiling fractions of petroleum are converted

into low boiling gasoline by cracking. Propane and hydrogen are
produced from propane as a result of fission of C – H linkages. In the
case of higher alkanes, fission of C – C linkages occurs more readily.
The presence of catalysts like oxides of chromium, vanadium and
molybdenum, however, accelerates the fission of C – H linkage.
Pyrolysis in the presence of a catalyst is used in the manufacture of
alkenes.

The mechanism of cracking is still obscure, but it is believed to be a free

radical as illustrated below:

CH3CH2CH3 CH3CH2CH2 + H 
 CH3CH = CH2 + H 2

CH3CH2 + CH3 
 CH2=CH2 + CH4

The products formed during cracking of alkanes depend upon: (i) the
structure of alkane, (ii) the pressure employed, and (iii) the presence or
absence of a catalyst.

3.5.6 Combustion

Alkane’s burn in excess of air or oxygen to give carbondioxide and

water. This reaction is known as combustion and is the most important
of all their reactions. Combustion is highly exothermic and accounts for
their use as valuable fuels. It is a free radical chain reaction and requires
a very high temperature for its initiation. Once the reaction is started, the
subsequent chain-carrying steps proceed readily with the evolution of a
large amount of energy. For example, the heat of combustion of pentane
is 2549 kJ mol-1.

CH3CH2CH2CH2CH3 + 8O2 
 5CO2 + 6H2O + 2549 kJ mol
-1

The large quantity of heat evolved can be a source of extensive power.

Hence, the use of petrol, diesel etc., as fuels in internal combustion
engines. The burning of alkanes also produces carbon black, which is
used in the manufacture of Indian ink, printer’s ink, black pigments and
as a filler in rubber compounding.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.5.7 Reactions of Small Ring Compounds

Let us now study the reactions characteristic of small ring compounds,

such as cyclopropane ad cyclobutane.

Besides, the free radical substitution reactions that are characteristic of

cycloalkanes and of alkanes, in general, cyclopropane and, to some
extent, cyclobutane undergo certain addition reactions. You will recall
from your previous classes that the bonding in cyclopropane and
cyclobutane is not as strong as that in higher homologues. Hence, the
bonds in cyclopropane and cyclobutane are vulnerable to attack by
certain results. The sp3orbitals of the carbon atoms in cyclopropane
cannot undergo complete overlap with each other because the angles
between the carbon atoms of cyclopropane are geometrically required to
be 600. The ring sigma bonds of cyclopropane are, therefore, less stable
than sp3 sigma bonds that have the normal tetrahedral angle. These
addition reactions destroy the cyclopropane and cyclobutane ring
system, and yield open chain products. Some examples are given below:

In each of these reactions, a carbon-carbon bond is broken and the two

atoms of the reagent appear at the terminal carbon atoms.

Cyclobutane does not undergo most of the ring opening reactions of

cyclopropane; it gets hydrogenated under vigorous conditions.

So you can see that cyclobutane undergoes addition reactions less

readily than cyclopropane.
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CHM 102 MODULE 1

SELF ASSESSMENT EXERCISE 4

Complete the following reactions:

hv
1. CH3CH3 + Cl2 
 ……………………………………….

2. CH3CH3 + HNO3  ………………………………………

3. …………..….……………………...
CH2

Pt
4. CH3(CH2)5CH3  …………...…………………………..
670k

4.0 CONCLUSION

The alkanes are a group of relatively inactive compounds whose general

formula is Cn H 2n+2. The primary source of alkanes is by fractionation of
petroleum.

5.0 SUMMARY

In this unit you have learnt that:

Alkanes are compounds of the general formula CnH2n+2. Cycloalkanes

contain a ring of carbon atoms and have the general formula CnH2n.

 The chief source of alkanes is petroleum.

 The performance of gasoline for internal combustion engines is
rated by octane number. Cetane number is a measure of the
quality of diesel.
 Alkanes are nonpolar compounds. Their physical constants like
boiling point, density, etc., increase with increase in the number
of carbon atoms. Branching in the chain decreases the boiling
point.
 Alkanes are prepared by: (i) Wurtz reaction, (ii) Kolbe’s
electrolytic method,
(iii) hydrogenation of unsaturated hydrocarbons, (iv)
decarboxylation of carboxylic acids; (v) reduction of alkyl
halides, and (vi) hydrolysis of Grignard reagents.
 The main reaction of alkanes is combustion; heat for power
production is its chief outcome.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

 Halogenation of alkanes gives multiple substitutions. The order

of reactivity of halogens is F2 > Cl2 > Br2. Iodine does not react
at all.
 An alkane can be converted into its corresponding branched chain
isomer in the presence of aluminum chloride and hydrogen
chloride.
 When an alkane is heated to a high temperature (at about 875 K),
it decomposes into small molecules. This process is known as
paralysis.
 When alkanes with six or more carbon atoms are heated under
pressure in the presence of a catalyst, aromatic hydrocarbons are
produced.

ANSWER TO SELF ASSESSMENT EXERCISE 1

(a) CH3CH2CH2CH3

CH3
|
(b) CH3CHCHCH3
|
CH3

(c) CH2=CHCH2CH3

CH3 CH3
| |
(d) CH3C=CHCHCH3

ANSWER TO SELF ASSESSMENT EXERCISE 2

(a) electro negativity

(b) increases
(c) decreases
(d) nonpolar

68
CHM 102 MODULE 1

ANSWER TO SELF ASSESSMENT EXERCISE 3

ANSWER TO SELF ASSESSMENT EXERCISE 4

6.0 TUTOR-MARKED ASSIGNMENT

1. Give the products of the following reactions:

Na
(a) CH3CH2Br + CH3CH2Br 


LiAlH
4
(b) CH3CH2CH3   


H2/Pt
(c) CH3CH=CHCH2Cl  

(d) CH3CH3 + Cl2 hv




2 Cl
(e) CH3CHCH2CH3 
|
CH3
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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

2. Starting with CH2=CHCH2Br or (CH3)3CCl, how would you

prepare the following compounds:

3. Write the equation to show Wurtz reaction:

4. Complete the following equations:

7.0 REFERENCES/FURTHER READINGS

R.T. Morrison and R.N. Boyd, Organic Chemistry, (6th Ed.), India:
Prentice-Hall Pvt. Ltd.

Lloyd N. Ferguson, Textbook of Organic Chemistry, (2nd Ed.), Affiliated

East-West Press Pvt. Ltd.

S.M. Mukherji, S.P. Singh and R.P Kapoor, Organic Chemistry, Vol. I
and II Wiley Eastern Ltd.

P.L. Soni and H.M. Chawla, Textbook of Organic Chemistry, (24th Ed.),
Sultan Chand and Sons.

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CHM 102 MODULE 1

UNIT 3 ALKENES

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Classification of Alkenes
3.2 Physical Prosperities
3.3 Spectral Properties
3.4 Preparation of Alkenes
3.4.1 Dehydrohalogenation of Alkyl Halides
3.4.2 Dehydration of Alcohols
3.4.3 Wittig Reaction
3.4.4 Preparation of Dienes
3.5 Reactions of Alkenes
3.5.1 Addition of Halogens
3.5.2 Hydrohalogenation
3.5.3 Addition of Water
3.5.4 Hydroboration
3.5.5 Ozonolysis
3.5.6 Hydroxylation
3.5.7 Epoxidation
3.5.8 Addition to Conjugated Diene
3.5.9 Diels-Alder Reaction
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Reading

1.0 INTRODUCTION

In this unit, we shall discuss their chemistry in detail. Ethene, the

simplest alkene, was known to chemists in the eighteenth century and
was obtained in pure form in 1794. Alkenes, also called olefins, are
hydrocarbons which contain one or more carbon-carbon double bond(s).
Since alkenes evidently contain less than the maximum number of
hydrogen atoms, they are referred to as unsaturated hydrocarbons.

Alkenes are often found as plant products and in petroleum. Many

alkenes are biologically active compounds. For example, ethene induces
ripening in fruit.

In this unit, we will discuss structure of alkenes, their spectral and

physical properties, different methods for their preparation and finally,
we will study their important chemical reactions.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

2.0 OBJECTIVES

After studying this unit, you should be able to:

 classify the types of alkenes

 explain the structure of monoenes and dienes
 list their spectral and physical properties
 list the different methods for their preparation, and
 write down the important chemical, reactions of alkenes.

3.0 MAIN CONTENT

3.1 Classification of Alkenes

Alkenes can be classified on the basis of the number of double bonds

present in the molecule. Hydrocarbons containing one carbon-carbon
double bond are called monenes. The monoenes have the general
formula CnH2n.

Hydrocarbons containing two double bonds are called diolefins or

alkadienes or dienes. They have the general formula CnH2n-2 and are
isomeric with alkynes. Trienes have three double bonds and tetraenes
have four double bonds. The term polyene is used for hydrocarbons
containing more than four double bonds.

Dienes are divided into three main classes depending on the relative
positions of the two double bonds in the molecule: isolated or non-
conjugated dienes conjugated dienes and cumulated dienes. In
conjugated dienes, the two double bonds are separated by a single bond.
A typical conjugated diene skeleton is given below:

In isolated dienes, the two double bonds are separated by at least two
single bonds for which two typical skeletons are given below:

72
CHM 102 MODULE 1

In cumulated dienes, there are two double bonds around the same carbon
atom; a typical skeleton is given below:

Compounds that contain cumulated double bonds are known but are
very uncommon. The conjugated dienes are the most important among
the dienes. They show certain reactions that are not shown by monoenes
or other dienes. Thus, in this unit, we shall concentrate our attention on
monoenes and conjugated dienes.

Structure of Monoenes and Dienes

The carbon-carbon double bond is both an important structural unit and

an important functional group in organic chemistry. The shape of the
organic molecule is influenced by the presence of the double bond
which is also the site of most of the chemical reactions that alkenes
undergo. So it is necessary to understand the structure of these
molecules.

Carbon-carbon double bond is the distinguishing feature of the

monoenes and dienes. You have already studied about the bonding of
monoenes in Unit 1 of this course and learnt that the carbon atoms
involved in double bond formation are sp2 hybridised. The bond angle
around the sp2 hybridised carbon atoms is 120o (Fig. 5.1). Bonding in
dienes with isolated double bonds is similar to monoenes. Thus here we
shall discuss  bonds in conjugate and cumulated systems.

Fig 3.1: Orbital picture of ethene

Let us consider 1, 3-butadiene as an example of a conjugated diene,

CH2=CHCH=CH2
1, 3-butadiene

Each of the four carbon atoms of butadiene contains unhybridised

p-orbitals. The sideways overlap of unhybridised p-orbitals gives rise to
two localized  bonds, i.e. the bonds between C1 and C2 and C3 and C4

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

(Fig. 5.2). The four carbon atoms and the six hydrogen atoms of
butadiene lie in the same plane so that there is a certain amount of
overlapping between the electron clouds of the p-orbitals of C2 and C3.
This give rise to completely delocalised  -orbitals spread over all the
four carbon atoms. It is this delocalization of  electrons which imparts
stability to 1,3-butadiene.

Fig 3.2: Orbital structure of 1, 3-butadiene

In the allene molecule, the central carbon atom is sp hybridized while

the terminal carbon atoms are sp2 hybridised. The central carbon atom
forms a bond with each of the terminal sp2 hybridised carbon atom. The
remaining two p-orbitals of this carbon form two  bonds by sideways
overlapping with the p-orbitals of the terminal carbon atoms

Fig. 3.3. Molecular orbital picture of allene

SELF ASSESSMENT EXERCISE 1

Fill in the blank in the spaces given below:

1. Dienes are isomeric with …………………………………………

2. Polyenes contain more than ………………………..double bonds
3. Double bonds that alternate with single bond are …………dienes
4. In allene the central atom is …………..hybridised and the
terminal atoms are ………………………… hybridized.

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CHM 102 MODULE 1

3.2 Physical Properties

In general, the physical properties of alkenes are similar to those of the
corresponding alkanes. Like alkanes, the boiling points of a homologous
series of alkenes increase 20-30K per CH2 group except for the very
homologues. Like alkanes, branching in an alkene also lowers the
boiling point. Lower alkenes, from ethane to butane, are colourless
gases, higher ones, from C5 - C15, are liquids and the rest are solids at
temperature.

Alkenes are slightly more soluble in water than the corresponding

alkanes because the  -electrons are attracted to the partially positive
hydrogen of the water molecules.

3.3 Spectral Properties

In the UV spectrum, although the ethylenic chromophore shows an
absorption band below 200 nm, yet it is not of much practical value as
measurement of UV spectrum in this region is influenced by the
absorption of air and solvent molecules.

The ir spectra are quite useful for structure determination of alkenes.

The unsymmetrical alkenes are polar and absorb in the region between
160 and 1700 cm-1, whereas the symmetrical ones, being nonpolar, do
not absorb in this region. Further, depending upon the substituent, one or
more bands of medium intensity appear in the region between 3000 and
3100 cm-1 for >C=C-H stretching. The cis-and trans-isomers of the type
RCH=CHR may be distinguished by C-H deformation frequencies. The
cis-isomer absorbs at 675-730cm-1 and the trans-isomer at 960-975cm-1.

In the ir spectra of allenes, a band near 1950 cm-1 appears for the C=C
stretching vibration. The strong band at 850cm-1 arises from >C=CH2
wagging and is characteristic of allene. The characteristic -C=C-
stretching frequencies in conjugated systems is lower and appears
around 1600 cm-1

In the nmr spectra, the chemical shifts of olefinic protons are shifted
towards lower field than those of alkane protons. The exact position of
absorption depends on the location of the double bond in the
hydrocarbon chain. In general, proton on the terminal alkenyl carbon
absorb near  4.7 ppm, while the protons on the nonterminal carbon
absorb slightly farther downfield at  5.3 ppm. The protons  to a
double bond (CH2CH = CHCH2) appear at  2.06 ppm.

In conjugated dienes, the olefinic protons are more deshielded and

consequently resonance due to thee protons occurs downfield. In
conjugated dienes, the signal due to CH2 = protons appears at  5.3-5.7

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

ppm and that due to H – C = C proton at  4.0-4.5 ppm. In the nmr

spectra of the allenes, the alkene hydrogen give rise to signals at
 5.7-4.7 ppm.

In the mass spectra of alkenes, the molecular ion peak is usually distinct.
The fragmentation of interest for alkenes is the allylic cleavage.

3.4 Preparation of Alkenes

Synthetically, alkenes are prepared by introducing a double bond in
saturated hydrocarbons through elimination of atoms or groups from
two adjacent carbon atoms. The result is the formation of a double bond
between these two carbon atoms.

Alkenes can be prepared from alkyl halides, alcohol and ketones and
through cleavage reactions. Some important methods for the preparation
of alkenes are summarized in

Table 3.1 Preparation of alkenes

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CHM 102 MODULE 1

Let us discuss each method in detail.

3.4.1 Dehydrohalogenation of Alkyl Halides

Alkyl halides are converted into alkenes by dehydrohalogenation.

Dehydrohalogenation involves elimination of the halogen atom together
with a hydrogen atom from an adjacent carbon atom. The elimination is
brought about by treating the alkyl halide with a strong base. Thus,
bromoethane yields ethene when treated with potassium hydroxide in
alcoholic solution.

The function of hydroxide ion is to abstract hydrogen from the carbon

atom next to the halogen bearing carbon. The carbon halogen bond then
cleaves resulting in double bond formation.

Ease of hydrohalogenation of alkyl halides is: tert > sec >p

The alkyl halides, in which halogen is attached to a terminal carbon,

yield a single alkene but alkyl halides in which the halogen atom is
attached to a nonterminal carbon atom and both adjacent position have
hydrogen atoms yield a mixture of alkenes.

KOH (alc)
CH3CH2CH2CH2Cl    
 CH3CH2CH=CH2
Chlorobutane 1-butene

Cl
|
KOH (alc)
CH3CH2CHCH3    
 CH3CH=CHCH3 + CH3CH2CH=CH2
2-chlorobutane 2-butene 1-butene
(major) (minor)

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

In the first reaction, chlorobutane can lose hydrogen only from C2;
therefore, it gives only one product, i.e. 1-butene. However, in the
second reaction, 2-chlorobutene can lose hydrogen from any of the
two-  -carbon atoms and, hence, it gives a mixture of 2-butene (80%)
and 1-butene (20%). Now you may ask why 2-butene is the major
product. Dehydrohalogenation follows Saytzeff rule which says that the
more highly substituted alkene is the dominant product.

3.4.2 Dehydration of Alcohols

An alcohol is converted into an alkene by dehydration, i.e., elimination

of a molecule of water. Dehydration requires the presence of an acid and
the application of heat.

The alcohol is heated with sulphuric or phosphoric acid to a

temperature as high as 475 K. Dethydration is also brought about by
passing the alcohol vapour over alumina (Al2O3) at 625-675 K, e.g.,

In the case of secondary and tertiary alcohols other than 2-propanol,

there exists the possibility of the formation of more than one alkenes.
For example, in 2-butanol, hydrogen elimination can occur either from
C1 or C2. The direction and the rate of reaction again follow the Saytzeff
rule and hence 2-butenes, the more substituted alkene, is the major
product and 1-butene the minor one.

The ease of dehydration of various alcohols has been found to follow the
order: tert > sec > p.

3.4.3 Wittig Reaction

In 1954, George Witting reported a method of synthesising alkenes from

carbonyl compounds. This reaction is applicable to aldehyde and
ketones and leads to replacement of carbonyl oxygen by the
group=CRR’ (where R and R’ are hydrogen or alkyl group).

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CHM 102 MODULE 1

There are two main steps in Wittig reaction. In the first step, the
nucleophilic reagent triphenylphosphine reacts with primary or
secondary alkyl halide to give phosphonium salt

This phosphonium salt further reacts with a strong base, which abstracts
a weakly acidic  -hydrogen to give alkylidenetriphenylphosphorane
(the phosphorous ylide) commonly known as the Wittig reagent.

The phosphosrous ylide has a hybrid structure and it is the negative

charge on carbon that is responsible for their characteristic reactions.

The resulting phosphorous ylide attacks the carbonyl carbon to form

betaine which often undergoes elimination spontaneously to yield
alkene.

Betain: A molecule having non-ajacent charges opposite.

The mechanism of Wittig reaction has been the subject of much

discussion, BUT evidence is now strongly in favour of formation of an
intermediate betaine followed by ring closure and then fission.

Triphenyl
phosphine oxide alkene
betaine

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.4.4 Preparation of Dienes

Retro Diels – Alder Reaction: Dienes are usually prepared by the

adaptation of the methods used to make simple alkenes. However, 1,
3-butadiene is prepared by passing vapours of cyclohexene over heated
nichrome (Ni-Cr-Fe) alloy.

This reaction is also known as the retro Diels-Alder reaction as it is the

reversal of the Diels-Alder reaction which you will study in due course.

Other Methods for Preparation of Dienes: As stated above, dienes are

usually prepared by adaptation of the method used to make simple
alkenes. For example, 1, 4-dihydroxybutane on treatment with sulphuric
acid gives 1, 3-butadiene.

1,3-Butadiene can also be prepared from butane by the cracking process

using Cr2O3 as illustrated below;

SELF ASSESSMENT EXERCISE 2

Write equations for the preparation of alkene from the following starting
material. If there is more than one product indicate the major one.

Br
|
1. CH3CH2CHCH3

80
CHM 102 MODULE 1

CH3
|
2. CH3CCH2CH3
|
OH

CH3
3. C=O

CH3

3.5 Reactions of Alkenes

The double bond consists of a strong  bond and a weak  bond; so
most of the reactions of alkenes would involve the breaking of this
weaker bond.

In addition reactions of alkene, the  -bond is broken and the electron

pair comprising it, is used in the formation of two new  bonds. Thus,
two sp2 hybsridised carbon atoms are rehybridised to sp3 carbons.
Compounds containing  bonds are usually of higher energy than those
having  bonds. Consequently, addition reactions are usually
exothermic processes.

In the region of the double bond, there is a cloud of electrons above and
below the plane of bonded atoms. The  electrons are loosely held by
the nuclei and are thus easily available to electron-seeking reagent. Such
reagents are called electrophilic reagents or electrophiles and the typical
reaction of an alkene is the electrophilic addition. Some electrophilic
important reactions of alkenes are given in Table 3.2 and discussed
below:

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Table3.2: Reaction of Alkenes

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CHM 102 MODULE 1

3.5.1 Addition of Halogens

Halogens are quite reactive towards alkenes. Treatment of alkens with

halogens gives 1,2-dihalogenated alkenes.

Bromine and chlorine are particularly effective electrophilic addition

reagents. Fluorine tends to be too reactive and difficult to control for
most laboratory procedures and iodine does not react with alkenes.

Mechanism

Although bromoine is non-polar, it is nevertheless highly polarisable

and, in the vicinity of the nucleophilic double bond, the bromine
molecule becomes polarised and hence a partial positive charge (  +)
develops on one bromine atom and a partial negative charge (  -) on the
other. The  electrons of alkene attack the positive end of the polarised
bromine molecule, displacing bromide ion and forming a cyclic
bromonium ion.

The cyclic structure shields one side of the molecule and, for this reason,
Br attacks from the opposite side of the erstwhile double bond to give
trans product. This process is known as trans addition. This steric course
of the reaction is important in case of alkenes which can give rise to
different isomeric products.

Addition of bromine is extremely useful for detection of carbon-carbon

double bond. Rapid decolourisaion of bromine solution serves as a test
for the presence of the carbon-carbon double bond in a compound.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.5.2 Hydrohalogenation

An alkene is converted by hydrogen halide (halogen acid) into the

corresponding alkyl halide,

As long as the alkene is symmetrical, we get only one product. In case

of unsymmetrical alkene, the position of attachment of nucleophile is
governed by the nature of substituents. Addition of HBr to propene
should give two products, i.e, 1-bromopropane and 2-bromopropane.

However, only one product, 2-bromopropane, is produed. Such reactions

are called regiospecific reactions. Regiospecific: Only one of the two
directions of addition is observed. To explain the exclusive formation of
the product, the Russian chemist Markownikoff formulated a rule know
after him as Markownikoffs rule, which states that addition of a
hydrogen halide to an unsymmetrical alkene takes place in such a way
that the negative part of the reagent goes to that carbon atom of the
alkene which carries the lesser number of hydrogen atoms.

Markownikoffs rule can be explained on the basis of the relative

stabilities of carbocations which are of the order of tertiary, > secondary
> primary. Accordingly, the more substituted carbocation is formed as
an intermediate in preference to the less substituted one. For example, in
the addition of H+ to propane, there exists the possibility of the
formation of either a primary or a secondary carbocation. Since, the
secondary carbocation is more stable, addition of H+ gives exclusively
2-bromopropane via the more stable intermediate.

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CHM 102 MODULE 1

Peroxide Effect

You must be under the impression that addition to alkene always give
Markownikoffs product. But it is not so. After an extensive study of the
mechanism of addition of HBr to alkene, kharasch and Mayo found that
in the presence of peroxide the product obtained was not the one
predicted by Markownikoffs rule but it was contrary to the
Markownikoffs rule. Such additions are sometimes referred to as
anti-Markownikoff additions. Since the reversal of the addition reaction
is brought about in the presence of peroxide, it is known as the proxide
effect. For example, the addition of hydrogen bromide to propene in the
presence of peroxides give 1-bromopropane rather than
2-bromopropane.

The reaction intermediate in such additions is a free radical rather than a

carbocation. The mechanism is some what similar to that of
halogenation of an alkane, which will be dealt in the “Organic Reaction
Mechanism” course.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

SELF ASSESSMENT EXERCISE 3

Complete the following reaction

(1) CH3CH2CH=CH2 + HCl 

 ………………………………
peroxide
(2) CH3CHCH = CH2 + HBr    ……………………….
|
CH3
(3) + Br2 
 …………………………………

3.5.3 Addition of Water

Addition of H2O to alkene is known as hydration of alkene. Hydration

reaction occur when H2O, adds to alkenes in the presence of an acid
catalyst to yield an alcohol,

Like hydrogenation, addition of H2O to unsymmetrical alkene follows

Markownikoffs rule.
OH

Another method used to accomplish Markownikoffs hydration of an

alkene is oxymercuration-demercuration. Alkene reacts with mercuric
acetate in the presence of water to give hydroxyl-mercurial compounds
which on reduction accomplishes demercuration and produces an
alcohol. The products of oxymercuration is usually reduced with sodium
borohydride (NaBH4). Oxymercuration-demercuration reaction usually
gives better yield of alcohols than the addition of water with H2SO4.

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CHM 102 MODULE 1

3.5.4 Hydroboration
When an alkene reacts with borane, addition to the carbon-carbon
double bond takes place to yield an organoborane – a compound with a
carbon-boron bond. The reaction is known as hydroboration. Borane
(BH3) itself is unknown but its dimmer, diborane (B2H6) behaves as if it
were the hypothetical monomer (BH3)2. This reaction is very facile and
requires only few seconds for completion at 272 K and gives
organoboranes in very high yield.

CH2 = CH2 + (BH3)2 

 CH3CH2 – BH2

Since BH3 has three hydrogen, addition occurs three times to produce
triakylborane product e.g.

CH2 = CH2 + CH3CH2 – BH2  (CH3CH2)2BH

CH2 = CH2 + (CH3CH2)2BH2 
 (CH3CH2)3B

Hydroboration reaction is described as anti-Markownikoffs addition.

This is true only in literal sense, because hydrogen is the electronegative
portion of the molecule instead of the electropositive portion.

As shown above the hydrogen (as a hydride ion, H) goes to more
substituted carbon. The result appears to be anti-Markownikoffs
addition.

Organoborane are generally not isolated but are instead used directly as
reactive intermediates for further synthetic reaction. For example,
oxidation of organoborane by alkaline H2O2 gives corresponding
alcohol.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Treatment of organoboranes with a carboxylic acid leads to alkane,

3.5.5 Ozonolysis

In all the reactions of alkenes studied so far, the carbon skeleton of the
starting material was left intact. We have seen the conversion of the
carbon-carbon double bond into new functional groups (halide, alcohol,
etc) by adding different reagents, but the carbon skeleton was not broken
or rearranged. Ozonolysis is a cleavage reaction, i.e a reaction in which
the double bond is completely broken and alkene molecule is converted
into two smaller molecules.

Ozonolysis consists of two separate reactions, the first is oxidation of

alkene by ozone to give an ozonide; and the second is reduction of the
ozonide to yield cleavage product.

Some examples of ozonolysis are given below:

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CHM 102 MODULE 1

3.5.6 Hydroxylation

Alkenes are readily hydroxylated (addition of hydroxyl groups) to form

a dihydroxy compound (diol) known as glycols. The most popular
reagent used to convert an alkene to diol is cold alkaline aqueous of
potassium permanganate or osmium tetroxide.

3.5.7 Epoxidation

The double bond in alkene is converted into epoxide by means of

peracids. Perbenzoic acid (C6H5COO2H), monoperphthalic acid
(HO2CC6H4COO2H) and p-nitroperbenzoic acid have been used, e.g.

SELF ASSESSMENT EXERCISE 4

Predict the products of the following reactions:

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.5.8 Addition to Conjugated Diene

Alkadienes with conjugated system of double bonds undergo abnormal
addition reactions, e.g., when 1,3-butadience is treated with bromine,
two dibromo derivatives are obtained. One of these is 3, 4-dibromo – 1-
butene (due to 1:2 addition) and the other is 1, 4-dibromo-2-butene (due
to 1:4 addition), a major product.

Br Br Br Br
| | | |
CH2 = CHCH = CH2 CH2CHCH=CH2 + CH2CH=CHCH2
1,3-butadine 3, 4-dibromo-1-butane 1, 4-dibromo-2-butene
(minor) (major)

With excess of bromine, the 1, 4 addition as well as the 1, 2-addition

products would yield the same 1, 2, 3, 4-tetrabromonutane.

Mechanism

The mechanism of halogenation of 1, 3-butadiene is illustrated below:

Bromine may attach itself to either C1 or C2. The addition of the

bromine atom at C2 would give rise to an unstable primary localized
carbocation. But the bromine addition at C1 results in the formation of
resonance stabilized allylic cation. This also explains the enhanced
reactivity of dienes over isolated ethylenic double bonds. When the
allylic, carbocation is attacked by bromine ion (Br) to complete the
electrophic addition reaction, the attack can occur at either C1 or C3,
since both share the positive charge. The result is a mixture of 1, 2- and
1, 4-addition products, the latter formed in excess since it has the more
highly substituted double bond and is hence more stable.

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CHM 102 MODULE 1

3.5.9 Diels-Alder Reaction

In Diels-Alder reaction, a conjugated diene is treated with an

unsaturated compound called the dienophile (diene-lover) to yield, a
cyclic system. This reaction is named after the German chemists, Diel
and Alder. It is a very useful reaction for synthesizing cyclic systems.
The simplest Diels-Alder reaction is the reaction of 1, 3-butadiene with
ethane to yield cyclohexene. The resulting product (here cyclohexene) is
called the adduct.

This is a very slow reaction and it occurs only under conditions of heat
and pressure. Diels-Alder addition take place most rapidly and give the
highest yield if the alkene component has electron withdrawing groups
or the diene has electron donating groups. The raction has wide scope
because triple bonded systems also may be used as dienophiles. Some
important examples of Diels-Alder reaction are given below:

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

SELF ASSESSMENT EXERCISE 5

1. Write the structure of all possible carbocation intermediates in the

addition of HI to 2, 4-hexadiene
2. Which carbocation, of the above problem, would you expect to
be more stable?

4.0 CONCLUSION
In this unit, we have studied the classification of alkanes, their physical
and chemical properties. In addition, we have explained their structures
and methods of preparation.

5.0 SUMMARY
 Hydrocarbons containing one carbon-carbon double bond are
known as monoene or olefins. Hydrocarbons containing two
double bonds are known as alkedienes or dienes. Dienes are
divided into three classes, i.e., conjugated dienes, isolated dienes
and cumulated dienes.
 In general, the physical properties of alkenes are similar to the
corresponding alkanes.
 Alkenes are generally prepared by the elimination of atoms or
groups from the adjacent carbon atoms. Two such reactions are
dehydrohalogenation of alkyl halides and dehydration of
alcohols. The ease of dehydrohalogenation of alkyl halide or
dehydration of alcohol is:
tert >sec >p
 Alkenes can also be prepared from aldehydes or ketones by
Wittig reactions.
 Dienes are prepared by retro Diels-Alder reactions
 The main reactions of alkenes are electrophilic addition reactions.
These reactions include addition of halogen, addition of alkyl
halide, addition of water, etc.
 Alkenes can be oxidised by ozone, permanaganate and osmium
tetroxide. Alkenes on ozonolysis give adldehydes or ketones and
on oxidation give 1, 2-diol.
 Addition of halogen to conjugated dienes give normal 1,
2-addition product as a minor product and abnormal 1, 4-addition
product as a major product.
 Alkenes undergo Diels-Alder reaction.

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CHM 102 MODULE 1

ANSWER TO SELF ASSESSMENT EXERCISE 1

a) alkyne
b) four
c) conjugated
d) sp; sp2

ANSWER TO SELF ASSESSMENT EXERCISE 2

ANSWER TO SELF ASSESSMENT EXERCISE 3

ANSWER TO SELF ASSESSMENT EXERCISE 4

(a)

(b)

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

(c)

ANSWER TO SELF ASSESSMENT EXERCISE 5

(a)

 
CH3CH  CHCH  CHCH3 H
 CH3CH 2 CHCH  CHCH3  CH3CHCH 2CH  CHCH3
(Addition of H+ to the other double bond gives identical intermediate)

(b) The first carbocation shown would be more stable because it is

resonance stabilized allylic carbocation, i.e.

6.0 TUTOR-MARKED ASSIGNMENT

(1) Give a structural formula for the carbocation intermediate that

leads to the principle product in following reaction:

(2) Identify the alkene obtained on hydration/dehydrohalogenation of

each of the following compounds:

(3) Give the product formed when HBr react with 2-methyl-2butene
in presence of peroxide and in absence of peroxide.

(4) Arrange the following alkenes in order of decreasing stability.

R2C=CR2; R2C=CH2; CH2-CH2; R2C=CHR; RHC =CHR; RCH=CH2

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CHM 102 MODULE 1

(5) Complete the following reactions:

7.0 REFERENCES/FURTHER READING

R.T. Morrison and R.N. Boyd, Organic Chemistry, (6th Ed.),

India: Prentice-Hall Pvt. Ltd.

Lloyd N. Ferguson, Textbook of Organic Chemistry, (2nd Ed.), Affiliated

East-West Press Pvt. Ltd.

S.M. Mukherji, S.P. Singh and R.P Kapoor, Organic Chemistry, Vol. I
and II Wiley Eastern Ltd.

P.L. Soni and H.M. Chawla, Textbook of Organic Chemistry, (24th Ed.),
Sultan Chand and Sons.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

UNIT 4 ALKYNES

CONTENTS

1.0 Introduction
2.0 Objectives
3.0 Main Content
3.1 Types of Alkynes
3.2 Physical Properties
3.3 Spectral Properties
3.4 Preparation
3.4.1 Dehydohalogenation of Dihalides
3.4.2 Dehalogenation of Tetrahalides
3.4.3 Alkylation of Ethyne
3.5 Acidity of Alkynes
3.6 Reactions of Alkynes
3.6.1 Electrophilic Addition
3.6.2 Reduction
3.6.3 Oxidation
4.0 Conclusion
5.0 Summary
6.0 Tutor-Marked Assignment
7.0 References/Further Readings

1.0 INTRODUCTION

In the previous two units, you have studied the chemistry of alkanes and
alkenes. We shall now study another kind of hydrocarbon known as
alkynes which contain carbon-carbon triple bond.

Ethyne, CH ≡ CH, the simplest alkyne, was burnt in the miners’ lamps
before electric lamps were developed. It is used in oxyacetylene torches
for cutting and welding metals. It is extensively used as a fuel gas. In
industry, it is the starting material for the preparation of many important
chemicals, e.g., ethanoic acid, chloroethene (vinyl chloride), propanone,
butanol, ethanol, etc.

A large number of naturally occurring compounds containing triple

bonds have been isolated from plant kingdom. For example, a triyne
from safflower has considerable activity against nematodes and
evidently forms part of the plant’s chemical defiance against infestation.

You will see in this unit that the carbon-carbon triple bond reacts with
many of the reagents that react with alkenes. You will also study the
most unique aspect of the chemistry of alkynes, the acidity of terminal
alkynes.

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CHM 102 MODULE 1

2.0 OBJECTIVES

After studying this unit, you should be able to:

 list the various kinds of alkynes

 list the physical and spectral properties of alkynes
 explain the various methods for the preparation of alkynes
 explain the acidity of terminal alkynes
 explain the chemical reactions of alkynes.

3.0 MAIN CONTENT

3.1 Types of Alkynes

Alkynes, also known as acetylenes, constitute the homogenous series of

open chain unsaturated hydrocarbons that contain one or more
carbon-carbon triple bond. Alkynes may be of two types: terminal and
internal. In the terminal alkynes, the triple bond lies at the end of the
carbon chain and in the internal alkynes, the triple bond lies anywhere
except at the terminal position.

CH3C  CH CH3CH2C  CH2CH3 CH3C  CC  CCH3

1-propyne 3-hexyne 2,4-hexdiyne
(terminal alkyne) (internal alkyne) (internal alkyne)

3.2 Physical Properties

The physical properties of alkynes are similar to those of corresponding

alkenes. They are all colourless and odourless (except ethyne). The first
three members, i.e., ethyne, propyne and 1-butyne, are gases at room
temperature; the next eight members are liquids and the higher members
are solids. The physical constants like melting points, boiling points and
densities increase gradually with the increase in molecular weight. The
increase in boiling point with increase in molecular weight is due to
increased London forces, as discussed in module 1 of this course.
Alkynes have slightly higher boiling points than the corresponding
alkenes and alkanes. Terminal alkynes have lower boiling points than
the isomeric internal alkynes and can be separated by careful fractional
distillation.

Alkynes share with alkanes and alkenes the properties of low density
and low water solubility. They are nonpolar and dissolve readily in
typical organic solvents, such as diethyl ether, chlorinated hydrocarbons,
etc.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.3 Spectral Properties

The alkynyl chromophore absorbs below 200 nm (  -  * transition) in

UV region which is often difficult to detect. Conjugation with a multiple
bond, however, results in a bathochromic shift.

The ir absorption region of compounds with a triple bond depends on

whether they contain alkyne hydrogen or not. Thus, in terminal alkynes,
RC  CH, there is one absorption band in the region of 3300-3100 cm-1
due to the C  CH stretching and another in the region of 2140-2100cm-1
due to -C  C- stretch. In the internal alkynes RC  CR, there is
absorption in the region of 2260-2190 cm-1 corresponding to the
–C  C- stretching.

The internal alkynes, RC  CR, have no alkynyl hydrogen, therefore,

they have no nmr absorption characteristics of alkynyl hydrogen. The
terminal alkynes, RC  CH, give an absorption signal between  2 and
3, characteristic of alkynyl proton. Thus, value for alkynyl proton is less
than the value of alkenyl protons. Let us suggest an explanation for this.

The chemical shift of a particular proton depends on the magnetic field

felt by it. As you know, the chemical shift as well as the magnetic field
felt by a particular proton depends on:

 the electronegativity of the carbon atom to which the proton is

attached,
 the way the proton is oriented to the neighbouring  electron
cloud, if any.

The sp hybridised carbon in alkynes is more electronegative than the sp2

hybridised carbon in alkenes. Hence, we could expect higher  value for
alkynyl protons than for alkenyl protons. But the orientation of the
alkynyl proton to the  electron cloud is unfavourable for higher 
values, as compared to the alkenyl protons.

The mass spectra of an alkyne give distinct molecular ion peak.

However, the fragmentation is often complex and not easily interpreted.

3.4 Preparation
Organic synthesis makes use of two major reaction types: one is
functional group transformation and the other is carbon-carbon bond
forming reaction. Both these strategies are applied to the preparation of
alkynes. In this unit, we shall discuss how alkynes are prepared by
elimination reactions and by adding alkyl group(s) to the smaller ethyne
unit. Some important methods of preparation of alkynes are outlined in
Table 4.1

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CHM 102 MODULE 1

Table 4.1: Preparation of Alkynes

3.4.1 Dehydrohalogenation of Dihalides

You have already seen in Unit 5 that an alkene can be prepared by the
elimination of HX from an alkyl halide. Similarly, an alkyne can be
prepared by the elimination of two molecules of HX from a dihalide.
The dihalide may be of the geminal or vicinal type. Geminal dihalide:
One in which both the halogen atoms are substituted on the same carbon
atom.

Vicinal dihalide: One in which halogen atoms are substituted on

adjacent carbon atoms.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

Since an alkyne contains a triple bond as compared to the double bond

in alkenes, two molecules of HX must be eliminated. Therefore, stronger
conditions are required to remove the second HX molecule. For
example, when 1, 2-dibromopropropane reacts with a strong base, a
two-fold elimination occurs and as a result a propyne is produced.

Br Br
| |
CH3CH CH2 KOH/C
HOH
-1
 CH3CH=CHBr 
2 5
 CH3C  CH
NaNH 2

1, 2-dibromo 1-bromo - propane

Propyne 1-propene

You have studied in Unit 5 that dihalides are prepared by the addition of
halogen to an alkene. Thus, the overall sequence of halogenation-
dehydrohalogenation provides an excellent method for going from an
alkene to an alkyne, e.g.

You may recall that alkenes can be prepared by elimination reactions of

alkyl halides, which again, can be obtained from alkanes. Thus, we can
say that alkane can serve as a starting material for the preparations of
alkynes.

Different bases can be used for dehydrohalogenation; sodium amide is

preferred, since it usually gives a higher yield.

The two-fold dehydrohalogenation follows the same mechanism as the

dehydrohalogenation of alkyl halide to alkenes.

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CHM 102 MODULE 1

3.4.2 Dehalogenation of Tetrahalides

Alkyne can also be prepared by dehalogenation of tetrahalides. For
example, propyne is formed when the vapours of 1, 1, 2,
2-tetrabromopropane are passed over heated zine.

This reaction does not have any synthetic importance, since the
tetrahalides themselves are usually prepared from alkynes. However, it
provides a method for the purification of alkynes.

3.4.3 Alkylation of Ethyne

Reactions that lead to the attachment of an alkyl group to a molecular
fragment are called alkylation.

In this sub-section, we shall see how alkynes are prepared by combining

smaller units to build larger carbon chains. One of these structural units
is ethyne itself. By attaching alkyl group to ethyne, more complex
alkynes can be prepared. For example.

Alkylation is a two-step process. In the first step, ethyne reacts with

sodium amide to give a sodium ethynide ion, the conjugate base of
ethyne.

In the second step, sodium ethynide ion attacks the C-I carbon atom of
1-iodobutane and pushes out the iodine ion, yielding the terminal
alkyne, 1-hexyne, giving an overall 86% yield.

Again, 1-hexyne can itself be converted into an alkynide anion, and can
be alkylated a second time to yield an internal alkyne. A different alkyl
halide can be used this time.

1- NaNH
2  CH (CH ) C  CCH CH
CH3(CH2)3C  CH    
 3 2 3 2 4
1-hexyne 2-CH3CH2Br 3-octyne

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

This reaction gives good yields of alkyne only with primary alkyl
bromoides and iodides.

Alkylation can also be carried out by reacting ethyne and Grignard

reagent, followed by the action of an alkyl halide,

SELF ASSESSMENT EXERCISE 1

Suggest a method for preparation of the following alkynes starting with

ethyne. Use any alkyl halide needed.

1. 2-Heptyne
2. 3-Heptyne

3.5 Acidity of Alkynes

You have already studied the Bronsted-Lowry theory of acids and bases
in Unit 2 of this course. According to Bronsted and Lowry, an acid is a
species that donates H+. In fact, any compound containing a hydrogen
atom can act as an acid under suitable conditions. Acid strength can be
measured by measuring dissociation constants and expressing the results
as values. Strong acids have lower pKa values than weak acids.

Hydrocarbons are usually not regarded as acids. Nevertheless, we can

consider the removal of a proton from a hydrocarbon by a very strong
base.

In this equation, the hydrocarbon acts as a Bronsted acid and the

conjugate base is a carbon anion or carbanion.

Approximate acidities of different types of aliphatic hydrocarbons have

been measured and their pKa values are given in Table 4.2

Table 4.2 Acidities of some hydrocarbons

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CHM 102 MODULE 1

From the data given in Table 4.2, we can see that there is a significant
difference in the acidity of alkynes and other hydrocarbons. The order of
acid strength of these hydrocarbons is:

CH  CH >CH2 = CH2 > CH3CH3

Conversely, the decreasing order of basic strength of the conjugate
anions resulting from these hydrocarbons should be:

- - -
CH3CH2 > CH2=CH> CH  C
alkanide alkenide alkynide
anion anion anion

This decreasing order of acidities and basicities of hydrocarbons can be

explained as follows:

Conjugated bases of alkanes, alkenes and alkynes have an electron pair

in sp3 , sp2 and sp orbitals, respectively, i.e,

As we proceed from the alkanide anion to alkynide anion, the s character

of the hybrid orbital increases and p character decreases. The alkanide
anion (sp3 hybridized) has 25% s character and 75% p character;
alkenide anion (sp2 hybridised) has 33.3% s character 64.6% p
character; and alkynide anion (sp hybridized) has 50% s character and
50% p character. You have already studied in your earlier classes that
electrons in s orbital are closer to the nucleus than those in p orbital.
Since s character is maximum in alkynide anion and minimum in
alkanide anion, the electron pair should be held most tightly in alkynide
anion and most loosely in alkanide anion. Alkenide anion lies in
between. In other words, the electron pair in alkynide anion should be
least available for protonation. As you know, the basic strength is more
if the electron pair is easily available for protonation.

Therefore, in the above series, alkynide anion is the weakest base and
alkanide anion is the strongest base. Conversely, alkyne is the strongest
acid and alkane the weakest acid.

This can be explained in another way also. On the basis of the above
discussion, we can say that the sp hybridized carbon would attract the

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

electrons pair constituting the C – H bond of an alkyne more than the

sp2 and sp3 hybridised carbons in alkene and alkane; respectively. This
implies that C – H bond in an alkyne would be more ionic and has a
tendency to donate a proton (H+), hence, ethyne would be more acidic as
compared to ethene or ethane.
Let us now compare its acidity with ammonia and water.

Addition of ethyne to sodamide in ether yields ammonia and sodium

ethynide.

HC  CH N H 2 H  NH 2  HC  C
stronger stronger weaker weaker
acid base acid base

Note:

HA H+ + A
acid conjugate
base

The stronger the conjugate base, the weaker the acid and vice-versa.

The weaker acid, H – NH2, is displaced from its salt by the stronger acid,
HC  CH. In other words, the stronger base, NH2 pulls the hydrogen ion
way from ethyne to yield a weaker conjugate base. HC  C-, since NH2
holds the hydrogen ion more tightly than HC  C-, ammonia must
necessarily be a weaker acid than ethyne.

Addition of water to sodium ethynide forms sodium hydroxide and

regenerates eithyne.


H  OH HC  C : N a 
 HC  C H  NaOH
stronger stronger weaker weak
acid base acid base

The weaker acid, ethyne, is displaced from its salt by the stronger acid,
H2O. Thus ethyne is a stronger acid than ammonia, but a weaker acid
than water, i.e.; the three compounds have the following order of acid
strength:

H 2 O  HC  CH  NH 3

SELF ASSESSMENT EXERCISE 2

Arrange the following bases in the increasing order of basic strength

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CHM 102 MODULE 1

HC  C, O H, N H 2
3.6 Reactions of Alkynes

Due to the presence of loosely held  electrons, alkynes undergo

reactions similar to those of alkenes. You will see in this unit that some
of the chemical characteristics of alkynes are similar to those of alkenes.
Characteristic reactions of alkynes include electrophilic additions,
reduction and oxidation. Some important reactions of alkynes are
summarized in Table 4.3

Table 4.3: Reactions of alkynes

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

3.6.1 Electrophilic Addition

Electrophilic addition reactions are characteristic of alkynes. Some
common electrophilic addition reactions are discussed below:

(i) Hydrohalogenation

Alkynes can add on the halogen acid (HX). The addition of halogen acid
cannot take place in the dark, but is catalysed by light or metallic
halides. Like alkenes, the addition is in accordance with Markownikoffs
rule; for example, ethyne combines with hydrogen bromide to form first
1-bromoethene and then 1, 1-dibromoethane.

The mechanism of these reactions is the same as in the

hydrohalogenation of alkenes, i.e.,

Note: If one of the carbon atoms involved in double bond formation

(with another carbon atom) carries a positive change, then the species is
called alkenyl cation.

Addition of another molecule of hydrogen bromide could give either

 
CH 3 C HBr (a secondary carbocation) or C H 2 CH 2 Br (a primary
carbocation). Since the secondary carbocation is more stable than the
primary carbocation, the reaction proceeds via the secondary
carbocation to form 1, 1-dibromoethane. Thus:

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CHM 102 MODULE 1

Because of the electron-withdrawing nature of bromine atom, the

availability of  electrons in 1-bromoethene is less than that in ethane.
Hence, the electrophilic addition (of HBr) to 1-bromoethene is much
slower than that to ethene,
In the presence of free radical initiators such as peroxides, anti
Markownikoff addition of HBr is observed as with alkenes. For
example, addition of HBr in the presence of peroxides to 1-butyne gives
1, 2-dibromobutane as shown below:

(ii) Halogenation

Alkynes react with chlorine and bromine to yield tetrahaloalkanes. Two

molecules of halogen add to the triple bond. A dihaloalkene is an
intermediate and can be isolated using proper reaction conditions.
Ethyne, for instance, on treatment with bromine water gives only 1,
2-dibromoethene whereas with bromine alone, it forms 1, 1, 2,
2-tetrabromoethane.

The addition of halogens to ethyne is stereoselective; the predominant

product is the trans isomer.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

SELF ASSESSMENT EXERCISE 3

Write chemical equation for the reaction of propyne with each of the
following reagents.

1. HCl
2. Cl2

3. HBr (in presence of peroxide)

(iii) Hydration
You have seen in previously that addition of a water molecule to an
alkene gives an alcohol. Similarly, addition of a water molecule to an
alkyne gives an enol. An enol has the – OH group attached to a
double-bonded carbon atom.

In fact, enols are very unstable and they isomerise (or tautomerise) to
give aldehydes or ketones. The process by which enols are converted
into adledhydes or ketones is called keto-enol isomerism or keto-enol
tautomerism. For example, when ethyne undergoes hydration, it gives an
aldehyode, i.e. ethanal, while, propyone gives a ketone, i.e. propanone.

The arrow is longer towards aldehyde or ketone side showing the

direction in which the equilibrium is favoured.

In case of unsymmetrical alkyne addition of water place in accordance

with Markowhikoff’s rule. The enol is converted into air aldehyde or
ketone by a mechanism similar to the hydration of a double bond. The
enol double bond is protonated to give a corbocation. The in the

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CHM 102 MODULE 1

example shown below is a protonated ketone. Instead of adding water,

this ion loses a proton to give ketone.

Now you may ask why carbocation is not attacked by water molecule to
give a diol, i.e.

This reaction does not occur, because it is reversible, and the

equilibrium between the ketone and the corresponding diol in most cases
favours formation of the ketone.

(iv) Hydroboration

Addition of borane to alkynes gives alkenyl boranes, which can be

oxidised by basic hydrogen peroxide to ketones via their enol.

The symmetrical internal alkynes give a single product while

unsymmetrical internal alkynes give a mixture of both the possible
ketones. For example, 3-hexyne gives 3-hexanone while 2-bexyne gives
a mixture of 2-hexanone and 3-hexanone.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

The terminal alkynes on hydroboration give aldehydes.

Another reaction of organoboranes is protonolysis. That is, the alkenyl

boranes, formed after the addition of borane to alkynes, on treatment
with ethanoic acid yield cis-alkenes. This reaction sequence provides
another method of converting alkynes to cis-alkenes.

SELF ASSESSMENT EXERCISE 4

Give the equation for hydroboration of a terminal alkyne.

3.6.2 Reduction

Like alkenes, alkynes undergo catalytic hydrogenation. The addition of

hydrogen to an alkyne takes place in two steps. First addition results in
the formation of an alkene; since an alkene can also undergo catalytic
hydrogenation, the second addition give an alkane. By using a calculated
amount of hydrogen and a poisoned catalyst, hydrogenation can be
stopped at the alkene stage. A catalyst mixed with a selective inhibiting
agent is called a poisoned catalyst. These catalysts selectively block the
hydrogenation of alkenes.

This is a stereoselective addition reaction giving predominantly cis

alkenes. In the absence of a poison, catalytic hydrogenation of an alkyne
gives the alkane. Stereoselective reaction is a’ reaction which yields
predominantly one isomer.

Now you can ask: can we modify the reduction of alkynes so as to get
only trans alkenes. The answer is yes; we can get only trans products,
but with a different reducing agent and through a different mechanism.

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If we carry out the reduction of an alkyne with sodium metal or lithium

metal in liquid ammonia, trans alkene is almost an exclusive product.
For example, 3-heptyne is reduced to trans 3-heptene is the following
way:

In the first step of this mechanism, the alkyne accepts one electron to
give a radical anion. The radical anion is protonated by ammonia solvent
to give an alkenyl radical; which gets further reduced by accepting
another electron to give an alkenyl anion. This species is again
protonated to give the alkene.

A radical anion has one centre with a negative charge and another, with
an unpaired electron.

Formation of the trans alkene is due to the rapid equilibration of the

intermediate alkenyl radical between the cis-and trans-forms. The
equilibrium lies on the side of the more stable trans species.

In other words, we can say reduction of alkyne to double bond can yield
either cis-alkene or trans-alkene, depending upon the choice of the
reducing agent.

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

SELF ASSESSMENT EXERCISE 5

Suggest a method for the synthesis of the following from 2-hexyne;

1. cis-2-hexene
2. trans-2-hexene
3. hexane

3.6.3 Oxidation

Reagents and reactions that lead to oxidative cleavage of alkenes also

lead to cleavage of alkynes. Addition of ozone to an alkyne produces the
ozonide. The ozonides on hydrolysis give 1, 2-dicarbonyl compounds,
which undergo oxidative cleavage to carboxylic acids by hydrogen
peroxide formed in the reaction. For example, 2-hexyne on ozonolysis
gives butanoic and ethanoic acids.

Same products are obtained when alkynes are oxidized by alkaline

permanganate and then hydrolysed using mineral acid.

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Oxidative cleavage reactions are used as a tool in structure

determination. The carboxylic acids formed would tell us which of the
carbon atoms were linked through the triple bond in the original alkyne.

SELF ASSESSMENT EXERCISE 6

Propose structures for alkynes that give the following products on

oxidative cleavage;

1. COOH
+ CH3COOH

2. CH3(CH2)7COOH + HOOC(CH2)7COOH

3. 2CH3CH2COOH

4.0 CONCLUSION

Ther are various types of alkynes of which acetylene is the most

popular. It is used in oxy-acetylene flames for cutting and welding
materials. We have given explanation for the acidity of terminal alkynes.

5.0 SUMMARY

 Alkynes are the hydrocarbons with one or more carbon-carbon

triple bond

 Alkynes may be of two type, i.e. terminal or internal.

 Physical properties of alkynes are more or less similar to alkenes
 Alkynes are preapred by alkylation of terminal alkymes or by a
two-fold elimination of HX from dihalide or by dehalogenation
of tetrahalides.
 Terminal alkynes are more acidic than alkanes or alkenes.
 Hydrohalogenation follows Markwonikoff’s rule.
 Halogens add to alkynes to give tetrahaloalkanes. Using proper
reaction conditions dihaloalkene can be isolated.
 Hydration of an alkyne gives an unstable enol which tautomerises
to give an aldehyde or a ketone.
 Hydroboration of alkynes may give ketones or aldehydes,
depnding on reaction conditions and the type of the alkyne.
 Hydrogenation of an alkyne in the presence of Pd, Pt or Ni
catalyst yields an alkane. By using poisoned catalyst, the
intermediate cis-alkane can be obtained. Reduction of an alkyne

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

with sodium or lithium in liquid ammonia gives the

trans-alkene.
 Ozonolysis of alkynes give carboxylic acids.

ANSWER TO SELF ASSESSMENT EXERCISE 1

NaNH , NH  
a) CHCH   2 
3  HC C Na


HC  C N CH3 (CH 2 ) Br  HC  C(CH2 ) CH3
3 3

NaNH .NH  
HC  C(CH2 )3 CH3 2 
3  Na C  C(CH ) CH
2 3 3

NaCC(CH2)3CH3 + CH3Br 
 CH3CC(CH2)3CH3

1. NaNH . NH
b) HCCH    2 
3  CHC(CH ) CH
2 2 3
2. CH3(CH2)2Br

NaNH  
CHC(CH2)2CH3   
2  Na C C(CH2)2CH3
NH3
 _
Na C  C (CH ) CH  CH CH Br  CH CH C  C (CH )2CH
2 2 3 3 2 3 2 2 3

ANSWER TO SELF ASSESSMENT EXERCISE 2

O H < HCC < NH2

ANSWER TO SELF ASSESSMENT EXERCISE 3

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CHM 102 MODULE 1

ANSWER TO SELF ASSESSMENT EXERCISE 4

ANSWER TO SELF ASSESSMENT EXERCISE 5

ANSWER TO SELF ASSESSMENT EXERCISE 6

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CHM 102 INTRODUCTORY ORGANIC CHEMISTRY I

6.0 TUTOR-MARKED ASSIGNMENT

1. How would you carry out the following reactions:

2. Predict the product of the following reactions of 1 – butyne:

3) How will you convert

a) 2-Bromopropane to propyne
b) 1-Bromopropane to 2-hexyne.

4) Suggest steps for the following transformations:

a) 2, 3-dibromopentane to trans-2-pentane
b) 3-methyl-1-butyne to trans-2-methyl-3-heptane

5) Show, by varying appropriate chemical equations, how each of

the following compounds could be converted to 1-hexyne:

a) 1, 2-Dibromohexane:
b) 1-Hexene
c) Hexane

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7.0 REFERENCES/FURTHER READING

R.T. Morrison and R.N. Boyd, Organic Chemistry,(6th Ed.), India:

Prentice-Hall Pvt. Ltd.

Lloyd N. Ferguson, Book of Organic Chemistry, (2nd Ed.), Affiliated

East-West Press Pvt. Ltd.

S.M. Mukherji, S.P. Singh and R.P Kapoor, Organic Chemistry, Vol. I
and II, Wiley Eastern Ltd.

P.L. Soni and H.M. Chawla, Sultan, Textbook of Organic Chemistry,

(24th Ed.), Chand and Sons.

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