UNESCO-NIGERIA TECHNICAL &

VOCATIONAL EDUCATION
REVITALISATION PROJECT-PHASE II

NATIONAL DIPLOMA IN
SCIENCE LABORATORY TECHNOLOGY

ORGANIC CHEMISTRY II
COURSE CODE: STC 221

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 YEAR II- SE MESTER II
THEORY
Version 1: December 2008

TABLE OF CONTENTS

WEEK 1 ETHERS……………………………………………………5

1.1 Structural relationship between water, alcohol and ethers

1.2 The functional group of ethers
1.3 The general formula of ethers
1.4 Simple and mixed ethers
1.5 Nomenclature of aliphatic ethers
1.6 Methods of preparation of ethers

WEEK 2 ETHERS CONTINUED………………………………….15

2.1 Mechanism of the formation of ethers by the Williamson reaction

2.2 Physical properties of diethyl ether
2.3 Chemical properties of ethers
2.4 Uses of diethyl ether

WEEK 3 AMINES……………………………………………………20

3.1 Structural relation between amines and ammonia

3.2 Methods of preparation of primary amines
3.3 Classification of amines as primary, secondary, tertiary and
quatenary
3.4 General formula for the classes of amines in 3.3 with examples
3.5 Use of curly arrows to show the reaction of an amine with hydrogen
ion

WEEK 4 AMINES CONTINUED…………………………………..28

4.1 Chemical reactions of primary amines including Hofmann’s,

Reaction, Nitrosation, and acylation
4.2 Use of curly arrows to show the mechanism of acylation of an

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 Amine with an acyl chloride.
4.3 Uses of amines

WEEK 5 CHEMISTRY OF AROMATIC COMPOUNDS………..33

5.1 Structure of benzene and its homologues

5.2 Aromaticity, resonance, resonance theory and 4n + 2 rule
5.3 Fulfilment of the rules in 5.2 for benzene and its homologues
5.4 Physical properties of benzene and alkyl benzene

WEEK 6 CHEMICAL REACTIONS OF BENZENE ……………..44

6.1 Physical and chemical properties of benzene

6.2 Chemical reactions of benzene, including Friedel-Crafts alkylation
and acylation,, nitration, Sulphonation and halogenation
6.3 Some examples of electrophilic and nucleophillic substitution
reactions of derivatives of benzene

WEEK 7 MECHANISM OF ELECTROPHILIC AND

NUCLEOPHILLIC SUBSTITUTION IN
AROMATIC COMPOUNDS……………………………..48

7.1 Mechanism of electrophilic and nucleophillic substitution

Reactions of monosubstituted benzene
7.2 Effects of substituents, solvents and orientation of incoming group

WEEK 8 THE CHEMISTRY OF PHENOL……………………….50

8.1 Preparation of phenol

8.2 Physical and chemical properties of phenol
8.3 Uses of phenol

WEEK 9 THE CHEMISTRY OF CARBONYL SUBSTITUTED

BENZENE…………………………………………………59

9.1 Preparation of benzaldehyde and benzophenone

9.2 Physical and chemical properties of benzaldehyde and
benzophenone
9.3 Uses of benzaldehyde and benzophenone

WEEK 10 THE CHEMISTRY OF BENZOIC ACID……………….67

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 10.1 Preparation of benzoic acid
10.2 Physical properties, chemical reactions and uses of benzoic acid

WEEK 11 THE CHEMISTRY OF BENZOIC ACID

DERIVATIVES…………………………………………..71

11.1 Preparation of benzoyl chloride and esters

11.2 Use of curly arrows to show the mechanism of the reaction between
benzoyl chloride and methanol
11.3 Uses of benzoyl chloride and benzoyl esters

WEEK 12 THE CHEMISTRY OF BENZAMIDE AND PHTHALIC

ANHYDRIDE………………………………………………72

12.1 Preparation of benzamide and phthalic anhydride

12.2 Use of curly arrows to show the mechanism of the reaction between
benzoyl chloride and ammonia

WEEK 13 THE CHEMISTRY OF BENZAMIDE AND PHTHALIC

ANHYDRIDE CONTINUED…………………………….73

13.1 Physical properties and chemical reactions of benzamide and

phthalic anhydride
13.2 Uses of benzamide and phthalic anhydride

WEEK 14 THE CHEMISTRY OF ANILINE……………………….74

14.1 Laboratory and industrial preparation of aniline

14.2 Physical properties and chemical reactions of aniline with emphasis
On the basic nature of aniline
14.3 Uses of aniline

WEEK 15 THE CHEMISTRY OF DIAZONIUM COMPOUNDS AND

AZO-DYES…………………………………………………81
15.1 Preparation of diazonium salts
15.2 Conversion of diazonium salts to chloride, bromide and cyano
compounds
15.3 Formation of a simple azo-dye

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5
W EEK 1: E T H E R S

1.1 Structural relationship between water, alcohol and ethers

The water molecule consists of two hydrogen atoms attached to an oxygen atom.
Alcohols and ethers may be regarded as organic derivatives of water in which one or both
hydrogen atoms of water are replaced by alkyl or aryl groups. In alcohols one hydrogen
atom of water is replaced while in ethers both hydrogen atoms are replaced. Alcohols and
ethers are therefore monoalkyl and dialkyl derivatives of water respectively. This
structural relationship between these classes of organic molecules is also reflected in the
properties possessed by them.

R substitutes R’ substitutes
H–O–H R–O–H R – O – R’
Water for H Alcohol for H Ether

From the structural point of view an alcohol, e.g., ethanol is intermediate between water
and diethyl ether:

H–O–H H – O – CH2CH3 CH3CH2 – O – CH2CH3

Water Ethanol Diethyl ether

Ethers in which one or both of the R groups are aromatic e.g., C 6H5 –, are also known.
This discussion will however be restricted to the aliphatic ethers.

1.2 Functional group of ethers

The functional group of ethers is called the alkoxy group. Table 1.1 shows the structure
of this functional group along with other functional groups you will meet in this course.

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T A B L E 1.1 Common Functional Groups

Functional Group Name Family of

Organic Compounds

H2C = CH2 Carbon-carbon double bond

Alkene

H–C=C–H Carbon-carbon Alkyne

triple bond

Benzene ring Aromatic

C – X (X = F, Cl, Br, I) Halogen atom Alkyl halide

C – OH Hydroxyl group Alcohol

C – O – R* Alkoxy group Ether

C – O – C – R* Acyl group Ester

C=O Carbonyl Aldehyde or

Ketones

C=O
OH Carboxyl group Carboxylic
Acid

C=O
G* (G = Cl or OR*) Acyl group Carboxylic
Acid
Derivatives
C–N– Amino group Amine

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R* is an abbreviation for any alkyl or aryl group; aryl is used for aromatic compounds in
the same way that alkyl is used for aliphatic compounds (for example methyl, ethyl,
isopropyl). A n aryl group is an aromatic compound with one hydrogen removed ( for
example, phenyl – the phenyl group is benzene with one hydrogen removed)

1.3 General formula of ethers

The general formula of ethers is R – O – R’; where R and R’ are alkyl groups. Names and
structures of some specific members of the homologous series are given below:

CH3 – O – CH3 CH3 – O – CH2CH3

Methoxymethane Methoxyethane

CH3CH2 – O – CH2CH3 CH3CH2 – O – CH2CH2CH3

Ethoxyethane Ethoxypropane

1.4 Simple and mixed ethers

With respect to the nature of the two R groups present in an ether, ethers may be
classified into two groups:

 Simple ethers: These are ethers in which the two R groups are the same, for
example methoxymethane and ethoxyethane.
 Mixed ethers: These are ethers in which the two R groups are different, for
example methoxyethane and Ethoxypropane.

1.5 Nomenclature of aliphatic ethers

Aliphatic ethers can be named in two ways:

 By using I.U.P.A.C. system

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  By using trivial system

1.5.1 Using I.U.P.A.C. system

In the I.U.P.A.C. system, aliphatic ethers are considered as derivatives of alkanes. This
means that ethers are derived from alkanes by the removal of one hydrogen atom of the
alkane and replacing it with an alkoxy group. Notice that in aliphatic ethers the two R
groups are alkane residues. In naming ethers by the I.U.P.A.C system therefore, we must
therefore decide which segment of the molecule is the alkoxy group and which is the
parent alkane. The longer R group is considered to be the parent alkane while the shorter
is viewed as incorporating the oxygen atom of the ether to form the alkoxy group. In
I.U.P.A.C. nomenclature therefore the general name for ethers is alkoxyalkane. Example
1.1 illustrates the I.U.P.A.C nomenclature of aliphatic ethers.

1.5.2 Using trivial system

In the trivial system of naming aliphatic ethers, the name of the ether is derived by
compounding the names of the two alkyl groups in the ether followed by ether. Table 1.1
illustrates this system of nomenclature.

Table 1.1: Some ethers named by the trivial system of nomenclature

NAME FORMULA
Dimethyl ether CH3 – O – CH3
Ethyl methyl ether CH3 – O – CH2CH3
Diethyl ether CH3CH2 – O – CH2CH3
Methyl phenyl ether C6H5 – O – CH3
Diphenyl ether C6H5 – O – C6H5

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1.6 Methods of preparation of ethers

There are several ways of preparing ethers. Two of these are:

 Simple ethers (those containing identical R groups) can be prepared by the

dehydration of an excess of an alcohol with concentrated sulphuric acid at about
140oC. In general the reaction, which occurs in two stages, can be represented by
the equations:

Stage 1: R – OH + H2SO4 R – O – SO2 – OH + H2O

Alcohol Alkyl
Hydrogensulphate

Stage 2: R – OH + R – O – SO2 – OH R – O – R + H2SO4

Diethyl ether

A specific example is the preparation of diethyl ether by dehydration of an excess of

ethanol using concentrated sulphuric acid as the dehydrating agent at a temperature of
140oC:

Stage 1: C2H5 – OH + H2SO4 C2H5 – O – SO2 – OH + H2O

Ethanol Ethyl hydrogensulphate

Stage: C2H5 – OH + C2H5 – O – SO2 – OH C2H5 – O – C2H5 + H2SO4

Diethyl ether

Notice that the essential conditions for the preparation of ether by the dehydration of
alcohol are:

1. The alcohol in excess

2. Concentrated sulphuric acid (supplying hydrogen ion)
3. temperature of 140oC

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In theory, all the catalyzing hydrogen ion is regenerated and the process could continue
indefinitely if the alcohol is added at an appropriate rate. In practice two factors prevent
this:

1. Accumulation of water diluting the mixture.

2. Side reactions especially of a reducing type, which use up the acid, e.g.,

C2H5OH + 2H2SO4 2C +5H2O +2SO2

To a certain extent, also, ethylene may be produced. It is found that a cm3 of concentrated
sulphuric acid will convert about 70a cm3 of ethanol to ether. The process is known as
“Williamson’s Continuous Etherification Process”. It has been in use for manufacturing
ether fo r over a century.

In spite of the fact that Williamson’s Continuous Etherification Process is best for
making simple ethers, mixed ethers can be produced by allowing an alcohol to react with
concentrated sulphuric acid and then heating with a different alcohol.

 Simple and mixed ethers can be prepared by the reaction between an alkyl halide
and the sodium derivative of an alcohol (the alkoxide):

The action of sodium on an alcohol yields the corresponding sodium alkoxide. In general,

2R – OH + 2Na 2R – O-Na+ + H2
Sodium
Alkoxide
EXAMPLE 1.1

Using I.U.P.A.C Nomenclature to name an ether

Name the following ethers using I.U.P.A.C nomenclature

(a) CH3 – O – CH3

(b) CH3 – O – CH2CH3

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 (c) CH3CH2 – O – CH2CH3

(d) CH3CH2CHCH2CH2CH3

OCH3

Solution
(a) The two R groups are of identical chain length therefore either can serve as the
parent alkane and the other becomes the alkoxy group.
Parent hydrocarbon: Methane
Alkoxy group: Methoxy
Name of ether: Methoxymethane

(b) The R group on the right of the oxygen atom is longer than the one on the left and
is therefore the parent alkane. The shorter R group constitutes the alkoxy group.
Parent hydrocarbon: Ethane
Alkoxy group: Methoxy
Name of ether: Methoxyethane

(c) The two R groups are of identical chain length therefore either can serve as the
parent alkane and the other becomes the alkoxy group.
Parent hydrocarbon: Ethane
Alkoxy group: Ethoxy
Name of ether: Ethoxymethane
(d) The two R groups are of different chain length therefore the longer, having six
carbon atoms, is the parent alkane while the shorter, having only one carbon atom
is the alkoxy group.

(e) Parent hydrocarbon: Hexane

Alkoxy group: Methoxy
Name of ether: Methoxyhexane

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Specifically, using ethanol as an example, sodium ethoxide is produced:

2CH3CH2OH +2Na 2CH3CH2ONa + H2

Sodium
Ethoxide

In the preparation of ethers from sodium alkoxide and an alkyl halide, it is usual to use
the alkyl iodide. The mixture of sodium alkoxide and alkyl iodide is heated under water-
reflux to yield the ether. The method can be used for both simple and mixed ethers. In
general, for simple ethers, the reaction is:

R – O-Na+ + R’X R – O – R’ + NaX

Sodium Simple ether
Alkoxide

A specific example of this method is the preparation of ethoxyethane, which is simple

ether. In this case sodium ethoxide and ethyl iodide are boiled under water-reflux:

CH3CH2I + CH3CH2ONa CH3CH2O CH2 CH3 + NaI

Ethyl iodide Ethoxyethane

In general, for mixed ethers, the reaction is:

R – O-Na+ + R’X R – O – R’ + NaX

Sodium Mixed ether
Alkoxide
A specific example of this method is the preparation of methoxyethane, which is a mixed
ether. In this case sodium methoxide and ethyl iodide are boiled under water-reflux:

CH3ONa + CH3CH2I CH3O CH2 CH3 + NaI

Sodium Methoxyethane
methoxide

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The preparation of ethers by reaction between sodium alkoxide and an alkyl halide is also
due to Williamson. It is of great theoretical value, showing clearly the structure of any
ether produced by it.

QUESTIONS AND PROBLEMS

1. Draw all of the alcohols and ethers of molecular formula C 4H10O, and name each
of the isomers drawn.
2. Ethers may be prepared by the removal of water (dehydration) between two
alcohols as shown. Give the structure(s) of the ethers formed by the reaction of
the following alcohol(s) under acidic conditions with heat.
H+
Example: CH3OH + HOCH3 CH3OCH3 + H2O
Heat

(a) 2CH3CH2OH ?

(b) CH3OH + CH3CH2OH ?

(c) (CH3)2CHOH + CH3OH ?

3. There are three isomers of molecular formula, C 3H8O, of which two are alcohols
and one an ether. Write structural formulae form all the three. How, by a chemical
test, would you decide which was the ether? How would you convert one of the
alcohols into ethanol?
4. Write the structural formula for:

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(a) Dimethyl ether
(b) Diisopropyl ether
(c) 3-Methoxyhexane
(d) Anisole
(e) 1,2-Epoxypentane

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W E E K 2: ETHERSCONTINUED

2.1 Mechanism of the formation of ethers by the Williamson reaction

The reaction between an alkyl halide and a sodium alkoxide in the Williamson ether
synthesis is a nucleophillic substitution reaction, the nucleophile being the alkoxide ion,
RO-. The approach most likely to induce reaction is along the axis line of the alkyl halide
molecule towards the alkyl group. This approach needs least output of energy. By
electromeric effect, the approach of the nucleophile intensifies the partial polarity of the
C – Iodine bond. By electron shift towards the halogen atom, a relatively slow heterolysis
of the halide molecule is produced and the nucleophile then combines, by utilizing lone
pair electrons in a fast reaction, with the carbonium ion. This is a S N1 reaction, rate-
controlled by the slow heterolysis.

2.2 Physical properties of diethyl ether

Some of the physical properties of diethyl ether are:

 It is a colorless, volatile liquid with a characteristic “ether” smell

 It boils at 36oC at 760 mmHg.

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  It is considerably less dense than water (0.72g/cm3)
 It is appreciably soluble in water (about 7g in 100g of water at room temperature)
 It is a highly inflammable liquid

2.3 Chemical properties of ethers

At the beginning of this topic the structural relationship between water, alcohols and
ethers was stated and mention was also made of the fact that these structural differences
are also reflected in the properties exhibited by these compounds. We shall now examine
this matter in greater details. Because of the attachment of hydrogen atoms to oxygen,
water is very reactive towards metallic sodium. Water reacts with metallic sodium to
form hydrogen and sodium hydroxide in a highly exothermic and rapid reaction:

2H2O + 2Na 2NaOH + H2

Such rapid release of large quantities of energy can lead to explosion. Alcohols resemble
water in the sense that they still have a hydrogen atom attached to oxygen and, like water,
alcohols also react with metallic sodium even though with much less violence than water.

2CH3CH2OH + 2Na 2CH3CH2ONa + H2

In ethers both hydrogen atoms of water have been replaced by alkyl groups and,
consequently, ethers lack the active hydrogen in water and alcohols and hence do not
react with metallic sodium.

CH3CH2OCH2CH3 + Na No reaction

Besides their effects on the chemical properties, these structural differences also affect
the physical properties of these compounds. For instance even though the C – O bond in
all the three classes of compounds are polar, ethers do not form hydrogen bonds to one
another because there is no – OH group in ethers. Alcohols and water on the other hand
are extensively hydrogen bonded because of the presence of the – OH group. Therefore

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ethers have much lower boiling points than alcohols of similar molecular weights but
higher boiling points than alkanes of similar mol ecular weights. Compare the following
examples:

CH3CH2CH2CH3 CH3 – O – CH2CH3 CH3CH2CH2OH

Butane Methoxyethane 1-Propanol
(An alkane) (An ether) (An alcohol)

M. W = 58 M. W = 60 M. W = 60
b.p. = -0.5oC B.P. = 7.9oC B.P. = 97.2oC

In general ethers are not a very reactive group. They are not affected by reducing and
oxidising agents (apart from combustion) and by alkali. Phosphorus pentachloride
liberates no hydrogen chloride from an ether. This negative behaviour is of structural
interest, showing the absence of the hydroxyl group in ethers.

Combustion, cleavage reactions with acids and formation of oxonium derivatives are
three chemical reactions of ethers which we shall consider.

1. Combustion

The ethers of common occurrence are extremely inflammable, burning to carbon dioxide
and water, e.g.,

(C2H5)2O + 6O2 4CO2 + 5H2O

When ordinary ether, diethyl ether, is in use, all flames in the vicinity should be
extinguished or there is serious danger of fire.

2. Cleavage Reactions with Acids

If boiled with hydriodic acid an ether is converted to water and one, or two, alkyl iodides,
according to whether it is a simple or mixed ether, e.g.,

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 C2H5 – O – C2H5 + 2HI 2C2H5I + H2O

CH3 – O – C2H5 + 2HI CH3I + C2H5I + H2O

By identification of the alkyl iodides, the alkyl groups present in the ether are determined.
Similarly, if heated with excess of concentrated sulphuric acid ethers are slowly
converted to alkyl hydrogensulphate and water. For example diethyl ether, under this
condition, is converted to ethyl hydrogensulphate and water.

(C2H5)2O + 2H2SO4 2C2H5HSO4 + H2O

3. Formation of oxonium derivatives

Like water ethers may form ionised compounds with halogen acids. For example
dimethyl ether forms a fairly stable, crystalline chloride in which the chlorine is present
in the ionised state. Such compounds are known as oxonium derivatives.

(CH3)2O + HCl (CH3)2O H+Cl-

This reaction is similar to the ionization f hydrogen chloride in water. The oxygen plays
the same part, as proton acceptor, in both cases.

H2O + HCl (H2O.H+)Cl-

2.4 Uses of diethyl ether

Some of the uses of diethyl ether are:

 It is used as an anesthetic. Inhalation of the vapour depresses the activity of
the central nervous system.
 It is used as solvent for fats, oils and resins. Very many organic substances
dissolve in it without reaction
 It is a valuable solvent in organic preparations.
 It mixes only slightly with water and, having a lower density, separates readily
from it as an upper layer

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  It has a very low boiling point, 36oC at 760 mmHg and is easily distilled away
by steam heat leaving behind solute of high boiling point.


QUESTIONS AND PROBLEMS

5. Compare and contrast ethanol and diethyl ether with respect to both physical and
chemical properties.
6. Which ethers correspond to the formula C 6H14O? How would you attempt to
establish the identity of each substance?
7. Describe Williamson’s synthesis, pointing out its theoretical importance as a
method for establishing the structure of ether.
8. The preparation of ether by the action of sulphuric acid on ethyl alcohol is often
described as a “continuous” process. Discuss the “continuous” nature of this
reaction.
9. Outline a possible laboratory synthesis of each of the following compounds from
alcohols and phenols:

(a) tert-Butyl methyl ether

(b) Phenetole (C6H5OC2H5)
(c) Isobutyl isopropyl ether

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W EEK 3: A M I N E S

3.1 Structural relationship between amines and ammonia

Amines are organic derivatives of ammonia in which one, two or all the hydrogen
atoms of ammonia have been replaced by alkyl groups. They are therefore classified with
respect to the number of hydrogen atoms of ammonia that have been replaced.

H–N–H R substitutes H–N–R R’ substitutes H–N–R

H for H H for H R’
Ammonia Primary amine Secondary amine

R” substitutes
for H

R”– N – R

R’
Tertiary amine

In addition to the above, there exist, also compounds which are tetraalkyl derivatives of
the compound, NH4OH, or, of its salts. They are known as quatenary ammonium bases or
salts, and are of the general type NR 4OH, or NR4X, were X represents a halogen atom.
Both types of compounds are highly ionised.

3.2 Nomenclature of amines

Several system of naming amines have evolved, including, of course, the I.U.P.A.C.
Nomenclature system; however, the I.U.P.A.C. names are not the most commonly used
names for amines. The nomenclature system, which is logical, easy to use and has gained
wide popularity, is known as the Chemical Abstracts or CA system. This system has been
approved for use by I.U.P.A.C. and is presented here. In the CA system the final –e of the
name of the parent compound is dropped, and the suffix, -amine is added. For instance,

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 CH3 – NH2 CH3CH2CH2 – NH2 CH3CH2CH2CHCH3

NH2

Methanamine Propanamine 2-Pentanamine

For secondary and tertiary amines, the prefix N – alkyl is added to the name of the parent
compound. For example,
CH3

CH3 – NH – CH2CH3 CH3 – N – CH3

N – Methylethanamine N,N – Dimethylmethanamine

3.3 Classification of amines

Amines are classified as primary (1 o), secondary (2o) or tertiary (3o) depending on
whether one, two or three hydrogen atoms of ammonia have been replaced by alkyl
groups.

 Primary amines: These are amines in which only one hydrogen atom of
ammonia has been replaced by an alkyl group. They have the general formula
RNH2, where R is an alkyl group. Examples of such amines are methanamine
(methyl amine) and ethanamine (ethyl amine).

CH3 –N – H C2H5 – N – H

H H

(or CH3NH2) (or C2H5NH2)

Methyl amine Ethyl amine

 Secondary amines: These are amines in which two hydrogen atoms of ammonia
have been replaced by alkyl groups. They have the general formula RNHR’,
where R and R’ are alkyl groups. Examples of secondary amines are dimethyl

22
 amine (N-Methylmethanamine), ethyl methyl amine (N-Methylethanamine) and
diethyl amine (N-Ethylethanamine).

CH3 – N – CH3 CH3CH2 – N – CH3

H H
(or (CH3)2NH) (or CH3CH2NHCH3)

Dimethyl amine Ethyl methyl amine

C2H5 – N – C2H5

(or (C2H5)2NH)

Diethyl amine

 Tertiary amines: These are amines in which all three hydrogen atoms of
ammonia have been replaced by alkyl groups. They have the general formula of
RR’R’’N, where R, R’ and R’’ are alkyl groups. Examples of tertiary amines are
trimethyl amine (N,N-Dimetylmethanamine) and diethyl methyl amine (N- Ethyl-
N-methylethanamine).

CH3 – N – CH3 CH3CH2 – N – CH2 CH3

CH3 CH3
(or (CH3)3N) (or (CH3 CH2)2N CH3)

Trimethyl amine Dimethylethyl amine

3.4 Preparation of primary amines

Primary amines can be prepared in several ways:

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  Primary amines can be prepared by the reaction of an alkyl halide and ammonia.
The alkyl halide (usually the iodide) is heated to about 100 oC with concentrated
ammonia in a sealed tube. However, the method is rarely used because a mixture
of primary, secondary and tertiary amines as well as quaternary ammonium salt is
obtained:

R – Br + NH3 R – NH2 + HBr

R – Br + R – NH2 R2NH + HBr

R – Br + R2NH R3N + HBr

R – Br + R3N R4N+Br-

The method is of theoretical interest because it clearly indicates the nature of the amines
as alkyl derivatives of ammonia. A specific example is the reaction between methyl
iodide and concentrated ammonia. The fist of the reaction is:

CH3I + NH3 CH3NH2 + HI

HI + NH3 NH4I

The following further stages could then occur, giving secondary and tertiary amines and
the quatenary iodide. These are difficult to separate.

CH3I + CH3NH2 (CH3)2NH + HI

CH3I + (CH3)2NH (CH3)3N + HI
CH3I + (CH3)3N (CH3)4N+I-

The hydrogen iodide is converted to ammonium iodide by excess ammonia present.

 Primary amines can be made by the reduction of a nitro compound. The reducing
agent can be hydrogen, catalyzed by Raney nickel or lithium aluminium hydride.

24
 Tin and concentrated hydrochloric acid can also be used as the reducing agent. In
general the reactions can be represented as:

Preparation of primary aliphatic amine using Raney nickel as catalyst:

Ni as cat
.R – NO2 + 3H2 R – NH2 + 2H2O

A specific example is the preparation of ethylamine from nitroethane:

Ni as cat
CH3CH2NO2 + 3H2 CH3CH2NH2 + 2H2O

Preparation of primary aliphatic amine using lithium aluminium hydride as

Catalyst:
LiAlH4
R – NO2 R – NH2

A specific example is the preparation of methylamine from nitromethane:

LiAlH4

CH3NO2 CH3NH2 + 2H2O

 Primary amines can be formed by the reduction of cyanides and amides with
lithium aluminium hydride.

Primary amines from cyanides:

LiAlH4
R – CN RCH2 – NH2
A specific example is the preparation of propanamine from ethyl cyanide:
LiAlH4

CH3CH2CN LiAlH4 CH3CH2CH2NH2

Primary amines from amides:

R – CO – NH2 LiAlH4 R – CH2 – NH2

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 A specific example is the formation of ethanamine from acetamide:
LiAlH4
CH3CONH2 CH3CH2NH2

It should be noted that an amide, RCONH2, is reduced to the amine with the same
number of carbon atoms, RCH2NH2, with lithium aluminium hydride but gives
the lower homologue, RNH2, in the Hofmann reaction

 Primary amines can be made by Hofmann degradation reaction. In this reaction an

amide is treated with bromine and alkali, and the resulting amine is distilled off.
Primary amines are formed.

R – CO – NH2 + Br2 + 4NaOH R – NH2 + Na2CO3 + 2NaBr + 2H2O

A specific example is the preparation of butanamide from pentanoic acid amide.

CH3(CH2)3CONH2 + Br2 + 4NaOH CH3(CH2)2CH2NH2 + Na2CO3 + NaBr + 2H2O

3.5 Basicity of amines

The simple primary aliphatic amines are very soluble in water. The solutions are
electrolytes and contain the hydroxyl ion, OH-, which gives them alkaline properties, e.g.

CH3NH2 + H2O = CH3NH3+ + OH-

Aqueous solutions of methylamine and ethylamine both turn red litmus blue. The amines
are considerably stronger bases than ammonia.

pKb

Ammonia 4.75

Methylamine 3.30

Ethylamine 3.33

26
A nitrogenous organic base in aqueous solution participates in the equilibrium:

XN: + H2O = XNH:H+ + OH-

In the above equation X is a trivalent group or combination of groups. The equilibrium

constant (or basicity constant) is given by the expression:

[XNH:H+][OH-]
Kb = [XN:]

The concentration of water is taken as constant since i is in large excess. As with acids
the quantity usually quoted for a base is not Kb but pKb where pKb = - log Kb. Then the
smaller the value of pKb , the stronger is the base. The strength of nitrogenous organic
bases increase in proportion to their readiness to take protons in combination, i.e., to the
availability of the unshared pair of electrons on the nitrogen atom.

XN: + H+ XN:H+

Since the inductive effect of alkyl groups is +I, i.e., electro-repelling, the replacement of
H by alkyl groups in the ammonia molecule, or in an amine, should render the unshared
pair of electrons more available and so produce a stronger base. This is true for primary
and secondary amines generally, as in the following (pKb values quoted).

NH3 C2H5NH2 (C2H5)2NH

4.75 3.33 3.07

However, the introduction of a third alkyl group reduces the basicity in aqueous solution,
e.g., (C2H5)3N, pKb == 3.12. This is caused by the fact that the ions from primary and
secondary amines can be readily solvated (i.e., in water hydrated) by hydrogen bonding
and this stabilizes the ions.

27
 (C2H5)2NH + H+ (C2H5)2NH2+

N OH2
(C2H5)2N+
N OH2

A tertiary amine ion, e.g. (C2H5)3NH+, has only a single H atom available for salvation
and the ion is less stabilized. This tends to reduce basicity in an aqueous medium. In a
solvent e.g. chlorobenzene, in which salvation by hydrogen bonding does not occur, the
order of increasing basic character in butylamines is primary secondary
tertiary, though in water the pKb values are3.39, 2.72 and 4.13.
The introduction of –I (i.e., electron attracting) atoms or groups such as F, Cl or NO2 into
the amine molecule adjacent to the nitrogen atom has the expected effect of making the
amine less basic. This occurs because the lone pair of electrons of the nitrogen atom
becomes less available for combination for combining with H+. For example, (F3C)3N has
no measurable basicity. If the –I group is carbonyl, C = O, the compound becomes an
amide, which is only very feebly basic in aqueous solution (pKb of acetamide is 14.5).
Acetamide forms a chloride with dry HCl in dry ether but the chloride is completely
hydrolysed in water.

28
W EEK 4: A M I N E S C O N T I N U E D

4.1 Physical properties of amines

Methylamine is gaseous (B.P. -6oC at 760 mmHg). Ethylamine (B.P. 19 oC at 760 mmHg)
is also gaseous under ordinary conditions. Propylamine (B.P. 49 oC at 760 mmHg) and
butylamine (B.P. 78oC at 760 mmHg) are liquids. All are very soluble in water. They
possess a peculiar odour, like ammonia with a fishy admixture. Methylamine burns in air;
this property distinguishes it from ammonia, which will not burn until the percentage of
oxygen by volume is raised to 25%.

4.2 Chemical reactions of amines

4.2.1 Basic character

As has been mentioned in section 3.5 the amines resemble ammonia in being basic. This
basic character of amines is reflected in their ability to form salts and to precipitate
metallic hydroxides as discussed below.

4.2.1.1 Salt formation

Like ammonia the amines form crystalline salts, of which the chlorides are most
frequently met. As an illustration, if a few cm3 of methylamine solution is reacted with
dilute hydrochloric acid and the mixture is evaporated off to dryness by steam heat, a
white solid will remain. This is methylammonium chloride.

CH3NH2 + HCl (CH3NH3)+Cl-

Compare: NH3 + HCl NH4+Cl-

If warmed with caustic alkali solution, this salt will liberate the free amine, detectable by
its fishy ammoniacal smell.

29
 (CH3NH3)+Cl- + Na+OH- Na+Cl- + H2O + CH3NH2

Compare: NH4+Cl- + Na+OH- Na+Cl- + NH3

Note that in these salts the chlorine is present as the chloride ion. In solution, the salts
precipitate silver chloride with dilute nitric acid and silver nitrate solution, the usual
analytical test for chloride ion.

Cl- + Ag+ AgCl

Compounds like methyl chloride, or chloroform, in which the chlorine is combined

covalently, give no such reactions.

The amines being weak bases,, their salts with strong acids are appreciably hydrolysed in
solution, and the solutions are acidic in consequence.
If the chloride of an amine is dissolved in as little water as possible and then a 10%
solution of platinum chloride is added, a white crystalline precipitate of the
corresponding platinichloride is thrown down.

2RNH3Cl + PtCl4 (RNH3)2PtCl6

Compare: 2NH4Cl + PtCl4 (NH4)2PtCl6

On ignition, the platinichlorides leave a residue of metallic platinum which can be

weighed. This serves as a method for determining the molecular weight of the base.

4.2.1.2 Precipitation of hydroxides

Since they contain a considerable concentration of hydroxide ions, solutions of amines

will precipitate insoluble hydroxides from salts of certain metals, e.g.,

30
 FeCl3 + 3CH3NH3+OH- Fe(OH)3 + 3CH3NH3+Cl-

ZnSO4 + 2CH3NH3+OH- Zn(OH)2 + (CH3NH3+)2SO42-

Compare similar actions of aqueous ammonia.

Secondary and tertiary amines have similar basic properties and form salts resembling
those of primary amines.

(CH3)2NH + HCl (CH3)2NH2+Cl-

(CH3)3N + HCl (CH3)3NH+Cl-

4.2.1.3 Action of aliphatic amines with nitrous acid

Amines react with nitrous acid in a way which depends on whether they are primary,
secondary or tertiary.
Primary aliphatic amines react to give gaseous nitrogen. The reaction is complex; for
example propanamine gives nitrogen almost quantitatively, but a mixture of other
compounds is also formed, among them being propene, propan-2-ol and a trace of
propan-1-ol.
Secondary amines react with nitrous acid to give nitroso compounds, which are yellow
oils. In general:

R2NH + HNO2 R2N – N = O + H2O

Tertiary amines react with nitrous acid to give solutions containing substituted
ammonium nitrite. Since these are salts formed by a weak acid and a weak base, they are
extensively hydrolysed.

31
 R3N + HNO2 = R3NH+NO2-

The above equilibrium lies to the left hand side. In effect therefore tertiary amines react
with nitrous acid at ordinary temperature to give no visible effect.

4.2.1.4 The carbylamine or isocyanide reaction

Primary amines react with chloroform and a solution of potassium hydroxide in ethanol
to form isocyano compounds. The carbylamines have unpleasant, rather nauseating smell.
They are quite poisonous. In general:

RNH2 + CHCl3 +KOH RNC +3KCl +3H2O

This reaction serves as an important test for primary amines, not given by secondary and
tertiary amines.

4.2.1.5 With acid chlorides and acid anhydrides

Primary and secondary amines react with acid chlorides and acid anhydrides to form
substituted amide. For example methyl amine reacts with acetyl chloride to form N-
methylacetamide

CH3NH2 + CH3COCl CH3CONHCH3

4.3 Quatenary ammonium compounds

These compounds are related to ammonium hydroxide, NH4OH, or its halogen salts, by
substituting the four hydrogen atoms of the (NH4) group by alkyl groups.
A tertiary amine will combine with the corresponding alkyl halide to produce a
quaternary ammonium halide. The iodide is usually used.

(CH3)3N + CH3I (CH3)4N+I-

If the alkyl groups differ, mixed quaternary compounds can be formed, e.g.,

32
 (CH3)3N + C2H5I (CH3)3C2H5 N+I-

These halogen compounds are salts and the halogen is present in ionized form. Solutions
of these salts are electrolytes and silver halides can be precipitated from by silver nitrate
solution, e.g.,

2(CH3)4N+I- + Ag2O + H2O 2AgI + 2(CH3)4N+OH-

(CH3)4N+I- + KOH KI + (CH3)4N+OH-

These quaternary ammonium bases are very much stronger, as alkalis, than ammonium
hydroxide. They are fully ionized and resemble sodium and potassium hydroxides in
alkaline behaviour. They are deliquescent solids, absorbing carbon dioxide from the air,
saponifying fats and precipitating metallic hydroxides from solution of their salts.

The very strongly basic character of these compounds arise from their having no non-
alkyl hydrogen combined with the nitrogen atom. Consequently they cannot take up OH-
to produce an unionized form and can only remain completely ionized, e.g.,
(CH3)4N+OH-. Compare the case of tertiary amine in which the cation retains one non-
alkyl H atom and can revert to a non-ionised system.

R3NH+ + OH- = R3N + H2O

33
W EEK 5: CHEMISTRY OF AROMATIC COMPOUNDS

The parent hydrocarbon for all aromatic compounds is benzene, C 6H6. The general
molecular formula for aromatic hydrocarbons is C nH2n-6. Toluene, C7H10 or C6H5CH3, is
the next homologue, followed by the xylenes, C 8H10 or C6H4(CH3)2. There is one structure
possible for benzene and toluene. There are however three isomeric xylenes. The
structures of benzene and its homologues are shown below.

5.1 The formula of benzene

The formula of benzene has offered a very complex problem to chemists. It as been under
investigations for over a hundred years and great masses of material have been written
about it. No final conclusion has as yet been reached and it is only possible to indicate
some of the main points at issue.

There is no doubt that the two most important matters which any acceptable formula of
benzene must explain are: (1) isomerism in benzene derivatives, (2) the behavior of
benzene in substitution and addition reactions.

5.2 Isomerism in benzene derivatives

Benzene and its derivatives are notable for very little isomerism. The experimental facts
show that there are no isomers for benzene itself in the aromatic series and, for a given
substituent, X, isomerism is completely covered by the following table:

Table 5.1 Isomerism in Benzene Derivatives

Compound Number of isomers

Benzene, C6H6 1
Monoderivative, C6H5X 1
Di-derivatives, C6H4X2 3
Tri-derivative, C6H3X3 3
Tetra-derivatives, C6H2X4 3

34
Penta-derivative, C6HX5 1
Hexa-derivative, C6X6 1

That is, the isomerism of benzene itself and all of its derivatives from a given substituent,
X, is covered by a total of 13 isomers. In contrast with this we may notice that there are 5
isomers for the alkane, C6H14, alone. Its various derivatives from a given substituent, X,
must run into scores if not hundreds, of isomers.

The structural formula of benzene put forward by Kekule (1865) has won general
acceptance in its main outline. Kekule suggested that the six carbon atoms of benzene are
arranged in the form of a regular hexagonal “ring”, with the carbon atoms all in the same
plane. Each carbon atom is combined with one hydrogen atom and all the hydrogen
atoms lie in the same plane as the hexagonal “ring” and one bond to combine the
hydrogen atom. To account for the fourth valency bond of each carbon atom, Kekule
suggested alternate single and double bonds round the “ring” producing a structure:

The whole molecule lies in the plane of the paper, except in so far as the atoms possess
“thickness”.

It is well known that mono-substitution of benzene by a given constituent, X, always

produces exactly the same product, C 6H5X. This could be explained in one of two ways,
viz,: (1) if one particular hydrogen atom is substituted every time; (2) if all the hydrogen
atoms were exactly equivalent to each other in the molecule, so that it makes no
difference which one is substituted. It has been experimentally proved that the second of
these possibilities is the true explanation. Kekule’s formula, giving a completely

35
symmetrical molecule, in which all hydrogen atoms are exactly equivalent to each other,
is quite satisfactory in this respect.

It should be noted that if the hydrogen atoms were not in the same plane of the hexagonal
ring, several isomers of benzene would exist. They could differ by having the six
hydrogen atoms arranged 0,6 or 1,5 or 2,4, etc., on different sides of the ring and would
undoubtedly be recognizably different in properties.

Since, in Kekule’s formula, all the carbon (and hydrogen) atoms are exactly equivalent to
each other, there can be only one mono-substitution product from it, as the experimental
facts require, i.e.,

By convention, the substituent is usually written in the “top” position as shown, but it
must be remembered that all the positions are, in fact, alike.

Once a particular carbon atom has been differentiated by acquiring a substituent, three
different relative positions for a second substituent are now distinguishable in Kekule
molecule. The corresponding isomers are named ortho-, meta- and para- (or o-, m- and
p-) as below:

36
By convention, the o- and m-derivatives are usually written with the substituents on the
right of the molecule. If written with the substituent

On the left, the relative positions are exactly the same and no new isomers are indicated,
e.g.,
If either of the two arrangements is turned over “on to its back”, it exactly produces the
other.

It should be noted that if two different substituents, X and Y, are introduced into the
benzene molecule, the o-, m- and p- relation is unchanged and thee are still only three
isomers of C6H3X3. These compounds are usually distinguished by (mentally) numbering
the carbon atoms as shown below, and stating, by numbers, the position of the
substituents as:

The student should satisfy himself that all other (superficially different) arrangements for
tri-substitution are, in fact, duplicates of one of the above, e.g.,

Is a duplicate of the 1,2,4- arrangement above.

37
With four substituents groups, two hydrogen atoms remain in the molecule, C 6H2X4. The
Kekule formula supplies three isomers of tis molecular formula, with two hydrogen
atoms in the orth-, meta- and para-positions. The three are:

The numbering may begin from any of the substituent groups.

With five substituents present, only one hydrogen atom remains, C 6HX5. This is the same
as C6H5X, but in reverse. Only one compound of this type is known for any one
substituent, X.

PentaXbenzene

Finally, the compound C6X6 resembles the case of benzene itself and only one compound
of this formula is known. The molecule is completely symmetrical, like that of benzene.

HexaXbenzene

38
In the above theoretical treatment of the Kekule formula, the derivatives given are in
complete accord with factual observations, and the same total of 13 compounds covers
the entire isomerism of benzene and all its derivatives from a given substituent, X. So far
the Kekule formula is completely adequate to explain isomerism.

The Kekule formula, however, requires more isomers than the facts supply. For example,
the two derivatives

I II
differ in structure. In (I), the two carbon atoms carrying the groups, X, are combined by a
single valency bond; in (II), by a double valency bond. There is no doubt that this
structural difference will produce recognizably different properties and so provide two
isomers of ortho-diXbenzene. Similarly, the compound C 6H2X4, Having the hydrogen
atoms in the ortho-position, should show two isomeric forms in Kekule’s formula but, in
fact, shows only one form. Kekule attempted to meet this difficulty by suggesting that the
two ortho-forms do exist, but in equilibrium mixture of constant composition, which
gives illusion of a single form. However, no evidence to support this theory was adduced.
Modern “resonance” theories applied to the Kekule theory have removed this difficulty.

5.3 The unsaturation in benzene in relation to the Kekule formula

The Kekule formula represents the benzene molecule as containing three double bonds of
the ethylenic type, thus:

H–C–H

H–C–H
Benzene
Ethylene

39
Ethylene possesses the typical addition properties of an unsaturated alkene hydrocarbon.
It forms addition compounds readily with chlorine, bromine, hydrogen halides, hydrogen,
hypochlorous acid, the elements of hydrogen peroxide, ozone, etc. It reaches saturation
by combining with two hydrogen atoms or their equivalent.

H–C–H H–C–H

+ H2
H–C–H H–C–H

It does not give substitution reaction under ordinary experimental conditions.

By analogy we would expect benzene to show similar addition properties and to reach
saturation by combining with six hydrogen atoms or their equivalent. It does give
addition reactions with hydrogen, chlorine and bromine (in chosen conditions) and ozone.
It reaches saturation by combining with six hydrogen atoms or their equivalent, as the
Kekule formula requires. Though two of the addition products, the ozonide and
benzenehexachloride, are rather unstable, there is undoubtedly some form of unsaturation
present in the benzene molecule. The difficulty is that benzene also gives substitution
reactions with nitric acid, sulphuric acid, chlorine and bromine (in suitable conditions)
and alkyl halides. It is clear therefore that the unsaturation is not of the usual ethylenic
double bond type and it must be admitted at once that the ordinary Kekule formula,
showing three ethylenic double bonds in the benzene molecule, is not satisfactory to
explain its behaviour in substitution reactions.

It is not possible here to deal with all the theories which have been devised to reconcile
these contradictions, but two of them (Thiele’s Theory and modern Resonance Theory)
will be briefly considered.

5.3. 1 Thiele’s conjugation theory

The structural system

40
 – C=C–C=C–

(i.e., a straight chain of four carbon atoms with alternate single and double bonds) is
known as a conjugated system. It has been found that if a compound containing such a
system reacts additively with bromine, the first two atoms of bromine added do not
necessarily saturate one of the existing double bonds. Instead, one atom of bromine may
be added to the first carbon atom and one to the fourth carbon atom of the conjugated
system, the remaining double bond being shifted to a position between the second and
third carbon atoms.

– C = CH – CH = CH – + Br2 – CHBr – CH = CH – CHBr –

To explain this, Thiele suggested that the double bonds in the conjugated system did not
absorb all the combining power of the carbon atoms but left all of them with residual
valency-power available. Then the two inner carbon atoms were able to saturate each
other’s residual bonds, leaving the end carbon atoms open to attack through their
unabsorbed valency power. This was envisaged in some such way as

– C = CH – CH = CH –.

The bromine atoms then combined at the ends of the system where “loose” combining
power are available. The two double bonds thereby become single bonds and the
unsaturation was transferred to the middle of the system.

Applying this “conjugation” idea to the ring system of benzene, we should obtain the
structure:

Here, since the conjugated system is completely closed, there are no “ends” with
unabsorbed valency power available where additive attack can readily take place; hence

41
the failure of benzene to react as a typical ethylenic compound and its tendency to show
substitution reactions.

However, further developments were unfortunate for this theory. There is no reason why
the closed conjugated system should be limited to six carbon atoms. A compound
containing eight carbon atoms and eight hydrogen atoms in a cyclic structure, with
alternate single and double bonds was prepares (cyclooctatetraene)

It showed ordinary additive, ethylenic properties and did not at all resemble benzene in
giving substitution reactions. Clearly then, the aromatic nature of benzene is specially
connected with the presence six carbon atoms in the ring.

5.3.2 The Resonance rheory

This theory is quite modern and only a very brief outline of it can be given. Adopting the
Kekule theory, there are two possible “extreme” structures for the benzene molecule, viz.,

and

The resonance theory states that when two structures may occur, associated with identical
(or very similar) energy content,, the actual state of the compound will be a “resonance”
state intermediate between the two extremes and associated with less energy than either.
In the resonance state, some of the properties of the theoretical, extreme structures are
suppressed – in the case of benzene, for example, the ethylenic properties are partly
suppressed and the “resonance hybrid” shows substitution reactions. The process of
hybridization involves modification of the electronic orbitals concerned in the valency
bonds. Resonance is very marked in benzene where the molecule is typically planar. It is

42
absent in cyclooctatetraene in which the molecule is not planar but “buckles” into three
dimensions.

In orbital terms the position is as follows. Supposing that the aromatic ring contains no
ethylenic double bonds, each carbon atom requires three valency bonds to maintain its
position, i.e., one bond each to two other carbon atoms and one to a hydrogen atom.
These bonds are supplied by hybridizing 2s atomic orbitals of each carbon atom with its
2px and 2py orbitals. This makes available three hybridized atomic orbitals for the carbon
atom and they can overlap with similar orbitals from two neighboring carbon atoms and
the s orbital of one hydrogen atom. The three bonds so produced are strong sigma bonds
and they are planar and inclined at 120 o to each other. The remaining single electrons
from the 2pz orbitals (six in all) are delocalized into a molecular orbital which
stretches round the entire benzene ring. These electrons constitute the aromatic sextet and
are free to move throughout the orbital. This resonance structure is at a low energy
level and consequently is strongly stabilized as is shown by figures of resonance energy
deduced from thermochemical investigations and calculations.

5.3.3 Aromaticity and the Huckel 4n + 2 rule

What properties do aromatic compounds have in common? As we saw previously

aromatic compounds are compounds whose molecular formula would lead us to expect a
high degree of Unsaturation and yet which are resistant to the addition reactions generally
characteristic of unsaturated compounds. Along with this resistance towards addition
reactions we also find evidence of unusual stability: low heats of hydrogenation and low
heats of combustion. Another feature of all aromatic compounds is that they are cyclic,
generally containing five-, six- or seven-membered rings and have flat molecules.

As stated earlier also to be aromatic a compound must have a molecule that contains
cyclic clouds of delocalized electrons above and below the plane of the molecule.
Furthermore the clouds must contain a total of (4n + 2) electrons. This means that
for the particular degree of stability that characterizes an aromatic compound,

43
delocalization alone is not enough. There must be a particular number of electrons: 2, 6,
or 10, etc. This requirement is called the 4n + 2 rule after its inventor Erich Huckel. The
rule is based on quantum mechanics and has to do with the filling of the various orbitals
that make up the cloud.

Let us examine the fulfillment of the rule in benzene and its homologues. Benzene and its
homologues, toluene and the xylenes, all have six electrons, the aromatic sextet, six, a
Huckel number corresponding to n = 1.

44
W EEK 6: SOME PROPERTIES AND REACTIONS OF BENZENE

6.1 Physical properties of benzene

Some of the physical properties of benzene are the following:

 It is a colorless, mobile liquid with a characteristic smell.

 It is insoluble in water but soluble in organic solvents, and it is itself a very good
solvent for organic compounds.
 It freezes at 5oC and boils at 80oC
 It has a density of 0.88 g/cm3 at 20oC
 Both liquid benzene and its vapour are highly poisonous, so that benzene must be
used with care.

6.2 Chemical properties of benzene

It is immediately obvious that benzene, C6H6, is deficient to the extent of eight hydrogen
atoms per molecule when compared with the corresponding alkane, hexane, C 6H14. From
this circumstance, with its apparently high degree of unsaturation, addition reactions
would be expected. In practice, benzene does give some addition reactions, though the
limit of the addition is six hydrogen atoms (or their equivalent) per molecule of benzene.
The characteristic behaviour of benzene is, however, to give substitution reactions. The
following account of the chemical properties of benzene is arranged so as to draw
attention to these different types of behaviour.

6.2.1 Addition reactions of benzene

(a) With Hydrogen

If benzene vapour is passed with hydrogen over nickel as catalyst at about 200 oC, the
addition product, cyclohexane, C6H12, is formed.

C6H6 + 3H2 C6H12

Under other conditions, dihydrobenzene, C 6H8, and tetrahydrobenzene, C6H10, may also
be obtained.

45
(b) With Ozone

If ozonised oxygen is passed through benzene at ordinary temperature, it forms

benzenetriozonide, a solid which explodes when heated.

C6H6 + 3O3 C6H6(O3)3

(C) With Chlorine and Bromine

If dry chlorine is passed through benzene boiling under reflux in the presence of the
strongest light possible, preferably sunlight or ultra-violet radiation, but with no material
catalyst present, benzenehexachloride is formed.

C6H6 + 3Cl2 C6H6Cl6

There are, in theory, nine isomeric compounds possessing this formula. One of the
compounds is in use as the insecticide “gammexane”.

Bromine behaves in a corresponding manner with benzene, under similar conditions.

Benzenehexachloride is not very stable. If treated with caustic alkali solution, it readily
loses the elements of 3HCl per molecule and leaves a trichlorobenzene.

C6H6 Cl6 + 3KOH C6H3Cl3 + 3KCl + 3H2O

6.2.2 Substitution reactions of benzene

In the following section, monosubstitution products only are considered. Certain di- and
tri-substitution products of benzene are noticed later.

(a) Chlorination and Bromination

If benzene is treated with dry chlorine, when boiling under reflux, with a catalyst (or
chlorine “carrier”) present, it will produce chlorobenzene. Several “carriers” are
available, e.g., iodine, iron wire, iron (III) chloride or pyridine.

C6H6 + Cl2 C6H5Cl + HCl

In this reaction, strong light must be avoided.

Bromination occurs in similar conditions, the best bromine “carrier” being anhydrous
aluminium bromide.

46
 Notice the contrasting sets of conditions suitable for chlorination of benzene by addition
and substitution:

Addition to C6H6Cl6 Substitution to C6H5Cl

Very strong light, sunlight if possible, as Feeble light, not stronger than diffused
catalyst daylight

No material catalyst present A catalyst or “carrier” present, e.g., iodine,

iron (III) chloride, pyridine

Conditions for bromination are similar.

(b) Nitration

If benzene is shaken well with a total of twice its own mass of concentrated nitric acid
and three times its mass of concentrated sulphuric acid, mixed together and added in
small amounts so that the temperature exceed 55oC, mononitrobenzene is produced.

C6H6 + HNO3 C6H5NO2 + H2O

(c) Sulphonation

Benzene sulphonates if heated under reflux with concentrated sulphuric acid for some
hours at about 180oC. Oil-bath heating is usually used. The product is benzenesulphonic
acid.

C6H6 + H2SO4 C6H5SO2OH + H2O

A more convenient Sulphonation can be carried out, without heating by the use of fuming
sulphuric acid.

(d) Reaction with Alkyl Halides. Friedel – Craft’s Reaction (Alkylation)

Benzene will react at ordinary temperature with methyl bromide, both reagents being dry,
in the presence of anhydrous aluminium chloride as catalyst. The product is toluene.

C6H6 + CH3Br C6H5CH3 + HBr

The mass of aluminium chloride should be one-third that of benzene

(e) Reaction with Acyl Halides. Friedel – Craft’s Reaction (Acylation)

47
Benzene will react at ordinary temperature with acetyl chloride, both reagents being dry,
in the presence of anhydrous aluminium chloride as catalyst. The product is
acetophenone.
C6H6 + CH3COCl C6H5CO CH3 + HCl

(f) With alkenes

Benzene reacts with an alkene in the presence of an acid to give an alkylbenzene. For
example propene reacts with benzene in the presence of sulphuric acid to produce (1-
Methylethyl)benzene:

C6H6 + CH3CH = CH2 C6H5CH(CH3)2 + HCl

48
WEEK 7: MECHANISM OF ELECTROPHILLIC AND
NUCLEOPHILLIC SUBSTITUTION IN AROMATIC COMPOUNDS

7.1 Reaction mechanism in aromatic electrophillic substitution

In spite of the fact that the detailed mechanism of electrophilic substitution

reaction varies from one reaction to another there are certain general
principles involved in the mechanisms of these reactions. The general
principle is that by some form of heterolysis, a positively charged ion (and
possibly a complex including a catalyst) is produced from the materials
used. This ion then attacks an electron-rich carbon atom in the benzene
molecule. This carbon atom becomes electron-rich in response to the
approach of a positively charged ion (electromeric effect), when a pair of pi
electrons shift towards it. A transient complex is formed by combination of
the benzene molecule and the attacking ion and its positive charge is
delocalizes over the aromatic nucleus. This is the slow, rate-determining
stage. Then a proton is released very rapidly from the complex into
combination with a base present in the reacting mixture. The residue is a
substituted benzene molecule. The following are the generally accepted
mechanisms. Apart from the electromeric effect (shown by curved arrow),
the influence of the aromatic nucleus may be ignored at this stage. The
benzene molecule, C6H6, is written as C6H5CH for the initial stage of each
reaction.

(a) Chlorination and Bromination

A catalyst is used, e.g., iron (III) chloride.

49
 FeCl3 + Cl2 = Cl+ + FeCl4-

(b) Nitration

Concentrated nitric acid in concentrated sulphuric acid produces nitronium

ion or the “nitryl cation”, NO2+, which is the electrophile:

2H2SO4 + HNO3 NO2+ + H3O+ + 2HSO4-

Then the first of the electrophilic substitution reaction takes place:

50
W EEK 8: CHEMISTRY OF PHENOL

8.1 Group characteristics of phenols

Phenols are aromatic compounds containing one or more hydroxyl groups directly
attached to a benzene nucleus. A clear distinction must be drawn between the phenols
which are nuclear substitution derivatives of benzene, and the aromatic alcohols which
contain the hydroxyl group in the side chain of the benzene ring. In this course we shall
be interested in phenols only and even here we shall be mainly concerned with the first
and simplest member of the group which is also called phenol. Table 1.1 shows the
classification of phenols as monohydric, dihydric and trihydric. This is based on the
number of hydroxyl groups which they contain.
T A B L E 1.1
Group Characteristics of phenols

Name of Phenol Formula M. P (o C) B.P (o C) .

Monohydric Phenols
Phenol (Hydroxybenzene) C6H5OH 42 182
Ortho-Cresol (o-hydroxytoluene) C6H4(CH3)OH 31 188
Meta-Cresol (m-hydroxytoluene) C6H4(CH3)OH 4 210
para-Cresol (p-hydroxytoluene) C6H4(CH3)OH 36 198

Dihydric Phenols
Catechol (o-dihydroxybenzene) C6H4(OH)2 104 –
Resorcinol (m-dihydroxybenzene) C6H4(OH)2 119 –
Quinol (p-dihydroxybenzene) C6H4(OH)2 169 –

Trihydric Phenol
Pyrogalol (1,2,3 trihydroxybenzene) C6H4(OH)2 132

51
 8.2 Introduction to phenol

The name phenol is applied to both the group of compounds containing one or more
hydroxyl groups attached directly to the benzene ring as well as to the simplest member
of these compounds. This simplest member is the subject of discussion this week; it is
also called hydroxybenzene and has the formula, C6H5OH.

8.3 Laboratory preparation of phenol

Phenol is usually prepared in the laboratory by diazotization of aniline and then heating
the diazotized solution in the presence of a dilute mineral acid.

C6H5N = NCl + H2O C6H5OH + N2 + HCl

8.4 Industrial preparation of phenol

Coal tar, chlorobenzene and sodium benzenesulphonate are some of the chemicals that
serve as the industrial starting materials for making phenol.

Coal tar has been a very old source of phenol along with aromatic hydrocarbons such as
benzene, toluene and the xylenes.

The Dow process is used for producing phenol from chlorobenzene. In this process
chlorobenzene is heated with dilute caustic alkali to 300oC at about 15 atmosphere
pressure, with a copper salt present as catalyst.

C6H5Cl + H2O C6H5OH

HCl +NaOH NaCl + H2O

52
Simple hydrolysis of chlorobenzene to phenol under laboratory conditions is not
practicable.

In the Sulphonation process, benzene is sulphonated by heating with concentrated

sulphuric acid at 180oC

C6H6 + H2SO4 C6H5SO3H + H2O

Sodium benzenesulphonate is then precipitated by the action of benzenesulphonic acid

with very concentrated brine.

C6H5SO3H + NaCl C6H5SO3Na + HCl

Sodium benzenesulphonate is then fused at 450o to 500oC with sodium hydroxide

producing sodium phenate.

C6H5SO3Na + C6H5OH C6H5OH + Na2SO3

C6H5OH + C6H5OH C6H5ONa + H2O

Free phenol may be produced by acidification, e.g., by carbon dioxide.

C6H5ONa + H2O + CO2 C6H5OH + Na2CO3

This process has the advantage of producing phenol fee from cresols.

8.5 Physical properties of phenol

Some of the physical properties of phenol are the following:

53
  It is a colorless crystalline solid smelling of disinfectant. The crystals are often
rather wet and discoloured.
 It has a melting point of 43oC and a boiling point of 181oC at 760 mmHg.
 It is fairly soluble in water at ordinary temperatures; about 8 g of phenol will
dissolve in 100 g of water. However the addition of increasing amounts of phenol
to a given amount of water causes the separation of two liquid layers – a saturated
solution of phenol in water above a saturated solution of water in phenol. Further
amounts of phenol will eventually cause the two layers to merge again. Water and
phenol are miscible in any proportion above 70oC.
 It is quite poisonous and the solid or its concentrated solution blisters the skin;
because of this it has to be handled with great care.

8.6 Chemical properties of phenol

In discussing chemical properties of phenol, the contributions made by both the hydroxyl
and benzene ring must be taken into account. Hence the chemical properties of phenol
will be discussed from two perspectives: properties due to the hydroxyl group and
properties due to the benzene ring.

8.6.1 Chemical properties of phenol due to the hydroxyl group

It might be expected that phenol will undergo dehydration, react with phosphorus
pentachloride, form esters and be oxidized just like ethanol, its aliphatic analogue, which
undergoes these reactions. Whether this is the case or not is discussed below.

 Action with phosphorus pentachloride

The reaction of phenol with phosphorus pentachloride to form chlorobenzene is only very
slight. The yield is very poor and the reaction is of no practical value.

54
  Ester formation

Heated under reflux with an anhydrous organic acid, with HCl gas or concentrated
sulphuric acid as catalyst, phenol gives no useful Esterification. Phenolic esters can,
however, be produced by the Schotten-Baumann reaction in which a solution of phenol
reacts with a benzoyl halide to form an ester. For example a solution of phenol in sodium
hydroxide solution reacts with benzoyl chloride to form phenyl benzoate.

C6H5COCl + NaOC6H5 C6H5CO2C6H6 + NaCl

 Oxidation

Phenol is resistant to oxidation and gives no simple oxidation products.

 Dehydration

Phenol is resistant to dehydration and gives no dehydration products with sulphuric acid.

 With iron (III) solution

Phenol gives a purple coloration with iron (III) chloride solution.

8.6.2 Chemical properties of phenol due to the benzene ring (Nuclear reactions)

Some of the nuclear reactions of phenol are the following:

 Bromination of phenol

If to a solution of phenol in water is added excess bromine-water, an immediate very pale

yellow precipitate of 2,4,6-tribromophenol is observed. The OH group renders all the
ortho- and para positions very reactive for halogenations. The NH 2 group has a very
similar effect in aniline. which gives a corresponding reaction with bromine water.

55
Under less vigorous conditions, a more controlled bromination is possible, e.g., in
solution in carbon disulphide at -30oC, phenol can be brominated to yield mainly p-
bromophenol

 Chlorination of phenol

Phenol can be chlorinated in stages. If phenol is dissolved in glacial acetic acid and
chlorine is passed in with cooling, 2,4-dichlorophenol is first formed; later 2,4,6-
trichlorophenol is produced.

 Nitration of phenol

56
Phenol nitrates very readily. If warmed with dilute nitric acid, it yields a mixture of o-
and p-nitrophenol.

In more drastic nitrating conditions, i.e., concentrated nitric acid and concentrated
sulphuric acid with temperature control, phenol yields 2,4,6-trinitropenol, which is
known as “picric acid”.

This acid is violently explosive when detonated and was used, at one time, for military
purposes.

 Sulphonation of phenol

Phenol sulphonates readily. If heated with concentrated sulphuric acid to 100 oC, it first
yields phenol-o-sulphonic acid as the main product, but further heating to about 180 oC
produces the para isomer also.

 Liebermann’s Nitroso Reaction

This reaction serves as a test for phenol. The reaction involves adding a little
concentrated sulphuric acid to phenol in a test tube followed by a few grains of sodium
nitrite. The mixture is then shaken and briefly warmed gently and then poured into cold
water. A red solution is observed which is due to the formation of p-nitrosophenol. If a
sample of the solution is made alkaline by sodium hydroxide it changes to blue or green.

57
This compound then condenses with another phenol molecule to produce an indophenol
which has indicator properties. It is red in acid and blue or green in alkali.

8.7 Acidity of phenol

Phenols are much more acidic than simple aliphatic alcohols but much less acidic than
carboxylic acids. Compare the following pKa values.

C6H5OH CH3OH C6H5CO2H

9.95 16 4.20

A well-known consequence of this relation is that benzoic acid decomposes carbonates

while phenol does not. Relative to CH3, the C6H5 group has a greater –I (electron-
attracting) effect, so that the hydroxyl H atom of phenol is more readily released as H+
than the corresponding atom of CH3OH and this makes phenol the stronger acid. On the
other hand, the absence of the –I (electron-attracting) C = O group in phenol weakens its
acidity as compared as compared with that of the carboxylic acid, C6H5CO2H.

Electron-withdrawing (-I) groups, e.g., NO2, halogens substituted in the aromatic

nucleus, tend to strengthen the acidity of phenols by reducing electron density on the
oxygen atom of OH and so allowing easier dissociation of the proton, H+.
Correspondingly, substituted +I groups, e.g., alkyl groups, weaken the acidity of phenol
though the effect is small. –I groups are more effective in the ortho- and para- positions
to the OH group than in the meta-. Compare the following figures.

pKa
Phenol 9.95
o-nitrophenol 7.20
p-nitrophenol 7.14
m-nitrophenol 8.35
2,4,6-trinitrophenol 1.02 (picric acid)
o-, m- and p-methylphenol 10.1 – 10.3 (cresols)

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USES OF PHENOL

1. Phenol is a good germicide and disinfectant. In 3% solution it is used as a

sterilizing agent.
2. Phenol is used in the manufacture of “Bakelite” Plastics.
3. Phenol is used in the manufacture of selective weed-killers such as Methoxone.
4. Phenol is used in the production of azo-dyes.

QUESTIONS AND PROBLEMS

8.1 How would you prepare in the laboratory a reasonably pure sample of phenol
starting from aniline? How and under what conditions does phenol reacts with (i)
bromine, (ii) sulphuric acid, (iii) nitric acid, (iv) nitrous acid?

8.2 Disregarding aromatic nuclear substitution, compare and contrast the chemical
behavior of ethanol with that of phenol.

59
WEEK 9: CARBONYL SUBSTITUTED BENZENE

9.1 Introduction to carbonyl substituted benzene

This week we shall study carbonyl substituted benzene. Many compounds exist in which
one hydrogen atom of the benzene ring has been removed and replaced by another atom
or group of atoms; such compounds are in general called monosubstituted benzenes. The
carbon-oxygen double bond is the functional group referred to as the carbonyl group.
This group can be substituted in the benzene ring to give two families of compounds
called aromatic aldehydes and aromatic ketones. In aromatic aldehydes one of the two
free valence bonds of the carbonyl group is bonded to hydrogen while the other bonds to
the benzene ring. Benzaldehyde is an example of aromatic aldehydes. With aromatic
ketones, two varieties are possible. In one variety both free valence bonds of the carbonyl
group are bonded to benzene ring. An example of such a variety is benzophenone. The
other variety consists of one free valence of the carbonyl group being bonded to the
benzene ring while the other is bonded to an alkyl group

9.2 Benzaldehyde

Benzaldehyde occurs in the glucoside amygdalin which occurs in bitter almonds.

Glucose, Benzaldehyde and hydrogen cyanide are the products obtained when bitter
almonds are hydrolyzed by the enzyme emulsin.

9.2.1 Laboratory preparation of benzaldehyde

Benzaldehyde can be prepared in the laboratory in several ways:

 By the hydrolysis of benzyl chloride.
 By distilling calcium benzoate and calcium formate.
 From toluene by the use of chromyl chloride.

60
When benzyl chloride and lead nitrate are boiled under air reflux for three hours, benzyl
chloride is hydrolyzed and oxidized in the course of the preparation to form
benzaldehyde.

C6H5CH2Cl + Pb(NO3)2 C6H5CHO + Pb(OH) + 2NO2

If anhydrous calcium benzoate and anhydrous calcium formate are ground together and
distilled dry, benzaldehyde and calcium carbonate are formed. This method is of little
practical value but has theoretical interest in providing evidence for the structure of
benzaldehyde.

Toluene will react with chromyl chloride, in carbon tetrachloride as solvent, to produce
addition compound. The reaction is often violent and cooling may be required. The
addition compound precipitates as a brown solid. When removed by filtration washed
with carbon tetrachloride and added slowly to cold water, it forms benzaldehyde.

C6H5CH3 + 2CrO2Cl2 C6H5CH3(CrO2Cl2)2

C6H5CH3(CrO2Cl2)2 +3H2O C6H5CHO + 4CrCl3 + 2H2CrO4 + 4H2O

9.2.2 Industrial preparation of benzaldehyde

Toluene is the principal raw material for the manufacture of benzaldehyde. There are two
variations in the industrial use of toluene to produce benzaldehyde. One variation
involves the chlorination and hydrolysis of toluene. In this process sunlight or ultraviolet
light acts as a catalyst for the reaction. The initial product formed is benzal chloride

C6H5CH3 + Cl2 C6H5CHCl2 + 2HCl

The benzal chloride is then boiled with calcium hydroxide to hydrolyse it.

61
C6H5CHCl2 + Ca(OH)2 C6H5CHO + CaCl2 + H2O

In this method the benzaldehyde is contaminated with chlorine compounds. The second
method avoids this type of impurity.

In the second method toluene is heated with manganese (IV) oxide and dilute sulphuric
acid. This mild oxidsing agent does not take the oxidation beyond the benzaldehyde
stage. Copper (II) sulphate is a useful catalyst for this reaction.

C6H5CH3 + 2MnO2 + H2SO4 C6H5CHO + 2MnSO4 + 3H2O

9.2.3 Physical properties of benzaldehyde

Some of the physical properties of benzaldehyde include the following:

 It is a colourless liquid having a boiling point of 179oC at 760 mmHg.
 It has a strong pleasant odour of almonds
 It is only slightly soluble in water, but miscible in any proportion with ether and
ethanol.

9.2.4 Chemical properties of benzaldehyde

There are really two kinds of functional groups in benzaldehyde: the carbonyl group and
the benzene ring. It is therefore expected that benzaldehyde should show chemical
properties of each group. We shall therefore consider the chemical properties of
benzaldehyde from two perspectives: reactions of the carbonyl group and those of the
benzene ring.

9.2.4.1 Reactions of the carbonyl group

The reactions of benzaldehyde which are due to the carbonyl group can be considered
under oxidation and reduction reactions, addition reactions, condensation reactions

62
chlorination and the Schiff’s reaction. We shall now consider each class of reactions in
turn.

9.2.4.1.1 Oxidation and reduction reactions of benzaldehyde

Benzaldehyde, like its aliphatic analogue acetaldehyde, is a reducing agent. It gives the
silver mirror reaction under the same conditions as acetaldehyde but more slowly.
However, whereas acetaldehyde rapidly undergoes the Fehling’s reaction, benzaldehyde
gives the reaction only slowly, if at all. This may be due to its low solubility in water
compared with acetaldehyde. With respect to reduction of warm chromic acid which
acetaldehyde readily undergoes, benzaldehyde is not normally oxidized in this way.
Oxidation of benzaldehyde involves the use of an alkaline medium for example alkaline
potassium permanganate in solution. This is because the product benzoic acid is not very
soluble in water and it is more convenient to hold it in solution as its sodium or potassium
salt during the oxidation.
There are also situations when both acetaldehyde and benzaldehyde are reduced. A good
example is their reduction using sodium and ethanol:

2Na + 2C2H5OH + C6H5CHO 2Na +2C2H5O- + C6H5CH2OH

2Na + 2C2H5OH + CH3CHO 2Na+ + 2C2H5O- + CH3CH2OH

9.2.4.1.2 Addition reactions of benzaldehyde

Both acetaldehyde and benzaldehyde form addition compounds with hydrogen cyanide
and sodium hydrogensulphite. In the reaction of the aldehydes with sodium
hydrogensulphite the two react together under ordinary conditions to form benzaldehyde
sodium hydrogensulphite
C6H5CHO + HSO3Na C6H5CH(OH)SO3Na

63
The aldehydes sodium hydrogensulphites are used in the purification of aldehydes and
ketones.
With hydrogen cyanide benzaldehyde reacts to form a cyanohydrin. However, because of
the poisonous nature of hydrogen cyanide the reaction is not normally carried this way. In
practice the benzaldehyde sodium hydrogensulphite is reacted with a concentrated
solution of potassium cyanide to form the cyanohydrin.

C6H5CH(OH)SO3Na + KCN C6H5CH(OH)CN + NaKSO3

9.2.4.1.3 Condensation reactions of benzaldehyde

In condensation reactions two relatively large molecules react to form a product with the
elimination of a small molecule eliminate. Benzaldehyde gives condensation reactions
with hydroxylamine and hydrazine and its derivatives. With hydrazine an oxime is
formed.

C6H5CHO + H2NOH C6H5CH = NOH + H2O

With hydrazine, benzaldehyde forms a hydrazone.

C6H5CHO + H2NNH2 C6H5CH = NNH2 + H2O

With phenyl hydrazine, benzaldehyde forms a phenyl hydrazone and with 2,4-
dinitrophenyl hydrazine it forms 2,4-dinitrophenyl hydrazone. The equations are
respectively shown below.

C6H5CHO + H2NNHPh C6H5CH = NNHPh + H2O

9.2.4.1.4 Reaction of benzaldehyde with phosphorus pentachloride

64
Benzaldehyde, like acetaldehyde, reacts with phosphorus pentachloride to form a gem-
dichloro compound. Alcohols react with the same reagent giving off fumes of hydrogen
chloride. In the case of benzaldehyde and other aldehydes no fumes of hydrogen chloride
is produced. This indicates the absence of the hydroxyl group in aldehydes.

C6H5CHO + PCl5 C6H5CHCl2 + POCl3

9.2.4.1. 5 Reaction of benzaldehyde with Schiff’s reagent

Benzaldehyde reacts with Schiff’s reagent on warming. This restores the purple color to
magneta solution decolorized by sulphur dioxide.

9.2.4.2 Reactions of the benzene ring (Nuclear reactions)

The group – CHO exercises a deactivating effect on nuclear reactions. Nuclear

substitution is, therefore, rather slow in the case of benzaldehyde. It can be nitrated by a
mixture of sodium nitrate and concentrated sulphuric acid at -10 oC to give chiefly m-
nitrbenzaldehyde.

9.3 Benzophenone
As mentioned in the introduction benzophenone, which is also called diphenyl ketone, is
an aromatic ketone having the two free valence bonds of the carbonyl group attached to
phenyl groups.

9.3.1 Laboratory preparation of benzophenone

Benzophenone can be prepared in the laboratory in several ways:

 By heating calcium benzoate:

(C6H5CO2)2Ca C6H5CO C6H5

65
  By the Friedel-Craft’s condensation between benzoyl chloride and benzene:
AlCl3
C6H6 + C6H5COCl C6H5CO C6H5 + HCl

Carbonyl chloride can be used instead of benzoyl chloride:

AlCl3
C6H6 + COCl2 C6H5CO C6H5 + HCl

66
67
W EEK 10: CHEMISTRY OF BENZOIC ACID

Benzoic acid occurs naturally as its benzyl esters in gum benzoin, a resin secreted by
certain trees. The free acid can be sublimed from the resin by heat.

10.1 Manufacture of benzoic acid

Nowadays benzoic acid is almost entirely manufactured from toluene. The toluene is
chlorinated at its boiling point, with no material catalyst present, but in sunlight or
ultraviolet radiation as catalyst (i.e., conditions for side chain chlorination), to the stage
of benzotrichloride.

C6H5CH3 + Cl2 C6H5CCl3 + 3HCl

The product is then hydrolysed by superheated water (or a hot suspension of calcium
hydroxide).

C6H5CCl3 + 2H2O C6H5CO2H + HCl

10.2 Laboratory preparation of benzoic acid

Benzoic acid can be prepared in several ways:

 By oxidation of Toluene or other Side-chain Compounds.

Toluene, C6H5CH3, or any related compound with a substituted side-chain can be

oxidized to benzoic acid. Such compounds with a substituted side-chain include
benzyl alcohol, C6H5CH2OH, benzyl chloride, C6H5CH2Cl and benzaldehyde,
C6H5CH2CHO.

 By hydrolysis of benzonitrile

68
 To benzonitrile is added some concentrated hydrochloric acid and the mixture
Heated under reflux. The nitrile is hydrolyzed and benzoic acid is produced.

C6H5CN + 2H2O C6H5CO2NH4

C6H5CO2NH4 + HCl C6H5CO2H + NH4Cl

10.3 Physical properties of benzoic acid

Benzoic acid forms white crystals with glistening, rather greasy appearance, melting at
121oC. It sublimes without decomposition and is volatile in steam. It is only sparingly
soluble in cold water (about 0.3%) but is about twenty times more soluble I boiling water.

10.4 Chemical properties of benzoic acid

Like other monosubstituted aromatic compounds, it is expected that benzaldehyde will

exhibit chemical properties due to the carboxyl group as well as due to the benzene ring.
Chemically benzoic acid resembles acetic acid very closely.

10.4 .1 Chemical properties of benzoic acid due to the carboxyl group

Reactions to be considered under this category include acidic behaviour, esterification

and action with phosphorus pentachloride.

 Acidic properties
As an acid benzoic acid reacts with bases to form salts. For example with potassium
hydroxide it forms potassium benzoate

C6H5CO2H + KOH C6H5CO2K + H2O

69
Benzoic acid also liberates carbon dioxide from hydrogencarbonate. For example with
sodium hydrogencarbonate sodium benzoate is formed and carbon dioxide carbon
dioxide is liberated.

C6H5CO2H + NaHCO3 C6H5CO2Na + H2O

With calcium oxide benzoic acid is converted to benzene upon heating a mixture of
benzoic acid and calcium oxide.

C6H5CO2H + CaO C6H6 + CaCO3

 Esterification

Benzoic acid esterifies readily. It reacts with ethanol in the presence of dry hydrogen
chloride as catalyst to form ethyl benzoate.

C6H5CO2H + C2H5OH C6H5CO2C2H5 + H2O

 With phosphorus pentachloride

If benzoic acid and phosphorus pentachloride (or thionyl chloride) are heated together ,
benzoyl chloride is produced and can be distilled off.

C6H5CO2H + PCl5 C6H5COCl + POCl3 + HCl

C6H5CO2H + SOCl2 C6H5COCl + SO2 + HCl

10.4 .1 Chemical properties of benzoic acid due to the benzene ring

Benzoic acid can be nitrated, chlorinated and sulphonated in conditions similar to those
for the corresponding reactions of benzene. The – COOH group is meta-directing. None
of the products is particularly important up to the present.

70
10.4 .1 Uses of benzoic acid
1. Benzoic acid is the principal constituent of “friar’s balsam”. The balsam is mixed
with very hot water. Some benzoic acid vaporizes with the steam. When inhaled,
it is supposed to have a beneficial effect on the bronchial mucous membrane.
Ammonium benzoate, taken by mouth, is used with beneficial effect on the
urinary system.
2. Benzoic acid has been used as a preservative for foodstuff, but its use is now
restricted.

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WEEK 11: CHEMISTRY OF BENZOIC ACID DERIVATIVES

72
W EEK 12: CHEMISTRY OF BENZAMIDE AND PHTHALIC
ANHYDRIDE

73
WEEK 13: CHEMISTRY OF BENZAMIDE AND PHTHALIC
ANHYDRIDE CONTINUED

74
WEEK 14: CHEMISTRY OF ANILINE

14.1 Classification of aromatic amines

Aniline is the simplest aromatic amine. In considering the aromatic amines, a very wide
range of compounds has to be covered and it is therefore important to consider the
classification of the aromatic amines. In the fist place we have the usual distinction
between nuclear and side-chain derivatives, e.g., aniline C 6H5NH2 (nuclear derivative)
and benzyl amine C6H5CH2NH2 (side-chain derivative). The second basis of classification
depends upon the successive replacement of hydrogen atoms in ammonia molecule by
hydrocarbon radicals. Thus when only one hydrogen atom is replaced, we have a primary
amine containing the group – NH2, e.g., aniline C 6H5NH2 ant toluidine C6H4(CH3)NH2.
When Two hydrogen atoms are replaced by hydrocarbon radicals, we get a secondary
amine with the NH group. Here we have to distinguish between
the true (wholly) aromatic amines, e.g. diphenylamine (C 6H5)2NH2 and the mixed
aliphatic-aromatic amines, e.g. N-methylaniline C 6H5NHCH3. Tertiary amines contain the
N group, all the hydrogen atoms of ammonia having been replaced by hydrocarbon
radicals. In this case also, we differentiate between “true” and “mixed” types, e.g.
between triphenylamine (C6H5)3N and N,N-dimethylaniline C6H5N(CH3)2. The Basis of
this classification into primary, secondary and tertiary amines is exactly the same as the
already considered one in the case of aliphatic amines. Data concerning the aromatic
amines are set out in Table 14.1; we shall however restrict our consideration in this
course to the primary aromatic amine aniline.

14.2 Laboratory and industrial

preparation of aniline

The laboratory and industrial methods for the preparation of aniline are essentially
similar. In both cases nitrobenzene is reduced to aniline. The difference lies in the choice
of the reducing agent to use. For economical reasons a cheaper reducing agent in
necessary for the industrial method.

75
14.2.1 Laboratory preparation of aniline

Aniline is prepared in the laboratory by the reduction of nitrobenzene by tin and

concentrated hydrochloric acid. In this process weighed quantities of nitrobenzene and
granulated tin are mixed and a measured volume of concentrated hydrochloric acid is
added in small quantities at a time. The reduction of nitrobenzene is effected partly by
 Oxidation of metallic tin to tin (II) ion, and partly by
 Further oxidation of tin (II) ions to tin (IV) ions.

Sn + 6H+ + C6H5NO2 3Sn2+ + 2H2O +C6H5NH2

3Sn2+ + 6H+ + C6H5NO2 3Sn4+ + 2H2O + C6H5NH2

The aniline is left in solution in the form of its chloride and the reduction is finished
when oily drops of nitrobenzene are no longer visible.

C6H5NH2 + HCl C6H5NH3+Cl-

Free aniline is liberated by the addition of excess sodium hydroxide solution.

C6H5NH3+Cl- + Na+OH- Na+Cl- + H2O + C6H5NH2

14.2.2 Industrial preparation of aniline

The reader should note that the reducing agent employed in the laboratory process is the
relatively more expensive metal tin; similarly in the conversion of the hydrochloride of
aniline, anilinium chloride, sodium hydroxide is used. Both of these materials are
relatively expensive to use in the industrial preparation of aniline. Iron is a more
commoner and less expensive metal than tin and is used in the industrial preparation. In
the industrial process also any anilinium chloride formed is converted to free aniline by

76
means of calcium hydroxide rather than the more expensive sodium hydroxide. A s has
been earlier stated both the laboratory and industrial preparation of aniline start from
nitrobenzene. In the industrial process weighed quantities of nitrobenzene and iron in the
form of coarse iron filings are mixed and measured volume of hydrochloric acid is added.
The reaction is represented by the following equation:

Fe + 6HCl + C6H5NO2 3FeCl2 + 2H2O +C6H5NH2

In practice the quantity of hydrochloric acid required can be reduced to one-fortieth of

that indicated by the stoichiometric equation above. The reason for this being the
extensive hydrolysis of iron (II) chloride formed in the reaction to produce hydrochloric
acid;

FeCl2 + 2H2O Fe(OH)2 + HCl

The reader should recall that such salts of a strong acid and a weak base are normally
hydrolysed in aqueous solutions. The hydrochloric acid formed is then available for the
action with iron.

Iron (II) chloride, on its own, can reduce nitrobenzene to aniline and the product, iron
(III) chloride, will hydrolyse regenerating hydrochloric acid:

C6H5NO2 + 6FeCl2 + 6HCl C6H5NH2 + 6FeCl3 + 2H2O

FeCl3 + 3H2O = Fe(OH)3 + 3HCl

14.3 Physical properties of aniline

The following are some of the physical properties of aniline:

77
  Aniline is a liquid at room temperature. Pure aniline is colourless oil with a
distinctive “earthy” smell. In practice it is always brown in colour because of the
presence of products of its oxidation by the air.
 Aniline is appreciably poisonous and in some individuals can produce symptoms
of poisoning by mere rubbing of contaminated clothing on the skin.
 Aniline boils at 184oC at 760 mmHg and melts at -6oC.
 Aniline is sparingly soluble in water

o Chemical Properties of Aniline

We shall consider the chemical properties of aniline from two perspectives:

 Reactions involving the amino group only, and
 Reactions occurring at the aromatic ring, i.e., nuclear reactions.

14.3.1 Reactions involving the amino group

The reactions taking place at the amino group are related to the basic property of aniline,
we shall therefore first of all examine the basic nature of aniline.

14.4.1.1 Basic Nature of Aniline

It is to be expected that all derivatives of ammonia be basic if in their formation the

unshared pair of electrons on the nitrogen atom of ammonia is not affected in any way.
Thus we expect the aliphatic, aromatic as well as the alicyclic amines to be basic. If we
compare the basicity of methyl amine, an aliphatic amine, with that of aniline, an
aromatic amine, we find that methyl amine is a much stronger base than aniline. The only
structural difference between methyl amine and aniline is the attachment of the amino
group, – NH2, to an aromatic ring in aniline and to an aliphatic chain in methyl amine.
The basicity of ammonia as well as of its derivatives is related to the availability of the
unshared pair of electrons on the nitrogen atom. The more the unshared pair is available
for bond formation the more basic the substance will be, while the less available they are

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the less basic the substance will be. The methyl group in methylamine has +I (electron-
repelling) effect and therefore tend to repel the unshared pair of electrons on the nitrogen
atom thereby making the unshared pair more available for bond formation. The phenyl
group, C6H5 –, in aniline is much less electron-repelling than the methyl group and thus
aniline is a much weaker base than methyl amine. There is another important
consideration in the basicity of aniline

In spite of the fact that it is a very weak base, aniline gives the following reactions:

1. Reaction with acids

Aniline forms crystalline salts resembling ammonium salts. These salts are strongly
hydrolysed in aqueous solution because aniline is a weak base. For example, aniline
reacts with hydrochloric acid to form anilinium chloride which is a crystalline solid.

C6H5NH2 + HCl C6H5NH3+Cl-

2. Action with Nitrous acid

At 5oC, or below, in solution in moderately concentrated hydrochloric acid, aniline

diazotizes with nitrous acid to give benzene diazonium chloride in solution.

C6H5NH2 + O = N – OH + HCl C6H5 – N = N – Cl + 2H2O

3. Reaction with Acyl Chlorides

Aniline reacts readily with an acyl chloride; for example with acetyl chloride at room
temperature, it reacts to produce the corresponding acyl anilide.

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 C6H5NH2 + ClCOCH3 C6H5NHCOCH3 + HCl

14.4.1.2 Nuclear Reactions of Aniline

1. Bromination of Aniline
If a little aniline is shaken with dilute hydrochloric acid to dissolve it and an excess of
bromine water is added, there will be observed an immediate white precipitate thrown
down. The precipitate is 2,4,6-tribromoaniline.

2. Sulphonation of Aniline

p-Aniline sulphonic acid, also called sulphanilic acid, is the principal product obtained
from the Sulphonation of aniline. In the reaction, aniline and concentrated sulphuric acid
are heated together, usually by oil-bath heating, at a temperature of 180 oC. Alternatively,
if aniline is reacted with sulphuric acid, the anilinium hydrogen sulphate formed is heated
to 180oC to produce sulphanilic acid.

EQUATIO
N

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Sulphanilic acid contains both the amino group, – NH 2, which is basic and the sulphonic
acid group, – SO3H, which is acidic. The acidic and basic groups can react with one
another to form an internal salt, and it is for this reason that the amino group is “masked”
and sulphanilic acid does not show some of the properties of a primary amine.

EQUATION

3. Nitration of Aniline

As well as being a nitrating agent, concentrated nitric acid is at the same time an
oxidizing agent; and because of its oxidizing power it cannot be used to nitrate aniline
directly because the latter is so readily oxidised. One way to circumvent the oxidation of
aniline by nitric acid in nitration reaction is to protect the amino group. The amino group
in aniline can be protected by acetylation to acetanilide, which can be nitrated.

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WEEK 15: CHEMISTRY OF DIAZONIUM COMPOUNDS AND
AZO-DYES

15.1 Diazotisation

Diazotisation is the reaction between primary aromatic amine and nitrous acid in the
presence of acid under very cold conditions to produce diazonium compounds. Aromatic
primary amines with the amino group attached directly to the ring will generally
diazotize; the case of aniline is important and typical.

15.2 Preparation of diazonium salts

The preparation of diazonium salts is illustrated by the preparation of benzene diazonium

chloride.

Concentrated hydrochloric acid (2.5 mole) is diluted with about twice its volume with
water. Aniline (1 mole) is added. It dissolves producing a solution of anilinium chloride
in moderate excess of hydrochloric acid. This solution is then cooled by ice-salt to 5 oC or
below and, with stirring, sodium nitrite solution (1.1 mole in twice its mass of water) is
gradually added at such a rate that the temperature does not rise above 5 oC. This is
continued until, after allowing time for reaction after the last addition of nitrite, a drop of
the liquid at once turns starch-iodide paper blue, i.e., excess nitrous acid is present.
Diazotisation is then complete and the liquid contains benzene diazonium chloride in
solution.

NaNO2 +HCl NaCl + HNO2

C6H5NH2 + O = N – OH + HCl C6H5 – N = N – Cl + 2H2O

Sulphuric acid may be used instead of hydrochloric acid. The diazonium salts are usually
unstable. They are not isolated after preparation but used at once for the production of
some other synthetic products by one of the following reactions.

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15.3 Reactions of diazonium compounds

1. Conversion to the corresponding hydrocarbon

This is best done by diazotising the amine in sulphuric acid and pouring the product into
boiling ethanol. The ethanol is oxidised to acetaldehyde and benzene is produced.
Nitrogen gas is evolved.

C6H5.N2.HSO4 +CH3CH2OH C6H6 + N2 + CH3CHO + H2SO4

2. Conversion to the Corresponding Phenol

The diazotized liquid is diluted with water and heated. At about 70 oC, rapid effervescence
occurs with nitrogen evolved. Phenol is produced (together with tarry material, produced
by coupling between phenol and unchanged diazonium compound).

C6H5.N2.HSO4 + H2O C6H5OH + N2 + HCl

3. Sandmeyer’s Reactions

These reactions use the diazonium compounds to introduce chlorine, bromine, iodine or
the cyanide group into the aromatic ring. Except in the case of iodine, copper (I) salts are
employed.

(a) Introduction of Chlorine

The diazotized solution is allowed to run, slowly and with stirring, into a warm solution
of copper (I) chloride in concentrated hydrochloric acid. Chlorobenzene is produced.

C6H5N2Cl C6H5Cl + N2

(b) Introduction of Bromine

The same procedure is adopted as in the case of chlorine, but copper (I) bromide, in
concentrated hydrobromic acid, is used instead of copper (I) chloride. Bromobenzene is
produced.

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 C6H5N2Cl + CuBr C6H5Br + N2 + CuCl

(c) Introduction of Iodine

The diazotized solution is run with stirring into warm, aqueous potassium iodide solution.
Iodobenzene is produced.

C6H5N2Cl + KI C6H5I + N2 + KCl

(d) Cyanide

The diazotized solution is run with stirring into warm solution of copper (I) cyanide in
potassium cyanide solution. Benzocyanide is produced.

C6H5N2Cl + CuCN C6H5CN + N2 + CuCl

In all Sandmeyer reactions, water tends to produce phenol in addition to the main
product. It is therefore usual to steam-distil the product from alkaline solution, which
retains the phenol as the non-volatile phenate of the alkali metal.

4. Reduction of Diazonium Compounds

If the diazotized solution is reduced with tin (II) chloride, it produces phenyl
hydrazonium chloride. In practice, the diazotized solution is saturated with sodium
chloride and then tin (II) chloride, in solution in concentrated hydrochloric acid, is added.
The mixture is left, cooled in ice, for several hours. The phenyl hydrazonium chloride
will then have crystallized out and may be filtered off.

C6H5N2Cl + 2SnCl2 + 4HCl C6H5NHNH3+Cl- + 2SnCl4

The free base may be liberated from the crystals by sodium hydroxide solution:

C6H5NHNH3+Cl- + Na+OH- C6H5NHNH2 + Na+Cl- + H2O

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 5. “Coupling” Reactions of Diazonium Compounds

These reactions are carried out chiefly with phenols. They produce azo-dyes and may be
used as a test for aniline (or, in general, a primary nuclear aromatic amine). The
following is a typical case.

Dissolve about 1g of 2-naphthol, C10H7OH, in about half a boiling tube of dilute sodium
hydroxide solution.

C10H7OH + NaOH C10H7ONa + H2O

Take about 1 cm3 of aniline, add about a quarter of a boiling tube of water and then an
equal volume of concentrated hydrochloric acid. Cool the solution well. With continuous
cooling under the tap (or, better, in ice-salt) diazotize this solution by adding a little of
sodium nitrite solution. Then add some of the diazotized solution to the alkaline 2-
naphthol solution. There is an immediate bright red precipitate of an azo dye.

C6H5NHNH2 + O = N – OH +HCl C6H5N = NCl + H2O

C6H5N = NCl + C10H7ONa C6H5N = N C10H7ONa + HCl

HCl + NaOH NaCl + H2O

“Coupling” takes place between the diazonium compound and the phenol with
elimination of hydrogen chloride which is neutralized by the excess alkali. The hydrogen
atom which is eliminated is in the para position to the Phenolic group, OH, when that
position is free; otherwise, in the ortho position. Coupling never occurs in the meta
position to the OH group.

15.4 The Azo-dyes

A dye is a compound which is itself colored and will impart, to a textile fiber, a color
which is not washed out by water.

All dyes are cyclic compounds. Azo-dyes are those containing the “azo” grouping,

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– N = N – . In general, to possess the properties of a dye, a compound must possess a
chromophore grouping inn one “half” of its molecule and an “auxochrome” grouping in
the other “half”. In azo-dyes, the azo group, – N = N –, is the chromophore group. Other
chromophores are the nitro group, NO2, and the quinonoid structure:

CH = CH
=C C=
CH = CH

The auxochrome group is either the Phenolic group, OH, or the primary amino-group (or
its alkyl derivatives), attached to an aromatic nucleus. Thus, a very simple azo-dye has a
structure of the type:

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