Chapter 13

Amines
Amines constitute an important class of organic compounds derived by
replacing one or more hydrogen atoms of NH3 molecule by alkyl/aryl group(s).

C6H5NH2 is the simplest example of arylamine

-NH2 primary amine

=NH secondary amine

≡ N tertiary amine

In the IUPAC system, the amines are regarded as

alkanamines, e.g. primary , secondary and tertiary amines are given below.

Structure

The nitrogen atom in amine is sp3 -hybridised with a pyramidal shape.

The bond angle is 107o in 10 & 20 amines.

In 30 amines it is 1080 by the presence of 3 bulk groups around ‘N’.

In NH3 and NH4+ Nitrogen is in sp3 -hybridisation.

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Page 2 of 43
Page 3 of 43
13.2 Ans: 10 amines Butan-1-amine, Butan-2-amine, 2-methyl propan-2-
amine,

20 amines : N- Ethylethanamine, N-methylpropanamine……

30 amines:N,N – Dimethylethanamine.

Position isomers:

Butanamine-1 & Butan-2-amine,

chain isomers:

Butan-1-amine 10, N-Methylethanamine 20, N,N-Dimethylmethanamine 30

Metamers:

N-Methylethanamine 20, N,N-Dimethylmethanamine 30

Methods of preparation of Amines:

1. Reduction of nitro compounds: Nitro compounds are reduced to amines

by passing H2/Ni or Pd, or Pt and also by reduction with metals in acidic
medium.
2. Nitroalkanes can also be similarly reduced to the corresponding
alkanamines.

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 1.Reduction of -NO2 to -NH2 is preferred with Fe & HCl Why?
𝐹𝑒
CH3CH2NO2 → CH3CH2NH2
𝐻𝐶𝑙

From the reducing agent- Fe & HCl,

FeCl2 + 2H2O→ Fe(OH)2 + 2HCl

• Reduction with iron scrap and hydrochloric acid is preferred because

FeCl2 formed gets hydrolysed to release hydrochloric acid during the
reaction.
• Thus, only a small amount of hydrochloric acid is required to initiate
the reaction.

2.Ammonolysis of alkyl halides:

To get the amine from the ammonium salt, it is to be treated with a base

2.Why the presence of a base is essential in the ammonolysis of alkyl

halides?

During ammonolysis of alkyl halides, the acid liberated during the reaction
combines with the amine formed, to form amine salt. Thus to liberate the free
amine from the salt, a base is needed.

R-X + NH3 → R-NH3X

Disadvantages of Ammonolysis

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1. It yield a mixture of primary secondary and tertiary amines and also a
quaternary ammonium salt. (aliphatic amines)
2. As the boiling point of these amines are almost close by, the separation of
these components become difficult by distillation.

3. Ammonolysis cannot be used to prepare aromatic amines.

3.Why is it difficult to prepare pure amines by ammonolysis of alkyl

halides?

• By ammonolysis of alkyl halides, a mixture of primary, secondary,

tertiary and quaternary amines are produced.
• As the boiling point of these amines are almost close by, separation
of the components become difficult by distillation.
𝑹𝑿 𝑹𝑿 𝑹𝑿
RNH2 + → R2NH + → R3X + → R4 N X

10 20 30 Quaternary ammonium salt

To get, primary amine as a major product excess of NH3 to be treated with

alkyl halide.

CH3Cl + NH3 (large excess) → CH3 NH2 , 10 amine – Methanamine.

The order of reactivity of alkyl halides ‘with amines is CH3I > CH3Br > CH3CI.

Aromatic amines could not be prepared by ammonolysis since aryl

halides are much less reactive towards nucleophilic substitution
reactions.

Board question:

Page 6 of 43
3.Reduction of nitriles or cyanides

Nitriles on reduction with LiAlH4 or catalytic hydrogenation or Na/Hg and ethanol

produce primary amines.

This reaction through the formation of Nitriles is used for ascending the amine
series, i.e., for preparation of amines containing one carbon atom more than the
starting amine.

4. Reduction of amides : The amides on reduction with LiAlH4 yield amines.

5.Gabriel phthalimide synthesis

Gabriel phthalimide synthesis is used for the preparation of primary amines.

Phthalimide on treatment with alc. KOH forms potassium salt of phthalimide
which on heating with alkyl halide followed by alkaline hydrolysis produces
the corresponding primary amine.

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4.Gabriel phthalimide synthesis is preferred for synthesizing
primary amines: (Aliphatic)

• Primary amine is formed by the nucleophilic attack of phthalimide ion

(SN2) on polar carbon atom of alkyl halide
• 2°or 3°amines are not formed in this synthesis. Therefore, Gabriel
phthalimide synthesis is preferred only for synthesizing primary
amines.(aliphatic)

Write the equation

5.Why aromatic primary amines cannot be prepared by

Gabriel phthalimide synthesis?

ANS. Gabriel phthalimide synthesis is used for the preparation of aliphatic

primary amines.
• Gabriel phthalimide synthesis is a SN2 reaction of phthalimide ion on
primary polar carbon atom.
• C6H5Cl do not undergo nucleophilic substitution due to the formation of
partial double bond between phenyl carbon and halogen.
• Therefore C6H5Cl or C6H5 Br does not react with Pot. phthalimide to give
N-phenyl phthalimide. Hence aromatic amines can’t be prepared by this
method.

6.Hoffmann Bromamide Degradation Reaction:

By treating an amide with bromine in an aqueous or ethanolic solution of

sodium hydroxide a primary amine with one carbon less than the parent amide
is formed.

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 6.Aniline gets coloured on standing in air for a long time. Why?

Due to the strong electron donating effect of NH2 group, the electron density
on the benzene ring increases. As a result, aniline is easily oxidized on
standing in air for a long time to form coloured products.

Board question

Intext question: 13.3 :

How will you convert (i) Benzene into aniline
(ii) Benzene into N, N-dimethylaniline
iii) Cl–(CH2 ) 4 –Cl into hexane-1,6-diamine

Page 9 of 43
 Physical Properties of Amines

1. The lower aliphatic amines are gases with fishy smell.

2. Primary amines with three or more carbon atoms are liquid and higher
members are all solids.
3. Lower aliphatic amines are water soluble because they can form hydrogen
bonds with water molecules, however the solubility decreases with increase in
hydrophobic alkyl group.
The order of solubility of amines in water is 10>20> 30 amines. The extend of
intermolecular H- bond between Amines and water decreases as the number of
hydrogen atom on amine decreases.

7.Ethyl amine is soluble in water where as aniline is not:

Ethylamine when added to water forms intermolecular H−bonds with

water. Hence, it is soluble in water.

However in aniline due to the presence of a large nonpolar

hydrophobic−C6H5 group, the extent of H-bonding decreases. Hence,
aniline is insoluble in water.

8.Butanol is more soluble in water than Butanamine?

The electronegativity of oxygen is 3.5 whereas that of Nitrogen is 3.

Thus the intermolecular hydrogen bond between water and butanol is more
stronger than that formed by Butanamine and water.

4. Boiling points order primary amines > secondary amines > tertiary amines.

9.Why 10amines have got higher boiling point than 30 amines?

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 • Due to the presence of two H-atoms in 10amines they undergo extensive
inter molecular hydrogen bonding with Nitrogen of the next molecule.
• Where as in 30 amines, by the absence of H-atom they cannot undergo
inter molecular hydrogen bonding.
• As the number of hydrogen atom decreases, the extend of H-bond formed
decreases. Therefore B.P of 10amines is more.

need not draw. Only for your understanding.

10.Boiling point of primary amine and alcohol which is more and why?

• Boiling point of alcohol is more than that of primary amine.

• The electronegativity of oxygen is 3.5 whereas that of Nitrogen is 3.
• Thus the intermolecular hydrogen bond in alcohol is more stronger than
that in primary amine.

• Out of Butanol and Butanamine, which is having higher boiling

point and why?

Same answer as above.

Tertiary amines do not have intermolecular association due to the absence

of hydrogen atom available for hydrogen bond formation.

Decreasing order of boiling point:

Carboxylic acid> Alcohol> Amine>Aldehyde >Ketone> Ether > Alkyl

halide> alkane

Page 11 of 43
chemical Properties of Amines:

Basic Strength of Amines

Amines act as Lewis bases due to the presence of lone pair of

electrons on the nitrogen atom.

More the Kb (dissociation constant of base), higher is the basicity of

amines.

Lesser the ‘pKb’ higher is the basicity of amines.

Aliphatic amines (CH3NH2) are stronger bases than NH3 due to the
electron releasing + I effect of the alkyl group.

Thus the increasing order of basic character of amines in the

gaseous phase is NH3 < 10 < 20 < 30

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Among aliphatic methyl amines, the order of basic strength in
aqueous solution is as follows

(C2H5 )2NH > (C2H5)3N > C2H5NH2 > NH3 ( 20 > 30> 10> NH3 for ethyl
amines)

(CH3)2NH > CH3NH2 > (CH3)3N > NH3 ( 20 > 10> 30> NH3 for methyl
amines)

Aromatic amines are weaker bases than aliphatic amines and

NH3,due to the fact that the electron pair on the nitrogen atom is
involved in resonance with the π-electron pairs of the ring. Thus
lone pair is not available for protonation.

Electron releasing groups (e.g.,-CH3,-OCH3,-NH2 etc.) increase the

basic strength of aromatic amines while electron withdrawing
groups (like – NO2, -X,-CN etc.) tend to decrease the basic character
of amines.

Ortho substituted aromatic amines are usually weaker bases than

aniline irrespective of the nature of substituent whether electron

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releasing or electron withdrawing. This is called ortho effect and is
probably due to sterric and electronic factors.

(i) Alkylation:

All the three types of amines react with alkyl halides to form
quaternary ammonium salt as the final product, provided alkyl
halide is present in excess.

Aromatic amines also undergo alkylation as given below.

Amines act as nucleophiles and attack on polar carbon atom of

alkyl halide to form mixture of amines..

The presence of lone pair of electrons on Nitrogen atom of amines

make them as nucleophiles.

ii) Acylation reaction:

Acylation reaction is the replacement of hydrogen atom of –NH2 or

>N–H group by the acyl group (RCO- group).

The products obtained by acylation reaction on amines are known

as amides

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11.Acylation is to be carried out in a strong base like pyridine.
Why?

C2H5NH2 + CH3COCl →C2H5NHCOCH3 + HCl (N-Ethylethanamide)

• The acylation reaction is carried out in the presence of a base

stronger than the amine, like pyridine,
• Pyridine removes HCl so formed as the side product and shifts
the equilibrium to the right-hand side.

Ethanamine on acetylation forms N- Ethylethanamide.

The mechanism involved in the formation of amide is as follows:

Acetanilide is N- phenylethanamide

Amines also react with benzoyl chloride (C6H5COCl). This reaction is

known as benzoylation.

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iii) Reaction of amines with carboxylic acids form salt at room
temperature. (no water as side product)

RCOOH + NH3 → RCOONH4

iv) Carbylamine reaction: (Isocyanide test)

Aliphatic and aromatic primary amines on heating with chloroform

and ethanolic potassium hydroxide form isocyanides or
carbylamines with a foul smell.

This reaction is known as carbylamine reaction or isocyanide test

and is used as a test for primary amine

Secondary and tertiary amines do not show this reaction.

Distinguish between Methylamine and dimethylamine-

Can be distinguished by Carbyl amine test.

v). Reaction with nitrous acid:

10, 20 & 30 amines react differently with nitrous acid ( HNO2 is

prepared from a mineral acid HCl and sodium nitrite.,NaNO2)

Primary aliphatic amines react with nitrous acid to form aliphatic

diazonium salts, which are unstable, liberate nitrogen gas and
alcohols.

Where as Aromatic amines react with nitrous acid at low

temperatures (273-278 K) to form a stable diazonium salts, do not
decompose to give N2 gas

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Secondary and tertiary amines react with nitrous acid in a different
manner.

Distinguish between Aniline and benzylamine:

can be distinguished by Nitrous acid test.

quantitative evolution of nitrogen is used in the estimation of amino

acids and proteins.

vi) Reaction with Arylsulphonyl chloride:

Benzenesulphonyl chloride (C6H5 SO2Cl), or Hinsberg’s reagent.

Hinsberg Test:

When amine is treated with Hinsberg reagent and then shaken with
aq. KOH Solution. The three amines 10, 20 & 30 behave differently.

(a)The primary amine on reaction with benzene sulphonyl chloride

yields N-ethyl benzene sulphonamide which is soluble in alkali.

(The hydrogen attached to nitrogen in sulphonamide is strongly

acidic due to the presence of strong electron withdrawing
sulphonyl group. Hence, it is soluble in alkali.)

C6H5SO2NH C2H5 + KOH → C6H5SO2NKC2H5 + H2O

(b) The secondary amine, yields N,N- diethyl benzene sulphonamide

,
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 which is insoluble in alkali

(Since N,N-diethyl benzene sulphonamide do not contain any

hydrogen atom attached to nitrogen atom, it is not acidic and hence

insoluble in alkali.)

(c) As there is no H- atom on ‘N’ atom of tertiary amines, it do not

react with benzene sulphonyl chloride.

This property of amines reacting with benzene sulphonyl chloride in

a different manner is used for the separation of a mixture of amines
and also for the distinction of primary, secondary and tertiary
amines.

Distinguish between Secondary and tertiary amines-

Using Hinsberg’s test

(vi) Electrophilic substitution reactions Aniline is a highly activating

group and ortho and para directing towards electrophilic
substitution reaction.

a) Bromination: Aniline reacts with bromine water at room

temperature to form a white precipitate of 2,4,6-
tribromoaniline.

Page 18 of 43
 To prepare mono substituted derivative,

activating effect of -NH2 group must be controlled.

It can be done by protecting the -NH2 group by acetylation with

acetic anhydride.

Then carrying out the desired substitution followed by

hydrolysis of the substituted amide forms the product.

12.Explain how the acetylation control the activating effect of

NH2 group of aniline.

• Aniline on acetylation form acetanilide. The lone pair of

electrons on nitrogen of acetanilide interacts with oxygen atom
due to resonance.

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 • Hence, the lone pair of electrons on nitrogen is less available
for donation to benzene ring by resonance. Thus the activating
effect of –NHCOCH3 group is less than that of amino group.

(b) Nitration:
Direct nitration of aniline is not possible as it is susceptible to
oxidation to form tarry products.

13.Nitration of Aniline form meta products also. Why?

OR 13.Although amino group is o, p− directing in aromatic

electrophilic substitution reactions, aniline on nitration gives a
substantial amount of m-nitro aniline: CBSE 2022

• Nitration is carried out with a mixture of Conc. H2SO4 +

Conc. HNO3. In the presence of these acids, most of aniline
gets protonated to form anilinium ion .

• Therefore in the presence of acids, the reaction mixture

consists of aniline and anilinium ion. The –NH2 group in
aniline is o,p –orienting and activating.

• While –NH3+ group in anilinium ion is m- directing and

deactivating. Thus a mixture of all the three –o, p and m-
derivatives are formed.

because of this reason, aniline on nitration gives a

substantial amount of m-nitroaniline.

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However, by protecting the –NH2 group by acetylation reaction with
acetic anhydride, the nitration reaction can be controlled and the p-
nitro derivative can be obtained as the major product.

c)Sulphonation:

Aniline reacts with concentrated sulphuric acid to form

anilinium hydrogensulphate.

This on heating with sulphuric acid at 453-473K produces p-

aminobenzene sulphonic acid, commonly known as sulphanilic
acid, as the major product.

14.What are Zwitter ions? Give example.

• Zwitter ions are neutral dipolar ions.

• In aqueous solution it is formed by the removal of proton from
acidic group and the acceptance of proton by a basic group.
example: Sulphanilic acid.

Page 21 of 43
15. Aniline does not undergo Friedel-Crafts reaction:
(CBSE 2020,2022, AI 2016, 2014).

• Ans. Friedel-Crafts reaction is carried out in the presence of

AlCl 3. But AlCl3 is Lewis acid and aniline is a Lewis base. Thus,
aniline reacts with AlCl 3 to form a salt

C6H5NH2 + AlCl3 → C6H5NH2+AlCl3-

• As a result N-atom acquires positive charge and acts as a

strong deactivating group for electrophilic reaction. Thus
aniline does not undergo the Friedel-Crafts reaction.

16.Can tertiary amines undergo acetylation reactions? Explain.

For an amine to undergo acetylation, it should have a replaceable

hydrogen atom. Tertiary amines cannot undergo acetylation as it
do not have hydrogen atom.
17.How can we prepare mono bromo aniline?
• Because of high activity of aromatic amines, substitution
tends to occur at all the o- and p- positions.
• Mono substituted aniline can be prepared by protecting –NH2
group by acetylation with acetic anhydride,

• then carry out the bromination followed by hydrolysis of

substituted amide.

Page 22 of 43
 Separation of Mixture of Amines (1°, 2° and 3°)
(a) Fractional distillation This method Is based on the boiling points
of amines and is used satisfactorily in Industry.

(b) Hinsberg’s chemical reactions. (Chemical method)

BASIC CHARACTER OF AMINES

1. Alkyl amines and ammonia ( CH3NH2 and NH3)

Which is more basic and why?
Alkyl amine is more basic than ammonia. CH3NH2 is more basic than NH3

Basic character of an amine is decided by the electron density on

Nitrogen and its ability to donate the electron pair for protonation.

a) The electrons density on nitrogen increases by the +I effect of alkyl

group. Thus the lone pair on nitrogen is more available for
protonation.
b) The ammonium ion thus formed from the amine gets stabilized by the
dispersal of the +ve charge by the +I effect of the alkyl group.
Thus Alkyl ammonium ion is more stable than the ammonium ion.

Thus alkyl amines are more basic than ammonia.

As the number of alkyl groups increase, basic nature of the amine will
also increase.
As the number of alkyl groups with +I effect increases, electron
density on nitrogen increases which increases the extent of
protonation.

Page 23 of 43
 The respective substituted ammonium ions formed from these amines
gets stabilized due to the more dispersal of the + ve charge by the + I
effect of the alkyl groups. Thus the increasing order of basic character
these amines in the gaseous phase is NH3 < 10 < 20 < 30

NH3 < CH3NH2 (10 ) < CH3)2 NH (20 ) < CH3)3N ( 30 )

2. Alkyl amines and ammonia in aqueous medium

a) Due to the +I effect of alkyl group, it pushes the electrons towards

nitrogen and makes the lone pair more available for protonation.
b) The substituted ammonium ion formed from the amine gets stabilized
due to dispersal of the +ve charge by the +I effect of the alkyl group. Thus
as the number of alkyl groups increase, basic nature of the amine will
also increase.
c) In aqueous phase, the substituted ammonium cations get stabilized not
only by +I effect of alkyl groups, but also by the solvation with water
molecules through H- bonding.
Greater the size of the ion, lesser will be the solvation and less stabilized
the ion. Thus the order of stability of ions is as follows: 10>20>30 and same
is the order for basicity.

The above order is opposite to that predicted by inductive effect.

d) When the alkyl group is small like –CH3 group, there is no steric
hindrance to H-bonding. But in other alkyl groups, steric hindrance also
to be considered for the H- bonding with water. Hence in higher alkyl
amines, the order of basicity based on solvation effect is unlike to methyl
amines.

Thus the cumulative effect of the +I effect, solvation effect and steric
hindrance decide basic character of amines in aqueous medium.

Page 24 of 43
 The stability of methyl ammonium ion due to H-bonding, predominates
over the stability due to +I effect of –CH3 groups, making CH3NH2 more
stronger than (CH3 )3N.

Thus the increasing order of basicity will be:

for Methyl amines is NH3 < 30 < 10 < 20

NH3 < CH3)3N ( 30 ) < CH3NH2 (10) < CH3)2 NH (20 ) Delhi 2019

For ethyl amines is NH3 < 10 < 30 < 20

NH3 < C2H5NH2 (10) < C2H5)3N ( 30 ) < C2H5)2 NH (20 ) CBSE 2018

3. Aryl amines and ammonia ( C6H5NH2 and NH3)

C6H5NH2 and NH3 , which is more basic? Board question
NH3 is more basic than aniline C6H5NH2

• In aniline or any other aryl amines, the –NH2 group is attached

directly to the benzene ring.
• Due to resonance the lone pair of electrons on nitrogen is in
conjugation with the benzene ring and hence less available for
protonation.

• The formed anilinium ion is less stabilized as it has only two

resonance structures than aniline which has five structures.

Where as in NH3 the Hydrogen atoms are neither with +I effect nor
with -I effect.
Thus aryl amines / aniline are weaker bases than ammonia.

Page 25 of 43
4.) pKb of aniline is more than that of methylamine . Justify
CBSE 2022, AI 2012, Delhi 2014

• pKb of aniline is more than that of methylamine, means aniline

is less basic than Methyl ammine.

• In aniline, the lone pair of electrons on the N-atom atom is delocalized

over the benzene ring.
• As a result the electron density on Nitrogen decreases and the lone pair
of electrons on N-atom are less available for protonation.

• The anilinium ion is less stable than aniline.

Where as in methylamine

• the electron density on the N-atom increases due to the +I effect of

methyl group.
• The methyl ammonium ion is stable through the dispersal of the
positive charge.
• As a result, aniline is less basic than methylamine
.
Thus, pKb of aniline is more than that of methylamine.

CH3CONH2 is a weaker base than CH3CH2NH2.

Due to the resonance, the lone pair of electrons on the nitrogen atom in
CH3CONH2 is delocalized over the ‘C=O’ group.

There is no such effect in CH3CH2NH2.

As the electron density on nitrogen of CH3CONH2 is less, it is a weaker base

than CH3CH2NH2.

Page 26 of 43
II. DIAZONIUM SALTS

The diazonium salts have the general formula – R N2+ X-

where R stands for an aryl group and – X ion may be C l– ,Br–,

HSO4 − , BF4 − , etc.

They are named by suffixing diazonium to the name of the parent

hydrocarbon from which they are formed, followed by the name of
anion such as chloride, hydrogen sulphate, etc.

The N2 + group is called diazonium group.

For example, – C6H5 N2+ Cl is named as benzene diazonium

chloride and

C6H5N2+HSO4 – is known as benzene diazonium hydrogen sulphate.

Benzene Diazonium Chloride (C6H5N2+Cl-)

Preparation (Diazotisation reaction)

• The excess acid in diazotisation reaction is necessary to

maintain proper acidic medium for the reaction.
• It prevent the combination of diazonium salt formed with the
undiazotised amine.

Page 27 of 43
Diazonium salts are prepared and used in aqueous solutions
because in solid state, they explode.

Properties

It is a colourless crystalline solid, soluble in water. It has tendency

to explode when dry.

Stability of Arene diazonium salts

Arene diazonium salts are relatively more stable than the alkyl
diazonium salt.

The arene diazonium ion is resonance stabilized, where as alkyl

diazonium ion cannot stabilize through resonance.

The resonating structures of arene diazonium ion are :

18.Diazonium salts of aromatic amines are more stable than those

of aliphatic amines: CBSE 2018

The diazonium salts of aromatic amines are more stable than those
of aliphatic amines. The ‘+ ve’ charge is dispersed on benzene ring
through resonance.

In aliphatic amines, there is no dispersal of + ve charge as it do not

have resonance structures.

Page 28 of 43
Physical Properties:

Benzenediazonium chloride is a colourless crystalline solid.

It is readily soluble in water and is stable in cold but reacts with

water when warmed.

It decomposes easily in the dry state.

Benzene diazonium fluoroborate is water insoluble and stable at

room temperature

Chemical Properties:

The reactions of diazonium salts can be broadly divided into two

categories, namely

(A) reactions involving displacement of nitrogen and

(B) reactions involving retention of diazo group.

A. Reactions involving displacement of nitrogen:

Sandmeyer reaction, Guttermann reaction, replacement by Iodide

ion, fluoride ion.

Replacement by Hydrogen:

Certain mild reducing agents like hypophosphorous acid

or ethanol reduce diazonium salts to arenes (Benzene) and

themselves get oxidised to phosphorous acid and ethanal,
respectively.

Page 29 of 43
C6H5N2Cl + H3PO2 → C6H6 + N2 + H3PO3 + HCl

Replacement by hydroxyl group: If the temperature of the

diazonium salt solution is allowed to rise upto 283 K, the salt gets
hydrolyzed to phenol.

C6H5N2Cl + H2O → C6H5OH+ N2 + HCl

Replacement by –NO2 group: When diazonium fluoroborate

is heated with aqueous sodium nitrite solution in the presence
of copper, the diazonium group is replaced by –NO2 group

B) Reactions involving retention of diazo group

What are azo compounds?

The azo products have an extended conjugate system having both

the aromatic rings joined through the–N=N–bond. These compounds
are often coloured and are used as dyes.

Coupling reactions

Benzene diazonium chloride reacts with phenol in which the phenol

molecule at its para position is coupled with the diazonium salt to
form p-hydroxy azo benzene. This type of reaction is known as
coupling reaction.
Similarly the reaction of diazonium salt with aniline yields p-amino
azo benzene.

Page 30 of 43
Page 31 of 43
Importance Of Diazonium salt:

From the above reactions, it is clear that the diazonium salts are very

good intermediates for the introduction of –F, –Cl, –Br, –I, –CN, –OH,

Page 32 of 43
–NO2 groups into the aromatic ring.

Aryl fluorides and iodides cannot be prepared by direct halogenation.

The cyano group cannot be introduced by nucleophilic substitution of

chlorine in chlorobenzene but cyanobenzene can be easily obtained

from diazonium salt.

Thus, the replacement of diazo group by other groups is helpful in preparing

those substituted aromatic compounds which cannot be prepared by direct

substitution in benzene or substituted benzene.

DISTINCTION BETWEEN PAIRS OF COMPOUNDS

( the equation to be written in two column)

Give one chemical test to distinguish between the following pairs of

compounds.

(i)Methyl amine and dimethyl amine

ANS. (i) Methyl amine and dimethyl amine can be distinguished by the Carbyl
amine test:
Methyl amine on heating with chloroform and ethanolic KOH form foul-
smelling isocyanides or carbylamines.
Whereas dimethylamine does not produce foul smell with CHCl3 & KOH.

ii)Secondary and tertiary amines (CH3)2NH & (CH3)3N

on reaction

Page 33 of 43
 Secondary and tertiary amines can be distinguished by Hinsberg‘s test.
(benzene sulphonyl chloride, C6H5SO2Cl). (CH3)2NH on reaction with
Hinsberg‘s reagent form a product which is insoluble in alkali.

Whereas tertiary amine will not react with the reagent.

For example,

N, N−diethylamine reacts with Hinsberg‘s reagent to form N,N−diethyl benzene

sulphonamide, which is insoluble in alkali.

Tertiary amines, do not react with Hinsberg‘s reagent.

(ii) Ethylamine and aniline

Ans. Ethylamine and aniline can be distinguished using the azo-dye test. The
diazonium salts of aromatic amines undergo coupling reactions with phenol or
aniline to form coloured compounds used as dyes.

No such dyes are formed by aliphatic amines. can be distinguished by its

reactions with nitrous acid also.

(iv)Aniline and benzyl amine can be distinguished by nitrous acid test.

Page 34 of 43
Benzyl amine reacts with nitrous acid to form unstable diazonium salt, which
gives alcohol with the evolution of nitrogen gas.

On the other hand, aniline does not evolve nitrogen gas as it form stable
diazonium salt with HNO2 at a low temperature

Similarly, Ethylamine and aniline also can be distinguished by nitrous

acid test.

v)Aniline and N-methyl aniline

can be distinguished by Carbyl amine test.

Aniline, being primary amine on heating with chloroform and ethanolic

potassium hydroxide, form foul-smelling isocyanides or carbylamines.

N-methyl aniline, being a secondary amine does not form foul smelling
isocyanide.

(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated

ferric .oxide

Due to the +I effect of−CH3 group, methylamine is more basic than water.
Therefore, in water, methylamine produces OH−ions by accepting H+ions from
water.

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Ferric chloride (FeCl3) dissociates in water to form Fe3+and Cl−ions.

Then, OH−ion reacts with Fe3+ion to form a precipitate of hydrated ferric oxide.

Sandmeyer Reaction

The Cl–,Br–and CN–nucleophiles can easily be introduced in the benzene ring

of diazonium salts in the presence of Cu(I)ion and Hydrogen halide.

6.Gatterman Reaction

Chlorine or bromine can be introduced in the benzene ring by treating the

diazonium salt solution with corresponding halogen acid in the presence of
copper powder.

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The best reagent to convert -OH to -Cl is SOCl2

Carboxylic acid to amide can be done by converting it into ammonium salt followed
by heating.

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13.5 How will you convert: (i) Ethanoic acid into methanamine (ii) Hexanenitrile into
1-aminopentane (iii) Methanol to ethanoic acid

(iii) Ethanamine into methanamine (v) Ethanoic acid into propanoic acid (vi) Methanamine into
ethanamine

(vii) Nitromethane into dimethylamine (viii) Propanoic acid into ethanoic acid

𝐾𝑀𝑛𝑂4
CH3CH2OH → CH3COOH
𝑂

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13.8 Accomplish the following conversions: (i) Nitrobenzene to benzoic acid (ii)
Benzene to m-bromophenol

iii) Benzoic acid to aniline

(iv) Aniline to 2,4,6-tribromofluorobenzene (v) Benzyl chloride to 2-

phenylethanamine

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(vi) Chlorobenzene to p-chloroaniline (vii) Aniline to p-bromoaniline

viii) Benzamide to toluene (ix) Aniline to benzyl alcohol

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13.10 An aromatic compound ‘A’ on treatment with aqueous ammonia and heating
forms compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’ of

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molecular formula C6H7N. Write the structures and IUPAC names of compounds A,
B and C

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