 In IUPAC system, amines are named as alkanamines,

Amines derived by replacement of ‘e’ of alkane by the word

 Amines can be considered as derivatives of ammonia, amine.
 obtained by replacement of one, two or all the three  In arylamines, –NH2 group is directly attached to the
hydrogen atoms by alkyl and/or aryl groups. For benzene ring. C6H5NH2 [aniline.] is the simplest
example: example of arylamine.
 . Thus in IUPAC system, C6H5–NH2 is named as
benzenamine.
13.4 Preparation of Amines
13.1 Structure of Amines
Amines are prepared by the following methods:
 Like ammonia, nitrogen atom of amines is
3
1. Reduction of nitro compounds
sp [3sigma+ 1LP ]hybridised and carries an unshared
pair of electrons.
 and the geometry of amines is pyramidal.
13.2 Classification
 Amines are classified as primary
iron scrap and hydrochloric acid is preferred because
 (1°), secondary (2°) and tertiary (3°)
FeCl2 formed gets hydrolysed to release hydrochloric acid
 Degree of nitrogen = degree of amines.
during the reaction.
2. Ammonolysis of alkyl halides

13.3 Nomenclature

The free amine can be obtained from the ammonium salt

by treatment with a strong base:

The order of reactivity of halides with amines is RI > RBr

>RCl.
Example 13.1
Write chemical equations for the following reactions:
(i) Reaction of ethanolic NH3 with C2H5Cl.
(ii) Ammonolysis of benzyl chloride and reaction of amine
so formed with two moles of CH3Cl.
Solution


In common system, an aliphatic amine is named by
prefixing alkyl group to amine, i.e., alkylamine as

MUKESH SHARMA DPS JODHPUR (1)

3. Reduction of nitrile
by LiAlH4 ,H2+Ni,Sn+4HCl
(ii) Benzamide is an aromatic amide containing seven
carbon atoms. Hence, the amine formed from benzamide
is aromatic primary amine containing six carbon atoms.
4. Reduction of amide

Intext Question
13.3 How will you convert
5. Gabriel phthalimide synthesis
(i) Benzene into aniline (ii) Benzene into N, N-
dimethylaniline (iii) Cl–(CH2)4–Cl into hexan-1,6-diamine?

13.5 Physical Properties

 the order of boiling points of isomeric amines is as
follows:
Primary > Secondary > Tertiary intermolecular
 due to association due Intermolecular hydrogen
in RX ,R should not be 3degree or aryland vinylic bonding
because 3RX gives elimination ,Ar-x don’t give subst
due to PDC
6. Hoffmann bromamide degradation reaction

Example 13.2 Write chemical equations for the following  Boiling points of amines, alcohols and alkanes of
conversions: almost the same molar mass are
(i) CH3–CH2–Cl into CH3–CH2–CH2–NH2 RCOOH> ROH>RNH2>RCHO>ROR>RX>RR
(ii) C6H5–CH2–Cl into C6H5–CH2–CH2–NH2 13.6 Chemical Reaction,
Solution  amines behave as base nucleophiles due to the
presence of unshared electron pair.
 1. Basic character of amines
Amines, being basic in nature, due to the presence of
unshared electron pair.
Example 13.3  react with acids to form salts.
Write structures and IUPAC names of
(i) the amide which gives propanamine by Hoffmann
bromamide reaction.
(ii) the amine produced by the Hoffmann degradation of
benzamide.
Solution
(i) Propanamine contains three carbons. Hence, the amide
Amine salts on treatment with a base like NaOH,
molecule must contain four carbon atoms. Structure and
regenerate the parent amine.
IUPAC name of the starting amide with four carbon atoms
are given below:

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pKb = –log KbLarger the value of Kb or smaller the value of  donating groups (– OCH3, – CH3) increase the
pKb, stronger is the base basicity
Basic character of amines – The order of increasing NAME OF AMINE PKB
basicity is
Phenylmethanamine C6H5 CH2NH2 4.70
Aromatic amines < Ammonia < Aliphatic amines
Aliphatic amines are stronger bases than ammonia Aniline C6H5NH2 9.38
due to +I effect of alkyl groups. N-Methylaniline 2
0
9.30
Aromatic amines are weaker bases than ammonia due to
0
N,N-Dimethylaniline 3 8.92
unshared electron pair on nitrogen atom to be in
conjugation with the benzene ring and thus making it less Example 13.4 Arrange the following in decreasing order of
their basic strength:
available for protonation C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
Solution
(C2H5)2NH > C2H5NH2 > NH3 > C6H5NH2
2. Alkylation

On the other hand, anilinium ion obtained by accepting a

proton can have only two resonating structures (kekule). 3. Acylation
reaction with acid chlorides, anhydrides by nucleophilic
substitution reaction.

 aniline (five resonating structures) is more stable than

anilinium ion. Hence, the proton acceptability or the
basic nature of aniline or other aromatic amines would
be less than that of ammonia.

Structure–basicity relationship of amines

The increasing order of basicity of amines in the
gaseous phase is
NH3 < 1 amine < 2 amine < 3 amine
The increasing order of basic strength in the case
of methyl-substituted amines and ethyl-substituted
amines in aqueous solution.

(i)A<T<P<S , (ii)A <P<T <S ,

The above order is due to the combined effect
 of steric hindrance of the alkyl group,
 inductive effect and
 salvation effect
 steric hinderence weightage is only in 30 benzoylation. reaction with benzoyl chloride (C6H5COCl).
 In the case of substituted aniline, electron- CH3NH2 +C6H5COCl → CH3NHCOC6H5 + HCl
Methanamine Benzoyl chloride N –Methylbenzamide
withdrawing groups (– NO2, – SO3, – COOH,
– X) decrease the basicity while electron 4. Carbylamine reaction [isocyanide test]

MUKESH SHARMA DPS JODHPUR (3)

Carbylamines reaction (or isocyanide test) – electron density. Thus –NH2 group is ortho and para
Used as test to distinguish 1 amine directing and a powerful activating group.
2 and 3 amines do not react to this test. (a) Bromination:

5. Reaction with nitrous acid

Nitrous acid is prepared in situ from a mineral acid and
sodium nitrate.
Primary aliphatic amines

Monobromintaion by reducing the activating effect of NH2

Aromatic amines

Secondary and tertiary amines react with nitrous acid in a

different manner.
6. Reaction with arylsulphonyl chloride
The lone pair of electrons on nitrogen of acetanilide
Hinsberg’s reagent ->Benzenesulphonyl chloride
interacts with oxygen atom due to resonance as shown
(C6H5SO2Cl), This reaction can be used for distinguishing
below:
and separating 1 , 2 , and 3 amines
(a) The reaction of benzenesulphonyl chloride with primary
amine yields N-ethylbenzenesulphonyl amide.

Hence, the lone pair of electrons on nitrogen is less

available for donation to benzene ring by resonance.
Therefore, activating effect of –NHCOCH3 group is less
than that of amino group.
(b) Nitration:
The amide formed is soluble in alkali because the
hydrogen attached to nitrogen is strongly acidic due to the
presence of a strong electron-withdrawing sulphonyl
group.
(b) Secondary amine

 in the strongly acidic medium, aniline is protonated

to form the anilinium ion which is meta directing.
That is why besides the ortho and para

it is not acidic and hence insoluble in alkali. derivatives, significant amount 47% of meta
derivative is also formed.
 However, by protecting the –NH2 group by
 (c) Tertiary amines do not react with benzenesulphonyl
acetylation reaction with acetic anhydride, the
chloride.
nitration reaction can be controlled and the p-nitro
7. Electrophilic substitution
derivative can be obtained as the major product.
 the maximum electron density is at Ortho- and para-
positions to the –NH2 group become centres of high

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 Gatterman reaction.

2. Replacement by iodide ion:.

(c) Sulphonation:
-
3. Replacement by F : reaction with fluor boric acid

4. Replacement by H: reaction with hypophosphorous acid

(phosphinic acid)

 Aniline does not undergo Friedel–Crafts reaction

(alkylation and acelytation). 5. Replacement by hydroxyl grou

II. DIAZONIUM SALTS

Primary aromatic amines form arenediazonium salts The
6. Replacement by –NO2 group:
stability of arenediazonium ion is explained on the basis of
resonance.

B. Reactions involving retention of diazo group coupling

reactions
13.7 Method of preparation of Diazonium Salts Coupling reactions (Electrophilic substitution reaction
Diazotisation The conversion of primary aromatic ofphenol and aniline with DIAZONIUM ions )

amines into diazonium salts

13.8 Physical Properties

 Benzenediazonium chloride is a colourless crystalline
solid.
Diazo test :- above reaction is used for aromatic
 Benzenediazonium fluoroborate is water insoluble and 0
amines onlyfor 1
stable at room temperature.
13.9 Chemical Reaction Example 13.5 How will you convert 4-nitrotoluene to 2-
Reactions that involve displacement of nitrogen bromobenzoic acid ?
 Replacement by halide or cyanide ion Solution
 Sandmeyer’s reaction

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