Chapter–13

Table 13.1: Nomenclature of Some Amines

Common Name Structural Formula IUPAC Name

Amines Ethyl amine CH3—CH2—NH2

CH3
Ethanamine

|
Isopropyl amine CH3 —CH—NH2 Propan-2-amine
Ethyl methyl amine CH3—CH2—NH—CH3 N-Methylethanamine

C2 H5
|
N, N-Diethylbutylamine C2 H5 — N — CH2 —CH2 —CH2 —CH3 N, N-Diethylbutan-1- amine
Allylamine CH2—CH—CH2—NH2 Prop-2-en-1-amine
Hexamethylenediamine H2N—(CH2)6—NH2 Hexane-1, 6-diamine
1. Introduction
NH2
Alkyl or aryl derivatives of ammonia are regarded as amines. These are obtained by replacing one or more
hydrogen atoms by alkyl or aryl groups. Amines are classified as primary, secondary or tertiary depending Aniline Benzenamine or Aniline
upon whether one, two or three atoms of hydrogen have been replaced by alkyl or aryl groups.
–H –H –H
NH3 +CH3
CH3 NH 2 +CH3
(CH3) 2 NH +CH3
(CH3) 3 N
Methyla min e Dimethyla min e Trimethyla min e NH2
1° (Primary) 2° (Secondary) 3° (Tertiary)
o-Toluidine CH3 2-Methylaniline
Thus, characteristic functional groups for 1°, 2° or 3° amines are:
| |
     —NH 2 —NH —N— H3C N CH3
Primary Secondary Tertiary
N, N-Dimethylaniline N, N-Dimethylbenzenamine
Amines are said to be ‘simple’ when all the alkyl or aryl groups are the same, and ‘mixed’ when they are
different.
There is another class of compounds wherein all the four hydrogen atoms of an ammonium salt have been
replaced by alkyl or aryl groups. Such compounds are named as quaternary ammonium salts. 4. Preparation of Amines: Amines are prepared by the following methods:
     [NH4 ]+ X  
4 H
 [ NR 4 ] X  (a) Reduction of nitro compounds:
4 R Ni
Tetra alkylammonium halide R—NO 2 + 3H 2
R—NH 2 + 2H 2 O
1° a min e
Unshared
Fe/HCl (conc.)
2. Structure of Amines electron CH3 —CH 2 —NO 2 + 6 [H]
CH3 —CH 2 —NH 2 + 2H 2 O
pair Nitroethane
or
Ethana min e
Like ammonia, nitrogen atom of amines is trivalent and carries Sn/HCl (conc.)
an unshared pair of electrons. Nitrogen orbitals in amines (b) Ammonolysis of alkyl halides:
are therefore sp3 hybridised and the geometry of amines is
pyramidal. Each of the three sp3 hybridised orbitals of nitrogen CH3 R—X + 2NH3
R—NH 2 + NH 4 X
(excess) 1° a min e
overlap with orbitals of hydrogen or carbon depending upon CH3 (Major product)
the composition of the amines. The fourth orbital of nitrogen
in all amines contains an unshared pair of electrons. Due to the If alkyl halide is in excess, the amine formed further reacts with alkyl halide to form 2°, 3° amines and
presence of unshared pair of electrons, the angle C—N—E, finally quaternary ammonium salts.
(where E is C or H) is less than 109.5°; for instance, it is 108° CH3 +R—X +R—X +R—X +
in case of trimethylamine as shown in Fig. 13.1 alongside. 108°
R—NH 2 R2 NH R3 N R4 N X–
1° a min e 2° a min e 3° a min e Quaternary
3. Nomenclature Fig. 13.1: Pyramidal Trimethylamine ammonium salt

In the trivial system, amines are named as alkylamine but in the IUPAC system, these are named as (c) Reduction of nitriles:
alkanamine (replacing ‘e’ of alkane with amine). Ni
R—C // N + 2H 2
R—CH 2 —NH 2
CH3—CH—CH2—NH2 C2H5 1° a min e

—CH2—N— Na (Hg)/C2 H5 OH
R—C // N + 4 [H]
R—CH 2 —NH 2
or LiAlH 4
1° a min e
2-Phenyl propanamine (1°)
N-Benzyl-N-ethyl benzenamine

Amines 525 526 Xam idea Chemistry–XII

 C N CH2—NH2 CH3

+ 4[H] LiAlH 4 H3C—N—H.......N—H

.......H H.......
Benzyl amine

(d) Reduction of amides: The hydrogen bonding between amine molecules is weaker than that between alcohols or carboxylic
LiAlH 4 /ether acids therefore amines have lower boiling points than the alcohols or carboxylic acids of comparable
R—CONH2 + 4 [H]
R—CH2 —NH 2 + H 2 O molecular masses.
Acid amide 1° a min e
(iv) The lower members are readily soluble in water, the solubility in water decreases and in organic
(e) Hoffmann’s bromamide degradation reaction:
solvents (alcohol and ether) increases with the increase in molecular weight.
R—CONH 2 + Br2 + 4NaOH
R—NH 2 + Na 2 CO3 + 2NaBr + 2H 2 O Solubility of all the three classes of aliphatic amines in water is due to the formation of hydrogen bond
Acid amide 1° a min e
between amine and water molecules. However, in higher amines, the alkyl group predominates over
(f) Gabriel phthalimide synthesis: the amino group with the result that they have less tendency for forming hydrogen bond with water.
O O This explains why the higher amines are insoluble in water.
Aromatic amines are insoluble in water. This is because of the larger hydrocarbon part. Thus, aniline
C + KOH C –+
NH NK is almost insoluble in water. However, all amines are quite soluble in organic solvents like benzene,
C C
ether, alcohol, etc.
O O 6. Basic Character of Amines: Amines have a lone pair of electrons on nitrogen atom due to which they
+R X behave as Lewis base. Basic character of amines can be better understood in terms of Kb and pKb values as
explained below.
O O + –
–+ R—NH 2 + H2 O R—NH3 + OH
C ONa
– + + R—NH
+ NaOH (aq) C N R
C ONa (1° amine)2 C + –
[R—NH3] [OH]
O O Kb =
[R—NH 2]
Aromatic amines cannot be prepared by this method because aryl halides do not undergo nucleophilic
  pKb = – log Kb
substitution with the anion formed by phthalimide.
Larger the value of Kb or smaller the value of pKb stronger is the base.
Preparation of Aniline:
(i) From nitrobenzene (a) Amines versus alcohols, ethers and esters: Since nitrogen is less electronegative than oxygen, it is in
a better position to accommodate the positive charge of the proton. Therefore, amines are more basic
NO2 NH2
than alcohols, ethers, esters, etc.
Sn/HCl (conc.)
+ 6[H] or
+ 2H2O (b) Alkylamines versus ammonia: In aliphatic amines, the electron-releasing alkyl groups stabilise
Fe/HCl (conc.) their ammonium cations by dispersing the positive charge, and in parent amines make the nitrogen
Nitrobenzene Aniline
unshared electrons more available for sharing with a proton. Thus, the basic character of aliphatic
(ii) By Hoffmann bromamide degradation reaction amines should increase with the increase of alkyl substitution. But it does not occur in a regular
manner as a secondary aliphatic amine is unexpectedly more basic than a tertiary amine in solutions.
CONH2 NH2
Basicity Order: (Et)2NH > Et3N > EtNH2 > NH3; (Me)2NH > MeNH2 > (Me)3N > NH3
+ Br2 + 4KOH + K2CO3 + 2KBr + 2H2O In gas phase, where the solvent effect is missing, the basic trend in nature is as expected,
i.e., tertiary amine > secondary amine > primary amine > ammonia.
Benzamide Aniline
Anomalous basic strength of tert-alkylamines: In aqueous solution, the substituted ammonium
5. Physical Properties
cations are stabilised not only by electron-releasing effect of the alkyl groups but also by solvation
(i) The lower members are combustible gases, members from C3 to C11 are volatile liquids and from C12
with water molecules. It is a combination of electron-releasing, H-bonding and steric factors that
onwards are solids. Lower aromatic amines are liquids while the higher ones are low melting solids.
determine the stability of the ammonium cations in solution and thereby resulting in the basic strength
(ii) Pure amines are almost colourless but develop colour on keeping in air for long time, especially, the
order of aliphatic amines as secondary > tertiary > primary amines.
aromatic amines. The colouration is due to oxidation of amines by air.
(c) Aromatic amines versus ammonia and aliphatic amines: Aromatic amines are weaker bases than
(iii) The boiling point increases with the increase in molecular weight. However, primary and secondary
amines have higher boiling points than the tertiary amines of the same molecular weight. This is again ammonia and aliphatic amines. Since resonance stabilises an aromatic amine more than it stabilises its
due to the possibility of intermolecular hydrogen bonding between molecules of primary as well as ammonium cation, the proton acceptability and thereby basic strength of aromatic amines would be
secondary amines. less. It may also be argued that due to resonance, unshared electrons on nitrogen in aromatic amines
are less available for sharing with a proton—a feature opposite to that in alkyl amines.

Amines 527 528 Xam idea Chemistry–XII

 (d) Effect of substituent on the basicity of aromatic amines: O O
(i) Electron-donating groups such as —CH3, —OCH3, –NH2, etc., increase the basicity while
electron-withdrawing substituents such as —NO2, —CN, halogens, etc., decrease the basicity of C— Cl C NH CH3
amines. The effect of these substituents is more at p- than at m-positions.
CH3 NH2 + + HCl
(ii) Among the isomeric toluidines, the basic strength with respect to aniline decreases as: Methyl amine
Benzoyl chloride N-Methylbenzamide
NH2 NH2 NH2 NH2
CH3 O O
> > >
CH3 NH2 C Cl C NH
CH3 aq. NaOH
+ + HCl
(iii) The order of basic strength of some amino compounds:
Aniline Benzoyl chloride Benzanilide
Ortho-substituted anilines are weaker bases than aniline irrespective of the nature of the substituent.
This is called ortho-effect and it is probably due to a combination of steric and electronic factors. (c) Reaction with chloroform (Carbylamine reaction):
D
NH2 NH2 NH2 NH2 NHCH3 NH2 NH2 R—NH 2 + CHCl3 + 3KOH (alc.) R—NC + 3KCl + 3H 2 O
Alkyl
carbyla min e
< < < < < <
NH2 NC
NO2 Br Cl CH3 OCH3

+ CHCl3 + 3KOH (alc.) + 3KCl + 3H 2O
7. Chemical Properties of Amines:
(a) Alkylation: Aniline Phenyl isocyanide
+CH3—CH2—Br
CH3—CH2—NH2 – HBr
(CH3—CH2)2NH (d) Reaction with nitrous acid:
Ethylamine Reaction with nitrous acid helps in distinguishing between amines. Primary amines react with nitrous
+CH3—CH2—Br – HBr acid to form alcohols.
NaNO /HCl
   R—NH 2 + HONO 2
R—OH + N 2 + H 2 O
+CH3—CH2—Br
(CH3—CH2)4NBr (CH3—CH2)3N 1° a min e
Tetraethyl Triethylamine Secondary amines react with nitrous acid to form a yellow green oily layer of N-nitrosoamines.
ammonium bromide N-Nitrosoamines on warming with a crystal of phenol and a few drops of conc. H2SO4 form green
(b) Acylation: solution which when treated with aqueous NaOH, turns deep blue and then red on dilution. This
reaction is called Liebermann’s nitroso reaction.
O O
|| ||    R 2 NH + HNO 2 R 2 N—N == O + H 2 O
Base
R—NH 2 + Rl —C—Cl
R—NH—C—Rl + HCl 2° A min e N - Nitrosoa min e
N - substituted amide
tert-Amines readily dissolve in nitrous acid forming crystalline trialkyl ammonium nitrite.
+
O O
Base CH2—CH3    R3 N + HNO 2 R3 NHNO 2–
(CH3—CH2)2NH + CH3—C—Cl CH3—C—N + HCl Trialkyl ammonium nitrite
Diethylamine Acetyl chloride CH2—CH3 (e) Diazotization:
N, N-Diethylacetamide + –
O NH2 N NCl
O
CH3—C 273– 278 K
+ NaNO2 + 2HCl + NaCl + 2H2O
CH3—CH2—NH2 + O CH3—C—NH—CH2—CH3 + CH3—COOH
Ethylamine CH3—C N-Ethylacetamide Aniline Benzenediazonium
O chloride

Acetic anhydride (f) Electrophilic substitution reactions:

O Due to resonance, electron density increases at ortho and para positions as compared to meta positions.
Therefore, —NH2 group directs the incoming group to ortho and para positions.
NH2 O NH—C—CH 3 + + +
NH2 NH2 NH2 NH2 NH2
+ CH3—C O + CH3—COOH
CH3—C
Aniline Acetanilide
O or
N-Phenylethanamide

Amines 529 530 Xam idea Chemistry–XII

 (i) Bromination: 8. Diazonium Salts
+
NH2 NH2 (a) General formula: RN 2 X –
+ +
Br Br where R stands for an aryl group and X– ion may be Cl–, Br–, HSO4–, BF4–, etc. The N 2 (—N / N) is
+ 3Br2 (aq) + 3HBr
called the diazonium group.
Aniline Br (b) Stability of diazonium salts:
2, 4, 6-Tribromoaniline
Arenediazonium salts are much more stable than alkyl diazonium salts. The stability of arene
O O diazonium salt is due to the dispersal of the positive charge over the benzene ring as shown below.
NH2 NH—C—CH 3 NH—C—CH3 NH2
(CH3CO)2O Br2 –
OH N N N N N N N N N N
Pyridine CH3COOH or
H+
Aniline N-phenylethanamide Br Br
(Acetanilide) (Major) p-Bromoaniline

(ii) Nitration: (c) Preparation of diazonium salts
+ –
NH2 NH2 NH2 NH2 NH2 N2 X
HNO3/H2SO4 NO2
+ + + NaNO2 + 2HX 273 – 278 K + NaX + 2H 2O
288 K
NO2
(47%) (2%) Aniline Benzene diazonium
NO2 salt
(51%)

This process of conversion of a primary aromatic amine into its diazonium salt is called diazotization.
In strongly acidic medium, significant amount of meta isomer is obtained. This is due to the 9. Chemical Properties of Diazonium Salts:
formation of anilinium ion which is meta directing. However, the p-nitro derivative can be
The reactions of diazonium salts can be divided into two categories, namely
obtained as the major product by protecting the —NH2 group by acetylation reaction.
(a) Reactions involving displacement of nitrogen.
O O
(b) Reactions involving retention of diazo group.
NH2 NH—C—CH 3 NH—C—CH 3 NH2 (a) Reactions involving displacement of nitrogen:
(CH3CO)2O HNO3/H2SO4 OH– (i) Replacement by halide or cyanide ion:
Pyridine 288 K or H+ +
Cu2 Cl2 /HCl
b_b
Aniline
ArN 2 X – ArCl + N 2 bbb
NO2 NO2 +
Cu2 Br2 /HBr
bb

(Major) p-Nitroaniline ArN 2 X – ArBr + N 2 b`b Sandmeyer’s reactions
+ bb
ArCN + N 2 bb
CuCN/KCN
(iii) Sulphonation: ArN 2 X –
a
+ – +
+ _b
NH2 NH3HSO4 NH2 NH3 Cu/HCl b
ArN 2 X –
ArCl + N 2 + CuX bb
H2SO 4 (conc.) 453-473 K +
Cu/HBr b`b Gatterman’s reaction
ArN 2 X
–
ArBr + N 2 + CuX bb
a
Anilinium
SO3H SO3
– (ii) Replacement by iodide ion:
hydrogensulphate +
Sulphanilic acid Zwitter ion ArN 2 Cl – + KI ArI + KCl + N 2
Benzene diazonium Iodobenzene
(iv) Friedel–Crafts reaction: chloride
+ – (iii) Replacement by fluoride ion:
NH2 NH2AlCl3
+ + D
ArN 2 Cl – + HBF4 ArN 2 BF 4– Ar—F + BF3 + N 2
+ AlCl3
Lewis acid (iv) Replacement by H:
Lewis base +
–
+ H3 PO 2 + H 2 O ArH + N 2 + H3 PO3 + HCl
Due to salt formation, nitrogen of aniline acquires positive charge and thus acts as a strong ArN 2 Cl
+
deactivating group and hence does not allow Friedel–Crafts reaction to occur. ArN 2 Cl – + CH3 —CH 2 —OH ArH + N 2 + CH3 —CHO + HCl

Amines 531 532 Xam idea Chemistry–XII

 (v) Replacement by hydroxyl group: CONH2 NH2
+ D
ArN 2 Cl – + H 2 O ArOH + N 2 + HCl
Phenol + Br2 + 4KOH + K2CO3 + 2KBr + 2H 2O
(vi) Replacement by —NO2 group:
Benzamide Aniline
+ – + –
N2Cl N2BF4 NO2 (c) Sandmeyer’s reaction: The Cl–, Br– and CN – nucleophiles can easily be introduced in the benzene in
NaNO2 the presence of Cu (I) ion. This reaction is called Sandmeyer’s reaction.
+ HBF4 + NaBF4 + N2
Cu, ∆ Cl
Fluoroboric acid Nitrobenzene

Cu2 Cl2 /HCl
(b) Reactions involving retention of diazo group: + N2
Coupling reaction: The reaction of diazonium salts with phenols and aromatic amines to form azo Chlorobenzene
compounds of the general formula, Ar—N—N—Ar is called coupling reaction. The mechanism is + –
N NCl Br
basically that of electrophilic substitution where the diazonium ion is electrophile. In this reaction, the
nitrogen atoms of the diazo group are retained in the product. The coupling with phenols takes place Cu2 Br2 /HBr
+ N2
in mildly alkaline medium while with amines, it occurs under faintly acidic conditions. For example,
– Benzene diazonium Bromobenzene
– 273-278 K, OH chloride
N NCl + OH N N OH + HCl CN
(pH 9-10)
Benzene diazonium Phenol p-Hydroxyazobenzene CuCN/KCN
chloride (orange dye) + N2
+
– 273-278 K, H Benzonitrile
N NCl + NH2 N N NH2 + HCl
(pH 4-5)
Benzene diazonium Aniline p-Aminoazobenzene
(d) Gatterman’s reaction: Chlorine or bromine can be introduced in benzene ring by treating the
chloride (yellow dye) diazonium salt solution with corresponding halogen acid in the presence of copper powder.
– 273-278 K, OH – Cl
NaO3S N NCl + N(CH3)2
Cu/HCl
Diazonium salt of N, N-Dimethylaniline + – + N2 + CuCl
Sulphanilic acid CH3 N2 Cl
NaO3S N N N + HCl Chlorobenzene
CH3
Methyl orange Br
Coupling generally occurs at the p-position, w.r.t., the hydroxyl or the amino group, if free, otherwise Cu/HBr
+ N2 + CuCl
it takes place at the o-position.
Bromobenzene
10. Some Important Name Reactions
(a) Gabriel phthalimide synthesis: This reaction is used for the preparation of aliphatic primary amines. (e) Carbylamine reaction (Isocyanide test): Aliphatic and aromatic primary amines when heated with
In this reaction, phthalimide is first of all treated with ethanolic KOH to form potassium phthalimide. chloroform and alcoholic solution of KOH give isocyanides (carbylamines) which have extremely
Potassium phthalimide on treatment with alkyl halide gives N-alkyl phthalimide, which on hydrolysis unpleasant smell.
with dilute hydrochloric acid gives a primary amine as the product. D
R—NH 2 + CHCl3 + 3KOH (alc.)
R—NC + 3KCl + 3H 2 O
O O O 1° a min e Alkyl
–+ isocyanide
C NH + KOH (alc.) C NK +R X C N R
C C C NH2 NC
O O O ∆
Phthalimide + CHCl3 + 3KOH (alc.) + 3KCl + 3H 2O
H2O/H+ COOH
R—NH2 + Aniline Phenyl
COOH isocyanide
1° amine
Phthalic acid
11. Uses of Amines:
(b) Hoffmann bromamide reaction: When a primary acid amide is heated with an aqueous or ethanolic (i) The quaternary ammonium salts of long chain aliphatic amines are used as detergents, e.g.,
solution of NaOH or KOH and bromine (i.e., NaOBr or KOBr), it gives a primary amine with one cetyltrimethyl ammonium chloride.
carbon atom less.
(ii) Low molecular mass aliphatic amines are used as reagents in organic synthesis and as intermediates in
R—CONH 2 + Br2 + 4NaOH
R—NH 2 + Na 2 CO3 + 2NaBr + 2H 2 O the manufacture of drugs.
Acid amide 1° a min e
(iii) Aniline is used in the manufacture of dyes, dye intermediates and sulpha drugs.

Amines 533 534 Xam idea Chemistry–XII

 12. Test for Amines
(a) Hinsberg’s test: In this test, the amine is first treated with Hinsberg’s reagent (benzenesulphonyl
chloride) and then shaken with aqueous KOH solution when the three amines behave in different ways.
(i) A 1° amine gives a clear solution which on acidification gives an insoluble N-alkyl benzene
sulphonamide.
O H O H O
+ KOH –
S Cl + H N R S N R K+ S N R
–HCl – H2O
O O O
Benzene N-Alkylbenzenesulphonamide Potassium salt
sulphonyl chloride (soluble in KOH)

(ii) A 2° amine gives an insoluble N, N-dialkyl benzene sulphonamide which remains unaffected on
addition of acid.
O R O R
S Cl + H N R S N—R + HCl
2° Amine
O O
Benzene N, N-Dialkylbenzene
sulphonyl chloride sulphonamide
(insoluble in KOH)

(iii) A 3° amine does not react at all.

KOH
C6 H5 SO 2 Cl + R3 N No reaction
Benzene sulphonyl 3° a min e
chloride
(b) Isocyanide test (Carbylamine test): Primary amines (aliphatic as well as aromatic) react with
chloroform in the presence of alcoholic KOH to form foul smelling carbylamine.
D
R—NH 2 + CHCl3 + 3KOH (alc.)
R—NC + 3KCl + 3H 2 O
1° a min e Alkyl isocyanide

NH2 NC
∆
+ CHCl3 + 3KOH (alc.) + 3KCl + 3H 2O
Aniline Phenyl isocyanide
Secondary and tertiary amines (aliphatic as well as aromatic) do not give this test.
(c) Azo dye test: It involves the reaction of any aromatic primary amine with HNO2 (NaNO2 + dil. HCl)
at 273–278 K followed by treatment with an alkaline solution of 2-naphthol, where a brilliant yellow,
orange or red coloured dye is obtained.
273-278 K
NH2 + HONO + HCl N NCl– + 2H2O
Aniline Benzene diazonium
chloride

OH OH
– Dil. NaOH
N NCl + N N + HCl
pH 9-10
Benzene diazonium
chloride
2-Naphthol 1-Phenylazo-2-naphthol
(Orange dye)

Aliphatic primary amines under these conditions give a brisk evolution of N2 gas with the formation
of primary alcohols, i.e., the solution remains clear.
273 - 278 K
RNH 2 + HONO R—OH + N2 - + H2 O
Alcohol
273 - 278 K
C 2 H5 NH 2 + HONO C 2 H5 OH + N 2 - + H 2 O
Ethyla min e Ethyl alcohol

Amines 535