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05 Amines

Amines can be considered as derivatives of ammonia obtained by replacement of one, two or all the three
hydrogen atoms by alkyl/aryl groups.
H3C—NH2 C6H5—NH2 H3C—NH—CH3 H3C—N—CH3
CH3
Classification of Amines
Amines are classified according to the number of carbon atoms bonded directly to the nitrogen atom.
NH2
H3C—NH2 H3C—NH—CH3 H3C—N—CH3 H3C—C—CH3
CH3 CH3
Primary (1°) Secondary (2°) Tertiary (3°) Primary (1°)

Methods of Preparation of Amines

1. Reduction of nitro compounds :
Nitro compounds are reduced to amines by passing hydrogen gas in the presence of finely divided
nickel, palladium or platinum and also by reduction with metals in acidic medium.
NO2 H2/Pd NH2
Ethanol
Sn + HCl

Fe + HCl

2. Reduction of nitriles(cyanides) and isonitriles (isocyanides) :

Nitriles on reduction with lithium aluminium hydride (LiAlH4) or catalytic hydrogenation produce
primary amines but isonitriles produce secondary amines.
LiAlH4

R—CN R—CH2—NH2
H2 / Ni

LiAlH4

R—N C R—NH—CH3
H2 / Ni

3. Reduction of amides :
Amides on reduction with lithium aluminium hydride (LiAlH4) produce amines.
O
(i) LiAlH4
R—C—NH2 R—CH2—NH2
(ii) H2O

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4. Ammonolysis of alkyl halides :
Alkyl halide on reaction with ethanolic solution of ammonia undergoes nucleophilic substitution in
which the halogen atom is replaced by amino (-NH2) group. The process of cleavage of C-X bond by
ammonia is known as Ammonolysis.
NH3 + R—X ⎯→ R—NH2
R—NH2 + R—X R—NH
R
R—NH + R—X R—N—R
R R
R
R—N—R + R—X R—N—RX
R R
Quaternary
ammonium salt
Ammonolysis reaction yields a mixture of primary, secondary, tertiary amines and also quaternary
ammonium salt. However primary amine can be obtained as major product taking large excess of
ammonia and quaternary ammonium salt will be major product if alkyl halide is taken in excess.
5. Gabriel phthalimide synthesis :
Gabriel synthesis is used for the preparation of 1° aliphatic amines.
Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of phthalimide
which on reaction with alkyl halide followed by alkaline or acidic hydrolysis produces the
corresponding primary amine.
O
C
(i) alc. KOH
NH R—NH2 (1° Aliphatic amine)
(ii) R–X
C
(iii) OH/H2O
O
Mechanism
O O O O
C C C C—O
Alc. KOH R—X OH/H2O
N—H NK N—R + R—NH2
C C C C—O
O O O O
Phthalimide Potassium salt N-Alkylphthalimide (1° amine)
of phthalimide

6. Hoffmann bromamide degradation reaction :

O
R—C—NH2 + Br2 + 4NaOH R—NH2 + Na2CO3 + 2H2O + 2NaBr
(1° amine)

Reagents that may be used for this reaction

1. X2 + alkaline medium
Br2 + NaOH
Br2 + KOH
2. NaOX (NaOCl, NaOBr etc.)
KOX (KOCl, KOBr etc.)
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Amines
Physical Properties of Amines
Solubility
1. Lower aliphatic amines are soluble in water because they can form hydrogen bonds with water
molecules.
2. Solubility decreases with increase in molar mass of amines due to increase in size of the
hydrophobic alkyl part.
3. Higher amines are essentially insoluble in water.

Boiling point
Primary and secondary amines are engaged in intermolecular association due to hydrogen bonding
between nitrogen of one and hydrogen of another molecule.
H R H
R—N—H N—H N—R

H H

H—N—R

H
This intermolecular association is more in primary amines than in secondary amines as there are two
hydrogen atoms available for hydrogen bond formation in it.
Tertiary amines do not have intermolecular association due to the absence of hydrogen atom required for
hydrogen bond formation.
The order of boiling points of isomeric amines is as follows:
Primary > Secondary > Tertiary

Chemical Reactions of Amines

(1) Reaction showing basic nature :

Amines being basic in nature react with acids to form salts.
RNH2 + HCl RNH3Cl

NH2 NH3Cl

+ HCl

Amine salts on treatment with a base like NaOH, regenerate the parent amine.
RNH3Cl + NaOH RNH2 + H2O + NaCl

(2) Acylation reaction :

Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and
esters by nucleophilic substitution reaction.
O
Base
C2H5—N—H + CH3—C—Cl C2H5—N—C—CH3 + H—Cl
H H O
Ethanamine N-Ethylethanamide

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C2H5 C2H5
Base
C2H5—N + CH3—C—Cl C2H5—N—C—CH3 + H—Cl
H O O
N-Ethylethanamine N,N-Diethylethanamide

C6H5—N—H + CH3—C—O—C—CH3 C6H5—N—C—CH3 + CH3COOH

H O O H O
Aniline/ Acetic anhydride N-Phenylethanamide
Benzenamine or Acetanilide

(3) Hoffmann's carbylamine reaction or isocyanide test :

Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium
hydroxide form isocyanides or carbylamines which are foul smelling substances.
CHCl3 + KOH
R—NH2 R—NC

Primary Amines Isocyanides
(aliphatic or aromatic)

Note: Dichlorocarbene is formed in this reaction.

(4) Reaction with Benzenesulphonyl chloride (Hinsberg’s reagent) :

O O
RNH2
S—Cl S—N—R + HCl
O O H
(N-alkylbenzenesulphonamide)
(soluble in alkali)

O H–N–R O
R
S—Cl S—N—R + HCl
O O R
(N,N-dialkylbenzenesulphonamide)
(insoluble in alkali)

O R–N–R
R
S—Cl No reaction
O
Note: Hinsberg test is used to distinguish between primary, secondary and tertiary amines.
These days benzenesulphonyl choride is replaced by p-toluenesulphonyl chloride (TsCl)
O
H3C S—Cl
O
(5) Reaction with nitrous acid (HNO2) :
HNO2

NaNO2 + HCl
Amine

NaNO2 + H2SO4

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Amines
(a) 1° Aliphatic amine
NaNO2+HCl
R—NH2 ROH + N2 + HCl

Mechanism
NaNO2 + HCl HNO2 + NaCl

H H
O=N—OH O=N—O N=O + H2O
H nitrosonium ion

H2O
R—NH2 + O=N R—N=N R—NN R + N2 ROH
(Diazonium ion) (major)
(highly unstable)

(b) 1° Aromatic amine

NH2 N N Cl

NaNO2 + HCl
(273-278 K)

(Benzene diazonium chloride)

If the temperature of the diazonium salt solution is allowed to rise upto 283K, the salt gets
hydrolysed to phenol.

(c) 2° Aromatic amine

R H R N=O
N N

NaNO2 + HCl / HNO2

N-alkyl-N-nitrosoaniline
(yellow oily liquid)

(d) 3° Aromatic amine

R R R R
N N

NaNO2 + HCl / HNO2

HNO2

NO
p-Nitroso-N,N-dialkylaniline

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Chemical reaction of Diazonium salts
A. Reactions involving displacement of nitrogen :
H3PO2 /
OH + H3PO3
H2O
(stable at room Temp.) I
(water insoluble) C2H5OH
+ CH3CHO
Cl
F N NBF4
KI  H2O Cu2Cl2 /
 HBF4
HCl
Fluoroboric
Benzene acid N NCl
Balz-Schiemann Br
reaction Diazonium
fluoroborate Cu2Br2 / Sandmeyer
reaction
HBr
NaNO2 Cu,  Cu/HCl Cu/HBr CN

NO2 Br
CuCN /
Cl
HCN

Gatterman reaction

B. Reactions involving retention of diazo group :

Coupling reaction of benzene diazonium chloride (ESR)
Benzene diazonium chloride reacts with aromatic compounds containing strongly activating
groups like –OH, –NH2, –NHR, –NR2
Ph 10-11
N N Cl + OH N N OH + Cl + H2O

p-Hydroxyazobenzene
(orange dye)

Ph 5-6
N N Cl + NH2 N N NH2 + Cl + H2O

p-Aminoazobenzene
(yellow dye)

(6) Electrophilic Substitution Reaction (ESR) :

Halogenation of Aniline
NH2 Br2 NH2
CS2 or CCl4 Br Br

Br2
H2O Br
2,4,6–Tribromoaniline
(white ppt.)

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Amines

Nitration of Aniline
NH2 NH2 NH2 NH2
NO2 'tarry'
HNO3 + H2SO4
+ + + Oxidation
288 K
NO2 product
NO2
2% 47% 51%

Illustration 1:
O O
NH2 HN—C—CH3 HN—C—CH3 NH2

CH3COCl HNO3 + H2SO4 H / H2O

Pyridine 288K

NO2 NO2

Sulphonation of Aniline
NH2 NH3HSO4 NH2 NH3

H2SO4 453-473K

Anilinium
hydrogensulphate
SO3H SO3
Sulphanilic acid/
Zwitter ion
p-Aminobenzene
sulphonic acid

Note:
Aniline does not show Friedel Crafts reaction (alkylation and acylation)
Reduction of Nitrobenzene

Fe/HCl or Sn/HCl
or H2/Pd NH2

NO2 Zn + NH4Cl
NH—OH

Fe + H2O
N=O
Nitro
Benzene
dilute
H2SO4
NH2
Electrolytic
H2SO4
Conc. Rearrangement
H2SO4
NH—OH HO NH2

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