PHYSICAL PROPERTIES PREPERATION

STRUCTURE
PHYSICAL PROPERTIES AMINES Colourless, soluble in water, decompose in
dry state
NH2
-
N2+X

NH3 Ammonia PHYSICAL STATE C6H5N2+Cl- is readily soluble in water

NaNO + 2HCl

2
273− 278K
→ + NaCl + 2H2O
Lower aliphatic amines are gases,

:
intermediate members are liquid
R-NH2 1° AMine (fishy odour), while higher members
N2+X
-

:
IMPORTANCE
are solid.
In preperation of substituded
R2NH 2° Amine SOLUBILITY
aromatic compounds which
cannot be prepared by direct DIAZONIUM SALTS
substituion in benzene or
Lower aliphatic amines are soluble substistude benzene.
R3N 3° Amine in water due to H-bonding, while higher RN2+X
-

amines (> C6) are insoluble in water.

1
So lub ility ∝
CHEMICAL PROPERTIES
:

Molecular weight

BOILING POINT X X
G
Primary and secondary amines at
te
rm
Cu
on
an + HX cti
forms intermolecular H-Bonding Re
HX
Cu
+
Re
a
ac er
while tertiary does not. tio ey
n N2+ X − dm
N F Sa
n
CN
R R Primary > Secondary > Tertiary
HBF

∆
4 CuC
N/KC
N

θ > 109° Amine Amine Amine

H 3PO 2 +
+ H2
O
KI
Cu
I
R OH
- C
6H
O H, H 2O ∆ 5N
H
H5 + 2, H

Pyramidal geometry C 6 Cu +

N=N OH N=N NH2

OH

PREPARATION

• Reduction of Nitro Compounds. CHEMICAL REACTION ELECTROPHIC SUBSTITUTION

IN GASESOUS PHASE
Sn/HCl or Fe/HCl NH2
RNO2  → RNH2 3° Amine > 2° Amine > 1° Amine > NH3
OrH2/pd
R-NC R-OH 3 Br2
B2 Br

C
Ca H3 Cl
H2O
• Ammonolysis BASIC NATURE O 2
rb +
yla KO HN Br
IN AQUEOUS PHASE
te min H
NH3 Due to the presence of lone
R-NH2 + H2O + Na+ X-
- NaoH
R-X R-NH3X NH2
pair on nitrogen amines are st
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
(C2H5)2NH > (C2H5)3N > (C2H5)NH2 > NH3
basic.
e
R-NH2 O (i) CH3COCl
Factors affecting basicity R'-
• Reduction of Nitriles (i) Inductive effect C-
Cl
(ii) Br2, CH3COOH
(Major)
Ac
R'
H2 /Ni
+
R− C ≡ N → R − CH2 − NH2 (ii) solvation effect yla
Na(Hg)/C 2H 5oH
OVERALL BASICITY ORDER
(iii) Steric hinderance tio
n
O Br
R-NH-R' NH2 NH2 NH2
Aliphatic Amine > Ammonia R-NH-C-R'
• Reduction of Amides > Aromatic Amine
HNO3
NO2
O
(i) LiAlH4 + +
=

R − C − NH2 R − CH2 − NH2 H2SO4, 288 K NO2

(i) H2O NH2 (51%) (47%) (2%)
TEST FOR AMINES NO2
• Hoffmann Bromamide Degradation reaction NH2
O
R − C − NH2 + Br2 + 4NaOH 
→ R − NH2 + Na2 CO3 + 2NaBr +2H 2O HINSBERG'S TEST (i) CH3COCl
(ii) Br2, CH3COOH

one carbon less amine is formed as compared to amides

NO2
• Gabriel Phthalimide synthesis NH2
O O PRIMARY AMINE SECONDARY AMINE TERTIARY AMINE
H2SO4
C C SO2Cl SO2-NHR SO2Cl SO2-NR2 SO2Cl
KOH NaOH
N - H 
RX
→ N - R  → RNH2
C C (1° Amine) + RNH2 + R2NH + R 3N No Reaction SO3H

O O ppt. soluble in ppt. insoluble in

CH3/AlCl3 No reaction
or CH3OCl/AlCl3
alkali alkali (due to salt formation)
Aromatic primary amines cannot be prepared by this method.