REVISION MAP

Amines
These are formed by the replacement of H of ammonia by alkyl/aryl group.

Classification and Properties of Amines Diazonium Salts

Methods of (C6H5N=
NCl )
=
+ –
Preparation of Amines
Physical Properties
Their solubility decreases but boiling Method of Preparation
Classification point increases with increase in HNO2 +
Amines are classified as: molecular mass. C6H5—NH2
or NaNO2 +HCl
C6H5N2Cl–
1° amine Diazonium
1° amine (RNH2), 2° amine (R2NH) and ? The order of bp is 1° > 2° > 3° 0°C
salt
3° amine (R3N). amines. (aromatic)

Basicity Physical Properties

The order of basicity They are colourless, unstable, soluble
Methods of Preparation
(i) In gaseous state, 3° > 2° > 1° in water, neutral to litmus.
amine.
(ii) In aqueous solution, 2° > 3° > 1°
Reduction of —NO2
> NH3 if R = C2H5 and 2° > 1° >
Raney Ni/Pt 3° > NH3 if R = CH3. Chemical Properties
—NO2 —NH2
metal + acid
¾
¾
¾

Reduction of —CN or —CONH2 Chemical Reactions +

¾
N=NCl–
=
LiAlH4
—CN —CH2NH2 ½ CuCl/HCl
or R¾
NH2 R'COCl C6H5Cl
R¾
N¾
C¾
R' (Sandmeyer's
—CONH2 (1°) Acylation reaction)

H O
Substituted amide Cu/HX
Hofmann Bromamide Reaction CHCl3 + KOH C6H5X
R¾
NC Gattermann reaction
NaOH Carbylamine
KI
—CONH2 —NH2 reaction C6H5I
Br2
C6H5SO2 Cl HBF4
N-alkylbenzene C6H5F
Hinsberg's sulphonamide
reagent H3PO2 + H2O
(soluble in alkali)
C6H6
Hofmann Ammonolysis H 2O
RX C6H5OH
NH3 RNH2 (1°)
–HX
RX Phenol
Hinsberg's p-hydroxy
R2NH (2°) N,N-dialkylbenzene (Coupling reaction)
azobenzene
RX reagent sulphonamide
R 3N R2NH (insoluble in alkali) (Orange dye)
(3°) (2°) Aniline
p-amino
(Coupling reaction)
azobenzene
(Yellow dye)
C6H5SO2Cl
Gabriel-Phthalimide Reaction R3N (3°) No reaction
KOH
Phthalimide K salt of
phthalimide
R
Br2
NaOH 2,4,6-tribromoaniline
1° amine N-alkyl H 2O
(aliphatic) phthalimide Electrophilic
RNH2 substitution (CH3CO)2O
(Here, R= C6H5) p-bromoaniline
Br2

(Here, R= C6H5) HNO3

m + o + p-nitroaniline
H2SO4
(47%) (2%) (51%)