CHAPTER

9 Amines

NH3(Excess) H+/H2O
H3C—CH2—X R—N=C=O
—HX HO–/H2O
[Ammonolysis]
O
O
Gabriel C (i) NH3 Hoffmann
Br2,KOH
Phthalimide O H3C—C—NH2 Bromamide
(ii) KOH,CH3—I H2O,HO– degradation
Synthesis C
(iii) H2O,H+
O
O
CH3NH2 Schimdt
Na(Hg)/EtOH HN3,H2SO4
R—CN RCH2NH2 R—C—OH Reaction
H2/Ni or LiAlH4/Et2O H3O+
R–NH2

H3O Fe/HCl or H2/Pd

R—NC R—NO2
or Sn/HCl
or SnCl2+HCl

LiAlH4/Et2O or Na/EtOH Cl—NH2

R—CH=N—OH R—MgX
H2/Ni

HCl CHCl3,KOH
R—NH3+Cl– R—NC
(Carbylamine test)

CH3Br CH3NH2 HNO2/H+

R—NHCH3 RCH2NH2 R—OH
Alkylation [But CH3—NH2CH3—O—CH3]
R—NH2
O
CH3COCl
R—NHCOCH3 N—R
Base (Acylation)
 NO2

—
Preparation O
Sn/HCl or Fe/HCl NaN3
Cl—C—
Reduction H3O+

OH
—
NH2

—
NH3/ZnCl2/300ºC Cl–NH2 – +
BrMg—

O=C—NH2
—

Br2/KOH
O=C=N—
Hoffmann Bromoamide H3O+
Degradation

NH2

—
Br— Br
Br2/H2O —
+
—NH3 Cl– H—Cl

—
Br
NHCOCH3 NHCOCH3 NH2

—
O
—

(CH3—C)2O HNO3,H2SO4 OH or
- Na 
—NHNa+ 288 K H
Pyridine

—
(Group Protection)
NO2 NO2

O NH2 NH2 NH2

—

—
O NH2 NO2
—

—C—Cl
—
Conc.HNO3
—NH—C— + +
Base Conc.H2SO4 —
NO2
—

Schotten Baumann Reactions [51%] [47%] [2%]

NO2
O 
NH2 NH3
—
—

O Cl—C—Cl
(1) Conc. H2SO4
—NH—C—NH—
Diphenyl Urea (2) 453-473K
—
—

SO3H SO3H
CHCl3
—N+C– No reaction
KOH Fridel Craft reaction
Carbylamine Test

P
W Amines 25
 Benzene Diazonium Chloride
Reaction Cl

—
—OH
HO— —N=N— Cu/HCl

Gatterman
reaction
—NH2 NH2 Br
—
Cu/HBr
H2N— —N=N—
Coupling reaction

C2H5OH/
H —NH—CH3
or H3PO2/
—

H3C—N— —N=N—

NaNO2/HCl[0º–5ºC]
OH
— OH

—
OH
+
H2O/H
—N=N— —NH2 283K
Cl
—

I
—
CuCl/HCl KI
Sandmeyer reaction

F
Br + HBF4 —
— CuBr/HBr NNCl –


– –
CN N2BF4

—
—

NO2
CuCN/KCN HBF4 —
NaNO2
Cu/

26 JEE (XII) Module-2 PW