Pharmaceutical organic chemistry -1,contains reactions of aliphatic amines like oxidation ,reduction of amines to pharmacy & life science students

1. ALIPHATIC AMINES

2. REACTIONS OF ALIPHATIC
AMINES
Alkylation Reaction
Hofmann’s Reaction
Acylation
Reaction with nitrous acid
Carbylamine formation
Oxidation
Reaction with Grignard
reagent

3. Alkylation of
amines
R NH2 R2NH R3N R4NH X
-+
RX+RX
-HX
+RX
-HX
primary
amine secondary
amine
tertiary
amine
quartenary
ammonium
salt
C6 5
H NH2 + CH3I C6 5
H NHCH3 + HI
aniline
methyl
aniline
C6 5
H NHCH3 + CH3 I
methyl
aniline
C6H5 N(CH3)2 + HI
N,N-Dimethyl aniline

4. Hofmann’s
elimination
R4N X
-+
R4 N OH
-+
+ AgX
3HC N
CH3
CH3
CH2CH2CH2OH
-
NH3C
CH3
CH3
+ CH2 CH CH3 + H2O
propene
trimethyl
aminetrimethyl n propyl
ammonuim hydroxide

5. Acylation of amines
RNH2 + R'COCl R'CONHR + HCl
acid
chloride
RNH2 + C6H5SO2Cl C6H5SO2NHR + HCl
R2NH + CH3SO2Cl C6H5SO2NR2 + HCl
C2H5NH2 + CH3COCl C2H5NHCOCH3 + HCl
phenyl sulphonyl
chloride
n ethyl acetamide
ethylamine acetyl
chloride
(CH3)2NH + C6H5COCl (CH3)2NCOC6H5 + HCl
N,N-Dimethyl
benzamide
NH2
CH3
+ (CH3CO)2O
+ CH3COOH
NHCOCH3
CH3

6. Reaction with Nitrous
acid
R NH2 + HONO ROH + N2 + H2O
C2H5NH2 + HONO C2H5OH + N2 + H2O
R2NH2 + HONO R2N N O + H2O
eg:
eg:
(CH3)2NH + HONO (CH3)2N N O
+ H2O
primary
amine
secondary
amine

7. C6H5 NH CH3 + HONO C6H5 N N O
CH3
+ H2O
N-Nitroso N methyl
aniline
N-methylaniline
R3N + HNO2 R3NHNO2
tertiary
amine

8. Carbylamine reaction
C2H5NH2 + CHCl3 + KOH C2H5NC + 3KCl + 3H2O
ethyl
amine
chloro
form
carbylamine
R NH2 + S C S
HgCl2
R NH C S + H2S
alkylisothio
cyanate
R2NH + S C S S C
SH
NR2
mustard oil reaction

9. oxidation
R CH2NH2 R
KMnO4
(O)
CH NH
H2O
RCHO + NH3
R
H
C
NH2R'
KMnO4
(O)
R C NH
R'
R C O
R'
+ NH3
KMnO4
(O)
2R2NH R N N R
R R
tertra alkyl
hydrazine
+ H2O
primary
amine
secondary
amine
R N
R
R
H2O2
(O)
R3 O
+ _
amine oxide
tertuary
amine

10. Reaction with Grignard reagent
RNH2 + R'MgX RNHMgX + R'H
alkanegrignard
reagent
R
NH
R
+ R'MgX R'H +
R NMgX
R
+ R'H

11. LETS GO AHEAD & SEE AGAIN