Organic Chemistry

914 CHAPTER 21 More About Amines • Heterocyclic Compounds

5. Synthesis of amines (Section 21.8).
   a. Gabriel synthesis of primary amines:

b. Reduction of an alkyl azide or a nitrile:

c. Reduction of a nitroalkane or nitrobenzene:

d.Aldehydes and ketones react (1) with excess ammoniaplus catalyst to form primary amines, (2) with a primary amine

followed by reduction with sodium triacetoxyborohydride to form secondary amines, and (3) with a secondary aminefollowed by

reduction with sodium triacetoxyborohydride to form tertiary amines:

6. Electrophilic aromatic substitution reactions.
   a.Pyrrole, furan, and thiophene (Section 21.9):

CCH 3

O

+ CH 3 CCl

S S

+ HCl

O

1. SnCl 4


2. H 2 O

N

H

N

H

+ Br 2

Br

NO 2

+ HBr

+ HNO 3

OO

+ H 2 O

(CH 3 CO) 2 O

C

R

R

excess NH 3

NaBH(OCCH 3 ) 3

O

H 2 , Pd/C

O CH NH 2 + H 2 O

R

R

C

R

R

NaBH(OCCH 3 ) 3

O

catalytic

H+

O +

+

CH 3 NH 2 C

CH 3 NH

CH 3

CH 3

CH 3

NCH 3

R

R

CH NHCH 3

R

R

catalytic

H+

O N

CH 3

CH 3

N

H 2 >metal

NO 2 + H 2 NH 2

Pd/C

CH 3 CH 2 CH 2 NO 2 + H 2 CH 3 CH 2 CH 2 NH 2

Pd/C

RBr H^2

Pd/C

H 2

Pd/C

−N

(^3) RNNN–
RCN RCH 2 NH 2
RNH 2

• NH ∆

1. HO− H 3 O+


2. R Br

+ Br–

+

O

O

NR + R NH 3

COOH

COOH

O

O