Page 1035 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 11.2. Aromatic Halogenation 1011
A. Chlorination SECTION 11.1
1 a F F F F Electrophilic Aromatic
Substitution
Cl
Cl 2 +
+
AlCl 3 Cl
25% Cl 73% 2%
2 b O O
CCl CCl
FeCl 3
Cl 2
Cl
3 c CH 3 NCS, CH 3
3
CH O CH 3 HClO 4 CH O CH 3
3
CCl 4 Cl 94%
O
O
4 d
NHCCH
NHCCH 3 3
) COCl
(CH 3 3
92%
Cl
5 e
O O Cl
NCS
2
3
O CH CO H O Cl
75% on
28 kg scale
B. Bromination
6 f NO 2 NO 2
Fe
Br 2
Br
85%

7 g CO H CO H
2
2
Br Br
HCl
Br 2
NH 2 NH 2
Br
8 h O
Br Br
CH 3 N N CH 3
Br NO
NO 2 N 2
O O
98%
H
CO H H SO 4 CO H
2
2
2
(Continued)