Page 1057 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Scheme 11.6. Aromatic Substitution via Diazonium Ions 1033
A. Replacement by hydrogen SECTION 11.2
1 a Br Br
Nucleophilic Aromatic
NH 2
Br Br 1) HONO Substitution
2) C 2 H 5 OH
Br 74–77%
Br
2 b
1) HONO
H 2 N NH 2
2) H 3 PO 2 76–82%
CH 3 CH 3 CH 3 CH 3
3 c + –
N 2 BF 4
H 3 PO 2
Cu 2 O
Cl Cl Cl Cl 97%
4 d Cl Cl
(CH 3 ) 3 CONO
Cl NH 2 Cl
DMF
68%
NO 2 NO 2
5 e
CH 3 CH 3
1) NaNO 2 ,
CH 3 CO 2 H
CH 3 NH 2 CH 3
2) FeSO 4 ,
DMF 76%
CH 3 CH 3
6 f OH OH
1) C 2 H 5 ONO
CO 2 H CO 2 H
2) NaBH 4
NHCO 2 C(CH 3 ) 3 3) HCl NH 3 + 72%
NH 2
B. Replacement by hydroxy
7 g CH 3 CH 3

1) HONO
2) H 2 O, Δ
Br Br 80–92%
OH
NH 2
8 h CH 3 CH 3
NH 2 OH
1) HONO
2) Cu(NO 3 ) 2 ,
CuO
95%
NO 2
NO 2
C. Replacement by halogen
9 i CH O CH O
1) HONO
2) Cu 2 Cl 2
Cl
NH 2 75–79%
10 j NH 2 Cl
O 2 N NO 2 1) HONO O 2 N NO 2
2) Cu 2 Cl 2
71–74%
(Continued)