Oxidation of arylamines, arylhydroxylamines and other derivatives 151
Table 4.1 Oxidation of arylamines and their derivatives with peroxydisulfuric acid
NH 2
NO 2
NO 2
NO 2
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
O 2 N
NH 2
NO 2
NO 2
CH 3
NO 2
NH 2
NO 2
CH 3
NO 2
NO 2
NH 2
CH 3
NO 2
NAc 2
NO 2
Ac 2 N
H 2 N
NO 2
NO 2
NH 2
NO 2
NO 2
NO 2
NO 2
NH 2
NO 2
F
NO 2
O 2 N
O 2 N
O 2 N
F
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
CH 3
NO 2
NO 2
CH 3
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
CH 3
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
NO 2
FF
20 % oleum, 98 % H 2 O 2 ,
25–30 °C, 24 hrs
30 % oleum, O 3 ,
20–25 °C, 48 hrs
7839
100 % H 2 SO 4 , 98 % H 2 O 2 ,
25–30 °C, 24 hrs
10 % oleum, O 3 ,
20–25 °C, 72 hrs
4939
100 % H 2 SO 4 , 98 % H 2 O 2 82139
20 % oleum, 88 % H 2 O 2 ,
20–25 °C, 18 hrs
54139
30 % oleum, 90 % H 2 O 2 ,
20–25 °C, 18 hrs
30 % oleum,
95 % H 2 O 2 , 25 °C,
10–14 days
39154
30 % oleum, 90 % H 2 O 2 ,
20–25 °C, 18 hrs^84
139
1a
2a
3
4a
5
7
6
1b
2b
(31)
(53)
(56)
(58)
(60)
(64)
(62)
58
139
153
(55)
(54)
(57)
(59)
(61)
(65)
(63)
Entry Substrate Conditions Product Yield (%)
93
139
153
4b
15 % oleum, O 3 ,
20–25 °C, 48 hrs^57
39
82143
Products from peroxydisulfuric acid oxidations are usually isolated in high yield and high
purity with potential by-products such as azo, azoxy and nitroso compounds usually absent.
Product isolation is usually facile; the product either precipitates from solution or can be
extracted, with any unreacted amine remaining in the acid liquors. Peroxydisulfuric acid is,
however, a very strong oxidant and some substrates are rapidly destroyed, which is the case for
polynitrophenylenediamines.^139 The reactivity of such substrates can be moderated by prior