Oxidation of arylamines, arylhydroxylamines and other derivatives 151Table 4.1 Oxidation of arylamines and their derivatives with peroxydisulfuric acid
NH 2
NO 2NO 2
NO 2O 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NO 2 NNH 2NO 2NO 2CH 3
NO 2NH 2
NO 2CH 3
NO 2NO 2
NH 2
CH 3
NO 2NAc 2
NO 2Ac 2 NH 2 NNO 2NO 2NH 2NO 2NO 2NO 2NO 2NH 2
NO 2F
NO 2O 2 NO 2 NO 2 NFNO 2
NO 2NO 2
NO 2NO 2NO 2
NO 2NO 2CH 3
NO 2NO 2CH 3
NO 2NO 2NO 2NO 2NO 2
NO 2
CH 3NO 2NO 2NO 2NO 2NO 2NO 2NO 2NO 2NO 2NO 2FF20 % oleum, 98 % H 2 O 2 ,
25–30 °C, 24 hrs30 % oleum, O 3 ,
20–25 °C, 48 hrs7839100 % H 2 SO 4 , 98 % H 2 O 2 ,
25–30 °C, 24 hrs10 % oleum, O 3 ,
20–25 °C, 72 hrs4939100 % H 2 SO 4 , 98 % H 2 O 2 8213920 % oleum, 88 % H 2 O 2 ,
20–25 °C, 18 hrs5413930 % oleum, 90 % H 2 O 2 ,
20–25 °C, 18 hrs30 % oleum,
95 % H 2 O 2 , 25 °C,
10–14 days3915430 % oleum, 90 % H 2 O 2 ,
20–25 °C, 18 hrs^841391a2a34a5761b2b(31)(53)(56)(58)(60)(64)(62)58139
153
(55)(54)(57)(59)(61)(65)(63)Entry Substrate Conditions Product Yield (%)93139
1534b15 % oleum, O 3 ,
20–25 °C, 48 hrs^573982143Products 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