The oxidative amination of 3-nitropyridines

3-Nitropyridine was reacted with ammonia or alkylamines and KMnO4 under several different conditions. Substitutions in the para position to the nitro group were obtained with high regioselectivity: with ammonia, 2-amino-5-nitropyridine (66%), with butylamine, 2-butylamino-5-nitropyridine (92%), with diethylamine, 2-diethylamino-5-nitropyridine (49%). Under the same conditions, with methyl-3-nitroisonicotinoate and diethylamine/KMnO4, methyl 2-diethylamino-5-nitroisonicotinoate (48%), with 4-acetyl-3-nitropyridine (protected by ethylene glycol) 2-diethylamino-4-acetyl-5-nitropyridine (72%, protected) and with 4-cyano-3-nitropyridine, 2-amino-4-cyano-5-nitropyridine (41%) were obtained. All yields are isolated.