Reaction of N-Nitroso- and N-Nitro-N-alkylamides with Amines

Article abstract of DOI:10.1021/jo00192a014

Several N-nitroso- and N-nitrocarboxamides have been characterized by 1H and 13C NMR spectroscopy.These compounds react with ammonia and aliphatic amines to afford mainly carboxamides of general formula RCONH2, RCONHR', or RCONR'R''.N-Nitrosocarboxamides and aromatic amines give poor yields of RCONHAr; by contrast, N-nitrocarboxamides and aromatic amines lead to RCONHAr in good yields.The higher thermal stability of the N-nitroamides as compared to N-nitrosoamides is advantageous in this connection; nevertheless, the principal advantage of the NNO2 group appears to be that it activates the nucleophilic attack to the carbonyl of the amide function more than the NNO group, as has been demonstrated by competitive experiments.The reaction of N-nitroso- and N-nitro-N-methylsulfonamides with ammonia and diethylamine has been studied as well; whereas N-methyl-N-nitro-p-toluenesulfonamide reacts as N-nitrocarboxamides, transnitration is predominant with N-methyl-N-nitroso-p-toluenesulfonamide.