Photolysis of some N-nitroso- and N-nitro-anilines in solution

Abstract

The photolyses of three N-methyl-N-nitrosoanilines and two N-methyl-N-nitroanilines in organic solvents have been studied in the range of 300–340 nm. The influence of solvent character and the presence or absence of oxygen play important roles in the product composition range. The primary photochemical process involves N–N fission, this being homolytic in aprotic solvents and heterolytic in methanol. Three novel mechanistic conclusions are proposed, namely photosolvolysis of a nitrosamine in methanol, photooxidation of nitrosamines in aprotic solvents and the production of biphenyl derivatives on photolysis of nitro-substituted nitrosamines and nitramines in aromatic solvents.