The mechanism of the Fischer-Hepp rearrangement of aromatic N-nitroso-amines

Abstract

Rate equations have been deduced for two possible mechanisms for the Fischer-Hepp rearrangement of aromatic N-nitroso-amines in acid solution: (a) for the commonly assumed intermolecular process involving de-nitrosation to the secondary amine and a free nitrosating agent, followed by a direct C-nitrosation of the secondary amine by this nitrosating agent, and (b) for a mechanism whereby rearrangement and de-nitrosation occur concurrently, by two separate reactions of the protonated N-nitroso-amine. All the experimental evidence supports mechanism (b), whilst most of it is incompatible with (a). Particularly diagnostic of the mechanism are (1) the observed rearrangement: de-nitrosation product ratios under certain limiting conditions, (2) the question of halide ion catalysis, and (3) the rate form found under the limiting condition of a large excess of added secondary amine.