Evidence for the formation of alpha-hydroxydialkylnitrosamines in the pH-independent solvolysis of alpha-(acyloxy)dialkylnitrosamines

The solvolytic decay of alpha-(acyloxy)dialkylnitrosamines in aqueous solutions involved a hydrogen-ion concentration-independent mechanism that led to the formation of nitrosiminium ion intermediates. The nitrosonium ion intermediates form alpha-hydroxydialkylnitrosamines by reacting with solvent water. The nitroso group mediated the decomposition of the alpha-(acyloxy)dialkylnitrosamines to alpha-hyroxydialkylnitrosamines by providing anchimeric assistance in a base-catalyzed reaction.