Cyclic alpha-acetoxynitrosamines: mechanisms of decomposition and stability of alpha-hydroxynitrosamine and nitrosiminium ion reactive intermediates

An analysis of the mechanism and kinetics of decomposition of alpha-acetoxy-N-nitrosopiperidine and alpha-acetoxy-N-nitrosopyrrolidine was conducted on the basis of common ion inhibition, thermodynamic parameters and azide ion trapping. The compounds, which have a reactivity difference of over two orders of magnitude, were found to be undergoing the process of decay via the generation of N-nitrosiminium ion intermediates. This is seen as proof of the highly unstable reactive nature of the two cyclic alpha-hydroxynitrosamines.