Kinetic Studies on the Formation of N-Nitroso Compounds IX. Nitrosyl Acetate as a Nitrosating Agent

Article abstract of DOI:10.1007/BF01120962

A study of the nitrosation of N-methylaniline and piperazine by nitrous acid in acetate buffer supports a mechanism covering both reactions, whose effective pathway depends on the relationship between the concentrations of nitrite ion, acetate ion, and nitrosatable substrate.In the case of N-methylaniline the only nitrosating agent is nitrosyl acetate, whereas in the nitrosation of piperazine the nitrous acidium ion and dinitrogen trioxide are also involved.The results obtained seem to show that nitrosation by nitrosyl acetate is diffusion controlled.On this assumpti on, the equilibrium constant of the reaction AcOH + HNO2 <*> AcONO + H2O has been estimated from kinetic measurements as approximately 1.4*E-8 M^-1.This means that the concentration of nitrosyl acetate in the medium must be extremely small, which explains the virtual impossibility of detecting it in aqueous solution except by kinetic methods. - (Keywords: Acetate buffer; Kinetics of nitrosation; Nitroso compounds; Nitrosyl acetate)