Evidence for the Formation of alpha-Hydroxydialkylnitrosamines in the pH-Independent Solvolysis of alpha-(Acyloxy)dialkylnitrosamines.

A kinetic study of the decay of alpha-(acyloxy)dialkylnitrosamines in aqueous solutions, at 25 degrees C, ionic strength 1 M (NaClO(4)), and 4% acetonitrile by volume, is reported. Rate constants for disappearance of the N-NO chromophore or appearance of benzaldehyde product increase with the introduction of electron-withdrawing groups into the acyloxy moiety. For some compounds, in some regions of pH, the kinetics are non-first-order.