13141-08-7Relevant articles and documents
α-(Acyloxy)dialkylnitrosamines: Effects of structure on the formation of N-nitrosiminium ions and a predicted change in mechanism
Hongliang, Cai,Fishbein, James C.
, p. 1826 - 1833 (2007/10/03)
The decay of α-(acyloxy)dialkylnitrosamines in aqueous solutions has been studied with a view toward elucidating mechanistic details and effects of structure on mechanism and reactivity. Rate constants (k1) for the pH-independent decay of 43 α-(acyloxy)dialkylnitrosamines have been determined. Observations from these and other experiments rule out decomposition via an anchimeric assistance mechanism involving the Z isomer that had previously been suggested. All of the reported data for most of the compounds is consistent with a mechanism involving the formation of N-nitrosiminium ions in or before the rate-limiting step. Structure -reactivity correlations indicate that the stability of α-(acyloxy)dialkylnitrosamines is determined by electronic properties of substituents at RN and RC as well as by the ability of substituents RC to engage in hyperconjugative interactions of C-H bonds with the developing cationic center in the transition state for nitrosiminium ion formation. Attachment of substituents of sufficient electron-withdrawing power at RN and RC results in a predicted change in mechanism to what appears to be an acyl group attack mechanism.