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| - α-(Acyloxy)dialkylnitrosamines: Effects of Structure on theFormation of N-Nitrosiminium Ions and a Predicted Change inMechanism
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| - The decay of α-(acyloxy)dialkylnitrosamines in aqueous solutions has been studied with a viewtoward 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. Observationsfrom these and other experiments rule out decomposition via an anchimeric assistance mechanism involvingthe Z isomer that had previously been suggested. All of the reported data for most of the compounds is consistentwith 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 electronicproperties of substituents at RN and RC as well as by the ability of substituents RC to engage in hyperconjugativeinteractions of C−H bonds with the developing cationic center in the transition state for nitrosiminium ionformation. Attachment of substituents of sufficient electron-withdrawing power at RN and RC results in apredicted change in mechanism to what appears to be an acyl group attack mechanism.
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