Nitrosative dealkylation of some symmetrical tertiary amines

Abstract

The rates of nitrosodealkylation of several symmetrical tertiary amines R₃N including trialkylamines (R = Me, Et, Prⁿ, and Buⁿ) and substituted trialkylamines (R = C₆H₅CH₂, triethanolamine, and nitrilotriacetic acid) have been measured in aqueous acetic acid–acetate buffers. The rate of formation of diethylnitrosamine was found to be first order in nitrous acid, triethylamine, and in the hydrogen ion concentration for pH >3.1. Rates increased with decreasing amine basicity. The rate equation was consistent with rapid, reversible nitrosation by nitrous acid or acetyl nitrite and a rate-determining subsequent elimination.