Nitrosamines from tertiary amines and dinitrogen tetraoxide

Abstract

A preparative nitrosolysis of aliphatic acyclic and cyclic tertiary monoamines to nitrosamines was brought about by treatment with dinitrogen tetraoxide in carbon tetrachloride at 0–45 °C. Dealkylation was restricted, where applicable, to demethylation. Competitive oxidation to an amide was observed in the formation of dibutylformamide from tributylamine. Diamine dinitrate salts, without nitrosamine formation, were obtained from 1,4-dimethylpiperazine and 1,4-diaza[2.2.2]bicyclo-octane; however, each dinitrate salt thermolysed at 180–200 °C to give a small amount of 1,4-dinitrosopiperazine. In acetic anhydride dinitrogen tetraoxide converted amines less efficiently, gave lower yields of nitrosamines, was less selective in dealkylation, and introduced the formation of by-products.