H. Ohmori, H. Maeda, C. Ueda
Aug 25, 1986
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Influential Citations
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Journal
Chemical & Pharmaceutical Bulletin
Abstract
Electrochemical transformation of five N-nitrosopiperidines and N-nitrosodibutylamine to the corresponding N-nitramines has been investigated in acetonitrile at -30°C. The nitramines are formed by the reaction of the radical cations, generated by one-electron transfer from the nitrosamines, either with dissolved oxygen (path 1) or with water which is contaminating or deliberately added to the medium (path 2) : the former is an overall one-electron process, and the latter is a two-electron process. The radical cations derived from N-nitroso-2, 2, 6, 6-tetramethylpiperidine and N-nitroso-2, 2, 6, 6-tetramethyl-4-piperidone give the nitramines exclusively via path 2, while the reaction of those from N-nitroso-2-ethylpiperidine and N-nitrosodibutylamine proceeds via path 1. Contributions of both pathways are suggested for the radical cations from N-nitrosopiperidine and N-nitroso-2, 6-dimethylpiperidine. It is proposed that path 2 becomes feasible when the radical cation exhibits a certain degree of stability as revealed by the observation of reversible character in the cyclic voltammetry of the parent nitrosamine.