| Budget Amount *help |
¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1986: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1985: ¥1,100,000 (Direct Cost: ¥1,100,000)
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| Research 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 nitrosoamines, 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-tetramethyl-piperidine and N-nitroso-2,2,6,6-tetramethylpiperidone 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.
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