21983-64-2Relevant academic research and scientific papers
Electrochemical Oxidation of N-Nitrosodialkylamines: Mechanism of N-Nitramine and β-Ketonitrosamine Formation
Masui, Masaichiro,Nose, Koichi,Terauchi, Satomi,Yamakawa, Eiko,Jeong, Jisook,at al.
, p. 2721 - 2730 (2007/10/02)
Electrochemical oxidation of N-nitrosamines (1) derived from symmetrical dialkylamines was investigated in acetonitrile in the presence of dissolved oxygen.On cyclic voltammetry at ambient temperature, 1 showed two or three irreversible anodic peaks, depending upon the structure.Macroscale electrolysis, either controlled potential or constant current, of 1 which showed three voltammetric peaks gave the corresponding nitramine (2) and N-alkyl-N-(2-oxoalkyl)nitrosamine (3) as the main products.In the case of 1 which showed two voltammetric peaks, however, the side chain oxidized nitrosamine 3 was not obtained.It is suggested that the oxygen atom incorporated in the products 2 and 3 originated from dioxygen dissolved in the medium, and that the numbers of electrons required for the formation of 2 and 3 are one and two, respectively.A possible reaction sequence, which involves the reactions of the radical cation (4) derived from 1 and a radical formed by intramolecular rearrangement of 4 with dioxygen, is proposed.Keywords---N-nitrosodialkylamine; N-nitramine; N-alkyl-N-(2-oxoalkyl)nitrosamine; electrochemical oxidation; cyclic voltammetry; controlled potential electrolysis; constant current electrolysis
