Abstract
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 sidechain 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.
