Re-examination of the anodic oxidation of N,N-dimethylaniline, using parametric method 3

A semi-empirical calculation (PM3) was applied to elucidate the anodic oxid ation mechanism of N,N-dimethylaniline (DMIA) and the dimerization of a cat ion radical (A) derived front DMA was ruled out. The heat of reaction value of the dimerization of A was 42.43 kcal/mol. We propose the following. Cat ion radical A reacts with DMA to generate another cation radical (D), This reaction,vas exothermic and the heat of reaction value and the activation e nergy were -0.35 kcal/mol and 1.31 kcal/mol, respectively Deprotonation of D by DMA gives neutral radical (E), which is oxidized to TMB by A. All thes e reactions were exothermic.