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 oxidation mechanism of N,N-dimethylaniline (DMA) and the dimerization of a cation radical (A) derived from DMA was ruled out. The heat of reaction value of the dimerization of A was 42.43 kcal/mol. We propose the following. Cation radical A reacts with DMA to generate another cation radical (D). This reaction was exothermic and the heat of reaction value and the activation energy 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 these reactions were exothermic.