Michida T, Osawa E, Yamaoka Y
Faculty of Pharmaceutical Sciences, Kobe-Gakuin University, Japan.
Chem Pharm Bull (Tokyo). 2000 Sep;48(9):1378-9. doi: 10.1248/cpb.48.1378.
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.
采用半经验计算方法（PM3）来阐明N，N-二甲基苯胺（DMA）的阳极氧化机理，并排除了由DMA衍生的阳离子自由基（A）的二聚反应。A二聚反应的反应热为42.43千卡/摩尔。我们提出以下观点。阳离子自由基A与DMA反应生成另一种阳离子自由基（D）。该反应是放热反应，反应热和活化能分别为-0.35千卡/摩尔和1.31千卡/摩尔。DMA使D去质子化生成中性自由基（E），E被A氧化为TMB。所有这些反应都是放热反应。
