N, N-ジメチルアニリンの陽極酸化反応による4, 4-メチレンビス(N, N-ジメチルアニリン)の生成機構

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Preparative constant-current electrolysis of N, N-dimethylaniline(100 mM, DMA) was carried out in dry acetonitrile containing Et_4NClO_4 to give N, N, N', N'-tetra-methylbenzidine(TMB) and 4, 4'-methlenebis(N, N-dimethylaniline)(MDMA). In the presence of HCl, DMA was quantitatively oxidized to TMB. Formation mechanism of MDMA was discussed using the results of semi-empirical calculations that were PM3 and AM1. The proposed mechanism by Hand and coworker was ruled out and an alternative one is suggested as follows. DMA undergoes one-electron oxidation at the anode and gives the corresponding N, N-dimethylaniline cation(A). Aydroxy ion, instead of DMA, abstracts a proton from A and gives H_2O and methyl(phenyl) aminomethyl radical(B). Breacts with DMA to give a 1-dimethylamino-4-(N-methyl-N-phenylamino) methl-2, 5-cyclohexadienyl radical(I). The radical decomposes to N-methylaniline and a 1-dimethlamino-4-methylene-2, 5-cycloheadienyl radical(J). The radical J reacts with DMA to give a 1-dimethylamino-4-(4-dimethylaminobenzyl)-2, 5-cyclohexadienyl radical(K), which is oxidized to MDMA by the anode.
社団法人日本薬学会の論文
2001-12-01