Anodic hydroxylation of 1-carbomethoxy-1,2,3,4-tetrahydrocarbazoles

1-Carbomethoxy-1,2,3,4-tetrahydrocarbazole (1) and its 7-methoxy derivative (2) were oxidized at carbon felt anodes in acetonitrile containing 0.2 M LiClO₄ and 2-17 M water at potentials on the rising portion of the primary oxidation peak to yield products formed by formal substitution of the C-1 H atom with hydroxide. The resulting 1-hydroxy-l-carbomethoxy-1,2,3,4-tetrahydrocarbazole and its 7-methoxy derivative were isolated in 44 and 22% yields, respectively, when sodium bicarbonate was used to control acidity of the medium. Structures were elucidated by NMR, IR, elemental analysis, and mass spectrometry. Voltammetry at carbon-paste and glassy carbon electrodes showed that the oxidations proceed by an ECE or DISPI pathway. The rate-determining step is the reaction of water with a cation radical electrochemically generated from 1 or 2, involving either proton abstraction or nucleophilic addition.