| Abstract: | The electrochemical oxidation of various substituted aryl cycloheptatrienes and cyclohepta‐1,3,5‐triene, the parent compound, in acetonitrile is investigated with the aid of cyclic voltammetry (CV), experiments at the rotating ring disk electrode (RRDE) and controlled potential electrolysis. 1‐(p‐methoxyphenyl)‐cycloheptatriene 2c , 1‐ and 3‐(p‐di‐methylaminophenyl)‐cycloheptatriene 2d , 3d are converted by anodic oxidation into the radical cations the main reaction of which is not the deprotonation. According to the proposed mechanism the electrochemical oxidation proceeds along the radical cation dimerization. The dimer cations ( 1 22+) decompose under deprotonation into tropylium ions 4 and starting compound. In the case of 1‐(p‐dimethylaminophenyl)‐cycloheptatriene 2d the deprotonation reaction can compete with the dimerization. The oxidation of the cycloheptatriene compounds is kinetically controlled by the homogeneous chemical steps rather than by the initial electron transfer. |
