Electron-organic Chemistry. IV. Structure—Anodic Potential Relationship and Electron-transfer-induced Reactions of [2.2]Para- and -Metaparacyclophanes

Abstract

Abstract The anodic peak potentials of [2.2]para- and -metaparacyclophanes were found to be highly dependent on the solvent. A cleavage reaction occured when [2.2]paracyclophane was electrolyzed anodically, using acids or alcohols as nucleophilic solvents, whereas lead tetraacetate oxidation in trifluoroacetic acid–dichloromethane gave nuclear substitution products. The cathodic reduction in hexamethylphosphoric triamide–lithium chloride–acetic acid gave 1,2-di-p-tolylethane and its Birch reduction products. On anodic oxidation, [2.2]metaparacyclophane gave a rearrangement reaction product, 4-hydroxy[2.2]metacyclophane. Possible reaction pathways for these reactions were formulated.