Electrochemical Oxidation of Some Mesocyclic Dithioethers and Related Compounds

Evidence supporting the hypothesis that suitable neighboring groups can facilitate oxidation at sulfur of substitutedv dialkyl sulfides has been previously presented.¹ Since all of these oxidations are irreversible, thermodynamic parameterscannot be directly sccured from the data. Recently, the existence of unusually stable aliphatic cation radicals derived fromcertain mesocyclic dithioethers was reported.² Further one-electron oxidation affords the corresponding dications whichhave been obtained as solid salts.³ The unusual stability of these compounds compared with ordinary alkyl sulfide cation radicals and dications has been attributed to intramoleculartransannular interaction between the sulfur atoms in whichan S-S bond is formed. These results suggested that reversibleelectrochemical oxidation might be observed with these compounds from which thermodynamic parameters could readilybe obtained and that transannular participation by one sulfuratom might facilitate oxidation of the other.