Electron-Transfer Reactions of Aromatic Thiolate Anions with Organic Oxidizing Agents

A number of aromatic thiolate anions was found to undergo oxidation by nitrosobenzene in dimethyl sulfoxide-tbutyl alcohol solvent. A reasonably stable radical anion was detected as an intermediate and tentatively identified as nitrosobenzene radical anion. The following aromatic thiols undergo oxidation to the disulfide by nitrosobenzene: 2-naphthalenethiol, benzenethiol, p-t- butylbenzenethiol, thiosalicylic acid, p-chlorobenzenethiol, and p- nitrobenzenethiol. Other oxidants were also studied, and are arranged in the following order according to their ability to dimerize potassium 2- naphthalenethiolate: azodicarbonamide > nitrosobenzene > maleic anhydride >> acrylonitrile > nitrobenzene > acrylamide. (D.L.C.)