Chemical and Electrochemical Oxidation of O,O,O-Trisubstituted Phosphorothioates and Triphenylphosphine Sulfide

Article abstract of DOI:10.1021/jo00156a006

The chemical and electrochemical oxidation of O,O,O-trialkyl phosphorothioates and triphenylphosphine sulfide are reported.Reaction of the latter compound with nitrosonium tetrafluoroborate produces a dimeric dication that is relatively stable in acetonitrile solution but rapidly decomposes upon attempted isolation.Electrooxidation of triphenylphosphine sulfide similarly gives a dimeric dication via the intermediacy of a dimer cation radical.Reaction of O,O,O-triethyl phosphorothioate with nitrosonium tetrafluoroborate produces bis(diethylphosphoryl)disulfide and the N-ethylacetonitrilium ion whereas its oxidation at the surface of platinum results in the formation of the N-ethylacetonitrilium ion and products that are not identified.