Organic Disulfides and Related Substances. 49. Preparation of Cyclic Thiosulfinates and Reactions with Thiols

Article abstract of DOI:10.1021/jo00246a039

The four stereoisomers of 1,2-dithiane-4,5-diol 1-oxide were prepared by oxidizing the corresponding dithianes with H2O2 in MeOH/H2O by using tungstic acid as a catalyst, MnO2 to destroy excess H2O2 and chromatography to separate products.These cyclic thiosulfinates (8,9,12, and 13), tohether with 1,4-dihydro-2,3-benzodithin 2-oxide (2), were converted to bisunsymmetrical disulfides, R^a(SSR^b)2 with p-toluenethiol and 3-mercaptopropanediol as models respectively for arene- and alkanethiols. 1,5-Dihydro-2,3,4-benzotrithiepin 2-oxide (5) gave the disulfide trisulfide s 6a and 6b, R^a(SSR^b)(SSSR^b), with these thiols but 6a and 6b were quite unstable.Mass spectra are discussed; tetramethylene sulfone may provide a useful matrix for both positive- and negative-ion FAB spectra of organosulfur compounds.