Sulfinic Acids and Related Compounds. 19. Synthesis and Properties of 1-Propane-, 1-Butane-, and 1-Pentanesulfinates Terminally Substituted with Di- and Trisulfide Functions

Article abstract of DOI:10.1021/jo00237a031

Preparation and reactions are compared, for n=3-5, of disulfide sulfinates with the structure RSS(CH2)nSO2Na (1) and of trisulfide bisalkanesulfinates with the structure 2S (5).The di- and trisulfides were prepared by reaction of cyclic thiosulfonates, and optimum preparations ot the thiosulfonates are considered.For 1, R was HO2CCH2CH2 (10-12), p-CH3C6H4 (13-15), C6H5 (16 and 17), 2,4,6-(CH3O)3C6H2 (n=4; 18), and H2N(CH2)2 (n=4; H in lieu of Na; 19).Several of the di- and trisulfides were sensitive to light (the trisulfides about equally).Much faster conversion for the disulfides occurred with heat for R = p-CH3C6H4 when n was 3 (13) or 4 (14) than when n was 5 (15); these results with 13-15 point as principal processes to homolysis with light but heterolysis with heat, the latter with operation of a neighboring-group effect of SO2Na on the SS bond.Sodium methanesulfinate readily forms a thiosulfonate with sulfur, and the implications of this reaction are developed for the chemistry of the trisulfide bissulfinates (5), where a novel rearrangement produces disulfide thiosulfonates (21, n=3-5).