SULFINIC ACIDS AND RELATED COMPOUNDS. 20. SYNTHESIS AND PROPERTIES OF SOME α, ω-ALKYLENEBIS(DITHIOALKANE-SULFINATES)

Abstract

Abstract Title compounds (1,3,4) having the structure NaO2S(CH2)nSS(CH2)mSS(CH2)nSO2Na were prepared with m[dbnd]4 and n[dbnd]3–5 by reaction of 1,4-butanedithiol with cyclic disulfide 1,1-dioxides. Products were prepared similarly where a hydrogen atom in the 2-and 3-positions of the (CH2)4 moiety was replaced with OH in erythro (12) and threo (14) relationships; careful exclusion of oxygen was necessary. The products 1, 3, and 4 when heated in D2O in the dark gave 1,2-dithiane (6) and the appropriate bissulfinate, [NaO2S(CH2)nS]2, apparently by a heterolytic mechanism. The relative stabilities (for m = 4) were n = 5 >> 3 > 4. Under UV light 1, 3, and 4 reacted more rapidly and at about the same rate as one another, apparently by a homolytic mechanism. The two dihydroxy products (12 and 14) were considerably less stable in solution than 1, 3, and 4 but underwent the same type of reaction, as shown by comparison of spectra of the products with those of authentic mixtures. At ca. 25°C, the half-survival ti...