Preparation of unsymmetrical disulfides by using sulfines1

Acidolytic cleavage of unsymmetrically substituted dithioacetal monoxides, ArCH(SR)S(O)Me has been used to prepare linear unsymmetrical disulfides RSSMe. Disproportionation was suppressed by the addition of a small amount of benzyl mercaptan. The required starting materials were conveniently obtained from appropriately substituted sulfines ArC(=SO)SR and methyl lithium. The following disulfides were prepared: R =n-C₄H₉ (73.5%), n-C₇H₁₅ (78%), Ph (77.3%), AcO(CH₂)₁₀ (81.5%).The unsymmetrical dithioacetal PhCH(SEt)SC₇H₁₅-n gave upon oxidation with one equivalent of peracid a mixture of two dithioacetal monoxides which on treatment with HClO₄ led to three disulfides. This result is discussed in term of the mechanism of acidolysis.