Chemistry of Bis (alkoxy carbonyl) poly sulfanes and Related Compounds

Bis(alkoxycarbonyl)polysulfanes 3-6 with up to six sulfurs have been prepared by reaction of dichlorosulfanes with 2 equiv of 0, 0-dialkyl thiocarbonetes (16). This method is compared to several literature methods for the preparation of 1-6 together with some new methods, including the hydrolysis of bis(alkoxydichloromethyl)-polysulfanes 18-21 in turn derived from the chlorination of bis(alkoxythiocarbonyl)polysulfanes. Related chemistry provided (methoxycarbonyl)disulfanyl chloride (15a), (methoxydichloromethyl)disulfanyl chloride (24a), (chlorocarbonyl)disulfanyl chloride (26), and bis(chlorocarbonyl)trisulfane (29), all in good yields. Bis(alkoxycarbonyl)polysulfanes 1-9 with up to nine sulfurs were isolated from the alcoholysis of (alkoxy carbonyl) (alkoxydichloromethyl)di-and-trisulfanes 30, 31, and 35 and (alkoxydichloromethyl) (chlorocarbonyl)polysulfanes 39-41. The higher sulfanes 7-9 were identified by their HPLC behavior where a plot of log (retention time) against the number of sulfurs was found to be linear. Mechanisms for the formation of these products are proposed.