Synthesis of dixanthates, dithiocarbonyl disulfides, and 1,3-oxathiolane-2-thione from diols and carbon disulfide: Model chemistry for Poly(disulfide) synthesis

Abstract

Polymers with disulfide linkages along the polymer chain have attracted interest for uses ranging from self-healing polymers to delivery of oligonucleotides to cells. Incorporation of carbon disulfide into monomers might provide a new route to poly(disulfide)s. Synthesis of such monomers from 1,2-ethanediol and 1,4-butanediol with KOH and CS2 gave the corresponding dixanthate monomers K+ ¯SC(S)O-(CH2CH2)n-OC(S)S¯ K+ (n = 1,2) on a ∼10 g scale in 50–62% yield. Synthesis of the related monoxanthate alcohols K+ ¯SC(S)O-(CH2CH2)n-OH (n = 1,2) followed by oxidative dimerization gave disulfide dimers (HO-(CH2CH2)n-OC(S)S)2 (n = 1, 2) representing structures of the simplest units of a polymer chain. Oxidation of the ethylene glycol dixanthate gave the known heterocycle 1,3-oxathiolane-2-thione.