Bunte salts, synthesis

Feldstein, R., Bunte Salt Polymers Synthesis. Reactivity and Properties. Ph.D. Dissertation, The American University, 1971. 

Thio-D-xylopyranose has been the sugar of this type most thoroughly investigated. Its synthesis was reported in 1961, independently and simultaneously from three different laboratories. With sodium thiocyanate, l,2-0-isopropylidene-5-0-p-tolylsulfonyl-a-D-xylofuranose (211) gives a thiocyanate that reacts with sodium sulfide to give l,2-0-isopropylidene-5-thio-a-D-xylofuranose (212). A better synthesis is the treatment of 211 with sodium thiosulfate, followed by reduction of the resultant Bunte salt with sodium boro-hydride. The same compound 212 is obtained by nucleophilic replacement of the 5-sulfonyloxy group in 211 by treatment with potassium thioacetate followed by deacetylation to 212, or by the reaction of 211 with sodium a-toluenethioxide, followed by scission of the resultant S-benzyl compound with sodium in liquid ammonia. 

The synthesis of sulfide-containing oligomers can be also achieved by means of Bunte salts—a high molecular weight compound, obtained by the following reaction [20] ... 

S Ag"" and a-bromoketones an alternative route to -keto-sulphides employs an aldehyde and LiCH(SPh)2, and treatment of the adduct with MeLi. Sulphur ylides are now shown to be capable of acting as C—S transfer agents, in addition to their well-known ability to alkylate through carbon. Among five products from cyclopropenium cations and are a 3-methylthio-cyclobutene and a 3-methylthiomethyl-cyclopropene. The use of Bunte salts in sulphide synthesis is illustrated by the synthesis of 1- of 2-naphthyl sulphides from the naphthols with sodium benzylthiosul-phate. ... 

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