Dithiols, polydisulfides

Polymers of = 1600—6500 with polydispersity 1.2—2.8 were prepared by addition of diolefins with dithiols and the following two-phase oxidation of the resulting polydisulfides. The effective oxidation (up to 92% of sulfoxide units) of polysulfides was conducted by using aqueous hydrogen peroxide in chloroform with or without heating. The formation of polysulfoxides was strongly supported by spectroscopic analysis. Poly(hexamethylene sulfoxide) obtained in this way was subject to Swern oxidation of primary or secondary alcohols, in which 1-octanol [111-87-5] and 6-undecanol [23708-56-7] were oxidized to give 1-octanal [124-13-0] and 6-undecanone [927-49-1], respectively, in quantitative yields (18). 

Goethals, E. J., and Silis, C., Oxidation of dithiols to polydisulfides by means of dimethylsulfoxides, Makromol. Chem., 119, 249, 1968. 

Also polymercaptals and polymercaptols were obtained from dithiols and aldehydes and ketones. Polydisulfides were prepared by air oxidation of... 

Oxidation of dithiols by air to polydisulfides in the presence of a mixture rrf tertiary amine and a copper salt [159,160] or in the presence of an inorgank basic compound has al been achieve [161] Unlike bromine, iodine was found to have efficiently oxidized the dithiols to polydisulfides [162,163]. Reduction of disulfide polymers back to dithiols was achieved either by using Na/liquid NH3 [164,165] or with a pyridine/acetic ad zanc mixture [166]. When DMSO was used as the readion medium, it also acted as an oxidizmg agent of dithiols to polydisulfides [167-169]. For example, poiy(i -phenylene disulfi ) prepared by the oxidation of l -dimercaptobenzeiK with DMSO... 

---