Thiolates xanthates

Antimony has a great affinity for charged sulfur ligands which include thiolates, xanthates (R0CS2 ), dithiocarbamates (R2NCS2 ), and dithiophosphates ((RO)2PS2 ). In contrast to arsenic, where this chemistry is limited to oxidation state III, antimony forms compounds in oxidation states III and V. The xanthate, dithiocarbamate, and dithiophosphate complexes are mostly made by reaction of antimony(III) halides or organohalides with Na, NH4, or Ag salts of the acids. Complexes... 

Substitution of chlorine on PVC by functional groups such as dithiocarbamate, thiolate, xanthate, and dithiophosphate were carried out in aprotic solvents such as dlmethylformamide (DMF) and hexamethylene phosphortri-amide (HMPA) by Okawara (4,5). Preliminary experiments conducted by Okawara indicate that a lower percentage of substitution of the chlorine by azide and thiophenoxide groups may also occur, even on PVC suspended in water, if a cationic surfactant is added to the slurry. We would like to report in this paper on the nucleophillic substitution of chlorine by thiolates and dithiocarbamates on PVC, carried out in slurry. A series of... 

There are also dithiocarbamates, [Os(S2CNEt2)2(PPh3)2]° +, similar xanthates, and pyridine 2-thiolates.1 ... 

Carbon disulfide is a valuable synthon (see Chapter 9, p. 147) which can be used for the synthesis of thiocarbonic acid derivatives. Thus, carbon disulfide reacts with ammonium polysulfide or hydrogen sulfide to give trithiocarbonic acid (70) or symmetrical esters (73) after reaction with an alkyl halide. With alkoxides or thiolates, carbon disulfide forms xanthates (77) or S-alkyl trithiocarbonates the latter by further treatment with alkyl, acyl or diazonium halides affords the derivatives (74)-(76) (Scheme 39). 

Thiols, thiocyanates or xanthates (the last two functionalities may be considered as masked thiols) are readily oxidized to sulphonic acids, with concentrated nitric acid, in reasonable yields, as indicated by equation Z422x 112>. Lead thiolates are also oxidized by excess nitric acid, to yield the corresponding sulphonic acid after treatment with acid, as shown in equation 35224. 

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