Alkyl trithiocarbonate

Under similar conditions, perfluoroalkyl iodides react with alkyl phosphates to give fluorinated phosphine oxides, phosphinates, and phosphines [54 (equation 49) The product formed depends upon the stoichiometry and type of iodide used. When sodium alkyl trithiocarbonates are used as substrates, perfluoroalkyl tri-thiocarbonates ate formed [55]. 

Tellurium bis[alkyl trithiocarbonates] are orange solids that decompose at 30° with deposition of tellurium. Decomposition also occurs in solutions in the presence of triethylamine or pyridine2. 

In aqueous solution acidified with acetic aied, disodium tellurapentathionate and potassium alkyl trithiocarbonates combined to form tellurium bis[ulkyl trithiocarbonates]2. 

Tellurium bis[alkyl trithiocarbonates] react with equimolar amounts of bromine or iodine to give tellurium (alkyl trithiocarbonate) bromides or iodides. An excess of bromine produced tellurium (alkyl trithiocarbonate) tribromide. An excess of iodine did not form the triiodide2. s... 

The tellurium bis[alkyl trithiocarbonates] need not be isolated. The dichloromethane or chloroform extract of the aqueous reaction mixture containing the tellurium compound can be treated with bromine or iodine1. Examples of tellurium (alkyl trithiocarbonate) halides prepared in this manner are ... 

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). 

Although the S-alkyl dithiocarbonate anion has been found to possess higher nucleophilicity towards O-alkyl xanthates as compared with the S-alkyl trithiocarbonate anion, step (ii) is so much faster than the other possible process ... 

In a similar fashion, alkyl trithiocarbonate complexes react with secondary amines to yield dithiocarbamates with concomitant elimination of the thiol (Eq. 41) (224, 226-228). 

The same group of workers also accounted for the thermal rearrangement reaction of di(ethylthio)propyl S-methyl xanthates and the rearrangement of 0,S-dialkyl dithiocarbonates that occurs under Friedel-Crafts reaction conditions. A new, general synthesis of l,3-dithiol-2-ones (451) is based on the acid-catalysed ring-closure reaction of the dithiocarbonates (452). The rearrangements of 2-aminoethyl alkyl trithiocarbonates (453) and alkylthio-thiocarbonyl thiocyanates (433) into dithiocarbonates (454) and alkylthio-thiocarbonyl isothiocyanates (455), respectively, have been described recently. 

OEthyl thionocarbamates have been obtained by ethanolysis of 1,3,4-oxadiazolium-2-thiolates, and S-alkyl N-(o)-mercaptoalkyl)-dithio-carbamates were produced by rearrangement of S-alkyl S -(o)-amino-alkyl)trithiocarbonates." Limitations in space preclude a discussion of the many papers reporting on the syntheses of a variety of heterocyclic compounds containing the thionocarbamate " or the dithiocarbamate (refs. 244, 418, 419, 513, 651, and 659—664) grouping. 

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