Thiocarbamoyl chlorides synthesis

In contrast to thioacyl chlorides, thiophosgene, CSCh, is readily accessible and conveniently handled making it an important reagent in the synthesis of thiocarbamoyl chlorides (15 ClCSNRa), 0-alkyl thiourethanes (ROCSNR 2), and thioureas (R2NCSNR2) (c/. Volume 6, Chapter 2.8). ... 

On the other hand, thiocarbamoyl chlorides (15) may be used in thioamide synthesis, though via carbon-carbon bond formation in Friedel-Crafts-type reactions (c/. Volume 2, Chapter 3.1). The approach is limited to fairly electron-rich aromatics such as alkylbenzenes, anisole, and furan, but fails for benzene equation (7) gives some details. - Phenol does not require a Lewis acid catalyst in the reaction with H CSCl, but gives a mixture of 2-/4-hydroxythiobenzamides along with O-phenyl thiocarba-mate. ... 

Another application of thiocarbamoyl chlorides (15) and related activated thiocarbonic acid derivatives in thioamide synthesis is found in their reaction with carbanions of highly CH acidic compounds EWG2CH2 to give thioamides EWG2CHCSNR2. ... 

In 1966 Martel and Duffaut [210] and Gronowicz and Ryan [86] reported the first synthesis of 0-triorganosilyl thiocarboxylates 83b from reacting thiocar-boxylic acids with triorganosilyl chlorides or triorganosilylamines, respectively. Since then, several preparation routes have been developed (1) RCOSH or M(RCOS) (M=alkali metal) + R SiCl [144] (2) RCOCl+R 3SiSLi [77] or (R 3Si)2S [202] (3) acyl thiocarbamoyl sulfides + R SiCl in the presence of triethylamine... 

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