5-Phenyl chlorothioformate

The Grignard reaction (c/. Volume 1, Chapter 1.16) was recently used in a highly efficient route to ketones through sequential coupling of 5-phenyl chlorothioformate in the presence of transition metal catalysts (equation 32). ° ... 

It should be noted that Kim and Jon also reported the synthesis of thioesters by the reaction of alkyl iodides with 5-phenyl chlorothioformate under similar irradiation conditions [79]. 

S -Phenyl chlorothioformate was used as a radical trap in the radical-mediated carboxylation approach (Scheme 18) [40b]. Among several carbonyl derivatives including phosgene and bis(thiophenyl) carbonate, 5-phenyl chlorothioformate gives the best result and works with primary, secondary, and tertiary alkyl iodides. In addition to the desired thioester, a small amount of the corresponding sulfide is isolated as a by-product. 

C7H5CIO2 1885-14-9) see Alacepril Camazepam Itraconazole Paroxetine t>-phenyl chlorothioformate (C7H5CIOS 1005-56-7) see Cladribine 4-phenylcinnoline... 

A new free-radical carbonylation strategy, employing S -phenyl chlorothioformates and alkyl halides, has been developed. Reaction with (Eu3Sn)2 furnishes the corresponding S -phenyl esters in moderate yields (Scheme 30). 

Aminolysis of phenyl dithioacetates,8 pyridinolysis of O-ethyl dithiocarbonates,9 reaction of pyrrolidine with O-ethyl 5-aryl dithiocarbonates,10 aminolysis of chlorothionformates,11 pyridinolysis of alkyl aryl thioncarbonates,12 reaction of anionic nucleophiles with nitrophenyl benzoate and its sulfur analogues,36 hydrolysis of methyl benzoate and phenyl acetate containing SMe, SOMe and S02Me substituents,42 solvolysis of phenyl chlorothioformate,79 synthesis of new thiadiazoles,124 examination of a neighbouring sulfonium group in ester hydrolysis,136 hydrolysis of V-type nerve agents,250 and the reactions of peroxymonosulfate ion with phosphorus(V) esters have all been looked at previously in this review. 

The specific rates of solvolysis of phenyl chlorothionoformate (PhOCSCl) were found to be remarkably similar to those reported previously for phenyl chlorothioformate (PhSCOCl). When analysed using the extended Grunwald-Winstein equation over the usual range of solvent types, these solvolyses showed essentially identical divisions... 

The method has also been used for the synthesis of symmetrical 1, n-diketones (n > 8) and long-chain dicarboxylic thiol esters by reaction of acyl chlorides or phenyl chlorothioformate, respectively, with l,n-di(chloromagnesio)alkanes in the presence of catalytic amounts of tris(acetylacetonato)iron(Scheme 4-243). ... 

Chlorothioformic phenyl ester (103) reacts under mild conditions wnth 2-aminothiazole to give 104 (Scheme 71) (266). 

Chlorothioformic phenyl ester, with 2-amino-thiazoles, 51... 

Studies of solvent effects in the solvolysis, in a variety of pure and binary aqueous solvents, of isobutyl chlorothioformate i-BuOCS Cl and isobutyl chloroformate (-BuOCO Cl at different temperatures concluded that, depending upon the solvent, the mechanism could be either an addition-elimination or an ionization process. However, a similar study of phenyl fluorothionoformate (PhOCSF) showed that its solvolysis was wholly an addition-elimination process. ... 

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