Methyl chlorothioformate

Molinate (27) (65USP3198786) is simply made from perhydroazepine and 5-ethyl chlorothioformate, while the recently introduced pyrazolate (28) (75GEP2513750) is synthesized from l,3-dimethylpyrazol-5-one, itself easily made from methylhydrazine and ethyl acetoacetate. Reaction of the pyrazolone with 2,4-dichlorobenzoyl chloride takes place on carbon at the 4-position, and then treatment with toluene-p-sulfonyl chloride gives pyrazolate. Difenzoquat (29) (75USP3922161) is readily available from 3,5-diphenylpyrazole by methylation. Ethofumesate (30) (69GEP1926139) is synthesized from p-benzoquinone (Scheme 8). 

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. 

Methyl and S-aryP thiocarboxylic esters can also be prepared directly from carboxylic acids if thiocyanates or chlorothioformates are used instead of thiols (equations 11 and 12). 

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