Thioacylation of Alcohols and Thiols

Thioacylation of Alcohols and Thiols. Thiobenzoyl chloride and Bu CHg-C(S)C1 have been used to prepare various thiono- and dithio-esters, e.g. the chiral (177). Dialkyl tetrafluorobis(thiono)succinates [CFgC(S)OR]a result from alcoholysis of - -CF2C(S)F]2, whereas the ortho-thioester (178) is obtained from -t-CF2C(S)F]2 and methanethiol.  

Carboxymethyl dithiocarboxylates are well-known thioacylating reagents, and have been the starting materials for the preparation of thionocarboxylates of different types, e.g. (179), which has proved to be an efficient sensitizer for photochemical reactions in the visible region (A 500 nm), and 

The thioacylating properties of (169) have already been mentioned, and thiono-esters are formed from it by reaction with alkoxides. Thioacylation of methoxide ion can also be achieved by R C(S)SSR , which is obtained from R CS2 R2NHa+ and R SC1. Dithiocarboxylates may be prepared in an analogous manner from mercaptides.  

Thioketens, which are now more readily available 27-429 tt n some years ago, are valuable reagents for the thioacylation of alcohols and thiols at room temperature. The thioketen (183), which is formed from the thioaldehyde (182) 

Katada, S. Tsuji, T. Sugiyama, S. Kato, and M. Mizuta, Chem. Letters, 1976, 441. 

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