Sulfenyl fluorides preparation

The best method for the preparation of CF3SF is the reaction of CFgSCl with HgFg in a nickel or platinum apparatus at 130°C, followed by removal of the reaction products by condensation in liquid nitrogen 144). Analogous reactions with metal fluorides lead to other sulfenyl fluorides 102,189) ... 

Chlorodifluorothioacetyl fluoride prepared by this reaction has a boiling point of 23° C. NMR characterization of this compound gave a low-field triplet and high-field doublet in a ratio of 1 2, as would be expected. However, a material boiling at 36° C had been reported earlier as chlorodifluorothioacetyl fluoride (54). This material was obtained by dehalogenation erf 2-chlorotetrafluoroethane-sulfenyl chloride with tin. In view of... 

Addition of a sulfenyl chloride to an alkene in the presence of silver fluoride affords (3-fluoro sulfides, as shown in equation (2).18 The same trans adducts can also be prepared from the sulfenyl chloride adducts and silver fluoride. An alternative procedure for the formal addition of methanesulfenyl fluoride to alkenes involves the use of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine tris(hy-drofluoride) as in equation (3).19... 

Further examples of the preparation of fluorinated sulfides from the reaction of alkenes with sulfenyl chlorides in the presence of alkali fluorides are presented in Table 38. ... 

ArSX), and among these the most used anionic carrier of the sulfenylium ions is the chloride anion . However, sulfenyl bromides have been also used whereas iodides and fluorides are unstable although they can be prepared in. Other sulfenylating... 

This synthesis of sulfenyl chlorides can also be used in the aliphatic series although here the limitation applies that most alkylsulfur halides are too unstable to be isolated from solution. In general, and also in the aromatic series, sulfenyl chlorides are easier to prepare than the bromides, whilst the iodides are known only in a few cases and the fluorides not at all. As an example, Schneider,665 chlorinating methanethiol in anhydrous carbon tetrachloride at —15°, obtained dimethyl disulfide dichloride [chloro(methyl)(methylthio)-sulfonium chloride] which passed into methanesulfenyl chloride when allowed to warm slowly to room temperature ... 

Nucleophilic substitution, e.g. the preparation of thiocyanates from lipophilic alcohols, can be facilitated by substrate hydrophilation via ammonioethanesulfonic acid esters (betylates)i . Mercaptans can be easily prepared from alcohols with inversion of configuration via thiolic esters prepared with thioacetic acid in the presence of 2-fluoro-pyridinium salts . C-Sulfenylation of / -dicarbonyl compounds with mercaptans by air oxidation in the presence of tetraethylammonium fluoride has been reported . Activated thiolic and selenolic esters can be prepared at room temperature from carboxylic acids and aryl thiocyanates or selenocyanates in the presence of tri-n-butylphosphine i. Phenylselenolactones have been obtained under very mild conditions from unsaturated acids and benzeneselenyl chloride. ... 

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