Disulfides sulfinyl chlorides

Benzisothiazoles are formed by the action of ammonia or amines on benzenesulfenyl halides bearing an o-carbonyl function (72AHC 14)43, 80MI41700). Analogous diphenyl disulfides behave similarly (77SST(4)339). Sulfinyl chlorides or phenylsulfoxides produce... 

Sulfinyl chlorides may be prepared from the corresponding thiols or disulfides by oxidative reactions rather than by reductions of sulfonyl compounds. A recent example, which improves the earlier procedure of Douglass, is given by equation (3)50. The chemistry of sulfinic acids and their derivatives has been reviewed51 52,53. 

Also, sulfinyl chlorides (precursors to sulfinate esters) have recently been prepared directly from disulfides (equation 3)23. 

Methyl disulfide, oxidation to methane-sulfinyl chloride by chlorine, 40, 62... 

Sulfenyl cldorides, sulfinic acids and sulfinyl chlorides were reduced in good yields by lithium aluminum hydride to disulfides [680], The same products were obtained from sodium or lithium salts of sulfinic acids on treatment with sodium hypophosphite or ethyl hypophosphite [507]. Sulfoxy-sulfones are intermediates in the latter reaction [507]. 

Sulfinyl chlorides.1 These reagents are generally prepared by reaction of sulfinic acids with thionyl chloride. They can be prepared more conveniently by reaction of the readily available disulfides in acetic acid with sulfuryl chloride yields are nearly quantitative. 

Buffer catalysis of the hydrolysis of phenyl (311 R = Ph) and methyl (311 R = Me) benzenesulfinates to give the sulfinic acid (312) and alcohol ROH is strongly accelerated by both carboxylate and amine components of the buffer which give Bronsted /i values of approximately unity on separate lines. The carboxylates are about 44 tunes more effective than amines of similar basicity. A concerted. S n2 mechanism with a hypervalent intermediate (313) is proposed for the nucleophilic reaction of these esters.286 The reaction of the thiosulfinate esters (314) with sulfenyl chlorides RSCI and sulfenate esters (315) to give sulfinyl chlorides and disulfides and sulfinate esters and disulfides, respectively, has been studied.287 Hydrolysis of 2-(3-aminophenyl)sulfonyl-ethanol hydrogensulfate gives under different conditions various products such as the ether (316) and the sulfone (317).288... 

A simple method of preparing sulfinic esters consists of oxidative chlorination of aliphatic thiols, thiophenols, or disulfides with chlorine in glacial acetic acid, followed by alcoholysis of the resulting sulfinyl chlorides 626... 

Sulfinyl chlorides are produced when disulfides are treated with SO2CI2 and trimethylsilyl acetate at 0°C. 

Pyrrole and 1-methylpyrrole can be sulfinylated by sulfinyl chlorides or A-(phenyl-sulfinyl)succinimide. The products are prone to rearrange to the 3-isomers on contact with acid <80JOC5336>. A phenylsulfinyl group has been introduced at C3 of the indole ring by 3-sulfenylation of AT-lithioindole with diphenyl disulfide, followed by A-sulfonylation and oxidation to the sulfoxide <89JOCi782>. Sulfenylindoles can be oxidized to sulfones by MCPBA <93JMC1425>. 

Sulfenyl, sulfinyl, and sulfonyl chlorides are reduced to symmetrical disulfides by the trichlorosilane-tri-n-propylamine system.4 Examples ... 

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