A New Route to Thio- and Selenosulfonates from Disulfides and Diselenides. Application to the Synthesis of New Thio- and Selenoesters of Triflic Acid

Abstract

Alkyl and aryl trifluoromethanethiosulfonates(1) (or selenosulfonates) were prepared in one step either from alkyl and aryl sulfenyl (or selenenyl) chlorides and sodium trifluoromethanesulfinate (3) or, more generally, from disulfides (or diselenides), 3, and bromine. The second method involved trifluoromethanesulfonyl bromide as key intermediate. Benzenethiosulfonates were obtained in a similar way from disulfides, benzenesulfinate, and bromine but benzeneselenosulfonates could not be obtained by the same method from diselenides.

Desulfitative Thioalkylation of Alkenes

“…S-Phenyl trichloromethanethiosulfonate (Cl 3 CSO 2 SPh, 1) was prepared in analogy to the work of Langlois for the synthesis of the CF 3 SO 2 SPh (Scheme 2). [33] Reduction of commercially available trichloromethanesulfonyl chloride (Cl 3 CSO 2 Cl) with sodium sulfite afforded sodium trichloromethanesulfinate (Cl 3 CSO 2 Na) that was treated with benzenesulfenyl chloride (PhSCl) to afford the thiosulfonate 1 in 83% overall yield as a colorless crystalline reagent.…”

Thiosulfonates as Emerging Reactants: Synthesis and Applications

“…Although unsymmetrical S ‐alkyl methanethiosulfonates ( 7 ) are formed in high yield in a preferred solvent, the stoichiometric amount of toxic silver waste is not beneficial in terms of the green credentials of this method. The groups of Langlois and Fujiki employed bromine (route 2) or iodine (route 3) for the activation of the disulfide bond resulting in a lower PMI. Unfortunately, reactions were performed in hazardous dichloromethane.…”

The Surface Modification of the Polypropylene by Aqueous Soluble CoII Phthalocyanine to Obtain Materials for Catalysis

“…The dependence of the catalytic activity of the obtained materials in the pH range of 4-12 is also not linear, the greatest activity is observed with pH values of 8-9. It is explained by shift of equilibrium (4) towards the existence of thiol as an ion RS -:…”

“…As an example, synthesis of thiuram sulfides, that are used as vulcanization accelerators as well as for the preparation of intermediates in the manufacture of dyes and synthetic pharmaceutical products. [4][5] Oxidation of R-SH compounds in air under temperature about 298 K can improve the quality of desired product. It accords to the modern concept of "green chemistry" also.…”