Abstract:The one-pot conversion of a mercaptan and an aryl methanesulfonate into a trithioorthoformate is described.

Abstract:A previous report has established the intermediacy of a sulfide-sulfonate ester in the one-pot conversion of an aryl mercaptan and a sulfonate ester into the corresponding trithioorthoformate. This report describes evidence for the sequential intermediacy of a bissulfide-sulfonate ester and a dithiosulfene in the conversion of the sulfide-sulfonate ester into the trithioorthoformate. A new sulfonate ester is shown to give the highest yield of trithioorthoformate.Key words: single electron transfer, sulfonate esters, sulfenes.RCsumC : Une publication antkrieure a Ctabli la participation d'un ester sulfure-sulfonate comme produit intermtdiaire dans la conversion dans un seul rtcipient d'un mercaptan arylique et d'un ester sulfonate en trithioorthoformate correspondant. Cette publication dkcrit la preuve de la participation intermkdiaire skquentielle d'un ester bisulfure-bisulfonate et d'un dithiosulfkne dans la prkparation du trithioorthoformate. On montre qu'un nouvel ester sulfonate donne les rendements les plus tlevts de trithioorthoformate.

Sodium hydride reductions of aryl methanesulfonates afford dimeric sulfone-sulfonate esters as well as products arising from SO bond rupture. SO bond rupture becomes more competitive as the LUMO energy of the sulfonate esterdeclines. Exploration of the chemistry of a sulfone-sulfonate ester revealed a complex novel reaction that resulted in the formation of, inter alia, a dichloromethanesulfonate ester and a trichloromethanesulfonate ester. The first successful approaches to the synthesis of the heretofore unknown trichloromethanesulfonates and dichloromethanesulfonates are reported. Introduction Phenyl methanesulfonate induces the condensation of ptoluenethiol and primary alcohols to afford sulfides (1). In pursuit of a variation of that approach to sulfide synthesis, phenyl benzenethiosulfonate was allowed to react with alkoxide ions. The expected sequence involved transformation of the thiosulfonate into a sulfonate ester and a thiolate anion with sequential thiolate anion alkylation by the newly formed sulfonate ester. Equation [I] depicts the outcome of such an experiment.

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