Selective hydrolysis of perfluorochloromethylsulfenyl chlorides

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

“…CF 3 SSPh has been previously obtained in one or two steps from very toxic reagents like trifluoromethanesulfenyl chloride (CF 3 SCl) [24][25][26] or bis(trifluoromethyl) trisulfide (CF 3 SSSCF 3 ). 27 In our experiment, it could result either from the reaction of thiophenol with CF 3 SO 2 SCF 3 (formed in situ by disproportionation of trifluoromethanesulfinic acid, as reported for nonfluorinated sulfinic acids 28 ) or, more probably, from the disproportionation of the thiosulfinate CF 3 S(O)SPh, 8 formed in situ from trifluoromethanesulfinic acid and thiophenol (Scheme 2).…”

“…Then, 4h was added and, after stirring as long as previously, 1h was obtained in the same yield. The same result was obtained when pure trifluoromethanesulfonyl bromide (8), previously prepared from bromine and an aqueous solution of 3, 44 was treated with 4h.…”

“…CF 3 SSPh has been previously obtained in one or two steps from very toxic reagents like trifluoromethanesulfenyl chloride (CF 3 SCl) − or bis(trifluoromethyl) trisulfide (CF 3 SSSCF 3 ) ) or, more probably, from the disproportionation of the thiosulfinate CF 3 S(O)SPh, formed in situ from trifluoromethanesulfinic acid and thiophenol (Scheme ).

2 Reaction of Thiols with Triflic Anhydride in the Absence of a Base

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“…This strategy was successful (the results will be given in future papers), but first, we had to prepare such reagents. At the moment, only one perfluorinated trifluoromethaneselenosulfonate (CF 3 SO 2 SeCF 3 ) has been described (from a surprising isomerization of CF 3 Se(O)OSCF 3 ) and only few trifluoromethanethiosulfonates, essentially CF 3 SO 2 SPh and CF 3 SO 2 SCF 3 , have been synthesized. Another one (CF 3 SO 2 −S−CCl 2 −CO−NPh i Pr) has been claimed to exhibit herbicidal properties .…”