Bis(perfluoroalkyl)sulfur oxyimines and silver bis(trifluoromethyl)sulfur oxyimine

Abstract

The first bis(perfiuoroalkyl)sulfur oxyimines, (CF3)2S(0)NH, CF3(C2Fa)S(0)NH, and (C2F5)2S(0)NH, have been synthesized by the reaction of ammonia with bis(perfluoroalkyl)sulfiir oxydifluorides. As typical of the compounds in the above series, the reactions of bis(trifluoromethyl)sulfur oxyimine have been investigated to produce the new compounds (CF3)2-S(0)NSCF3, (CF3)2S(0)NCN, (CF3)2S(0)NS(0)CF3, (CF3)2S(0)NC(0)CF3, (CF3)2S(0)NSi(CH3)3, and AgNS(0)(CF3)2.The last compound reacts with CH3I and CU to give (CF3)2S(0)NCH3 and (CF3)2S(0)NC1. With the exception of the silver salt which is a solid, these compounds are colorless liquids which have been characterized by infrared, nmr, and mass spectra as well as elemental analyses and vapor pressure data.Recently there has been considerable interest in the chemistry of compounds containing the sulfur oxyimine moiety >S 3 N-are grateful to Mr. R. A. De Marco for mass spectra. J. M. S. thanks the Alfred P. Sloan Foundation for a fellowship.

Bis(trifluoromethyl)sulfimide, bis(trifluoromethyl)-N-alkylsulfimides, and bis(trifluoromethyl)-N-alklysulfoxyimides

“…6 Also, we find that, in the presence of a primary amine, the reaction of ammonia and bis(trifluoromethy1)sulfur difluoride does occur readily to form the stable bis(trifluoromethy1)sulfimide, (CF~)ZS=NH.~ Oxidation of the latter with MCPBA at low temperature gives bis(trifluoromethy1)sulfoxyimide which was reported previously.6 discoloration occurs and lower yields result. A qualitative comparison of the hydrolytic stability of these compounds shows that the ease of hydrolysis decreases in the order S F 4 > CF3SF3 > (CF3)2SF2.…”

“…6 The new method is preferred since it involves a procedure with fewer steps. In the case where R = i-CqH7.…”

Bifluoride Ion Mediated SuFEx Trifluoromethylation of Sulfonyl Fluorides and Iminosulfur Oxydifluorides

“…[7] We found only nine examples of related bis(trifluoromethyl)sulfur oxyimine (3)c ompounds in the literature; [19] each was synthesized primarily by the alkylation of bis(trifluoromethyl)sulfur oxyimine (CF 3 ) 2 S(O)=NH (1), or the silver salt (CF 3 ) 2 S(O)=NAg(2;F igure 1C). [7] We found only nine examples of related bis(trifluoromethyl)sulfur oxyimine (3)c ompounds in the literature; [19] each was synthesized primarily by the alkylation of bis(trifluoromethyl)sulfur oxyimine (CF 3 ) 2 S(O)=NH (1), or the silver salt (CF 3 ) 2 S(O)=NAg(2;F igure 1C).…”

“…[7] We found only nine examples of related bis(trifluoromethyl)sulfur oxyimine (3)c ompounds in the literature; [19] each was synthesized primarily by the alkylation of bis(trifluoromethyl)sulfur oxyimine (CF 3 ) 2 S(O)=NH (1), or the silver salt (CF 3 ) 2 S(O)=NAg(2;F igure 1C). [7] Using am odified protocol with as light excess of TMSCF 3 (2.2 equiv), full consumption of the iminosulfur oxydifluoride starting materials was observed (determined by 19 FNMR analysis), giving the target bis(trifluoromethyl)sulfur oxyimine products 3a-3r in mostly excellent yields (Scheme 2). [7] Using am odified protocol with as light excess of TMSCF 3 (2.2 equiv), full consumption of the iminosulfur oxydifluoride starting materials was observed (determined by 19 FNMR analysis), giving the target bis(trifluoromethyl)sulfur oxyimine products 3a-3r in mostly excellent yields (Scheme 2).…”

Bifluoride Ion Mediated SuFEx Trifluoromethylation of Sulfonyl Fluorides and Iminosulfur Oxydifluorides

“…TheS uFEx trifluoromethylation protocol with iminosulfur oxydifluorides to access the scarcely known bis(trifluoromethyl)sulfur oxyimines 3 was next explored. [7] We found only nine examples of related bis(trifluoromethyl)sulfur oxyimine (3)c ompounds in the literature; [19] each was synthesized primarily by the alkylation of bis(trifluoromethyl)sulfur oxyimine (CF 3 ) 2 S(O)=NH (1), or the silver salt (CF 3 ) 2 S(O)=NAg(2;F igure 1C). [19a] Aselection of iminosulfur oxydifluorides (4a-4r)were prepared from the reaction of O = SF 4 gas with the corresponding primary amines under SuFEx conditions.…”