Stable fluorinated sulfuranes and sulfurane oxides. Synthesis and reactions

Article abstract of DOI:10.1021/ic50186a029

Bis(trifluoromethyl) sulfide, tetrafluoro-1,3-dithietane, and bis(trifluoromethyl) sulfoxide undergo oxidative addition when photolyzed with trifluoromethyl hypochlorite to form a new family of sulfuranes, bis(trifluoromethyl)bis(trifluoromethoxy)sulfurane (1) and tetrafluoro-1,3-tetrakis(trifluoromethoxy)dithietane (3), and of sulfurane oxides, bis(trifluoromethyl)bis(trifluoromethoxy)sulfurane oxide (2). Compounds 1 and 2 are hydrolyzed to bis(trifluoromethyl) sulfoxide and bis(trifluoromethyl) sulfone, respectively. Pyrolysis of 1, 2, or 3 gives bis(trifluoromethyl) sulfide, bis(trifluoromethyl) sulfoxide, and tetrafluoro-1,3-dithietane, respectively, plus bis(trifluoromethyl) peroxide. With primary amines, 1 and 2 yield N-alkylbis(trifluoromethyl)sulfimides and sulfoxyimides, and with N,N′-diethylaminotrimethylsilane, imine formation occurs. Sulfurane oxide 2 forms a new type of stable sulfurane oxide (4), bis(trifluoromethyl)bis(hexafluoroisopropylidenimido)sulfurane oxide, with lithium hexafluoroisopropylidenimine. Sulfurane 1 acts in a similar manner with the nucleophile but the sulfurane 5 is not isolated. Compounds 1 and 2 form α,α,α-(trifluoromethyl)anisole derivatives with substituted phenols. Secondary and tertiary alcohols are dehydrated by 1 or 2 to olefins but symmetrical alkyl ethers result when primary alcohols are reacted.