Some Chemistry of Fluorinated Octahedral Sulfur Compounds

Abstract

Reactive nucleophiles such as C6F5SLi and CF3SLi readily attack cis-SF4(OCF3)2, SF5CI, CF3SF4CI, and cis- CF3SF4CF3 to form (Rf)2S3 and (Rf)2S2 (Rf = CeFs, CF3) plus CF20, RpSCl, CF3C1, and CF4, respectively. With CeFsLi,cw-SF4(OCF3)2 yields (C6Fs)2SF2, (CsFsSO, CeFs, and CF20; SF5CI gives (C6F5)SO and C6F6; CF3SF4CI forms (C6Fs)2S, CeFe, and CF3C1; and C1T-CF3SF4CF3 produces CF3SF2CF3 and CsFe. With LiN=C(CF3)2, ew-SF4X2 (X =OCF3, OS02F) gives SF3X=NCF(CF3)2; m-CF3SF4CF3 forms (CF3)2SF2=NCF(CF3)2 and (CF3)2SF2=NC(CF3)2-N=C(CF3)2; and [formula ommited]. yields (CF3)2CFN=SF2(CF2)2SF2=NCF(CF3)2. In reactions with alcohols, ROB (R = (CF3)2(CB3)C, CB3(CB2)8CB2, (CB3)3C, C6B5CB2CB2), dv-SF4(OCF3)2 produces the respective olefins (CF3)2-C=CB2, CB3(CB2)7CB==CB2, (CB3)2C=CB2, and C6B5CB=CB2. © 1978, American Chemical Society. All rights reserved.