Reactions of hexafluoroacetone with sulfur-containing compounds

Article abstract of DOI:10.1021/ic50208a018

Reactions of hexafluoroacetone with simple alkyl sulfides were studied. With trimethylene sulfide, a concerted addition reaction resulted in the formation of a six-membered ring, (CF₃)₂COSCH₂CH₂CH₂; with tetramethylene sulfide, dimethyl sulfide, or dimethyldisulfane, insertion into the α position occurred to give SCH[C(OH)(CF₃)₂]CH₂CH ₂CHC(OH)(CF₃)₂, HO(CF₃)₂CCH₂SCH₂C(CF ₃)₂OH, and HO(CF₃)₂CCH₂SSCH₂C(CF ₃)₂OH, respectively. With thiophosphoryl chloride, where no α-hydrogen is present, oxidative addition at sulfur (II) gave OC(CF₃)₂C(CF₃)₂OS=PCl₃, No reaction was observed with F-alkyl sulfides under the conditions used, with the exception that those with active functional groups such as NH₂ behave as primary aliphatic amines in their reactions with hexafluoroacetone; e.g., with H₂N(CF₃)COCH₂CH₂O and H₂N(CF₃)CSCH₂CH₂S, (CF₃)₂C=N(CF₃)COCH₂CH₂O, (CF₃)₂C=N(CF₃)CSCH₂CH₂S, and HO(CF₃)₂CNH(C-F₃)CSCH₂CH ₂S were obtained. No reaction was observed when a sulfur-phosphorus mixed ligand such as SCH₂C-H₂SPSCH₂CH₂SPSCH ₂CH₂S or ethylene sulfide was reacted with hexafluoroacetone. When (CF₃)₂C(OH)SH was mixed with SCl₂ and Cl₂, compounds such as HO(CF₃)₂CSSSC(CF₃)₂OH and HO(CF₃)₂CSSC(CF³)₂OH were formed, respectively. The latter two compounds as well as (CF₃)₂C(OH)SH, when reacted with SF₄, gave hexafluorothioacetone. (CF₃)₂C(OH)SH also was reacted with ClF in Pyrex glass to give (CF₃)₂C(OH)₂.