Reactions of Hexafluoroacetone with Sulfur-Containing Compounds

Abstract

Reactions of hexafluoroacetone with simple alkyl sulfides were studied. With trimethylene sulfide, a concerted additionreaction resulted in the formation of a six-membered ring, (CF3)2COSCH2CH2CH2; with tetramethylene sulfide, dimethyl sulfide, or dimethyldisulfane, insertion into the a position occurred to give SCH[C(OH)(CF3)2]CH2CH2CHC(OH)(CF3)2, HO(CF3)2CCH2SCH2C(CF3)2OH, and HO(CF3)JCCH2SSCH2C(CF3)2OH, respectively. With thiophosphoryl chloride, where no a-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 NH2behave as primary aliphatic amines in their reactions with hexafluoroacetone; e.g., with H2N(CF3)COCH2CH2O and H2N(CF3)CSCH2CH2S, (CF3)2C=N(CF3)C0CH2CH20, (CF3)2C=N(CF3)CSCH2CH2S, and HO(CF3)2CNH(C-F3)CSCH2CH2S were obtained. No reaction was observed when a sulfur-phosphorus mixed ligand such as SCH2C- H2SPSCH2CH2SPSCH2CH2S or ethylene sulfide was reacted with hexafluoroacetone. When (CF3)2C(OH)SH was mixed with SC12 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 C1F in Pyrex glass to give (CF3)2C(OH)2. © 1980, American Chemical Society. All rights reserved.