1490-33-1Relevant articles and documents
Reactions of hexafluoroacetone with sulfur-containing compounds
Mir, Qui-Chee,Shreeve, JeaN'Ne M.
, p. 1510 - 1514 (1980)
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.
Martin
, p. 2944,2946 (1964)
Remarkable effect of metal fluoride catalyst on reaction of hexafluoropropene, sulfur and vinyl ethers. Convenient synthesis of 2,2-bis(trifluoromethyl)-4-R-thietanes, 3,3-bis(trifluoromethyl)-5-R-1,2- dithiolanes and 2,2-bis(trifluoromethyl)-4-R-1,3-dithiolanes
Petrov, Viacheslav A.,Marshall, Will
experimental part, p. 1144 - 1155 (2011/02/16)
It was demonstrated that the outcome of the reaction of hexafluoropropene, sulfur and vinyl ether strongly depends on the catalyst and reaction conditions. The reaction of HFP and Sx leading to the formation of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1) when it is catalyzed by CsF, proceeds under milder conditions and is easier to control compared to KF catalyzed process. The order of addition of reagents plays a crucial role on the outcome of the reaction. For example, the addition of vinyl ether to pregenerated solution of 1 in DMF solvent results in slow reaction, leading to the corresponding 2,2-bis(trifluoromethyl)-4-R-thietanes in 8-91% yield, and it is catalyzed by either by KF or CsF. The addition of second mole of sulfur to the solution of 2,2-bis(trifluoromethyl)-4-R-thietanes in the presence MF catalyst leads to insertion of sulfur into thietane ring with the formation of the corresponding cyclic disulfides-3,3-bis(trifluoromethyl)-5-R-1,2- dithietanes. On the other hand, the addition of second mole of sulfur to the solution of 1 in DMF in the presence of CsF catalyst, followed by addition of vinyl ether results in exothermic reaction, and it produces the corresponding 2,2-bis(trifluoromethyl)-4-alkoxy-1,3-dithiolanes in good yield. It was also demonstrated that 2,2-bis(trifluoromethyl)-4-R-thietanes can undergo disproportionation under action of fluoride anion, producing a mixture of the corresponding 1,2-dithiolane and CF2C(CF3)CH 2CFHOR. The nucleophilic attack of fluoride anion in this case proceeds selectively on the carbon of the thietane ring, bearing alkoxy group. The structure of 2,2-bis(trifluoromethyl)-4-R-thietanes forming as the result of 2 + 2 cycloaddition reaction between hexafluorothioacetone generated in situ from dimer 1 and vinyl ether was firmly supported by single crystal X-ray diffraction data, obtained for thietane bearing t-BuO-group.
Methyl-halogenated Allyl Methyl Sulfoxides and Sulfones and the Synthesis of Halogenated Sulfines
Holoch, Jan,Sundermeyer, Wolfgang
, p. 269 - 278 (2007/10/02)
Allyl methyl sulfoxides R1R2R3C-S(O)-CH2CH=CH2 1a-7a (R1, R2, R3 = H, F, Cl, CF3) as well as the corresponding sulfones 1b-7b were synthesized.The sulfoxides substituted at the methyl group are in equilibrium with the allyl sulfenates R1R2R3-S-OCH2CH=CH2 depending on temperature and kind of substitution.By pyrolysis of the sulfoxides 2a, 3a, 4a, and 7a the sulfines Cl2C=SO and (CF3)2C=SO could be prepared, and evidence for the existence of the sulfines ClFC=SO and F2C=SO could be obtained.The new pentenes 12 and 14 are described.
