- Reactions of hexafluoroacetone with sulfur-containing compounds
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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.
- Mir, Qui-Chee,Shreeve, JeaN'Ne M.
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- Spectroscopy of hexafluorothioacetone, a blue gas
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In this study, the vibrational and electronic spectra of hexafluorothioacetone, a novel blue gas, were explored for the first time. Despite the emergence of several problems, complete analysis of the vibrational spectra has been obtained and the UV-visible absorption spectra has been successfully surveyed.
- Clouthier,Joo
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- 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
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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.
- Petrov, Viacheslav A.,Marshall, Will
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experimental part
p. 1144 - 1155
(2011/02/16)
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- Methyl-halogenated Allyl Methyl Sulfoxides and Sulfones and the Synthesis of Halogenated Sulfines
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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.
- Holoch, Jan,Sundermeyer, Wolfgang
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p. 269 - 278
(2007/10/02)
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- Bis(trifluoromethyl)sulfine, (CF3)2C=SO: New Syntheses and Some Reactions
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New methods for the synthesis of bis(trifluoromethyl)sulfine (sulfoxide) (9) are reported.Pyrolysis, photolysis, and hydrolysis of the compound were investigated as well as the typical behaviour in reactions with the thiocarbonyl group (thiophosgene), with anthracene (Diels-Alder addition) and halogens.
- Elsaesser, Andreas,Sundermeyer, Wolfgang
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p. 4553 - 4560
(2007/10/02)
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- Preparation of hexafluoroisobutylene
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The process for preparing hexafluoroisobutylene which comprises reacting, at elevated temperatures, ketene or a ketene-generating compound with hexafluorothioacetone. Hexafluoroisobutylene is a known valuable monomer, which forms polymers of exceptional thermal, chemical and mechanical properties, particularly when copolymerized, such as with vinylidene fluoride.
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- Pesticidal compositions containing phosphoric esters and divalent sulphur compounds
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Pesticidal composition comprising: a pesticidal, phosphoric ester the molecule of which has at least one alkyl group of 1 to 3 carbon atoms, 0.05 to 10% of an agent stabilizing the said ester against decomposition by protonisation, together with adjuvants characterized in that the stabilizing agent comprises at least one sulphur compound containing per molecule at least one divalent sulphur atom of which one valence is bonded to an atom chosen from sulphur, carbon, nitrogen, hydrogen, and metals capable of giving a salt, the other valence being bonded to an atom chosen from hydrogen, the carbon atom already noted, a second carbon atom, the nitrogen atom already noted, a second nitrogen atom, the metal atom already noted in the case of a metal of valence greater than one, a second atom of metal and oxygen when the first valence is not attached to an atom of hydrogen, the proportion of sulphur calculated with reference to the weight of the sulphur compound being between 5 and 99%. Process for stabilizing a phosphoric ester of which the molecule possesses at least one alkyl group containing 1 to 3 carbon atoms characterized in that there is added to the phosphoric ester or to a mixture which contains it, 0.05 to 10% calculated on the weight of the phosphoric acid ester of an agent capable of stabilizing the said phosphoric ester against protonisation and comprising at least one sulphur compound such as that defined thereupon.
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