- BEITRAEGE ZUR CHEMIE DER SCHEFELHALOGENIDE 15. DICHLOR-FLUOR-TRIFLUOROMETHYLSULFURAN, CF3SCl2F
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The preparation of the sulfurane CF3SCl2F is reported.Upon sublimation of the sulfonium salt CF3SCl2+AsF6- the compounds CF3SCl2F and AsF5 coexist in the gaseous phase.After trapping AsF5 as KAsF6 extremely instable CF3SCl2F is isolated and characterised by IR-, Raman- and 19F-NMR-spectroscopy.
- Minkwitz, Rolf,Nass, Ulrike
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- Bis, N-Chlorobis(F-methyl)sulfimide, and N-Fluorobis(F-methyl)sulfimide
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The first member of a new class of stable sulfimides, bis, (CF3)2S=NN=S(CF3)2, results from the photolysis of (CF3)2S=NCl.The latter is prepared by reacting (CF3)2S=NH with ClF in the presence of CsF.Under similar conditions, (CF3)2S=NH reacts with SF4 to give (CF3)2S=NF.
- Kumar, Ramesh C.,Shreeve, Jean'ne M.
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- Copper(I)-mediated direct trifluoromethylthiolation of allylic halides with elemental sulfur and (trifluoromethyl)trimethylsilane
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Abstract A new method has been developed for the copper-mediated trifluoromethylthiolation of allylic halides by using potassium fluoride, elemental sulfur, and (trifluoromethyl)trimethylsilane in anhydrous N,N-dimethylformamide. This protocol provides facile access to a variety of allylic trifluoromethyl thioethers in moderate to good yields under mild, ligand-free reaction conditions.
- Li, Jue,Wang, Peiqiang,Xie, Fei-Fei,Yang, Xi-Gang,Song, Xiao-Nan,Chen, Wei-Dong,Ren, Jiangmeng,Zeng, Bu-Bing
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supporting information
p. 3568 - 3571
(2015/06/08)
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- Metal-free oxidative trifluoromethylthiolation of terminal alkynes with CF3SiMe3 and elemental sulfur
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A metal-free oxidative trifluoromethyl-thiolation of terminal alkynes using readily available CF3SiMe3 and elemental sulfur at room temperature has been developed. This reaction provides an efficient and convenient method for the preparation of alkynyl trifluoromethyl sulfides bearing a wide range of functional groups. Preliminary investigation revealed that elemental sulfur instead of air acted as the oxidant.
- Chen, Chao,Chu, Lingling,Qing, Feng-Ling
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supporting information; experimental part
p. 12454 - 12457
(2012/09/05)
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- GASEOUS DIELECTRICS WITH LOW GLOBAL WARMING POTENTIALS
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A dielectric gaseous compound which exhibits the following properties: a boiling point in the range between about ?20° C. to about ?273° C.; non-ozone depleting; a GWP less than about 22,200; chemical stability, as measured by a negative standard enthalpy of formation (dHf0); a toxicity level such that when the dielectric gas leaks, the effective diluted concentration does not exceed its PEL; and a dielectric strength greater than air.
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- Photochemical Behaviour of (CF3S)2CS in Rare Gas Matrix
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Infrared spectra have been recorded of (CF3S)2CS in the gas and solid phase as well as isolated in noble gas matrix; the Raman spectra of the liquid have also been taken.The analyses of the spectra show that this compound consists of a complex mixture of conformers.By photolysis in a matrix with ligth of wavelength > 300 nm the distribution of the conformers changes and with light of wavelength > 530 nm this change can be reversed.The threshold for photochemical decomposition in the matrix is about 300 nm.The decomposition products consist of an equimolar mixture of CF3SCF3 and CS2. - Keywords: Bis(trifluormethyl)thiocarbonate, Vibrational Spectra, Comformers, Rare Gas Matrix, Photochemical Behaviour
- Schlosser, Karl,Willner, Helge
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p. 161 - 167
(2007/10/02)
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- Preparation of Perfluorinated Hexakis(alkylthio- and -seleno)ethanes
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The perfluorinated perhetero-substituted ethanes 2a - c are prepared by irradiation of the thiocarbonates 1a - c.Upon UV-irradiation (λmax = 300 nm) bis(trifluoromethyl) trithiocarbonate (1a) decomposes by a cage process to give carbon disulfide, trifluoromethyl- and trifluoromethylthiyl radicals.In the solvent cage these radicals partly dimerize producing 3.The formation of 2a is interpreted in terms of a competition between this combination process and trapping of trifluoromethyl radicals by 1a, forming 4a, which then dimerizes.A similar mechanistic pathway is pro posed for the formation of 2b and 2c.
- Schlosser, Karl
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p. 1083 - 1088
(2007/10/02)
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- Photochemical Behaviour of Bis(trifluoromethylthiyl)trithiocarbonate in Solution
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Bis(trifluoromethylthiyl))trithiocarbonate showes electronic transitions at 496 nm (n?*), 299 nm (??*) and 259 (n?*).Photolysis with 254 and 300 nm light at 200 and 309 K in pentane, and at 371 K in heptane yields a mixture of CS2 and perfluorinated compounds such as F3CSCF3, F3CSSCF3, (F3CS)3C-C(SCF3)3, (F3CS)2C=C(SCF3)2, (F3CS)3CH and F3CS-substituted solvent.The concentration of these newly formed products versus time of irradiation has been monitored.The primary photochemical process is the intramolecular decomposition into CS2 and F3CS and F3C radicals which dimerize in a solvent cage.The formation of (F3CS)3C-C(SCF3)3 is interpreted in terms of a competition between this combination process and trapping of trifluoromethyl radicals by (F3CS)2CS, forming (F3CS)3C, which subsequently dimerizes.On irradiation at 496 nm (n?*) no photochemical process has been observed. - Key words: Bis(trifluoromethylthiyl)trithiocarbonate, Electronic Spectra, Photochemical Behaviour, Tris(trifluoromethylthiyl)methyl Radical
- Schlosser, Karl
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p. 172 - 178
(2007/10/02)
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- Nucleophilic reactions of lithium bis(trifluoromethyl)sulfimide
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Lithium bis(trifluoromethyl)sulfimide, LiN=S(CF3)2, is a moderately stable precursor to several new bis(trifluoromethyl)sulfimides. With (CH3)3SiCl, CF3C(O)Cl, CNCl, CF3SO2F, ClSO2F(SO2Cl2), and OPF2Cl, (CH3)3SiN=S(CF3)2, CF3C(O)N=S(CF3)2, NCN=S(CF3)2, CF3SO2N=S(CF3)2, ClSO2N=S(CF3)2, and OPF2N=S(CF3)2 are formed. The bis[bis(trifluoromethyl)sulfimides] (CH3)2Si[N=S(CF3)2]2 and CO[N=S(CF3)2]2 result with (CH3)2SiCl2 and COCl2. With the exception of the carbonyl compound which is a stable white crystalline solid, all of the sulfimides are moderately stable liquids of low volatility.
- Morse, Stanley D.,Shreeve, Jean'ne M.
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p. 2169 - 2172
(2007/10/14)
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- High-pressure interaction of sulfur hexafluoride with carbon disulfide and carbonyl sulfide
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Sulfur hexafluoride has been found to react with carbon disulfide and carbonyl sulfide. At a minimum of 485° (1360 atm) with carbon disulfide the products are (CF3)2S, (CF3)2S2, carbon, and sulfur. Carbonyl sulfide reacts at 500° (270 atm) forming CF4, SOF2, and sulfur. No reaction takes place with carbon monoxide or carbon dioxide at conditions up to 500° (4000 atm). Graphite reacts at 500° (135 atm) forming CF4 and SF4 in a reaction which becomes nearly quantitative at 500° (4000 atm). When (CF3)2S2 is combined with carbon disulfide at 540° (4000 atm) the products include carbon, sulfur, and fluoroalkanes. The observed interaction of CO2, COS, and CS2 with SF6 can be best explained by an initial reaction which results in the formation of SF4, COF2 or CSF2, and sulfur.
- Hagen, Arnulf P.,Callaway, Bill W.
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p. 2825 - 2827
(2007/12/03)
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