- Reactions of trifluoromethylthiocopper with halomethanes
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The reaction of trifluoromethylthiocopper with halomethanes, namely di-and triiodo-, dibromodichloro-, dibromochlorofluoro-, dibromo-difluoro-, bromochlorofluoro-, phenyltrichloro-, bromocyano-and dibromofluoro-methanes, has been investigated in detail. In addition to the expected compounds, the formation of unusual products such as bis (trifluoromethyl) trithiocarbonate, dimethyl (trifluoromethylthio) benzene, bis (trifluoromethylthio) fluoromethane, (trifluoromethylthio) carbonyl fluoride, carbon disulfide, carbon tetrachloride, trifluoromethylthio-benzoate, etc. was observed. In some cases, bis (trifluoromethylthio) mercury has been used instead of trifluoromethylthiocopper. The mechanism of formation of the various products and their mass spectral fragmentation behavior are described.
- Munavalli,Rossman,Rohrbaugh,Ferguson,Durst
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- Synthesis and biological screening of trifluoromethylthioarsenicals
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The title compounds have been prepared from the reaction of trifluoromethylthiocopper and alkyl mono- and di-haloarsines.This communication describes their synthesis, biological screening and mass spectral fragmentation behavior.
- Munavalli, S.,Rossman, D. I.,Rohrbaugh, D. K.,Ferguson, C. P.,Buettner, L.
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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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