- Reactions of cycloalkanecarboxylic acids with SF4. II. Fluorination of gem-dichlorocyclopropanecarboxylic acids with SF4
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Treatment of gem-dichlorocyclopropanecarboxylic acids with SF4 yields many rearranged products, i.e. 1,1-difluoro-substituted olefins.The mechanism of the rearrangement is discussed. - Keywords: Cycloalkanecarboxylic acids; Sulphur tetrafluoride; Rearrangement mechanism; Stereochemistry; NMR spectroscopy; IR spectroscopy
- Pustovit, Yu. M.,Ogojko, P. I.,Nazaretian, V. P.,Rozhenko, A. B.
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p. 231 - 236
(2007/10/02)
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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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- REDUCTION OF SOME POLYHALOGENATO- AND POLYACETOXY-ALLYLIC COMPOUNDS USING TRIBUTYLTIN HYDRIDE IN THE PRESENCE OR ABSENCE OF A PALLADIUM CATALYST. II.REDUCTION OF 1,1,1,4-TETRACHLOROBUT-2-ENE
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The radical tributyltin hydride reduction of 1,1,1,4-tetrachlorobur-2-ene yields a mixture of the expected 1,1,4-trichlorobut-2-ene and 1,1,4-trichlorobut-1-ene resulting from preferential abstraction of a chlorine atom from the trichloromethyl group.The palladium-catalyzed reduction follows an entirely different course, giving 1,1-dichlorobutadiene exclusively and quantitatively.The palladium-catalyzed reaction involves an oxidative addition-β-elimination process leading to dichlorobutadiene and a dichloropalladium(II) species.Tributyltin hydride reduction of palladium(II) to palladium(0) completes the catalytic cycle.
- Guibe, F.,Xian, Yang Ting,Balavoine, G.
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p. 267 - 272
(2007/10/02)
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- CHEMISTRY OF DIENES AND THEIR DERIVATIVES. XIX. DIRECTION OF THE LOW-TEMPERATURE CHLORINATION OF 1-CHLORO-1,3-BUTADIENE (α-CHLOROBUTADIENE) IN THE PRESENCE OF AN INHIBITOR OF RADICAL REACTIONS
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During the low temperature (-20 to 0 deg C) chlorination of α-chlorobutadiene (94-95 deg C conversion) in the presence of tert-butylpyracatechol 1,1-, 1,2- and 1,4-dichloro-1,3-butadienes, 3,4,4- and 1,3,4-trichloro-1-butenes, 1,1,4-trichloro-2-butene, and the products from further chlorination of the 1,1- and 1,2-dichloro-1,3-butadienes (a mixture of 1,1,3,4- and 1,2,3,4-tetrachloro-1-butenes) are formed in ratios 1.6:0.5:21.8:6.5:50.2:13.7:5.7.Variation of the temperature in the investigated range does not have a significant effect on the ratios of the chlorination products.
- Avagyan, S. P.,Airapetyan, R. Kh.,Kaplanyan, E. E.,Mkryan, G. M.
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