- Mechanism of the metathesis between carbon tetrachloride and (η1-allyl)iron complexes. A radical chain reaction of overall five-thirds order
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Chemical, kinetic, and stereochemical studies of the metatheses between CCl4 and η-CpFe(CO)2CH2CH=CR2 (R = H, Me) show that the reaction proceeds via a radical chain mechanism that involves the generation of the initiating radicals by a prequilibrium homolysis of the iron-allyl bond in the starting material. The ultimate product is formed by an SH2′ reaction between ?CCl3 and η-CpFe(CO)2CH2CH=CR2. The reaction follows a rate law with an unusual 5/3 total order: rate = kobsd[η-CpFe(CO)2CH2CH= CH2][CCl4]2/3.
- Lee, Mei-Tsu,Waterman, Paul S.,Magnuson, Roy H.,Meirowitz, Randy E.,Prock, Alfred,Giering, Warren P.
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p. 2146 - 2149
(2008/10/08)
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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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- REACTION OF ALLYL HALIDES WITH HALOFORMS AND ALKALI UNDER THE CONDITIONS OF INTERPHASE CATALYSIS
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The reaction of allyl halides with haloforms and alkali in the presence of interphase transfer catalysts gives cyclopropanes and 4,4,4-trihalogeno-1-butenes.The latter are formed by nucleophilic substitution of the halogen in the allyl halide by the trihalogenomethyl anion.
- Mandel'shtam, T. V.,Kharicheva, E. M.,Labeish, N. N.,Kostikov, R. R.
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p. 2143 - 2148
(2007/10/02)
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