- Stille cross-coupling of secondary and tertiary α-(trifluoromethyl)-benzyl chlorides with allylstannanes
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A Stille cross-coupling reaction was developed that delivers for the first time trifluoromethyl-substituted homoallyl compounds from α-(trifluoromethyl)benzyl chlorides and allylstannanes. This reaction proceeds even with low catalyst loadings (1 mol%) vi
- Punna, Nagender,Harada, Kyosuke,Shibata, Norio
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supporting information
p. 7171 - 7174
(2018/07/05)
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- An efficient dehyrohalogenation method for the synthesis of α,β,β-trifluorostyrenes, α-chloro-β,β- difluorostyrenes and E-1-arylperfluoroalkenes
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Dehydrofluorination of 1-aryl-1,2,2,2-tetrafluoroethanes (ArCHFCF 3) and 1-aryl-1-chloro-2,2,2-trifluoroethane (ArCHClCF3) using lithiumhexamethyldisilazide (LHMDS) in tetrahydrofuran (THF) at room temperature produced 1,2,2-trifluorostyrene and 1-chloro-2,2-difluorostyrene, respectively, in very good isolated yields. Dehydrofluorination of 1,2,2,3,3,3-hexafluoro-1-phenyl-propane (PhCHFCF2CF3) and 1,2,2,3,3,4,4,4-octafluoro-1-phenyl-butane (PhCHFCF2CF 2CF3) using LHMDS produced the corresponding substituted olefins (1-phenyl-1,2,3,3,3-pentafluoroprop-1-ene and 1-phenyl-1,2,3,3,4,4,4- pentafluorobut-1-ene) in good yield and high E-selectivity. Dehydrofluorination of 1-chloro-1-phenyl-2,2,3,3,3-pentafluoropropane (PhCHClCF2CF 3) and 1-chloro-1-phenyl-2,2,3,3,4,4,4-heptafluorobutane (PhCHClCF2CF2CF3) produced a mixture of the corresponding E and Z olefins (PhCClCFCF3 and PhCClCFCF 2CF3) in good yield.
- Anilkumar,Burton, Donald J.
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p. 1174 - 1184
(2007/10/03)
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- Fungicidal compounds having a fluorovinyl-or fluoropropenyl-oxyphenyloxime moiety and process for the preparation thereof
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A fungicidal compound of formula (I) having a fluorovinye- or fluoropropenyl-oxyphenyloxime moiety and stereoisomers thereof are useful for protecting crops from fungal diseases: wherein, X is CH or N; Y is O or NH; R1is hydrogen, C1-4alkyl, or halogen-substituted C1-4alkyl, R2is a phenyl group optionally carrying one or more substituents selected from the group consisting of C1-4alkyl, C1-4alkoxy, methylenedioxy and halogen; or a naphthyl group; and R3is hydrogen or CF3.
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- Antifungal azole derivatives having a fluorinated vinyl group and process for preparing same
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An antifungal compound of formula (I) or a pharmaceutically acceptable salt thereof: wherein: X is CH or N; Y is O, R1and R2are each independently F or Cl; R3is a thiophenyl, naphthyl, or phenyl group, the phenyl group being optionally substituted with one or more substituents selected from the group consisting of C1-4alkyl, C1-4haloalkyl, C1-4alkoxy, methylenedioxy and halogen; and R4is H or trifluoromethyl.
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- Catalytic phosphorylation of polyfluoroalkanols 17. * Synthesis and the stereochemistry of tris(α-trifluoromethylbenzyl) phosphates
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Catalytic phosphorylation of α-trifluoromethylbenzyl alcohols with POCl3 taken in a ratio of 3 : 1 under particular temperature conditions afforded predominantly symmetrical tris(α-trifluoromethylbenzyl) phosphates. The latter were obtained as mixtures of two diastereomers with a statistical ratio of the components.
- Goryunov,Petrovskii,Shcherbina,Zakharov
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p. 1085 - 1087
(2007/10/03)
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- MECHANISMS OF FREE-RADICAL REACTIONS. XX. REACTIVITY IN THE FREE-RADICAL HALOGENATION REACTIONS OF ARYLFLUOROALKANES
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The free-radical chlorination and bromination of meta- and para-substituted benzyl fluorides and 1,1-difluoro-2-phenylethane and also the chlorination of 1-fluoro-2-arylethanes by phenylchloroiodonium chloride and the bromination of meta- and para-substituted benzyl bromides were studied by the method of competing reactions.In all cases a good correlation is observed between log krel and the Brown ?+ constants.In cases where change in the reactivity in the transition from one reaction series to another is due mainly to the polar effect of the substituent whilethe selectivity is measured in relation to the polar effect direct relationships are observed between the reactivity and the selectivity.
- Dneprovskii, A. S.,Eliseenkov, E. V.
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p. 711 - 719
(2007/10/02)
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- FLUORAL HEMIACETAL, A NEW REAGENT FOR AROMATIC TRIFLUORO ALKYLATION
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α trifluoroalkylation of benzene was carried out in various conditions (catalyst and solvent) by using the readily available fluoral hemiacetal 1 as reagent.The good selectivity observed during the reaction was explained by the HSAB concept.
- Guy, A.,Lobgeois, A.,Lemaire, M.
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p. 361 - 366
(2007/10/02)
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- Proton-Transfer Reactions. 4. Near-Unity Kinetic Isotope Effects for Hydron Exchange and Dehydrofluorination Reactions
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Rates and isotope effects are reported for benzylic hydron exchange and dehydrofluorination reactions of C6H5CiHClCF3 (I) and C6H5CiH(CF3)2 (II) in alcoholic sodium alkoxide solutions.Reactions of I were studied in ethanol and isotop
- Koch, Heinz F.,Dahlberg, Donald B.,Lodder, Gerrit,Root, Karen S.,Touchette, Nancy A.,et al.
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p. 2394 - 2398
(2007/10/02)
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- MECHANISMS OF FREE-RADICAL REACTIONS. XIII. MECHANISM AND SELECTIVITY OF THE FREE-RADICAL HALOGENATION OF ALKYL AROMATIC HYDROCARBONS WITH FLUOROALKYL SUBSTITUENTS
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The free-radical chlorination and bromination of 1-fluoro-2-arylethanes and 1,1,1-trifluoro-2-arylethanes was studied by the method of competing reactions.In all cases a good correalation between log krel and the Brown ?+ constants was observed.The variation of the selectivity in the transition from one reaction series to the other indicates that two independent factors which determine the reactivity (the change in the dissociation energy of the C-H bond and the polar effect of the substituents) have a simultaneous effect.
- Dneprovskii, A. S.,Eliseenkov, E. V.,Mil'tsov, S. A.
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p. 317 - 324
(2007/10/02)
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- Proton-Transfer Reactions. 1. Partitioning of Carbanion Intermediates Generated by Reactions of Alkenes with Alkoxide Ions in Alcohol
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Nucleophilic reactions with sodium alkoxide in alcohol have been studied with various gem-difluoroalkenes of general structure C6H5CR=CF2.Rates and Arrhenius paramaters 3 (M -1 s-1) at -50 deg C, ΔH* (kcal mol-1), and ΔS*, (eu)> are respectively: R = -CF3 (II), 105, 9, and -23; -CF2Cl (III), 135, 10 and -19; -CF2CF3 (IV), 40.6, 9, and -23; -CF2H (V), 3.63, 11, and -19.Reactions proceed via carbanion intermediates, and the products from reaction with ca. 0.3 N sodium ethoxide in ethanol are: II, 85percent vinyl ether and 15percent saturated ether; III, 100percent allylic ether; IV; 74percent vinyl ether, 22percent allylic ether, and 4percent saturated ether; V, >98percent allylic ether.The observed product distribution suggest the following order of leaving group ability for fluoride in different environments: -CF2H >> -CF2OR > -CF2CF3 >> -CF3.Solvent protonation of the carbanion is apparently slower than fluoride ion ejection from all groups studied other than trifluoromethyl.Product isotope effects (PIE), kH/kD, for the protonation of the carbanion generated from II by reaction in ethanol are 1.50 (-78 deg C) and 1.86 (20 deg C) and by reaction in methanol are 1.22 (-78 deg C).
- Koch, H. F.,Koch, J. G.,Donavan, D. B.,Toczko, A. G.,Kielbania, A. J.
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p. 5417 - 5423
(2007/10/02)
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