- A Novel Laser-induced Synthesis of 1,1-Dichloroethylene from 1,1-Dichloroethane
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The laser-induced photochlorination of 1,1-dichloroethane followed by its dehydrochlorination has been examined in a flow reactor under normal pressure at 25 - 200 deg C, which has been proved to be a novel direct synthesis of vinylidene chloride.
- Oshima, Yoshito,Iguchi, Kayoko,Tominaga, Hiro-o,Koda, Seiichiro
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- PROCESS FOR THE PRODUCTION OF CHLORINATED METHANES
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The present invention provides processes for the production of chlorinated methanes via the direct chlorination of methane. The processes include a dehydrochlorination and/or chlorination step that converts up to 100% of the higher chlorinated alkanes in a process stream from the methane chlorination reaction into more highly chlorinated alkanes. These more highly chlorinated alkanes can be easily removed from the process stream. The use of a cost effective feedstream of crude methane is thus rendered possible, without additional capital expenditure for the sophisticated separation equipment required to separate ethane and other hydrocarbon components from the methane feed.
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Paragraph 0062; 0063
(2017/04/11)
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- A study of trichloroethylene hydrofluorination using a kinetic model
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The kinetic features of catalytic hydrofluorination of trichloroethylene and 2-chloro-1,1,1-trifluoroethane on chromium fluoride/magnesium fluoride catalyst were studied. The effect of pressure and addition of various components of the reaction mixture at the reactor inlet was studied using the developed model.
- Dmitriev,Trukshin,Smykalov
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p. 771 - 776
(2007/10/03)
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- Catalytic decomposition of alkyl chloroformates by hexabutylguanidinium chloride
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Hexabutylguanidinium chloride (0.5 molar %) efficiently decomposes alkyl chloroformates into chlorides, with low alkenes formation, via a S(N)2 mechanism as demonstrated from substituents effects and asymmetric chloride synthesis.
- Foulon, Frederique,Fixari, Bernard,Picq, Dominique,Le Perchec, Pierre
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p. 3387 - 3390
(2007/10/03)
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- Heterogeneous catalyzed synthesis of 1,1,1,2-tetrafluoroethane from 1,1,1,2-tetrachloroethane - thermodynamics and reaction pathways
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1,1,1,2-Tetrachloroethane and its fluorinated derivatives, as well as trichloroethene, were fluorinated by hydrogen fluoride in the presence of a preconditioned chromia catalyst.The reaction pathways were derived under different conditions.Fluorinated haloalkanes are formed both by dehydrochlorination/hydrofluorination mechanisms as well as a chlorine/fluorine exchange mechanism.Thus, beside fluorinated alkanes considerable amounts of halo-olefins occur in the product mixture.A survey is given of the reaction pathways showing their dependence on the reaction conditions.These are discussed with respect to the calculated thermodynamic data. - Keywords: Heterogenous catalysis; Chlorofluorocarbon; Hydrofluorocarbon; Halocarbon; Fluorination; HFC-134a formation
- Kohne, A.,Kemnitz, E.
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p. 103 - 110
(2007/10/03)
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- EFFECT OF STRUCTURAL FACTORS ON THE REACTIVITY OF C-H BONDS IN CHLOROALKANES IN REACTION WITH A CHLORINE ATOM AND WITH THE COMPLEX OF THE CHLORINE ATOM WITH o-DICHLOROBENZENE
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The competition reaction of dichloroethanes, 1,1,2-trichloroethane, and 1-chlorobutane in o-dichlorobenzene was investigated over a wide range of temperature (-20 to +80 deg C) and solvent concentrations (0-7 M).The selective action of the solvent is consistent with a mechanism involving attack on the C-H bonds of the chloroalkanes by free chlorine atoms and by ArH -> Cl ? complexes.Equations were obtained for the selectivity of the investigated processes on the basis of the proposed mechanism.The parameters of the obtained equations reflect the relative reactivityof the C-H bonds during chlorination by chlorine atoms and ArH -> Cl complexes and also the capacity of the solvent for the complex formation.It was shown that the reactivities of the C-H bonds during attack by chlorine atoms and ArH -> Cl complexes are described by a correlation equation including the inductive effect of the substituents on the reaction center and also stabilization of the obtained radicals through conjugation and hyperconjugation effects.
- Aver'yanov, V. A.,Zarytovskii, V. M.,Shvets, V. F.
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p. 1832 - 1839
(2007/10/02)
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- Kinetics of Cl(2PJ) Reactions with the Chloroethanes CH3CH2Cl, CH3CHCl2, CH2ClCH2Cl and CH2ClCHCl2
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The kinetics of the reactions Cl(2PJ) + RHCl -> RCl + HCl were investigated over the temperature range 257-426 K for RHCl = CH3CH2Cl (k2), CH3CHCl2 (k3), CH2ClCH2Cl (k4), and CH2ClCHCl2 (k5).Cl(2PJ) was produced by 355 nm pulsed laser photolysis of Cl2 and monitored by time-resolved resonance fluorescence spectroscopy.The data are adequately described by the following Arrhenius expressions (units are cm3 molecule-1 s-1, errors are 2? and refer to precision only): k2=(2.34+/-0.42)E-11exp, k3=(8.19+/-1.84)E-12exp,k4=(2.21+/-0.51)E-11exp, and k5=(4.88+/-1.41)E-12exp.Under some experimental conditions evidence for Cl(2PJ) regeneration via a secondary reaction was observed.At 258+/-1 K, deviations of Cl(2PJ) temporal profiles from first-order behavior were attributable to the reactions RCl + Cl2 -> RCl2 + Cl(2PJ)(kj).By modeling the observed C(2PJ) temporal profiles, we found the rate constant kj to lie in the range (5-12)E-14 cm3 molecule-1 s-1 for all RCl investigated.The reactivity trends observed in reactions of Cl2PJ) with C2HXCl(6-x), x=3-6, are discussed.
- Wine, P. H.,Semmes, D. H.
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p. 3572 - 3578
(2007/10/02)
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- EFFECT OF o-DICHLOROBENZENE ON THE SELECTIVITY OF PHOTOCHLORINATION OF 1,1,2-TRICHLOROETHANE
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The selective action of o-dichlorobenzene on the photochlorination of 1,1,2-trichloroethane at 20 deg C was investigated.It was shown that the selectivity of the process is determined exclusively by the / ratio.The obtained data confirm the scheme for the selective action of aromatic solvents which presupposes the formation of ArH Cl ? complexes.The latter act together with the chlorine atoms as attacking particles during radical chlorination of the C-H bonds, and their concentration is determined by the steady state and not by the complexing equilibrium.
- Aver'yanov, V. A.,Zarytovskii, V. M.,Shvets, V. F.,Treger, Yu. A.
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p. 2229 - 2231
(2007/10/02)
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