- Allylic isomerization of dichlorobutenes catalyzed by iron-containing nanoparticles stabilized in polymeric matrices
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Iron-containing clusters obtained by the decomposition of iron complexes in a solution-melt of a polymeric matrix exhibit catalytic activity in the isomerization of dichlorobutenes. The activity of the clusters stabilized in the polytetrafluoroethylene and polyethylene matrices depends on the nature of the stabilizing matrix and the content of the metal in it, i.e., on the size and structure of the cluster, and substantially exceeds the activity of supported metals and powders The clusters in the polytetrafluoroethylene matrix are more active than those in polyethylene. The dependence of the catalytic activity on the metal content has an extreme character, and for the polyethylene matrix it achieves a maximum at a metal content of ~10%. In catalysts with this composition, the particle size increases to 4-5 nm, and the distance between them is shortened, on the average, to 10 nm, which leads to interaction of the cluster particles with each other.
- Zagorskaya,Zufman,Rostovshchikova,Smirnov,Gubin
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- PROCESS FOR PRODUCING 1,2,3,4-TETRACHLOROHEXAFLUOROBUTANE
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The present invention provides a process for producing 1,2,3,4-tetrachlorohexafluorobutane having a high purity at a low cost industrially and efficiently. The process for producing 1,2,3,4-tetrachlorohexafluorobutane according to the present invention comprises a step of allowing 1,2,3,4-tetrachlorobutane to react with a fluorine gas to prepare a reaction product containing 1,2,3,4-tetrachlorohexafluorobutane and hydrogen-containing compounds as an impurity, and a step of introducing the reaction product into single or plural distillation columns and distilling to separate the hydrogen-containing compounds from the reaction product and thereby preparing purified 1,2,3,4-tetrachlorohexafluorobutane wherein the at least one of distillation columns has a theoretical plate number of 15 or more.
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Page/Page column 3
(2011/05/16)
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- AN IMPROVED PROCESS FOR THE PREPARATION OF 2,3,-DICHLORO 1,3,BUTADIENE FROM 1,3 BUTADIENE
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The present invention relates to an improved process for the production of 2,3-Dichloro 1,3-Butadiene which comprises Chlorinating Butadiene, in liquid phase, in the presence of chlorinated solvents and phase transfer catalyst, Distilling the solvent, Distilling the formed 3,4-dichlorobutene-1, 1,4-dichlorobutene-2; and 1,2,3,4-Tetrachlorbutane; under reduced pressure,chlorinating the separated 3,4-dichlorobutene-1 and 1,4-dichlorobutene-2 to give 1,2,3,4-Tetrachlorobutane.,double Dehydrochlorinating the 1,2,3,4-Tetrachlorobutane using methanol,alkali and inhibitors under atmosphere of 1% oxides of nitrogen in nitrogen atmosphere the total period of Dehydrochlorinating being in the range of 15-33 hours to give 2,3-Dichloro 1,3-Butadiene and separating methanol to get 2,3-Dichloro 1,3-Butadiene
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Page/Page column 6
(2011/06/16)
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- Process for production of 3,4-dichlorobutene-1
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3,4-Dichlorobutene-1 is produced by a process comprising the step of contacting 1,4-dichlorobutene-2 with either 1) a ferric carboxylate catalyst of the formula where R is an alkyl or alkenyl group of 4-18 carbon atoms, a cycloalkyl or cycloalkenyl group of 6-18 carbon atoms or an aryl group selected from phenyl, benzyl, xylyl, tolyl, and naphthyl groups, whereby a portion of the 1,4-dichlorobutene-2 is isomerized to form 3,4-dichlorobutene-1, or 2) a ferric carboxylate catalyst of the formula where R, R′ and R″ are independently alkyl or alkenyl groups of 4-18 carbon atoms, cycloalkyl or cycloalkenyl groups of 6-18 carbon atoms or aryl groups selected from phenyl, benzyl, xylyl, tolyl, and naphthyl groups, the sum of m, n and o is 3 and m, n and o are independently 0, 1 or 2, whereby a portion of the 1,4-dichlorobutene-2 is isomerized to form 3,4-dichlorobutene-1.
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Page/Page column 4
(2011/02/17)
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- PRODUCTION PROCESS FOR 1,2,3,4-TETRACHLOROHEXAFLUOROBUTANE AND REFINING PROCESS
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The production process for 1,2,3,4-tetrachlorohexafluorobutane of the present invention is characterized in that 1,2,3,4-tetrachlorobutane is reacted with fluorine in the presence of a solvent containing hydrogen fluoride. The 1,2,3,4-tetrachlorobutane may be obtained by chlorination of 3,4-dichlorobutene-1. Further, the present invention provides as well a process of refining 1,2,3,4-tetrachlorohexafluorobutane obtained in the manner described above. According to the present invention, 1,2,3,4-tetrachlorohexafluorobutane which is useful, for example, as a synthetic raw material for hexafluoro-1,3-butadiene used as an etching gas for semiconductors can industrially efficiently be produced by using 1,2,3,4-tetrachlorobutane which is a by-product of chloroprene and which has so far been disposed.
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Page/Page column 4-5
(2010/06/14)
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- Catalytic conversions of chloroolefins over iron oxide nanoparticles: 1. Isomerization of dichlorobutenes in the presence of iron oxide nanopaticles immobilized on silicas with different structures
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The influence of the support nature and electronic state of iron oxide nanoclusters on the catalytic properties of supported systems was studied for dichlorobutene isomerization. A sample with a Fe content of 2.5 wt.% on the activated silica matrix containing FeIII and FeII ions in the paramagnetic state exhibits the highest activity. The activity of iron on silica gel enhances with the appearance of magnetically ordered nanoclusters of γ-iron oxide formed at the iron content on the catalyst as high as 15 wt.%. An increase in the catalyst activity is favored by the formation of two states of iron (FeIII and FeII) that occurs under the synthesis conditions or during the action of a reactant.
- Rostovshchikova,Smirnov,Tsodikov,Bukhtenko,Maksimov,Kiseleva,Pankratov
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p. 1418 - 1424
(2007/10/03)
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- Process for isomerizing dichlorobutenes
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This invention relates to a process for isomerizing 1,4-dichloro-2-butene to yield 3,4-dichloro-1-butene or 3,4-dichloro-1-butene to yield 1,4-dichloro-2-butene, characterized in that the catalyst used comprises a compound of the formula CpFe(CO)2X, wherein Cp denotes a cyclopentadienyl derivative of the general formula (I), wherein R1to R5mutually independently denote H, C1to C12alkyl, C5to C8cycloalkyl, which may in turn bear C1to C12alkyl groups, C6to C14aryl, alkylaryl, arylalkyl, wherein two adjacent residues may together form saturated or unsaturated C3to C14cycles, or denote—SiR6R7R8, wherein R6to R7may mutually independently mean C1to C4alkyl, C5to C8cycloalkyl or C6to C14aryl, and X denotes F, Cl, Br.
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Page column 4-6
(2008/06/13)
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- RELATIONSHIPS OF ISOMERIZATION OF THE ALLYLIC TYPE.
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The authors report the results of thermodynamic and kinetic studies of allylic rearrangements of dichlorobutenes. It is shown that the controlling step in allylic rearrangement of dichlorobutenes is monomolecular decomposition of the pi -allyl complex of 1,4-DC-2-B with the catalyst. Therefore all attempts at activation of catalysts of allylic rearrangement are aimed at change of the charge density on the metal (Cu), facilitating migration of chlorine. The effective activating influence of the surface of inorganic supports, such as aluminum oxide, on isomerization of dichlorobutenes in presence of copper naphthenate was demonstrated for the first time left bracket 10 right bracket . The optimal ratio of copper naphthenate to Al//2O//3, doubling the yield of 3,4-DC-1-B by isomerization of 1,4-DC-2-B, was found with the aid of design of experiments.
- Levanova,Yanshevskaya,Asatryan,Saakyan,Kostand'yan,Malkhasyan,Martirosyan
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p. 790 - 793
(2007/10/02)
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- ELECTROCHEMICAL CHLORINATION OF BUTADIENE
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An Electrochemical chlorination of butadiene was investigated at 25 deg C by using an H-type cell with a CoCl2-MeCN anolyte and an NH4Cl-H2O catholyte separated by an anion-exchange membrane.The electrolysis gave 3,4-dichloro-1-butene and trans-1,4-dichloro-2-butene in high current efficiencies.
- Takasu, Yoshio,Matsuda, Yoshiharu,Shimizu, Akinori,Morita, Masayuki,Saito, Mitsutaka
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p. 1685 - 1686
(2007/10/02)
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- Three-Component Reactions. IX. Methoxychlorination of Butadiene. 1. Composition of Reaction Mixtures Obtained Using Either an Excess of Butadiene or an Excess of Chlorine
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Methoxychlorination of butadiene with 2 mol chlorine gives saturated secondary addition products 5-15, which were found identical with methoxychlorination products of unsaturated primary addition products 1-4 (investigated by capillar GLC). 1,2 and 3 add chlorine and methanol with high regioselectivity (80-90percent); meso and erythro isomer predominate in MARKOVNIKOV products from 1 and 2 (87percent diastereoselectivity). 5-7 and 11-15 were separated by preparative GLC for structural analysis.
- Beger, J.,Schiefer, H.,Movsumzade, M.M.,Gurbanov, P.A.
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p. 599 - 609
(2007/10/02)
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- Process for working up liquid copper-containing catalyst waste from isomerization reactions of dichlorobutene
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Improved working up of the waste from an isomerization reaction of dichlorobutene by precipitating the copper catalyst used in said process by adding a polar solvent and removing the resulting precipitate by filtration.
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