- METHODS FOR SELECTIVELY HYDROGENATING SUBSTITUTED ARENES WITH SUPPORTED ORGANOMETALLIC CATALYSTS
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Methods for selectively hydrogenating substituted arenes with a supported organometallic hydrogenating catalyst are provided. An exemplary method includes contacting a substituted arene-containing reaction stream with hydrogen in the presence of a supported organometallic hydrogenating catalyst under reaction conditions effective to selectively hydrogenate the substituted arenes to the cis isomer with high selectivity. In this method, the supported organometallic hydrogenating catalyst includes a catalytically active organometallic species and a Br?nsted acidic sulfated metal oxide support.
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Paragraph 0037
(2016/06/28)
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- (ALKYLPHENYL)ALKYLCYCLOHEXANE AND METHOD FOR PRODUCING (ALKYLPHENYL)ALKYLCYCLOHEXANE OR ALKYLBIPHENYL
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Disclosed is a method for producing an (alkylphenyl)alkylcyclohexane comprising a step wherein an alkylbenzene and an alkylcyclohexene or alkylcyclohexanol are condensed in the presence of an acid catalyst. Also disclosed is an (alkylphenyl)alkylcyclohexane represented by the formula (8) below. An (alkylphenyl)alkylcyclohexane obtained by such a production method is converted into an alkylbiphenyl, a biphenylpolycarboxylic acid or a biphenylpolycarboxylic acid anhydride. This production method enables to easily and selectively obtain an (alkylphenyl)alkylcyclohexane and an alkylbiphenyl. (8) (In the formula, R1-4 represent an alkyl group having 1-4 carbon atoms, m represents an integer of 0-2, n' represents an integer of 2-5, and the other conditions are as defined in claim 18.)
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Page/Page column 23-24
(2008/06/13)
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- Supramolecular cluster catalysis: Facts and problems
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By checking the chemistry underlying the concept of "supramolecular cluster catalysis" we identified two major errors in our publications related to this topic, which are essentially due to contamination problems. (1) The conversion of the "closed" cluster cation [H3Ru3(C6H6) (C6Me6)2(O)]+ (1) into the "open" cluster cation [H2Ru3 (C6H6)(C6Me6)2 (O)(OH)]+ (2), which we had ascribed to a reaction with water in the presence of ethylbenzene is simply an oxidation reaction which occurs in the presence of air. (2) The higher catalytic activity observed with ethylbenzene, which we had erroneously attributed to the "open" cluster cation [H2Ru3 (C6H6)(C6Me6)2 (O)(OH)]+ (2), was due to the formation of RuO2·nH2O, caused by a hydroperoxide contamination present in ethylbenzene.
- Süss-Fink, Georg,Therrien, Bruno,Vieille-Petit, Ludovic,Tschan, Mathieu,Romakh, Vladimir B.,Ward, Thomas R.,Dadras, Massoud,Laurenczy, Gabor
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p. 1362 - 1369
(2007/10/03)
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- METHOD FOR THE PRODUCTION OF NON-AROMATIC HYDROCARBONS
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The invention relates to a method for the production of long-chain, branched-chain and/or cyclic hydrocarbons. A low molecular weight alkyl halide and a fused salt are firstly prepared. The fused salt contains an electrophilic compound and a reducing agent and is free from oxygen and oxygen compounds. The alkyl halide is then brought into contact with the fused salt such that long-chain, branched-chain and/or cyclic hydrocarbons are formed in the fused salt. The hydrocarbons formed in the fused salt are drawn off and can subsequently be separated from unreacted starting materials. By means of the above method, hydrogen can be produced during the reaction of the low molecular weight alkyl halide. The risk of oxidation of the alkane produced to give carbon monoxide or carbon dioxide is avoided by means of the reducing conditions in the fused salt. The product distribution can be controlled by means of suitable selection of the composition of the fused salt. Highly-branched hydrocarbons are produced with the preferred application of a sodium chloroaluminate fused salt.
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- Oxidative transformations of cyclohexane, methylcyclopentane, and pentane on treatment with superelectrophiles based on polyhalomethane and aluminum halides
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Cyclohexane and methylcyclopentane dimerize into dimethyldecalins on treatment with superelectrophilic systems containing polyhalomethanes (CBr4, CCl4, CHCl3) and aluminum halides (AlBr3, AlCl3). At 2
- Akhrem,Churilova,Vitt
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- Ionization Energies and Entropies of Cycloalkanes. Kinetics of Free Energy Controlled Charge-Transfer Reactions.
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Enthalpies and entropies of ionization (ΔH0ion and ΔS0ion) of alkylcyclohexanes, as well as cycloheptane, cyclooctane, and trans-Decalin, have been determined by charge-transfer equilibrium measurements.Values of ΔHion, in units of kcal mol-1 (or eV), range from 229.6 (9.96) for cycloheptane to 210.7 (9.14) for trans-Decalin.A major effect of alkyl substitution is observed following substitution at a site α to a tertiary hydrogen atom (as from methylcyclohexane to 1,2-dimethylcyclohexane), or following replacement of a tertiary hydrogen atom (as from methylcyclohexane to 1,1-dimethylcyclohexane).In both cases, ΔH0 ion decreases by ca. 5 kcal mol-1.Entropies of ionization are near zero for alkylcyclohexanes but range up to 5 cal deg-1 mol-1 for nonsubstituted cycloalkanes (cyclooctane).The charge-transfer reactions involving the cycloalkanes are shown to be fast processes; i.e., the sum of the reaction efficiencies (r=k/kcollision) of the forward and reverse processes is near unity.The efficiencies of these processes appear to be determined uniquely by the overall free energy change (or equilibrium constant K).Specifically, the reaction efficiencies are defined, within a factor of 2 by the relation r=K/(1+K), which can be justified by using transition-state theory applied to the decomposition of a collision complex over surfaces lacking energy barriers.These reactions are defined as intrinsically fast processes in that they are slowed only by the overall reaction thermochemistry and not by any properties or reactions of the intermediate complex.
- Sieck, L. Wayne,Mautner, Michael
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p. 3646 - 3650
(2007/10/02)
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