- Immobilization of Carbonylcobalt Catalyst by Poly(4-vinylpyridine) (P4VP) through N→Co Coordination Bonds: The Promotional Effect of Pyridine and the Reusability of Polymer Catalyst
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A carbonylcobalt catalyst, immobilized by poly(4-vinylpyridine) (P4VP) through N→Co coordination bonds, has been prepared by solvothermal method. It has been revealed that the pyridine fragments in the polymer catalyst act not only as promoters to improve the catalytic performance of the carbonylcobalt catalyst for alkoxycarbonylation of ethylene oxide to methyl 3-hydroxypropanoate but also as stabilizers to enhance the reusability of the polymer catalyst. Furthermore, the polymer catalyst could be easily separated by filtration and reused with only a slight loss of catalytic efficiency.
- Liu, Yu-Bing,Wang, Yi-Ning,Lu, Hai-Meng,Liang, Shuang,Xu, Bo-Lian,Fan, Yi-Ning
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supporting information
p. 3159 - 3164
(2016/11/29)
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- CHEMICAL COMPOUNDS
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The invention concerns compounds of Formula (I) or pharmaceutically-acceptable salts thereof, wherein R1 to R5 have any of the meanings defined hereinbefore in the description: processes for their preparation, pharmaceutical compositions containing them and their use in the treatment of cell proliferative disorders.
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Paragraph 0564-0565
(2014/12/09)
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- Solvent effect and reactivity trend in the aerobic oxidation of 1,3-propanediols over gold supported on titania: Nmr diffusion and relaxation studies
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In recent work, it was reported that changes in solvent composition, precisely the addition of water, significantly inhibits the catalytic activity of Au/TiO2 catalyst in the aerobic oxidation of 1,4-butanediol in methanol due to changes in diffusion and adsorption properties of the reactant. In order to understand whether the inhibition mechanism of water on diol oxidation in methanol is generally valid, the solvent effect on the aerobic catalytic oxidation of 1,3-propanediol and its two methyl-substituted homologues, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol, over a Au/TiO2 catalyst has been studied here using conventional catalytic reaction monitoring in combination with pulsed-field gradient nuclear magnetic resonance (PFG-NMR) diffusion and NMR relaxation time measurements. Diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Combined NMR diffusion and relaxation time measurements suggest that molecular diffusion and, in particular, the relative strength of diol adsorption, are important factors in determining the conversion. These results highlight NMR diffusion and relaxation techniques as novel, non-invasive characterisation tools for catalytic materials, which complement conventional reaction data. In solvent company: The solvent effect on the aerobic catalytic oxidation of 1,3-propanediol and its two methyl-substituted homologues, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol, over a Au/TiO 2 catalyst has been studied. The results show that diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Copyright
- D'Agostino, Carmine,Kotionova, Tatyana,Mitchell, Jonathan,Miedziak, Peter J.,Knight, David W.,Taylor, Stuart H.,Hutchings, Graham J.,Gladden, Lynn F.,Mantle, Mick D.
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p. 11725 - 11732
(2013/09/12)
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- Catalytic performance of [Bmim][Co(CO)4] functional ionic liquids for preparation of 1,3-propanediol by coupling of hydroesterification- hydrogenation from ethylene oxide
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In this paper, synthesis of 1,3-propanediol (1,3-PDO) through coupling of hydroesterification-hydrogenation from ethylene oxide (EO) catalyzed by 1-butyl-3-methylimidazolium cobalt tetracarbonyl [Bmim][Co(CO)4] functional ionic liquid which was prepared by metathesis reaction between [Bmim]Cl and KCo(CO)4 has been studied. The structure of [Bmim][Co(CO)4] was characterized by FT-IR and 1H NMR. Using [Bmim][Co(CO)4] as catalyst and [Bmim]PF6 as solvent, 1,3-PDO was prepared for the first time by coupling of hydroesterifaction of EO and hydrogenation of methyl 3-hydroxypropionate (3-HPM). The yield of 3-HPM can reach 90.8%, while the yield of 1,3-PDO up to 82.9%. The catalyst can be separated from the product mixture by extraction with deionized water and recycled several times without significant loss of catalytic efficiency. A possible reaction mechanism has also been proposed.
- Guo, Zhenmei,Wang, Hengsheng,Lv, Zhiguo,Wang, Zhihui,Nie, Tao,Zhang, Weiwei
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experimental part
p. 3668 - 3672
(2011/12/02)
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- Methods for preparing 3-hydroxy-propionate and 1,3-propylene glycol
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The invention disclosed a method for producing 3-hydroxy-propionate and 1,3-propylene glycol by using epoxide as raw material. In the method, a transitional metal cobalt catalyst and a cocatalyst for the hydroesterification reaction among epoxide, carbon monoxide, and alcohol were chosen, and a hydrogenation catalyst for hydrogenating 3-hydroxy-propionate as well as the corresponding process conditions were selected for producing 3-hydroxy-propionate and 1,3-propylene glycol.
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Page/Page column 3-4
(2008/06/13)
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- Highly active and selective palladium catalyst for hydroesterification of styrene and vinyl acetate promoted by polymeric sulfonic acids
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Highly efficient, selective and recyclable palladium catalyst systems for hydroesterification of styrene and vinyl acetate were realized by using 1,2-bis(di-tert-butylphosphinomethyl)benzene as ligand and polymeric sulfonic acids of limited SO3H loadings as promoter. The Royal Society of Chemistry 2005.
- Ooka, Hirohito,Inone, Tsutomu,Itsuno, Shinichi,Tanaka, Masato
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p. 1173 - 1175
(2007/10/03)
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- METHODS OF MANUFACTURING DERIVATIVES OF β-HYDROXYCARBOXYLIC ACIDS
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Preparation of derivatives of β-hydroxycarboxylic acid, including β-hydroxycarboxylic acid esters, α,β-unsaturated carboxylic acids, esters of α,β-unsaturated carboxylic acid, and alkoxy derivatives.
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Page/Page column 7-9
(2008/06/13)
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- Process for the carbonylation of oxiranes
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A process is described for the carbonylation of an oxirane, such as ethylene oxide, which comprises reacting the oxirane under carbonylation conditions with carbon monoxide in a solvent, such as alkanol, for example methanol, in the presence of a cobalt catalyst and of an N-alkylated azole promoter, such as 1-methylpyrazole, and recovering the resulting carbonylation product, such as an alkyl ester of 3-hydroxypropionic acid, for example methyl 3-hydroxypropionate.
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- Process for preparing 1,3-alkanediol from epoxide derivative
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A process for preparing an 1,3-alkanediol through carbonylation of an epoxide derivative includes the steps of (a) reacting an epoxide derivative with alcohol and carbon monoxide in a solvent at a temperature from about 30 to about 150° C. and at a pressure from about 50 to about 3000 psig in the presence of a catalyst system including an effective amount of a cobalt catalyst and an effective amount of a promoter to afford a reaction mixture including a 3-hydroxyester or derivative thereof in an amount of from 2 to about 95% by weight, (b) separating the reaction product and solvent from the catalyst and promoter, (c) reacting said reaction product and solvent with hydrogen at a temperature from about 30 to about 350° C. and at a pressure from about 50 to about 5000 psig in the presence of a catalyst system for hydrogenation to prepare a hydrogenation product mixture including a 1,3-alkanediol, and (d) recovering the 1,3-alkanediol from the hydrogenation product mixture. Catalyst systems for carrying out the inventive processes are also provided.
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Page column 7-8
(2008/06/13)
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- Enantiomerically pure tetrahydro-5-oxo-2-furancarboxylic esters from dialkyl 2-oxoglutarates
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Enantiomerically pure tetrahydro-5-oxo-2-furancarboxylic esters can be prepared either by enzymatic resolution of the racemic γ-lactones themselves or by bioreduction with baker's yeast of dialkyl 2-oxoglutarates and subsequent cyclization of the resulting dialkyl 2-hydroxyglutarates. The best results were obtained by the former route, by which the desired compounds were isolated in high enantiomeric excess. Bioreductions were less satisfactory. In fact the hydroxyester intermediates were initially formed as racemic mixtures and their final enantiomeric enrichment was reached by asymmetric destruction, occurring in the bioreaction medium, however at the same time large amounts of alkyl 4-hydroxybutanoates were formed as side products.
- Drioli, Sara,Nitti, Patrizia,Pitacco, Giuliana,Tossut, Laura,Valentin, Ennio
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p. 2713 - 2728
(2007/10/03)
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- Reactions of β-Lactones with Potassium Alkoxides and Their Complexes with 18-Crown-6 in Aprotic Solvents
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The mechanism of the reaction of β-lactones (2-oxetanones) with potassium alkoxides in aprotic solvents was investigated.Despite previous suggestions, the attack of alkoxide ion occurs on the carbonyl carbon atom of β-lactones, cleaving the acyl-oxygen bond to yield the corresponding potassium alcoholate of the respective β-hydroxycarboxylic acid ester.Next, the unsaturated ester is formed due to potassium hydroxide elimination.The nature of the alkoxide used and complexation of alkali metal cation by crown ether have no significant effect on the reaction course in aprotic solvents.
- Kurcok, Piotr,Jedlinski, Zbigniew,Kowalczuk, Marek
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p. 4219 - 4220
(2007/10/02)
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