- Methods for preparing 1,2-cyclohexanedicarboxylate or phthalic acid ester
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The invention relates to methods for preparing a plasticizer 1,2-cyclohexanedicarboxylate and phthalic acid ester by a biomass route. The preparation method of 1,2-cyclohexanedicarboxylate comprises the following steps: 1. crotonaldehyde, formaldehyde and fumarate (or maleate) are subjected to a D-A cycloaddition reaction under the catalysis of organic base so as to generate diester-substituted cyclohexenecarboxaldehyde; 2. the product is subjected to decarbonylation under a transition metal catalyst to generate cyclohexenedicarboxylate; and 3. cyclohexenedicarboxylate undergoes hydrogenationof a double bond under a transition metal catalyst to generate 1,2-cyclohexanedicarboxylate. The preparation method of phthalic acid ester comprises the following steps: 1. crotonaldehyde, formaldehyde and fumarate (or maleate) are subjected to a D-A cycloaddition reaction under the catalysis of organic base so as to generate diester-substituted cyclohexenecarboxaldehyde; and 2. the product undergoes decarbonylation/aromatization under a transition metal catalyst to generate phthalic acid ester.
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Paragraph 0060-0063
(2019/05/02)
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- Recyclable cobalt(0) nanoparticle catalysts for hydrogenations
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The search for new hydrogenation catalysts that replace noble metals is largely driven by sustainability concerns and the distinct mechanistic features of 3d transition metals. Several combinations of cobalt precursors and specific ligands in the presence of reductants or under high-thermal conditions were reported to provide active hydrogenation catalysts. This study reports a new method of preparation of small, monodisperse Co(0) nanoparticles (3-4 nm) from the reduction of commercial CoCl2 in the absence of ligands or surfactants. High catalytic activity was observed in hydrogenations of alkenes, alkynes, imines, and heteroarenes (2-20 bar H2). The magnetic properties enabled catalyst separation and multiple recyclings.
- Büschelberger, Philipp,Reyes-Rodriguez, Efrain,Sch?ttle, Christian,Treptow, Jens,Feldmann, Claus,Jacobi Von Wangelin, Axel,Wolf, Robert
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p. 2648 - 2653
(2018/05/30)
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- Titanium(III)-Oxo Clusters in a Metal-Organic Framework Support Single-Site Co(II)-Hydride Catalysts for Arene Hydrogenation
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Titania (TiO2) is widely used in the chemical industry as an efficacious catalyst support, benefiting from its unique strong metal-support interaction. Many proposals have been made to rationalize this effect at the macroscopic level, yet the underlying molecular mechanism is not understood due to the presence of multiple catalytic species on the TiO2 surface. This challenge can be addressed with metal-organic frameworks (MOFs) featuring well-defined metal oxo/hydroxo clusters for supporting single-site catalysts. Herein we report that the Ti8(μ2-O)8(μ2-OH)4 node of the Ti-BDC MOF (MIL-125) provides a single-site model of the classical TiO2 support to enable CoII-hydride-catalyzed arene hydrogenation. The catalytic activity of the supported CoII-hydride is strongly dependent on the reduction of the Ti-oxo cluster, definitively proving the pivotal role of TiIII in the performance of the supported catalyst. This work thus provides a molecularly precise model of Ti-oxo clusters for understating the strong metal-support interaction of TiO2-supported heterogeneous catalysts.
- Ji, Pengfei,Song, Yang,Drake, Tasha,Veroneau, Samuel S.,Lin, Zekai,Pan, Xiandao,Lin, Wenbin
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p. 433 - 440
(2018/01/17)
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- Synthesis of 1,4-Cyclohexanedimethanol, 1,4-Cyclohexanedicarboxylic Acid and 1,2-Cyclohexanedicarboxylates from Formaldehyde, Crotonaldehyde and Acrylate/Fumarate
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Valuable polyester monomers and plasticizers—1,4-cyclohexanedimethanol (CHDM), 1,4-cyclohexanedicarboxylic acid (CHDA), and 1,2-cyclohexanedicarboxylates—have been prepared by a new strategy. The synthetic processes involve a proline-catalyzed formal [3+1+2] cycloaddition of formaldehyde, crotonaldehyde, and acrylate (or fumarate). CHDM is produced after a subsequent hydrogenation step over a commercially available Cu/Zn/Al catalyst and a one-pot hydrogenation/oxidation/hydrolysis process yields CHDA, whereas 1,2-cyclohexanedicarboxylate is obtained by a Pd/C-catalyzed tandem decarbonylation/hydrogenation step.
- Hu, Yancheng,Zhao, Zhitong,Liu, Yanting,Li, Guangyi,Wang, Aiqin,Cong, Yu,Zhang, Tao,Wang, Feng,Li, Ning
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supporting information
p. 6901 - 6905
(2018/06/04)
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- PROCESS FOR HYDROGENATION OF POLYCARBOXYLIC ACIDS OR DERIVATIVES THEROF
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The disclosure provides a process for hydrogenation of polycarboxylic acids or derivatives thereof, including: hydrogenation of polycarboxylic acids or derivatives thereof in the presence of a catalyst, wherein the catalyst includes an active metal and a
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Paragraph 0041; 0042; 0043
(2013/06/27)
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- NEW COMPOUNDS FOR THE TREATMENT OF CNS DISORDERS
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The invention relates to novel pyrazolopyrimidinones according to formula (I). The new compounds shall be used for the manufacture of medicaments, in particular medicaments for the treatment of conditions concerning deficits in perception, concentration, learning or memory. The new compounds are also for the manufacture of medicaments for the treatment of Alzheimer's disease. Further aspects of the present invention refer to a process for the manufacture of the compounds and their use for producing medicaments.
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Page/Page column 77
(2011/02/24)
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- NEW COMPOUNDS FOR THE TREATMENT OF CNS DISORDER
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The invention relates to novel pyrazolopyrimidinones according to formula (I). The new compounds shall be used for the manufacture of medicaments, in particular medicaments for the treatment of conditions concerning deficits in perception, concentration, learning or memory. The new compounds are also for the manufacture of medicaments for the treatment of Alzheimer's disease. Further aspects of the present invention refer to a process for the manufacture of the compounds and their use for producing medicaments.
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Page/Page column 29-30
(2011/09/20)
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- CATALYTIC SYNTHESIS OF N-ALKYLOCTAHYDROISOINDOLES
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Catalytic hydroamination of 1,2-bis(hydroxymethyl)cyclohexane by aliphatic nitriles over a nickel catalyst yielded a series of N-alkyl-substituted octahydroisoindoles.Conditions for their synthesis were selected.The IR, PMR, and mass spectra and the proba
- Kozintsev, S. I.,Zhavrid, A. S.,Serzhanin, A. I.,Kozlov, N. S.
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p. 1346 - 1348
(2007/10/02)
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- Conformational Equilibrium in 8-Methyl-cis-2-thiahydrindane and 8-Methyl-cis-2-oxahydrindane by 13C NMR Spectroscopy
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The preferred conformation of 8-methyl-cis-thiahydrindane has been both estimated by 13C NMR chemical shifts and determined by low temperature 13C NMR spectroscopy to be the conformer with the methyl group equatorial with respect to the cyclohexane ring.This result is in disagreement with the interpretation of the temperature dependence of the CD spectra of (+) and (-) 8-methyl-cis-2-thiahydrindane, whereby the conformation with the methyl group axial with respect to the cyclohexane ring was claimed to be the preferred conformation.The preferred conformation of the related oxygen heterocycle, 8-methyl-cis-2-oxahydrindane, has been estimated by 13C NMR chemical shifts to be the conformer with the methyl group axial with respect to the cyclohexane ring.Possible reasons for these observations are discussed.
- Willer, Rodney L.
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p. 261 - 265
(2007/10/02)
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- Studies on Organic Fluorine Compounds. XXXI. Oxidative Coupling of Ketone Enolates and Trimethylsilyl Enol Ethers by Means of Cu(OTf)2
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The oxidative coupling of ketone enolates and trimethylsilyl enol ethers by means of cupric trifluoromethanesulfonate is described in detail. 1,4-Diketones were effectively prepared by treating lithium enolates with Cu(OTf)2 in i-PrCN. 1,3-Cyclopentanedione derivatives were synthesized through intramolecular coupling of 2,4-pentanedione derivatives.Treatment of trimethylsilyl enol ethers with Cu(OTf)2 in i-PrCN also afforded the corresponding coupling products. Keywords---Oxidative coupling; cupric trifluoromethanesulfonate; 1,4-diketones; 1,3-cyclopentanediones; trimethylsilyl enol ether
- Kobayashi, Yoshiro,Taguchi, Takeo,Morikawa, Tsutomu,Tokuno, Etsuko,Sekiguchi, Shoh
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p. 262 - 267
(2007/10/02)
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