- METHOD FOR PRODUCING ALCOHOL
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The present invention provides a method for selectively producing an alcohol by efficiently hydrogenating a lactone. The present invention is a method for producing an alcohol, the method including hydrogenating a substrate lactone represented by Formula (1), in the presence of a catalyst described below, to produce an alcohol that is represented by Formula (2). In the formulae, R represents a divalent hydrocarbon group which may have a hydroxyl group. The catalyst comprises: metal species including M1 and M2; and a support supporting the metal species, and wherein M1 is rhodium, platinum, ruthenium, iridium, or palladium; M2 is tin, vanadium, molybdenum, tungsten, or rhenium; and the support is hydroxyapatite, fluorapatite, hydrotalcite, or ZrO2.
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Paragraph 0104; 0106
(2022/02/05)
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- Chemoselective and Site-Selective Reductions Catalyzed by a Supramolecular Host and a Pyridine-Borane Cofactor
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Supramolecular catalysts emulate the mechanism of enzymes to achieve large rate accelerations and precise selectivity under mild and aqueous conditions. While significant strides have been made in the supramolecular host-promoted synthesis of small molecules, applications of this reactivity to chemoselective and site-selective modification of complex biomolecules remain virtually unexplored. We report here a supramolecular system where coencapsulation of pyridine-borane with a variety of molecules including enones, ketones, aldehydes, oximes, hydrazones, and imines effects efficient reductions under basic aqueous conditions. Upon subjecting unprotected lysine to the host-mediated reductive amination conditions, we observed excellent ?-selectivity, indicating that differential guest binding within the same molecule is possible without sacrificing reactivity. Inspired by the post-translational modification of complex biomolecules by enzymatic systems, we then applied this supramolecular reaction to the site-selective labeling of a single lysine residue in an 11-amino acid peptide chain and human insulin.
- Morimoto, Mariko,Cao, Wendy,Bergman, Robert G.,Raymond, Kenneth N.,Toste, F. Dean
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supporting information
p. 2108 - 2114
(2021/02/06)
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- Ruthenium-p-cymene Complex Side-Wall Covalently Bonded to Carbon Nanotubes as Efficient Hybrid Transfer Hydrogenation Catalyst
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A half-sandwich ruthenium-p-cymene organometallic complex has been immobilized at Single Walled Carbon Nanotubes (SWNT) sidewalls through a stepwise covalent chemistry protocol. The introduction of amino groups by means of diazonium-chemistry protocols leads the grafting at the outer walls of the nanotubes. This hybrid material is active in the transfer hydrogenation of ketones to yield alcohols, using as hydrogen source 2-propanol. SWNT?NH2?Ru presents a broad scope, performing the reaction under aerobic conditions and can be recycled over 9 consecutive reaction runs without losing activity or leaching ruthenium out. Comparison of the activity with related homogeneous catalysts reveals an improved performance due to the covalent bond between the metal and the material, achieving turnover frequencies as high as 192774 h?1.
- Blanco, Matías,Cembellín, Sara,Agnoli, Stefano,Alemán, José
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p. 5156 - 5165
(2021/11/05)
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- Synthesis of new rhodium(III) complex by benzylic C[sbnd]S bond cleavage of thioether containing NNS donor Schiff base ligand: Investigation of catalytic activity towards transfer hydrogenation of ketones
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A new rhodium(III)-triphenylphosphine mixed ligand complex, [Rh(PPh3)(L)Cl2] (1) is synthesized by benzylic C[sbnd]S bond cleavage of L-CH2Ph ligand (where, L-CH2Ph = 2-(benzylthio)-N-(pyridin-2-ylmethylene)aniline). The complex is thoroughly characterized by several spectroscopic techniques. Geometry of the complex is confirmed by single crystal X-ray crystallography. Electronic structure, redox properties, absorption and emission properties of the complex were studied. DFT and TDDFT calculations were carried out to interpret the electronic structure and absorption properties of the complex respectively. The synthesized Rh(III) complex was tested as catalyst towards transfer hydrogenation reaction of ketones in iPrOH and an excellent catalytic conversion was observed under mild conditions.
- Biswas, Sujan,Das, Akash,Kumar Manna, Chandan,Kumar Mondal, Tapan,Naskar, Rahul
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- Selective palladium nanoparticles-catalyzed hydrogenolysis of industrially targeted epoxides in water
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Palladium nanoparticles, with core sizes of ca. 2.5 nm, were easily synthesized by chemical reduction of Na2PdCl4 in the presence of hydroxyethylammonium salts and proved to be efficient for the selective hydrogenolysis of various aromatic, alkylphenyl, aliphatic epoxides in water as green solvent. Capping agents of the metal species were screened to define the most suitable micellar nanoreactors on two target substrates of industrial interest, epoxystyrene and 7,8-epoxy-2-methoxy-2,6-dimethyloctane. In our conditions, the hydrogenolysis of epoxystyrene proved to be pH-dependent, producing either the diol under acidic conditions, or the sweet-smelling 2-phenylethanol in the presence of a base. Promisingly, 7,8-epoxy-2-methoxy-2,6-dimethyloctane was completely and selectively hydrogenated into Florsantol, a sandalwood odorant at a multigram scale (40 g and up to 175g). A general mechanism for the palladium nanoparticles-catalyzed hydrogenolysis of terminal epoxides was proposed according to steric and electronic properties and finely corroborated with deuterium labelling experiments.
- Duval, Marion,Deboos, Victor,Hallonet, Agnès,Sagorin, Gilles,Denicourt-Nowicki, Audrey,Roucoux, Alain
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p. 261 - 268
(2021/03/22)
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- Hydrogen-Catalyzed Acid Transformation for the Hydration of Alkenes and Epoxy Alkanes over Co-N Frustrated Lewis Pair Surfaces
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Hydrogen (H2) is widely used as a reductant for many hydrogenation reactions; however, it has not been recognized as a catalyst for the acid transformation of active sites on solid surface. Here, we report the H2-promoted hydration of alkenes (such as styrenes and cyclic alkenes) and epoxy alkanes over single-atom Co-dispersed nitrogen-doped carbon (Co-NC) via a transformation mechanism of acid-base sites. Specifically, the specific catalytic activity and selectivity of Co-NC are superior to those of classical solid acids (acidic zeolites and resins) per micromole of acid, whereas the hydration catalysis does not take place under a nitrogen atmosphere. Detailed investigations indicate that H2 can be heterolyzed on the Co-N bond to form Hδ-Co-N-Hδ+ and then be converted into OHδ-Co-N-Hδ+ accompanied by H2 generation via a H2O-mediated path, which significantly reduces the activation energy for hydration reactions. This work not only provides a novel catalytic method for hydration reactions but also removes the conceptual barriers between hydrogenation and acid catalysis.
- Deng, Qiang,Deng, Shuguang,Gao, Ruijie,Li, Xiang,Tsang, Shik Chi Edman,Wang, Jun,Zeng, Zheling,Zou, Ji-Jun
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p. 21294 - 21301
(2021/12/17)
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- METHOD FOR PRODUCING BIO ALCOHOL FROM INTERMEDIATE PRODUCTS OF ANAEROBIC DIGESTION TANK
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The present invention relates to a method for producing a bio-alcohol by reacting a mixture of volatile fatty acid with methanol in 2 through 11 in a reactor in the presence of a 280 °C-membered alkaline earth metal catalyst or 400 °C transition metal catalyst formed based on a support.
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Paragraph 0043-0048
(2021/05/25)
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- Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
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The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
- Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
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supporting information
p. 5665 - 5679
(2021/08/16)
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- Synthesis and characterization of silica-coated magnetite nanoparticles modified with bis(pyrazolyl) triazine ruthenium(II) complex and the application of these nanoparticles as a highly efficient catalyst for the hydrogen transfer reduction of ketones
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We present a facile and efficient method for modifying the surface of silica-coated Fe3O4 magnetic nanoparticles (MNPs) with bis(pyrazolyl) triazine ruthenium(II) complex [MNPs@BPT–Ru (II)]. Field emission-scanning electron microscopy, thermogravimetric/derivative thermogravimetry analysis, X-ray powder diffraction, Fourier-transform infrared spectroscopy, vibrating sample magnetometry, and energy-dispersive X-ray spectrometry analyses were employed for characterizing the structure of these nanoparticles. MNPs@BPT–Ru(II) nanoparticles proved to be a magnetic, reusable, and heterogeneous catalyst for the hydrogen transfer reduction of ketone derivatives. In addition, highly pure products were obtained with excellent yields in relatively short times in the presence of this catalyst. A comparison of this catalyst with those previously used for the hydrogen transfer reactions proved the uniqueness of MNPs@BPT–Ru(II) nanoparticle which is due to its inherent magnetic properties and large surface area. The presented method also had other advantages such as simple reaction conditions, eco-friendliness, high recovery ability, easy work-up, and low cost.
- Mobinikhaledi, Akbar,Moghanian, Hassan,Ajerloo, Bahram,Dousti, Fatemeh
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- One-pot synthesis of 1,3-butanediol by 1,4-anhydroerythritol hydrogenolysis over a tungsten-modified platinum on silica catalyst
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Chemical production of 1,3-butanediol from biomass-derived compounds was first reported by 1,4-anhydroerythritol hydrogenolysis over a Pt-WOx/SiO2 catalyst. The reaction proceeded by ring opening hydrogenolysis of 1,4-anhydroerythritol followed by selective removal of secondary OH groups in 1,2,3-butanetriol, and an overall 1,3-butanediol yield up to 54% was then obtained. The performance of the Pt-WOx/SiO2 catalyst for 1,4-anhydroerythritol hydrogenolysis was closely correlated with that for glycerol hydrogenolysis to 1,3-propanediol. The optimized Pt-WOx/SiO2 (Pt: 4 wt% and W: 0.94 wt%) catalyst showed 57% yield of 1,3-propanediol.
- Asano, Takehiro,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi
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supporting information
p. 2375 - 2380
(2020/05/14)
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- Enzymatic Oxidation of Butane to 2-Butanol in a Bubble Column
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Unspecific peroxygenases have recently gained significant interest due to their ability to catalyse the hydroxylation of non-activated C?H bonds using only hydrogen peroxide as a co-substrate. However, the development of preparative processes has so far mostly concentrated on benzylic hydroxylations using liquid substrates. Herein, we demonstrate the application of a peroxygenase for the hydroxylation of the inert, gaseous substrate butane to 2-butanol in a bubble column reactor. The influence of hydrogen peroxide feed rate and enzyme loading on product formation, overoxidation to butanone and catalytic efficiency is investigated at 200 mL scale. The process is scaled up to 2 L and coupled with continuous extraction. This setup allowed the production of 115 mmol 2-butanol and 70 mmol butanone with an overall total turnover number (TTN) of over 15.000, thereby demonstrating the applicability of peroxygenases for preparative hydroxylation of such inert, gaseous substrates at mild reaction conditions.
- Perz, Frederic,Bormann, Sebastian,Ulber, Roland,Alcalde, Miguel,Bubenheim, Paul,Hollmann, Frank,Holtmann, Dirk,Liese, Andreas
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p. 3666 - 3669
(2020/06/17)
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- PROCESS FOR PRODUCING 2-BUTANOL FROM GAMMAVALEROLACTONE
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A process is disclosed for selectively producing 2-butanol from GVL by using at least one transition metal catalyst selected from the group consisting of iron, ruthenium, cobalt, rhodium and iridium.
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Paragraph 0082-0083; 0091
(2020/02/05)
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- PROCESS FOR MAKING FORMIC ACID UTILIZING LOWER-BOILING FORMATE ESTERS
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Disclosed is a process for recovering formic acid from a formate ester of a C3 to C4 alcohol. Disclosed is also a process for producing formic acid by carbonylating a C3 to C4 alcohol, hydrolyzing the formate ester of the alcohol, and recovering a formic acid product. The alcohol may be dried and returned to the reactor. The process enables a more energy efficient production of formic acid than the carbonylation of methanol to produce methyl formate.
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Paragraph 00184; 00185
(2019/02/15)
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- Modeling and optimization of lipase-catalyzed hydrolysis for production of (S)-2-phenylbutyric acid enhanced by hydroxyethyl-β-cyclodextrin
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An efficient reactive system was established to produce (S)-2-phenylbutyric acid (2-PBA) through the enzymatic enantioselective hydrolysis of 2-phenylbutyrate ester (2-PBAE) in aqueous medium. Lipase CALA from Canadian antarctica and hexyl 2-phenylbutyrate (2-PBAHE) were identified upon screening as the best enzyme and substrate, respectively. Adding hydroxyethyl-β-cyclodextrin (HE-β-CD) to improve the solubility of the substrate resulted in a 1.5 times increase in substrate conversion while retaining a high enantioselectivity compared with that when HE-β-CD was not added. The effects of lipase concentration, substrate concentration and HE-β-CD concentration, temperature, pH, and reaction time on enantiomeric excess and conversion rate were investigated, and the optimal conditions were identified using response surface methodology (RSM). Under the optimal conditions, namely 50 mg/mL lipase CALA, 30 mmol/L substrate, 60 mmol/L HE-β-CD, pH of 6.5, temperature of 83 °C and reaction time of 18 h, the enantiomeric excess and overall conversion rate were 96.05% and 27.28%, respectively. This work provides an efficient alternative method for improving the conversion of aromatic ester substrates by including β-cyclodextrin in an aqueous hydrolysis reaction system.
- Zhang, Panliang,Cheng, Qing,Xu, Weifeng,Tang, Kewen
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- Construction of PQQ-enzyme multi-immobilized electrodes for electrocataltyic reduction of carbonyl compounds
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A thin poly(arylamine) (PAA) and poly(acrylic acid) (PAAc) layers-coated graphite felt (GF) electrode immobilizing all mediation components of pyrroloquinolinequinone (PQQ), diaphorase (Dp), oxidized nicotinamide adenine dinucleotide (NAD+) and alcohol dehydrogenase (ADH) to construct a complete bioelectrochemical reactor was prepared and applied to electrocatalytic reduction of carbonyl compounds in a phosphate buffer at constant potential of -0.65 V vs. Ag/AgCl. The carbonyl compounds were reduced to the corresponding alcohols with high current efficiency (97.2 - 100%) and high yield (97.4 - 100%), respectively.
- Kashiwagi, Yoshitomo,Ono, Tetsuya,Yoshida, Kentaro,Ito, Toshinori,Sakurai, Nobuki
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p. 1216 - 1225
(2018/08/06)
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- Chiral C2-symmetric η6-p-cymene-Ru(II)-phosphinite complexes: Synthesis and catalytic activity in asymmetric reduction of aromatic, methyl alkyl and alkyl/aryl ketones
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Chiral C2-symmetric bis(phosphinite) ligands and their binuclear ruthenium(II) complexes have been synthesized and used as catalysts in the ruthenium-catalyzed asymmetric transfer hydrogenation of aromatic, methyl alkyl and alkyl/aryl ketones using 2-propanol as both the hydrogen source and solvent in the presence of KOH. Under optimized conditions, all complexes showed high catalytic activity as catalysts in the reduction of various ketones to corresponding chiral secondary alcohols. Products were obtained with high conversions (99%) and moderate to good enantioselectivities (82% ee). Furthermore, C2-symmetric bis(phosphinite) ligands and their binuclear ruthenium(II) complexes were characterized by multinuclear NMR spectroscopy, FT-IR spectroscopy, LC/MS-MS and elemental analysis.
- Karaka?, Duygu Elma,Aydemir, Murat,Durap, Feyyaz,Baysal, Ak?n
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p. 430 - 439
(2017/12/06)
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- Catalytic Transfer Hydrogenation of Biomass-Derived Carbonyls over Hafnium-Based Metal–Organic Frameworks
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A series of highly crystalline, porous, hafnium-based metal–organic frameworks (Hf-MOFs) have been shown to catalyze the transfer hydrogenation reaction of levulinic ester to produce γ-valerolactone by using isopropanol as a hydrogen donor. The results are compared with their zirconium-based counterparts. The role of the metal center in Hf-MOFs has been identified and reaction parameters optimized. NMR studies using isotopically labeled isopropanol provide evidence that the transfer hydrogenation occurs through a direct intermolecular hydrogen transfer route. The catalyst, Hf-MOF-808, can be recycled several times with only a minor decrease in catalytic activity. The generality of the procedure has been demonstrated by accomplishing the transformation with aldehydes, ketones, and α,β-unsaturated carbonyl compounds. The combination of Hf-MOF-808 with the Br?nsted-acidic Al-Beta zeolite gives the four-step one-pot transformation of furfural to γ-valerolactone in good yield of 75 %.
- Rojas-Buzo, Sergio,García-García, Pilar,Corma, Avelino
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p. 432 - 438
(2017/12/28)
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- Colloids for Catalysts: A Concept for the Preparation of Superior Catalysts of Industrial Relevance
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Compared to conventional preparation methods for supported heterogeneous catalysts, the use of colloidal nanoparticles (NPs) allows for a precise control over size, size distribution, and distribution/location of the NPs on the support. However, common colloidal syntheses have restrictions that limit their applicability for industrial catalyst preparation. We present a simple, surfactant-free, and scalable preparation method for colloidal NPs to overcome these restrictions. We demonstrate how precious-metal NPs are prepared in alkaline methanol, how the particle size can be tuned, and how supported catalysts are obtained. The potential of these colloids in the preparation of improved catalysts is demonstrated by two examples from heterogeneous catalysis and electrocatalysis.
- Quinson, Jonathan,Neumann, Sara,Wannmacher, Tanja,Kacenauskaite, Laura,Inaba, Masanori,Bucher, Jan,Bizzotto, Francesco,Simonsen, S?ren B.,Theil Kuhn, Luise,Bujak, Dajana,Zana, Alessandro,Arenz, Matthias,Kunz, Sebastian
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supporting information
p. 12338 - 12341
(2018/09/06)
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- Highly selective hydrogenation of Α, Β-unsaturated carbonyl compounds over supported Co nanoparticles
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A nitrogen-doped porous carbon materials (CPNs) with supported Co nanoparticles (Co@CPNs) with lamellar structure, high surface area and excellent magnetic properties was synthesized successfully by one-pot method. The Co@CPNs exhibited an excellent catalytic activity with 99% conversion and selectivity for hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) under the pressure of H2. In addition, the Co@CPNs were further investigated in the kinetic study and selective hydrogenation of the other α, β unsaturated carbonyl compounds. The study of the Co@CPNs indicated that it was suitable for selective hydrogenation of the α, β unsaturated carbonyl compounds in the industry.
- Jiang, Pengbo,Li, Xinlin,Gao, Wenbin,Wang, Xiang,Tang, Yu,Lan, Kai,Wang, Bin,Li, Rong
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- An artificial synthetic pathway for acetoin, 2,3-butanediol, and 2-butanol production from ethanol using cell free multi-enzyme catalysis
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Upgrading ethanol to higher order alcohols is desired but difficult using current biotechnological methods. In this study, we designed a completely artificial reaction pathway for upgrading ethanol to acetoin, 2,3-butanediol, and 2-butanol in a cell-free bio-system composed of ethanol dehydrogenase, formolase, 2,3-butanediol dehydrogenase, diol dehydratase, and NADH oxidase. Under optimized conditions, acetoin, 2,3-butanediol, and 2-butanol were produced at 88.78%, 88.28%, and 27.25% of the theoretical yield from 100 mM ethanol, respectively. These results demonstrate that this artificial synthetic pathway is an environmentally-friendly novel approach for upgrading bio-ethanol to acetoin, 2,3-butanediol, and 2-butanol.
- Zhang, Liaoyuan,Singh, Raushan,Sivakumar,Guo, Zewang,Li, Jiahuan,Chen, Fanbing,He, Yuanzhi,Guan, Xiong,Kang, Yun Chan,Lee, Jung-Kul
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p. 230 - 242
(2018/01/12)
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- SNS-Ligands for Ru-Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions
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A detailed study of literature-known and novel S-containing pincer-type ligands for ruthenium-catalyzed homogeneous hydrogenation and dehydrogenation reactions was carried out. The scope and limitations of these catalysts were carefully investigated, and it was shown that simple bench-stable SNS-Ru complexes can be used to facilitate the hydrogenation of a variety of different substrates at a maximum H2 pressure of 20 bar under operationally simple, easy to scale up, glovebox-free conditions by using starting materials and reagents that do not require any special purification prior to use. It was also shown that such complexes can be used to catalyze the dehydrogenative coupling of alcohols and amines to get amides as well as for the dehydrogenative dimerization of alcohols to esters.
- Sch?rgenhumer, Johannes,Zimmermann, Axel,Waser, Mario
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supporting information
p. 862 - 870
(2018/06/18)
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- Aqueous Hydrogenation of Levulinic Acid to 1,4-Pentanediol over Mo-Modified Ru/Activated Carbon Catalyst
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A highly efficient and green process was developed for direct conversion of levulinic acid into 1,4-pentanediol over Mo-modified Ru/activated carbon (AC) catalyst in a continuous fixed-bed reactor. The Ru–MoOx/AC catalyst was found to be efficient for the aqueous-phase hydrogenation of levulinic acid to 1,4-pentanediol, whereby a high yield (96.7 mol %) of 1,4-pentanediol was obtained under mild reaction conditions (70 °C, 4 MPa H2).
- Cui, Jinglei,Tan, Jingjing,Zhu, Yulei,Cheng, Fangqin
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p. 1316 - 1320
(2018/03/21)
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- Two efficient pathways for the synthesis of aryl ketones catalyzed by phosphorus-free palladium catalysts
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Allylic alcohols, 1-buten-3-ol, 1-penten-3-ol and 1-octen-3-ol, reacted with aryl iodides (iodotoluene, 4-iodotoluene, 4-iodophenol and 4-iodanisole) under Heck reaction conditions to form corresponding saturated aryl ketones in one step. The same products were obtained in a two-step tandem reaction consisted of the Heck coupling of allylic alcohols with aryl iodides, followed by hydrogenation. Reactions were catalyzed by phosphorus-free palladium precursors modified with the menthol-substituted imidazolium chlorides. Formation of crystalline palladium nanoparticles, of the diameter up to 65 nm, in the reaction mixture was evidenced by TEM.
- Wirwis,Feder-Kubis,Trzeciak
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- CATALYST FOR ONE CARBON-REDUCTION REACTION, AND METHOD FOR PRODUCING ONE CARBON-REDUCTION COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a method for producing selectively a one carbon-reduction compound, using a compound having a primary hydroxy group, a carboxyl group, or an alkoxycarbonyl group, or a lactone compound, as a substrate. SOLUTION: A method of obtaining a one carbon-reduction compound includes the reaction of a compound as a substrate represented by formula (1-1) or (1-2) or (1-3) with hydrogen in the presence of a catalyst in which a metal selected from Ru, Rh, Pd, Ir, and Pt is supported on a support selected from CeO2, hydroxyapatite, ZrO2, TiO2, hydrotalcite, SiO2, MgO, and Al2O3 (R1-R3 independently represent H, a substituted/unsubstituted monovalent hydrocarbon group, or a monovalent group in which two or more hydrocarbon groups are bound together through a linking group; R1-R3 may form a ring with adjacent carbon; L is a substituted/unsubstituted divalent hydrocarbon group or the like; and n is an integer of 0 or greater). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0060; 0070; 0071
(2018/07/28)
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- Catalytic conversion of biomass-derived levulinic acid into alcohols over nanoporous Ru catalyst
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Several Ru-based catalysts were investigated under the same reaction conditions for levulinic acid (LA) hydrogenation. All LA conversion was 100% with the catalysts but the selectivity was different. The mina product was ?-valerolactone (GVL) by using powder Ru, Ru/C, and Ru/Al2O3 catalysts, yet it was 2-butanol (2-BO) and 2-pentanol (2-PO) with nanoporous Ru (NP-Ru) as catalyst. Several other nanoporous metal, e.g., Ni, Fe, Co, and Cu catalysts have been investigated for LA hydrogenation under the same reaction conditions, but the main product was still GVL with little 2-BO and 2-PO accompanied by serious leaching of catalyst. Results showed that NP-Ru play a positive role in the activation of GVL, which is generally difficult to achieve with mono-metallic catalysts unless under strict reaction ocnditions.
- Lv, Jinkun,Rong, Zeming,Sun, Liming,Liu, Chengyun,Lu, An-Hui,Wang, Yue,Qu, Jingping
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p. 975 - 979
(2018/03/05)
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- A new anthraquinoid ligand for the iron-catalyzed hydrosilylation of carbonyl compounds at room temperature: New insights and kinetics
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The reaction of 1-((2-(pyridin-2-yl)ethyl)amino)anthraquinone with either Fe(HMDS)2 or Li(HMDS)/FeCl2 allowed the preparation of a new anthraquinoid-based iron(ii) complex active in the hydrosilylations of carbonyls. The new complex Fe(2)2 was characterized by single-crystal X-ray diffraction, infrared spectroscopy, NMR, and high resolution mass spectrometry (electrospray ionization). Superconducting quantum interference device (SQUID) magnetometry established no spin crossover behavior with an S = 2 state at room temperature. This complex was determined to be an effective catalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 63 min-1 with a broad functional group tolerance by just using 0.25 mol% of the catalyst at room temperature, and even under solvent-free conditions. The aldehyde hydrosilylation makes it one of the most efficient first-row transition metal catalysts for this transformation. Kinetic studies have proven first-order dependences with respect to acetophenone and Ph2SiH2 and a fractional order in the case of the catalyst.
- Raya-Barón, álvaro,Galdeano-Ruano, Carmen P.,O?a-Burgos, Pascual,Rodríguez-Diéguez, Antonio,Langer, Robert,López-Ruiz, Rosalía,Romero-González, Roberto,Kuzu, Istemi,Fernández, Ignacio
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supporting information
p. 7272 - 7281
(2018/06/04)
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- On the direct use of CO2 in multicomponent reactions: Introducing the Passerini four component reaction
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We introduce a novel isocyanide-based multicomponent reaction, the Passerini four component reaction (P-4CR), by replacing the carboxylic acid component of a conventional Passerini three component reaction (P-3CR) with an alcohol and CO2. Key to this approach is the use of a switchable solvent system, allowing the synthesis of a variety of α-carbonate-amides. The reaction was first investigated and optimized using butanol, isobutyraldehyde, tert-butyl isocyanide and CO2. Parameters investigated included the effect of reactant equivalents, reactant concentration, solvent, catalyst, catalyst concentration and CO2 pressure. Of the other parameters, the purity of the aldehyde and its tendency to oxidize was one of the most critical parameters for a successful P-4CR. After optimization, a total of twelve (12) P-4CR compounds were synthesized with conversions ranging between 16 and 82% and isolated yields between 18 and 43%. Their structures were confirmed via1H and 13C NMR, FT-IR and high resolution mass spectrometry (ESI-MS). In addition, three (3) hydrolysis products of P-4CR (α-hydroxyl-amides) were successfully isolated with yields between 23 and 63% and fully characterized (1H, 13C NMR, FT-IR and ESI-MS) as well.
- Onwukamike, Kelechukwu Nnabuike,Grelier, Stéphane,Grau, Etienne,Cramail, Henri,Meier, Michael A. R.
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p. 31490 - 31495
(2018/09/25)
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- Conversion of levulinic acid to γ-valerolactone over Ru/Al2O3-TiO2 catalyst under mild conditions
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Novel catalytic material with high catalytic activity and hydrothermal stability plays a key role in the efficient conversion of levulinic acid (LA) to γ-valerolactone (GVL) in water. In this study, mixed oxides Al2O3-TiO2, Al2O3-MoO3 and Al2O3-Co3O4 were synthesized by co-precipitation using aqueous solution of NaOH as precipitant. Ru catalysts supported on mixed oxides were prepared by impregnation method and their catalytic performances were tested in the hydrogenation of LA to GVL on a fixed bed reactor. The physicochemical properties of the catalysts were characterized by XRD, H2-TPR, NH3-TPD, and BET techniques. The TiO2 component significantly affected the acidity of the catalyst, and thus its catalytic activity for the GVL yield was affected. The desired product GVL with a yield of about 97% was obtained over the Ru/Al2O3-TiO2 catalyst under mild conditions (WHSV = 1.8 h?1, T = 80 °C). Moreover, the catalyst Ru/Al2O3-TiO2 exhibited excellent thermal stability in the test period of time.
- Wang, Ruifeng,Chen, Lungang,Zhang, Xinghua,Zhang, Qi,Li, Yuping,Wang, Chenguang,Ma, Longlong
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p. 40989 - 40995
(2019/01/03)
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- Investigation of the Reaction Pathways of Biomass-Derived Oxygenate Conversion into Monoalcohols in Supercritical Methanol with CuMgAl-Mixed-Metal Oxide
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Reaction pathways for the conversion of cellulose into C2–C6 monoalcohols by supercritical methanol depolymerization and hydrodeoxygenation (SCM-DHDO) over a CuMgAl oxide catalyst have been elucidated using a range of model compounds. SCM-DHDO of intermediate oxygenates including glycerol, methyl lactate, and 1,2-ethanediol produces similar products as those produced from the SCM-DHDO of cellulose. The pathway to C2–C6 monoalcohols occurs through rapid C?C coupling reactions between methanol and diols followed by C?C scission between vicinal alcohol groups to produce two monoalcohols. Methyl-branched monoalcohols are produced through a methyl shift in a secondary diol followed by dehydration. Esters are produced by dehydrogenative coupling between an adsorbed methoxy and a primary alcohol. Both dehydrogenation to a ketone and esterification to a methyl ester are in equilibrium with the corresponding alcohol and were reversible. Dehydration of diols is the slowest observed reaction and not a main pathway to monoalcohols. SCM-DHDO of glucose, dihydroxyacetone, and cellulose all produced similar high molecular weight species indicating that condensation of intermediates can produce undesired side products.
- Galebach, Peter H.,Thompson, Sean,Wittrig, Ashley M.,Buchanan, J. Scott,Huber, George W.
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p. 4007 - 4017
(2018/11/23)
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- AN ECO-FRIENDLY PROCESS FOR HYDROGENATION OR/AND HYDRODEOXYGENATION OF ORGANIC COMPOUND USING HYDROUS RUTHENIUM OXIDE CATALYST
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The invention discloses aneco-friendly process for hydrogenation (alkenealkene, carbonyl compound and aromatic) and hydrodeoxygenation (methoxy phenols) of organic compound using hydrous ruthenium oxide (HRO) and its supported form as a recyclable heterogeneous catalyst in aqueous medium with good yield of desired compounds (70-100%) under mild reaction conditions. The invention also discloses hydrogenation of organic compound such as alkene, carbonyl compound and substituted aromatic and also for the processes that involve hydrodeoxygenation, for example, lignin derived aromatic (methoxy phenols).
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Page/Page column 13; 19, 20
(2017/08/01)
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- Surface-Plasmon-Mediated Hydrogenation of Carbonyls Catalyzed by Silver Nanocubes under Visible Light
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Plasmonic nanoparticles are exciting and promising candidates for light-activated catalysis. We report herein the use of plasmonic nanocubes for the activation of molecular hydrogen and the hydrogenation of ketones and aldehydes via visible light irradiation at 405 nm, corresponding to the position of the plasmon band of the nanocubes, at 80 °C. Only 1 atm of molecular hydrogen is required to access, using catalytic amounts of silver, primary, and secondary alcohols, with complete chemoselectivty for C=O over C=C reduction. The resulting catalytic system was studied over a scope of 12 compounds. Exposure to other wavelengths, or absence of light failed to provide activity, thus proving a direct positive impact of the plasmonic excitation to the catalytic activity. By varying the irradiation intensity, we studied the relationship between plasmon band excitation and catalytic activity and propose a potential reaction mechanism involving plasmon-activated hot electrons. This study expands the scope of reactions catalyzed by free-standing plasmonic particles and sheds light on H2 activation by silver surfaces.
- Landry, Michael J.,Gellé, Alexandra,Meng, Beryl Y.,Barrett, Christopher J.,Moores, Audrey
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p. 6128 - 6133
(2017/09/15)
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- Half-sandwich ruthenium(II) complexes with water-soluble Schiff base ligands: Synthesis and catalytic activity in transfer hydrogenation of carbonyl compounds
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New ionic Schiff-base ligands have been synthesized by condensation of (3-formyl-4-hydroxybenzyl)triphenylphosphonium and 3-(3-formyl-4-hydroxybenzyl)-1-methyl-1H-imidazol-3-ium chloride and hexafluorophosphate salts with N,N-dimethylethylenediamine. Treatment of the dimeric derivative [{RuCl(μ-Cl)(η6-p-cymene)}2] with two equivalents of these ligands allowed the preparation of novel mononuclear water-soluble Ru(II) complexes, which proved to be catalytically active in the transfer hydrogenation of ketones and aldehydes under aqueous conditions.
- Azizi Talouki, Somayeh,Grivani, Gholamhossein,Crochet, Pascale,Cadierno, Victorio
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p. 142 - 148
(2016/12/23)
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- Ru(II) mediated C[sbnd]H activation of 1-(biphenylazo)naphtholSynthesis and catalytic evaluation for transfer hydrogenation of ketones
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New cyclometalated ruthenium(II) complexes of the type [Ru(L)(CO)(EPh3)2] (L?=?di-anionic CNO- donor of 1-(biphenylazo)naphthol; E?=?P, As) have been synthesized by the reaction using [RuHCl(CO)(EPh3)3] (E?=?P, As) with 1-(biphenylazo)naphthol ligand (H2L). The 1-(biphenylazo)naphthol ligand and ruthenium complexes are characterized by analytical, spectral (FT–IR, UV–Vis, 1H NMR and 31P NMR) methods. The molecular structure of ruthenium complex 1 was further confirmed by single crystal X-ray diffraction method. The catalytic efficiency of ruthenium complex 1 was evaluated for the transfer hydrogenation of various ketones to alcohols with excellent conversion up to 99% in the presence of i-PrOH/KOH at 82?°C.
- Ramesh, Madhan,Prabusankar, Ganesan,Venkatachalam, Galmari
-
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- Ru(III) mediated C–H bond activation of N-(naphthyl)salicylaldimine and related Schiff base ligands: Synthesis, structure, DFT study and catalytic activity
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New family of cyclometalated ruthenium(III) Schiff base complexes of the general composition [Ru(LON)(LCNO)(EPh3)] (L = Schiff base ligands of CNO- and ON-donors; E = P, As) have been synthesized and characterized by elemental analysis, FT–IR, UV–Vis and EPR spectral methods. The molecular structure of one of the complexes [Ru(LON)(LCNO)(PPh3)] (5) was determined by X-ray crystallography. The Schiff base ligands readily undergo cyclometalation with the ruthenium metal precursor by C–H activation at the peri-position. These Schiff base ligands coordinated to metal center as di-anionic tridentate CNO-donor and bi-dentate ON-donor in these cycloruthenium complexes. TD–DFT calculations were also carried out for the complex (5). The catalytic activity of the complex [Ru(LON)(LCNO)(PPh3)] (5) was performed and found to be an efficient catalyst for the transfer hydrogenation of ketones with excellent conversion in the presence of i-PrOH/KOH at 80 °C in 2 h.
- Ramesh, Madhan,Kumar, Madhu Deepan,Jaccob, Madhavan,Kaleeswaran, Dhananjayan,Venkatachalam, Galmari
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- Synthesis of the [(η6-p-cymene)Ru(dppb)Cl]PF6 complex and catalytic activity in the transfer hydrogenation of ketones
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Catalysis under mild conditions is of great importance to various chemistry areas, particularly for the development of novel active compounds and for natural products modifications, among others. In this study, the synthesis, characterization, and evaluation of the catalytic activity of a new ruthenium(II) compound, [(η6-p-cymene)Ru(dppb)Cl]PF6 (A) where dppb=1,4-bis(diphenylphosphine)butane, is presented. Catalytic activity of the new Ru(II) compound was tested on hydrogen transfer reaction in various substrates, acetophenone, benzophenone, cyclohexanone, and methyl-ethyl-ketone. Potassium hydroxide was used as base, whereas isopropanol served as both solvent and hydrogen source. Samples comprising substrate: base: catalyst at a 200 : 20 : 1 ratio were poured into 5?mm tubes and monitored in situ at 40, 50, and 60?°C in a 600?MHz NMR spectrometer. The complex was active in the transfer hydrogenation of ketones, achieving conversions superior to 90% within 4?h at 60?°C, which suggests under mild conditions. Therefore, in situ monitoring the reactions through 1H NMR was a valuable technique to establish the possible catalytic mechanism of Ru(II) precatalyst.
- Higuera-Padilla, Angel Ruben,Batista, Alzir Azevedo,Colina-Vegas, Legna,Villarreal, Wilmer,Colnago, Luiz Alberto
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p. 3541 - 3551
(2017/10/31)
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- A method for preparing [...] butanol
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The invention relates to a preparation method of sec-butyl alcohol. According to the preparation method, sec-butyl acetate generated through reaction between mixed C4 fractions and acetic acid is used as a raw material and is directly hydrogenated under the action of a copper-based solid catalyst to prepare sec-butyl alcohol with coproduct being ethanol, and in a fixed bed reactor the feed mass space velocity of sec-butyl acetate is 0.1-2.0h, the molar ratio of hydrogen to sec-butyl acetate is (2-40):1, the reaction temperature is 200-280 DEG C and the reaction pressure is 2.0-9.0MPa to directly prepare sec-butyl alcohol and cogenerate ethanol. The detailed preparation method refers to the specification. The conversion per pass of sec-butyl acetate is over 95%, the selectivity of sec-butyl alcohol is over 95% and ethanol is coproduced. The preparation method has the advantages that the energy consumption is reduced; circulation of mass raw materials is not needed, so the process flow is shortened; no other wastes are generated, so the process is clean; and separation is simple.
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-
Paragraph 0021; 0022; 0023; 0024; 0025; 0026; 0027-0034
(2017/06/13)
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- Ruthenium-phenol catalysts and method of preparing menthone from isopulegol
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The present invention is directed towards a catalyst which is obtainable by contacting in situ a ruthenium precursor and a phenol derivative. Furthermore, the present invention is directed towards the use of said catalyst in transfer hydrogenation reactions. In particular, the present invention is directed to a method for preparing menthone starting from isopulegol.
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Page/Page column 26
(2017/11/09)
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- Hydrogen-Free Gas-Phase Deoxydehydration of 2,3-Butanediol to Butene on Silica-Supported Vanadium Catalysts
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The gas-phase deoxydehydration of 2,3-butanediol to butene was investigated in a plug flow reactor over SiO2-supported vanadium oxide, γ-alumina, P/ZSM-5, and MgO catalysts with acid/base sites of varying strengths. 5 wt % vanadium on SiO2 (i.e., 5V/SiO2) showed the best performance with 100 % conversion and up to 45.2 % butene selectivity. The combination of weak acid sites and polymeric VOx surface species provided the 5V/SiO2 catalyst with bifunctional capabilities to achieve both dehydration and transfer hydrogenation, which allowed it to catalyze the deoxydehydration of 2,3-butanediol to butene even in the absence of H2. As 2,3-butanediol is a common yet underutilized biomass product, this reaction may provide a viable route for a biomass-to-chemicals application for 2,3-butanediol.
- Kwok, Kelvin Mingyao,Choong, Catherine Kai Shin,Ong, Daniel Sze Wei,Ng, Joy Chun Qi,Gwie, Chuandayani Gunawan,Chen, Luwei,Borgna, Armando
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p. 2443 - 2447
(2017/07/12)
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- Influence of the functional groups of multiwalled carbon nanotubes on performance of Ru catalysts in sorbitol hydrogenolysis to glycols
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Different functional groups (i.e. [sbnd]NH2, [sbnd]COOH, [sbnd]OH and nitrogen-doping) modified CNTs (denoted as AMCN, CMCN, HMCN and NMCN, respectively) supported ruthenium catalysts (Ru/AMCN, Ru/CMCN, Ru/HMCN and Ru/NMCN) were prepared by incipient wetness impregnation method. They were fully characterized by XRD, TG, Raman, XPS, TPD and TEM to elucidate the relationship between the physical property and their catalytic performance. TEM results shown that Ru particles were well dispersed on the surface for all the samples with the size of 1.48–1.99 nm. The effects of functional groups of carbon nanotubes (CNTs), nitrogen doping and base additive types on activity and selectivity of ethylene glycol (EG) and propylene glycol (1,2-PD) were investigated. In addition, the activity and final products distribution were much influenced by the properties of functional groups on CNTs and the type of metal cation of the base promoters, which probably participated in the reaction for accelerating a retro-aldol reaction for C[sbnd]C cleavage. Among the catalysts, Ru supported on AMCN exhibited the best catalytic activities and glycols selectivities than on MCN, CMCN, HMCN and NMCN.
- Guo, Xingcui,Dong, Huihuan,Li, Bin,Dong, Linlin,Mu, Xindong,Chen, Xiufang
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- Structure/activity relationships applied to the hydrogenation of α,β-unsaturated carbonyls: The hydrogenation of 3-butyne-2-one over alumina-supported palladium catalysts
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The gas phase hydrogenation of 3-butyne-2-one, an alkynic ketone, over two alumina-supported palladium catalysts is investigated using infrared spectroscopy in a batch reactor at 373?K. The mean particle size of the palladium crystallites of the two catalysts are comparable (2.4?±?0.1?nm). One catalyst (Pd(NO3)2/Al2O3) is prepared from a palladium(II) nitrate precursor, whereas the other catalyst (PdCl2/Al2O3) is prepared using palladium(II) chloride as the Pd precursor compound. A three-stage sequential process is observed with the Pd(NO3)2/Al2O3catalyst facilitating complete reduction all the way through to 2-butanol. However, hydrogenation stops at 2-butanone with the PdCl2/Al2O3catalyst. The inability of the PdCl2/Al2O3catalyst to reduce 2-butanone is attributed to the inaccessibility of edge sites on this catalyst, which are blocked by chlorine retention originating from the catalyst's preparative process. The reaction profiles observed for the hydrogenation of this alkynic ketone are consistent with the site-selective chemistry recently reported for the hydrogenation of crotonaldehyde, an alkenic aldehyde, over the same two catalysts. Thus, it is suggested that a previously postulated structure/activity relationship may be generic for the hydrogenation of α,β-unsaturated carbonyl compounds over supported Pd catalysts.
- Morisse, Clément G.A.,McInroy, Alastair R.,Anderson, Craig,Mitchell, Christopher J.,Parker, Stewart F.,Lennon, David
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p. 110 - 118
(2017/01/05)
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- A acetic acid C3 - C5 alkyl ester hydrogenation production of the C3 - C5 alkyl alcohol and producing ethanol system
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The invention relates to a C3-C5 alkyl alcohol and ethanol production system through acetic acid C3-C5 alkyl ester with hydrogen. The system comprises an acetic acid C3-C5 alkyl ester gasifier, a raw material preheating device, a mixing valve, a hydrogenation reactor, a high pressure buffering tank, a low pressure buffering tank, a crude alcohol separation tower, an ethanol dehydration tower, an ethanol dehydration tower reflux tank and a C3-C5 alkyl alcohol distillation tower. By using the system, the process is simple, the required equipment is few, the environment is protected, main by-product emission is avoided, and the system has high adaptability; the heat of the whole process is utilized in a stepped manner, the heat efficiency is high, and energy consumption is low.
- -
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Paragraph 0049; 0050; 0051; 0052; 0054; 0056; 0058
(2017/08/25)
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- Method and device for preparing sec butanol
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The present invention provides a method and a device for preparing sec butanol, and the method is as follows: (1) sec-butyl acetate is introduced into a first-stage catalytic distillation column, excessive C1-C3 alcohols are added simultaneously for ester exchange, the sec butanol as a product falls into a tower kettle to collect, and the unreacted C1-C3 alcohols and reaction product acetic acid C1-C3 esters partly are sent into a second-stage catalytic distillation column for further reaction separation; (2) excessive sec-butyl acetate is added into the second-stage catalytic distillation column, the acetic acid C1-C3 esters are distilled off from the top of the column, and then congealed to partly reflux to the top of the second-stage catalytic distillation column and partly use as a product to collect; and (3) the sec butanol obtained by the step (2) and the unreacted sec-butyl acetate are returned to the first-stage catalytic distillation column for further reaction separation. The purity of the sec butanol obtained by the method is high above 99.9%, the purity of the separated acetic acid C1-C3 esters is more than 99%, at the same time, the method has the advantages of simple process and easy operation, compared with the process of butylene hydration for preparing the sec butanol, energy consumption is greatly reduced, and cost is saved.
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-
Paragraph 0033-0034
(2017/05/18)
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- Chemocatalytic Conversion of Cellulosic Biomass to Methyl Glycolate, Ethylene Glycol, and Ethanol
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Production of chemicals and fuels from renewable cellulosic biomass is important for the creation of a sustainable society, and it critically relies on the development of new and efficient transformation routes starting from cellulose. Here, a chemocatalytic conversion route from cellulosic biomass to methyl glycolate (MG), ethylene glycol (EG), and ethanol (EtOH) is reported. By using a tungsten-based catalyst, cellulose is converted into MG with a yield as high as 57.7 C % in a one-pot reaction in methanol at 240 °C and 1 MPa O2, and the obtained MG can be easily separated by distillation. Afterwards, it can be nearly quantitatively converted to EG at 200 °C and to EtOH at 280 °C with a selectivity of 50 % through hydrogenation over a Cu/SiO2 catalyst. By this approach, the fine chemical MG, the bulk chemical EG, and the fuel additive EtOH can all be efficiently produced from renewable cellulosic materials, thus providing a new pathway towards mitigating the dependence on fossil resources.
- Xu, Gang,Wang, Aiqin,Pang, Jifeng,Zhao, Xiaochen,Xu, Jinming,Lei, Nian,Wang, Jia,Zheng, Mingyuan,Yin, Jianzhong,Zhang, Tao
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p. 1390 - 1394
(2017/04/14)
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- Facile and effective approach for oxidation of boronic acids
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This present work illustrates facile and effective approach for oxidation of boronic acids using environmentally benign dimethyl carbonate (DMC) as a solvent with H2O2 as an oxidant at room temperature. In contrast to previous reaction reports, which make use of metal catalyst, hazardous reagent and oxidants that creates environmental concern. This method provides good to excellent yield of products and showed better tolerance towards various functional groups present on boronic acids. Moreover, this developed process is an alternative in terms of inexpensive, non toxic and easy reaction conditions.
- Wagh, Ravindra B.,Nagarkar, Jayashree M.
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supporting information
p. 4572 - 4575
(2017/11/03)
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- MANUFACTURING METHOD OF 2-METHYLTETRAHYDROFURAN
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PROBLEM TO BE SOLVED: To provide a method for simply and efficiently manufacturing 2-methyltetrahydrofuran from levulinic acid under a mild condition. SOLUTION: The manufacturing method of 2-methyltetrahydrofuran manufactures 2-methyltetrahydrofuran from levulinic acid in the presence of a following metal catalyst. The metal catalyst is a catalyst having following M1 and M2 as metal species carried on an acidic carrier. (M1) at least one kind of metal selected from the group consisting of rhodium, platinum, ruthenium, iridium and palladium. (M2) at least one kind of metal selected from the group consisting of vanadium, molybdenum, tungsten and rhenium. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0057-0059
(2017/12/12)
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- Efficient and recyclable Ru(II) arene thioamide catalysts for transfer hydrogenation of ketones: Influence of substituent on catalytic outcome
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Six cationic ruthenium(II) arene thioamide complexes with the general molecular formula [Ru(η6-p-cymene)(PPh3)(L)]+ [where, L = pyridine-2-thioamide and its derivatives] have been successfully synthesized from the reaction of [Ru(η6-p-cymene)Cl2]2 with chelating thioamide ligands and PPh3 in methanol in 1:2 M ratio respectively. All the complexes were isolated as their BPh4?salts and were fully characterized by analytical and spectral (FT-IR, UV-Vis and1H-NMR) methods. The solid-state structure of one of the complexes, [Ru(η6-p-cymene)(PPh3)(L4)]BPh4 (4) (L4 = N-(2, 4, 6-Trimethylphenyl)pyridine-2-thiocarboxamide) has been established by X-ray single crystal diffraction which indicates a pseudo-octahedral (piano-stool) coordination geometry is present in the complex. The ruthenium(II) complexes have been examined for the transfer hydrogenation of various aromatic, heterocycle and cyclic ketones. The formation of ruthenium(II) hydride is confirmed by 1H- NMR and is proposed as the catalytic intermediate in this reaction. Under the optimized conditions, these ruthenium complexes served as excellent catalyst precursors which smoothly reduce the ketones with conversion up to 100%. The influence of other variables on the transfer hydrogenation reaction such as solvent, base, temperature, time, catalyst loading and substrate scope is also reported. Furthermore, the catalyst could be easily recovered and reused at least three times without obvious loss of conversions.
- Kanchanadevi, Appukutti,Ramesh, Rengan,Semeril, David
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- Aqueous-Phase Hydrogenation of Saturated and Unsaturated Ketones and Aldehydes over Supported Platinum-Rhenium Catalysts
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The hydrogenation rates of C=C and C=O bonds in methyl vinyl ketone and crotonaldehyde were measured over a series of silica-supported Pt-Re catalysts (1:1 atomic ratio of Pt/Re) in liquid water with H2 (15 psig) at 333 K. The hydrogenation of methyl vinyl ketone did not produce any unsaturated alcohol because of the rapid hydrogenation of C=C relative to that of C=O. The addition of Re to Pt impacted the rate of C=C hydrogenation negatively in methyl vinyl ketone and crotonaldehyde, but promoted the selectivity of C=O hydrogenation in crotonaldehyde in which the unsaturated alcohol increased from 5 % on Pt to 21 % on Pt-Re. The addition of Re to Pt also promoted the rate of C=O hydrogenation in 2-butanone, whereas little effect was observed during the hydrogenation of butanal. The results of electron microscopy and H2 chemisorption on the Pt-Re catalysts showed the increasing interaction between Pt and Re with the increasing metal weight loading, and results from rate measurements suggest that oxophilic Re can be used to promote the Pt-catalyzed hydrogenation of carbonyl groups in multifunctional molecules.
- Falcone, Derek D.,Hack, John H.,Davis, Robert J.
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p. 1074 - 1083
(2016/04/05)
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- Manganese(III) porphyrin anchored onto multiwall carbon nanotubes: An efficient and reusable catalyst for the heterogeneous reduction of aldehydes and ketones
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Reduction of a variety of carbonyl compounds with NaBH4, using Mn-porphyrin, meso-tetrakis(4-hydroxyphenyl)porphyrinatomanganese(III), supported onto functionalized multiwall carbon nanotubes has been investigated. The heterogeneous catalyst was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis spectroscopy. The amount of catalyst loading on the nanotubes was determined by atomic absorption spectroscopy. Thermogravimetric analysis (TGA) demonstrated that the nanocatalyst was thermally stable to almost 300 °C, exhibiting high thermostability of the catalyst over a broad range of temperatures. This heterogeneous catalyst proved to be an efficient catalyst in the aerobic reduction of various aldehydes and ketones with NaBH4. In the presence of the nanocatalyst, NaBH4 can readily reduce a variety of aldehydes in good to excellent yields (50-100%) and ketones in excellent yields (100%) to their corresponding alcohols. The separation of the catalyst is very simple and economic. Also, FTIR spectra after four successive cycles showed that the catalyst was strongly anchored to the nanotubes.
- Rayati, Saeed,Bohloulbandi, Elaheh,Zakavi, Saeed
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p. 638 - 649
(2016/03/12)
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- Ketone hydrogenation catalyzed by a new iron(II)-PNN complex
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The formal FeII-hydride complex [Fe(H)(CO)(MeCN)LPNN](BF4) (1) (LPNN = 2-[(di-tert-butylphosphino)methyl]-6-[1-(mesitylimino)ethyl]pyridine) catalyzes the hydrogenation of ketones under mild conditions (room temperature, p(H2) = 4 bar) and short reaction times (1-3 h) in the presence of catalytic amounts of KHMDS as a base. The reaction presumably proceeds via a dearomatization/rearomatization mechanism. However, in comparison with the reaction of related iron-PNP complexes, the reaction mechanism seems to be different, and an enolate formation step appears to precede catalysis. Moreover, the catalytic performance of the PNN system is inferior under similar conditions, and this observation is probably a consequence of an intramolecular deactivation pathway, which involves reductive proton migration within a dearomatized FeII-hydride complex to form a catalytically inactive Fe0 species. The weaker electron-donating properties of the PNN ligand system, when compared with analogous PNP-based ligands, cause the dearomatized PNN iron(ii)-hydride intermediate to be less electron-rich and consequently more prone to the intramolecular reductive elimination pathway. This result is in line with the need for electron-rich metal hydrides for efficient hydrogenation catalysis to take place.
- Butschke,Feller,Diskin-Posner,Milstein
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p. 4428 - 4437
(2016/07/06)
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- Synthesis and catalytic evaluation of ruthenium(II) benzhydrazone complex in transfer hydrogenation of ketones
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Synthesis of new air stable octahedral ruthenium(II) carbonyl complex bearing O, and N-bidentate benzhydrazone ligand is reported. It has been characterized by elemental analysis, spectral methods and single crystal X-ray diffraction method. The new catalyst has been effectively applied to the transfer hydrogenation reaction of various ketones using isopropanol as a solvent and KOH as a base at 82 °C and the maximum conversion is achieved up to 100%.
- Manikandan, Thimma Sambamoorthy,Saranya, Sundar,Ramesh, Rengan
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supporting information
p. 3764 - 3769
(2016/07/26)
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