10343-99-4Relevant articles and documents
Selective hydrogenation of quinolines into 1,2,3,4-tetrahydroquinolines over a nitrogen-doped carbon-supported Pd catalyst
Ren, Yongshen,Wang, Yanxin,Li, Xun,Zhang, Zehui,Chi, Quan
, p. 16694 - 16702 (2018)
In this study, we have developed a sustainable method for the hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines under mild conditions over a nitrogen-doped carbon-supported Pd catalyst with abundant porous structures (abbreviated as Pd/CN). The mesoporous structure of the nitrogen-doped carbon support was prepared by the pyrolysis of glucose and melamine using eutectic salts of KCl and ZnCl2 as the porogen. Due to the high nitrogen content in the support, Pd nanoparticles were homogeneously dispersed on the surface of nitrogen-doped carbon materials with an ultra-small size of 1.9 nm in a narrow size distribution. The as-prepared Pd/CN catalyst showed high catalytic activity towards the hydrogenation of quinolines at 50 °C and 20 bar H2, affording the corresponding 1,2,3,4-tetrahydroquinolines with yields in the range of 86.6-97.8%. More importantly, the Pd/CN catalyst was highly stable without the loss of its catalytic activity during the recycling experiments. The use of renewable resources to prepare the catalyst makes this method promising for the sustainable 1,2,3,4-tetrahydroquinolines from the hydrogenation of quinolines.
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Weidel
, p. 491 (1881)
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Hydrogenation Pathway of Quinolines over Raney Nickel and Ru/C
Okazaki, Hiroshi,Onishi, Kiyotaka,Soeda, Mahito,Ikefuji, Yoshio,Tamura, Ryuji,Mochida, Isao
, p. 3167 - 3174 (1990)
Quinoline, 2-methylquinoline, and 8-methylquinoline were hydrogenated over Raney Nickel (R-Ni) under 10 atm hydrogen pressure at about 200 deg C and over ruthenium on carbon (Ru/C) under 100 atm hydrogen pressure at 150 deg C.All the substrates were commonly hydrogenated into the initial products, 1,2,3,4-tetrahydroquinolines.The initial products were competitively converted over R-Ni to the final products, decahydroquinolines, directly or via 5,6,7,8-tetrahydroquinolines which were mainly formed from the initial products by isomerization.Ru/C promoted exclusively the direct hydrogenation of 1,2,3,4-tetrahydro derivatives to the final products.The hydrogenation and isomerization of 1,2,3,4-tetrahydroquinoline was completely inhibited in the competitive hydrogenation of quinoline and isoquinoline over R-Ni.Such features of these substrates are explained by the strong basicity of 1,2,3,4-tetrahydroisoquinoline.Roles of 1,2,3,4-tetrahydroisoquinoline are much moderate on Ru/C, where the ?-coordination may be important.The effects of methyl substituent and different reactivities of quinoline and isoquinoline are discussed in terms of the steric hindrance on adsorption, heats of hydrogenation, basicities, and electronic properties of the related compound, which are calculated according to the MNDO-PM3 method.
Recyclable Rh-PVP nanoparticles catalyzed hydrogenation of benzoic acid derivatives and quinolines under solvent-free conditions
Chaudhari, Chandan,Imatome, Hirotaka,Nishida, Yoshihide,Sato, Katsutoshi,Nagaoka, Katsutoshi
, p. 55 - 60 (2019)
Various transition metal nanoparticles, prepared by microwave-assisted alcohol reduction method were examined for hydrogenation of benzoic acid to cyclohexanecarboxylic acid under solvent-free conditions. Rh metal was the most effective catalyst over other metal catalyst. The catalyst showed moderate to high yield for the hydrogenation of substituted benzoic acid and substituted quinolines. Rh-PVP was recycled four times with a minor loss in catalytic activity.
Enzyme Cascades in Whole Cells for the Synthesis of Chiral Cyclic Amines
Hepworth, Lorna J.,France, Scott P.,Hussain, Shahed,Both, Peter,Turner, Nicholas J.,Flitsch, Sabine L.
, p. 2920 - 2925 (2017)
The increasing diversity of reactions mediated by biocatalysts has led to development of multistep in vitro enzyme cascades, taking advantage of generally compatible reaction conditions. The construction of pathways within single whole cell systems is much less explored, yet has many advantages. Herein we report the generation of a successful whole cell de novo enzyme cascade for the diastereoselective and/or enantioselective conversion of simple, linear keto acids into valuable cyclic amine products. The pathway starts with carboxylic acid reduction that triggers a transamination, imine formation, and subsequent imine reduction. Construction and optimization of the system was achieved by standard genetic manipulation and the cascade required only starting material, amine donor, and whole cell catalyst with cofactors provided internally by glucose metabolism. A panel of synthetic keto acids provided access to piperidines in high conversions (up to 93%) and enantiomeric excess (up to 93%).
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Ponomarev et al.
, (1966)
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King,Henshall,Whitehead
, p. 1373 (1948)
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Selective Catalytic Hydrogenation of Heteroarenes with N-Graphene-Modified Cobalt Nanoparticles (Co3O4-Co/NGratα-Al2O3)
Chen, Feng,Surkus, Annette-Enrica,He, Lin,Pohl, Marga-Martina,Radnik, J?rg,Topf, Christoph,Junge, Kathrin,Beller, Matthias
, p. 11718 - 11724 (2015)
Cobalt oxide/cobalt-based nanoparticles featuring a core-shell structure and nitrogen-doped graphene layers on alumina are obtained by pyrolysis of Co(OAc)2/phenanthroline. The resulting core-shell material (Co3O4-Co/NGratα-Al2O3) was successfully applied in the catalytic hydrogenation of a variety of N-heteroarenes including quinolines, acridines, benzo[h], and 1,5-naphthyridine as well as unprotected indoles. The peculiar structure of the novel heterogeneous catalyst enables activation of molecular hydrogen at comparably low temperature. Both high activity and selectivity were achieved in these hydrogenation processes, to give important building blocks for bioactive compounds as well as the pharmaceutical industry.
Hydrogenation of arenes and N-heteroaromatic compounds over ruthenium nanoparticles on poly(4-vinylpyridine): A versatile catalyst operating by a substrate-dependent dual site mechanism
Fang, Minfeng,MacHalaba, Nataliya,Sanchez-Delgado, Roberto A.
, p. 10621 - 10632 (2011)
A nanostructured catalyst composed of Ru nanoparticles immobilized on poly(4-vinylpyridine) (PVPy) has been synthesized by NaBH4 reduction of RuCl3·3H2O in the presence of the polymer in methanol at room temperature. TEM measurements show well-dispersed Ru nanoparticles with an average diameter of 3.1 nm. Both powder XRD patterns and XPS data indicate that the Ru particles are predominantly in the zerovalent state. The new catalyst is efficient for the hydrogenation of a wide variety of aromatic hydrocarbons and N-heteroaromatic compounds representative of components of petroleum-derived fuels. The experimental data indicate the existence of two distinct active sites in the nanostructure that lead to two parallel hydrogenation pathways, one for simple aromatics involving conventional homolytic hydrogen splitting on Ru and a second one for N-heteroaromatics taking place via a novel heterolytic hydrogen activation on the catalyst surface, assisted by the basic pyridine groups of the support.
Nano-Ni-MOFs: High Active Catalysts on the Cascade Hydrogenation of Quinolines
Yun, Ruirui,Ma, Zi-Wei,Hu, Yang,Zhan, Feiyang,Qiu, Chuang,Zheng, Baishu,Sheng, Tian
, p. 2445 - 2451 (2021)
Abstract: The reduction of nitrogen-containing heterocyclic compounds in aqueous medium under mild condition is quite challenging. In view of metal–organic frameworks (MOFs) possess adjustable pore size and modifiable organic linkers, MOFs could be used in heterogeneous catalysis. Herein, Three Nano-Ni-MOFs, MOF-74-Ni, MOF-69-Ni, and Ni–NH2 (constructed from similar ligands and Ni2+ ions) are introduced for hydrogenating of azacyclo-compounds. As expected, Ni–NH2 shows outstanding activity of hydrogenation of quinoline under mild conditions, due to the moderate pore size and the modified –NH2 function group, which makes the substrate anchored on the surface of the framework facilitate the following catalysis process. Theoretical calculations identified that the –NH2 group at the catalyst facilitates the H2 heterolytic dissociation for the hydrogenation reactions. Graphic Abstract: Compared to MOF-74-Ni and MOF-69-Ni, the catalyst of Ni–NH2 shows outstanding activity of hydrogenation of quinoline, due to the modified –NH2 function group which makes the substrate anchored on the surface of the framework facilitate the following catalysis process[Figure not available: see fulltext.]
HDN activities of methyl-substituted quinolines
Kim,Simons, Jack,Massoth
, p. 201 - 206 (2002)
Catalytic hydrotreating has become an important process for removal of sulfur and nitrogen from petroleum due to increasing environmental constraints. The HDN reactivities of quinoline (Q) and several methyl-substituted quinolines (MQ) were determined over a NiMo/Al2O3 catalyst and a CoMo/Al2O3 catalyst using a fixed-bed reactor at 613 K and 3.1MPa. For HDN activity, methyl groups on the aromatic ring gave about the same conversion as for Q, while methyl groups on the N ring gave considerably lower HDN conversions, except for 2-MQ, which was higher. Results were essentially the same for the NiMo and CoMo catalysts. All MQs and Q rapidly reached equilibrium between Q and THQ1 (and their respective methyl analogs). Total and HDN activities were roughly related to their respective equilibria, except for 2-MQ, in which the methyl group provided a positive influence. The rate constants for the formation of o-propylaniline from THQ1 correlated well with the electrostatic potential on the N atom of the respective THQl.
Organometallic Synthesis of Bimetallic Cobalt-Rhodium Nanoparticles in Supported Ionic Liquid Phases (CoxRh100?x@SILP) as Catalysts for the Selective Hydrogenation of Multifunctional Aromatic Substrates
Rengshausen, Simon,Van Stappen, Casey,Levin, Natalia,Tricard, Simon,Luska, Kylie L.,DeBeer, Serena,Chaudret, Bruno,Bordet, Alexis,Leitner, Walter
, (2020/12/22)
The synthesis, characterization, and catalytic properties of bimetallic cobalt-rhodium nanoparticles of defined Co:Rh ratios immobilized in an imidazolium-based supported ionic liquid phase (CoxRh100?x@SILP) are described. Following an organometallic approach, precise control of the Co:Rh ratios is accomplished. Electron microscopy and X-ray absorption spectroscopy confirm the formation of small, well-dispersed, and homogeneously alloyed zero-valent bimetallic nanoparticles in all investigated materials. Benzylideneacetone and various bicyclic heteroaromatics are used as chemical probes to investigate the hydrogenation performances of the CoxRh100?x@SILP materials. The Co:Rh ratio of the nanoparticles is found to have a critical influence on observed activity and selectivity, with clear synergistic effects arising from the combination of the noble metal and its 3d congener. In particular, the ability of CoxRh100?x@SILP catalysts to hydrogenate 6-membered aromatic rings is found to experience a remarkable sharp switch in a narrow composition range between Co25Rh75 (full ring hydrogenation) and Co30Rh70 (no ring hydrogenation).
Aromatic compound hydrogenation and hydrodeoxygenation method and application thereof
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Paragraph 0094-0095; 0114-0122, (2021/05/29)
The invention belongs to the technical field of medicines, and discloses an aromatic compound hydrogenation and hydrodeoxygenation method under mild conditions and application of the method in hydrogenation and hydrodeoxygenation reactions of the aromatic compounds and related mixtures. Specifically, the method comprises the following steps: contacting the aromatic compound or a mixture containing the aromatic compound with a catalyst and hydrogen with proper pressure in a solvent under a proper temperature condition, and reacting the hydrogen, the solvent and the aromatic compound under the action of the catalyst to obtain a corresponding hydrogenation product or/and a hydrodeoxygenation product without an oxygen-containing substituent group. The invention also discloses specific implementation conditions of the method and an aromatic compound structure type applicable to the method. The hydrogenation and hydrodeoxygenation reaction method used in the invention has the advantages of mild reaction conditions, high hydrodeoxygenation efficiency, wide substrate applicability, convenient post-treatment, and good laboratory and industrial application prospects.
