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.
Mild hydrogenation of quinoline to decahydroquinoline over rhodium nanoparticles entrapped in aluminum oxy-hydroxide
Fan, Guang-Yin,Wu, Jie
, p. 81 - 85 (2013)
An Rh/AlO(OH) catalyst was prepared by a sol-gel method. This catalyst showed an excellent catalytic performance for the complete hydrogenation of quinoline to decahydroquinoline at relatively mild conditions. The growth of Rh-particle size and the decrease in the number of surface hydroxyl groups during heat treatment resulted in a significant decrease in catalytic properties. The excellent catalytic performance of the fresh Rh/AlO(OH) was attributed to the cooperation between the hydroxyl groups on the support and on the active metal centers.
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.
NanoRu@hectorite: A heterogeneous catalyst with switchable selectivity for the hydrogenation of quinoline Dedicated to Professor Irina Petrovna Beletskaya in recognition of her contributions to the field of metal-catalysed reactions.
Sun, Bing,Khan, Farooq-Ahmad,Vallat, Armelle,Süss-Fink, Georg
, p. 310 - 314 (2013)
A versatile nano-structured catalyst composed of ruthenium nanoparticles intercalated in hectorite (nanoRu@hectorite) catalyzes the hydrogenation of quinoline (100 C, 30-60 bar H2) with switchable selectivity: In water, 1,2,3,4-tetrahydroquinoline is formed with yields >99%, while in cyclohexane the fully hydrogenated decahydroquinoline is obtained with yields >99%, the mean turnover frequencies being 222 h-1 and 89 h -1, respectively. The reaction in cyclohexane proceeds via both intermediates, 1,2,3,4-tetrahydroquinoline and 5,6,7,8-tetrahydroquinoline.
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.
A comparison between silica-immobilized ruthenium(II) single sites and silica-supported ruthenium nanoparticles in the catalytic hydrogenation of model hetero- and polyaromatics contained in raw oil materials
Bianchini, Claudio,Dal Santo, Vladimiro,Meli, Andrea,Moneti, Simonetta,Moreno, Marta,Oberhauser, Werner,Psaro, Rinaldo,Sordelli, Laura,Vizza, Francesco
, p. 47 - 62 (2003)
HDS and HDN are very important hydrotreating reactions that remove sulfur and nitrogen from fossil fuels where they are contained in various organic compounds, which include polyaromatic heterocycles, aliphatic and aromatic thiols and amines, thioethers, disulfides, and nitriles. A comparative study of the hydrogenation of various heterocycles, model compounds in raw oil materials, by either Ru(II) complex immobilized on mesoporous silica or Ru(0) nanoparticles deposited on the same support was conducted. The single-site catalyst contained the molecular precursor [Ru(NCMe)3(sulphos)](OSO2 CF3) tethered to partially dehydroxylated high-surface-area silica through hydrogen bonds between silanol groups of the support and SO3- groups from the sulphos ligand [-O3S(C6H4) CH2C(CH2PPh2)3] and the triflate counter anion. The heterocycles (benzo[b]thiophene, quinoline, indole, acridine) were hydrogenated to cyclic thioethers or amines. Ru(II)-based catalysts were much more efficient for the hydrogenation of S-heterocycles than for N-heterocycles.
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%).
Effect of Zr on catalytic performance of unsupported Ni(Zr)Mo and Ni(Zr)W sulfide catalysts for quinoline hydrodenitrogenation
Jiang, Zongxuan,Li, Can,Liu, Tiefeng,Liu, Xinyi,Zhang, Cen
, (2020)
To increase the dispersion of active species and full utilization of active metals are of great importance for hydrodenitrogenation (HDN) performance of unsupported hydrotreating catalysts. Herein, a series of unsupported Ni(Zr)MoS and Ni(Zr)WS catalysts were prepared from Ni(Zr) layered double hydroxide (LDH) precursors. The Zr species remarkably promote the dispersion and reducibility of NiMo and NiW composite species. Also, the total HDN rate constants are increased from 2.42 h?1 to 9.18 h?1 for Ni(Zr)MoS and from 5.68 h?1 to 23.0 h?1 for Ni(Zr)WS, and exhibit a maximum at a Zr/Ni atomic ratio of about 0.04. The HDN selectivities indicate that the Zr species increase the number of superficial active sites without affecting their structure. The present work shows that the crystallinity of LDH precursors is crucial to the structure of unsupported sulfide catalysts, and a suitable amount of Zr could be a dispersive promoter to increase the HDN activity.
Facile Synthesis of Size-Controlled Nitrogen-Doped Mesoporous Carbon Nanosphere Supported Ultrafine Ru Nanoparticles for Selective Hydrogenation of Quinolines
Huang, Minghua,Jiang, Haibin,Tian, Zhengbin,Wang, Guang-Hui
, p. 17000 - 17004 (2020)
Nitrogen-doped mesoporous carbon nanosphere (NMCS) with tunable sizes and uniform mesoporosity was synthesized by a facile soft-templating method. During the synthesis, F127 (PEO–PPO–PEO triblock copolymer) could be used not only as a soft template to generate the mesostructure but also as a size-control agent to tailor the size of NMCS in a relatively wide range of 100 to 700 nm. In addition, the synthesis process was simple and suitable for large-scale production. Moreover, the NMCS was used as support of ultrafine Ru nanoparticles (Ru/NMCS), which exhibited good catalytic performances for selective hydrogenation of quinolones. It is expected that the simple synthetic strategy for the NMCS can generate extensive interest in many catalysis and sorption applications.
Support effect on conversion of quinoline over ReS2 catalyst
Bassi,Villarroel,Gil-Llambias,Baeza,García-Fierro,Martínez,Olivera,Leiva,Escalona
, p. 3170 - 3176 (2016)
The conversion of quinoline over ReS2 supported on γ-Al2O3, SiO2, ZrO2 and TiO2 catalysts in a batch reactor at 300°C and 5 MPa of hydrogen pressure was studied. The catalysts were prepared by wet impregnation with a loading of 1.5 atoms of Re per nm2 of support. The catalysts were characterized by N2 adsorption, X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD). The Re(x)/supports catalysts displayed high activities for the conversion of quinoline, although negligible formation of N-free compounds (hydrodenitrogenation) were observed. The intrinsic activities of ReS2 were modified by the support decreased in the order: Re/TiO2 > Re/ZrO2 > Re/SiO2 > Re/γ-Al2O3. The highest activity displayed by the Re/TiO2 catalyst was correlated with the Re dispersion and formation of ReS2 species. Meanwhile, the lower conversion of quinoline over the Re/ZrO2, Re/SiO2 and Re/γ-Al2O3 catalysts was related to the combined effect of the textural properties of catalysts and the formation of ReS(2-x) species on the supports.
