767-92-0Relevant articles and documents
PRODUCTION METHOD OF CYCLIC COMPOUND
-
Paragraph 0057; 0059; 0062-0063, (2021/05/05)
PROBLEM TO BE SOLVED: To provide an industrially simple production method of a cyclic compound. SOLUTION: A production method of a cyclic compound includes a step to obtain a reduced form (B) by reducing an unsaturated bond in a ring structure of an aromatic compound (A) by means of catalytic hydrogenation of the aromatic compound (A) or its salt using palladium carbon as a catalyst under a normal pressure, in which the aromatic compound (A) has one or more ring structures selected from a group consisting of a five membered-ring, a six membered-ring, and a condensed ring of the five membered-ring or the six membered-ring with another six membered-ring, a hetero atom can be included in the ring structure, and the aromatic compound (A) can have one or two side chains bonded to the ring structure and does not have any carbon-carbon triple bond in the side chain. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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).
A confined thermal transformation strategy to synthesize single atom catalysts supported on nitrogen-doped mesoporous carbon nanospheres for selective hydrogenation
Tian, Zhengbin,Wang, Guang-Hui,Wang, Wenquan,Zheng, Yan
, p. 25488 - 25494 (2021/12/07)
Carbon-supported single-atom catalysts (SACs) have brought considerable attention to heterogeneous catalysis, but they, however, often suffer from low activity due to the mass transfer limitation. Herein, we report a soft-templating method to synthesize core-shell mesostructured polymer nanospheres with metal nanoclusters (M-NCs, M = Pd, Pt) as the core, which can be easily converted into nitrogen-doped mesoporous carbon nanosphere (NMCS) supported SACs (M1/NMCS) after a confined thermal transformation process. Through this strategy, Pd1/NMCS and Pt1/NMCS are successfully prepared with rich porosity and high N content. The abundant N species in M1/NMCS can be employed as anchoring sites to capture and stabilize the single metal atoms. In addition, the mesoporous structure of M1/NMCS is beneficial for the mass transfer and the exposure of active sites. Benefiting from such a unique structure, the as-obtained Pd1/NMCS exhibits excellent activity, selectivity, and long-term stability in the selective hydrogenation of quinoline.
Aromatic compound hydrogenation and hydrodeoxygenation method and application thereof
-
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.
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 (2021/01/05)
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.]
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
, (2020/08/19)
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.
Highly efficient one-pot multi-directional selective hydrogenation and N-alkylation catalyzed by Ru/LDH under mild conditions
Zhang, Sishi,Xu, Jie,Cheng, Hongmei,Zang, Cuicui,Sun, Bin,Jiang, Heyan,Bian, Fengxia
supporting information, (2020/03/30)
Atomic economy, non-toxicity, harmlessness and multidirectional selectivity advocated by green chemistry have increasingly become a hot and difficult research topic. Herein, we present a highly efficient, one-pot tandem and easy-to-operate method through which we could directly produce a broad range of multi-directional selective hydrogenated amines or N-alkyl aliphatic amines using aromatic nitro compounds as raw materials. Ru/LDH with characteristics of layered mesoporous structure, well dispersed small Ru nanoparticles and LDH stabilization to the Ru NPs was employed as the catalyst. It is remarkable that multi-directional superb chemoselectivity to aromatic amines, alicyclic amines as well as N-alkyl aliphatic amines could be achieved with excellent catalytic activity and recyclability by tuning reaction conditions over 5wt%Ru/LDH-2. Additionally, this catalytic system also exhibited attractive activity and multi-directional chemoselectivity in the hydrogenation of quinoline and its derivatives with solvents of different polarity. Chemoselectivity to 5,6,7,8-tetrahydroquinoline derivatives could reach as high as 95.6 %.
One-pot dual catalysis for the hydrogenation of heteroarenes and arenes
Chatterjee, Basujit,Kalsi, Deepti,Kaithal, Akash,Bordet, Alexis,Leitner, Walter,Gunanathan, Chidambaram
, p. 5163 - 5170 (2020/09/07)
A simple dinuclear monohydrido bridged ruthenium complex [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] acts as an efficient and selective catalyst for the hydrogenation of various heteroarenes and arenes. The nature of the catalytically active species was investigated using a combination of techniques including in situ reaction monitoring, kinetic studies, quantitative poisoning experiments and electron microscopy, evidencing a dual reactivity. The results suggest that the hydrogenation of heteroarenes proceeds via molecular catalysis. In particular, monitoring the reaction progress by NMR spectroscopy indicates that [{(η6-p-cymene)RuCl}2(μ-H-μ-Cl)] is transformed into monomeric ruthenium intermediates, which upon subsequent activation of dihydrogen and hydride transfer accomplish the hydrogenation of heteroarenes under homogeneous conditions. In contrast, carbocyclic aryl motifs are hydrogenated via a heterogeneous pathway, by in situ generated ruthenium nanoparticles. Remarkably, these hydrogenation reactions can be performed using molecular hydrogen under solvent-free conditions or with 1,4-dioxane, and thus give access to a broad range of saturated heterocycles and carbocycles while generating no waste.
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 (2020/11/30)
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.
PtRuNi/C novel nanostructures of platinum-ruthenium island-on-Ni/Ni(OH)2 nanoparticles for the selective hydrogenation of quinoline
Chen, Bing Hui,Liao, Jianhua,Pei, An,Ruan, Luna,Wang, Jiexiang,Yang, Kai,Zhang, Huan,Zhu, Lihua
, (2020/04/27)
Ni/C was successfully synthesized via hydrazine hydrate reduction at room temperature (RT). Pt/C, Ru/C and PtRu/C were prepared via an impregnation method. PtNi/C, RuNi/C and PtRuNi/C were synthesized via a chemical replacement method. The characterization results revealed that PtRuNi nanoparticles (NPs) were highly and uniformly dispersed on carbon black in PtRuNi/C. PtRuNi/C showed a novel nanostructure in which PtRu islands (PtRu nanoclusters or PtRu binary atoms) covered Ni/Ni(OH)2 NPs. PtRuNi/C trimetallic nanomaterial exhibited an optimum catalytic performance (turnover frequency (TOF) = 211.4 h?1 and selectivity for the production of 1,2,3,4-tetrahydroquinoline (py-THQ) > 99%) in the selective hydrogenation of quinoline at 60 °C under 5.0 MPa H2. The catalytic properties of PtRuNi/C were significantly improved as compared to bimetallic (PtNi/C, RuNi/C and PtRu/C) and monometallic (Ni/C, Pt/C and Ru/C) nanomaterials due to its unique nanostructure, with an observed nano-synergy effect among Pt-, Ru- and Ni-related species.
