533-37-9Relevant articles and documents
Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application
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Paragraph 0159-0165, (2021/07/31)
The invention discloses a pincerlike manganese complex, a preparation method thereof, a ligand for preparation, a preparation method of the ligand, a catalyst composition taking the complex as an active component and application of the catalyst composition. According to the pincerlike manganese complex, a cycloalkyl ring is introduced into a ligand framework, and by regulating and controlling the cyclic tension, flexibility and steric hindrance of the cycloalkyl ring, the reactivity and stability of the manganese metal center can be effectively adjusted, and the catalytic activity and substrate applicability of a manganese metal system are remarkably improved. The catalyst composition taking the pincerlike manganese complex as an active component has the advantages of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of preparing quinoline or pyridine derivatives by catalyzing dehydrogenation coupling reaction of o-amino aromatic alcohol or gamma-amino alcohol, ketone or secondary alcohol; and the synthesis advantages of low cost and stable performance are embodied, the operation is simple, and the yield is high.
Direct synthesis of ring-fused quinolines and pyridines catalyzed byNNHY-ligated manganese complexes (Y = NR2or SR)
Han, Mingyang,Lin, Qing,Liu, Qingbin,Liu, Song,Ma, Ning,Solan, Gregory A.,Sun, Wen-Hua,Wang, Zheng,Yan, Xiuli
, p. 8026 - 8036 (2021/12/27)
Four cationic manganese(i) complexes, [(fac-NNHN)Mn(CO)3]Br (Mn-1-Mn-3) and [(fac-NNHS)Mn(CO)3]Br (Mn-4) (whereNNHis a 5,6,7,8-tetrahydro-8-quinolinamine moiety), have been synthesized and evaluated as catalysts for the direct synthesis of quinolines and pyridines by the reaction of a γ-amino alcohol with a ketone or secondary alcohol;NNHS-ligatedMn-4proved the most effective of the four catalysts. The reactions proceeded well in the presence of catalyst loadings in the range 0.5-5.0 mol% and tolerated diverse functional groups such as alkyl, cycloalkyl, alkoxy, chloride and hetero-aryl. A mechanism involving acceptorless dehydrogenation coupling (ADC) has been proposed on the basis of DFT calculations and experimental evidence. Significantly, this manganese-based catalytic protocol provides a promising green and environmentally friendly route to a wide range of synthetically important substituted monocyclic, bicyclic as well as tricyclicN-heterocycles (including 50 quinoline and 26 pyridine examples) with isolated yields of up to 93%.
Cu-Catalyzed Pyridine Synthesis via Oxidative Annulation of Cyclic Ketones with Propargylamine
Sotnik, Svitlana O.,Subota, Andrii I.,Kliuchynskyi, Anton Y.,Yehorov, Dmytro V.,Lytvynenko, Anton S.,Rozhenko, Alexander B.,Kolotilov, Sergey V.,Ryabukhin, Sergey V.,Volochnyuk, Dmitriy M.
, p. 7315 - 7325 (2021/05/29)
A Cu-catalyzed, easily scalable one-pot synthesis of fused pyridines by the reaction of cyclic ketones with propargylamine is described. The protocol was optimized based on the results of more than 30 experiments. The highest product yields were achieved in i-PrOH as a solvent in the presence of 5.0 mol % CuCl2 in air. In contrast to the well-known Au-catalyzed protocol, our procedure is "laboratory friendly", cost-effective, and suitable for preparing dozens of grams of fused pyridine-based building blocks and does not require a high-pressure autoclave technique. Decreasing the catalyst amount in the reaction to 1.25 mol % CuCl2 provided a yield comparable to that achieved with 5 mol % catalyst, though a longer reaction time was required. A plausible reaction mechanism was proposed. The scope and limitation of the reaction were studied using 24 different cyclic ketones as starting materials. The fused pyridine yield decreased among cyclic ketones in the following order: six-membered ? eight-membered > five-membered ～seven-membered. The elaborated reaction conditions demonstrated tolerance to a number of protective functional groups in ketone such as ester, tert-butoxycarbonyl (Boc)-protected amine, and acetal moieties.
Palladium acetate-catalyzed one-pot synthesis of mono- And disubstitued pyridines
Mikami, Shunya,Toyota, Masahiro
, p. 1315 - 1321 (2019/08/01)
A Pd-catalyzed one-pot synthesis of mono- and disubstituted pyridines was developed. The substituted pyridines were obtained from ketones or an aldehyde and 1,3-diaminopropane using a combination of catalytic Pd(OAc)2 and Cu(OAc)2. High-concentration reaction conditions enabled this catalytic reaction to be acid-free.
Production process of 2,3- cyclopenteno pyridine
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Paragraph 0005; 0006, (2018/09/08)
2,3-cyclopenteno pyridine has physiological activity of resisting ulcer and resisting cancer, is an important medical intermediate and alkaloid, is also used for preparing plant protective agents, synthetic resin, antioxidants and the like, and is currently used for the side chains of a fourth-generation injection-use aminothiazole cephalosporins, which is cefpirome, and the quantity demanded in developing countries, such as China and India, is growing rapidly at present. The invention provides a production process of the 2,3- cyclopenteno pyridine. The specific process is as follows: (1) preparation of 4,5,6,7-tetrahydro-2-oxo-3-formyl cyclopenteno pyridine, (2) preparation of 2-chloro-2,3-cyclopenteno pyridine, and (3) preparation of the 2,3-cyclopenteno pyridine.
An ion liquid law synthesis of pharmaceutical intermediates 6, 7 - dihydro - 5H - cyclopenta (b) pyridine preparation method (by machine translation)
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Paragraph 0013; 0014; 0016; 0018; 0020, (2017/08/27)
The invention relates to the preparation of the intermediate compound, in particular to a pharmaceutical intermediate ion liquid law synthesis of 6, 7 - dihydro - 5H - cyclopenta (b) pyridine of the preparation method. The preparation method comprises: (1) ion the liquid carries catalyst BMImZnCl3 Preparation, (2) in order to cyclopentanone and propiolic as raw materials, in BMImBF4 /BMImZnCl3 Under catalytic system, microwave heating to synthesize medicine intermediate 6, 7 - dihydro - 5H - cyclopentane (b) pyridine, after the reaction the reaction liquid organic solvent extraction, drying, distillation, to get the content in the range of 99.0% product of the above, the yield is 70% -75%. The invention in the ionic liquid microwave synthesis of 6, 7 - dihydro - 5H - cyclopentane and [b] pyridine, mild reaction conditions, the reaction time is short, reaction selectivity and high yield, the ionic liquid catalyst can be recycled, operation and after treatment is simple, and is a highly efficient, environment-friendly synthetic method. (by machine translation)
Preparation method of cefpirome intermediate, namely, 6,7-dihydro-5H-cyclopentane (b) pyridine
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Paragraph 0014; 0015; 0016; 0017; 0018; 0019; 0020; 0021, (2017/08/27)
The invention relates to preparation of a medical intermediate, in particular to a preparation method of a cefpirome intermediate, namely, 6,7-dihydro-5H-cyclopentane (b) pyridine. Cyclopentanone and propargylamine are used as raw materials, a key intermediate, namely, 6,7-dihydro-5H-cyclopentane (b) pyridine of cefpirome is synthesized in an autoclave and an organic solvent by taking a ferric nitrate activated carbon carrier as a catalyst, reaction liquid is filtered and then is adjusted to be alkalescent by using ammonia water, an organic layer is rectified to obtain a product of which the content is 99.0% or more, and the yield reaches 68-72%. The preparation method provided by the invention takes the ferric nitrate activated carbon carrier as the catalyst for high-pressure synthesis, the reaction condition is mild, the reaction time is short, the operation is simple and convenient, the after-treatment is simple, the yield is high, the obtained product contains few impurities, the content is 99.0% or more, and meanwhile, the catalyst and the solvent are easy to recycle.
2 - (b benzene phosphine base ethyl) - (5, 6, 7, 8 - tetrahydro quinolyl) amine ruthenium complex preparation method and application thereof
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Paragraph 0055; 0056; 0057; 0058; 0059, (2017/06/19)
The invention discloses a preparation method and application of 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine ruthenium complexes. A ligand 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine is firstly prepared, and then reacted with RuHCl(CO)(PPh3)3 and RuCl2(PPh3)3 for preparing a complex 1 and a complex 2 which are different in structure, and then the 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine ruthenium complex 1 or complex 2 is used to catalyze a condensation reaction of an amino alcohol and a secondary alcohol or a ketone, so that pyridine and quinoline derivatives are synthesized. The preparation method is simple, good in stability, and the catalyst is high in catalytic activity and has the usage amount only being 0.025% by molar of a substrate. The preparation method is applied to production of pyridine and quinoline derivatives, the method is simple, environmental pollution is small, the yield is high and the cost is low.
Au-complex containing phosphino and imidazolyl moieties as a bi-functional catalyst for one-pot synthesis of pyridine derivatives
Yang, Da,Liu, Huan,Wang, Dong-Liang,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
, p. 323 - 330 (2016/09/23)
The complex of Au-L1 containing imidazolyl ring and the phosphine-ligated-Au moiety was synthesized and applied as the efficient bi-functional catalyst for the one-pot sequential condensation/annulation reaction for the synthesis of pyridine derivatives. It was found that, as for Au-L1, the involved imidazolyl group acted as a Lewis base to catalyze the condensation of carbonyl compounds with propargylamine to form the imino intermediate, and the involved Au+-complex species with alkynophilicity corresponded to the subsequent activation of imino-tailed alkynyl to afford dehydropyridine intermediate. The latter proceeded auto-oxidation reaction to afford the pyridine derivatives. The observed sequential catalysis over Au-L1 proved more efficient than that over the mechanical mixtures of the Au-complex (Au-L2) and N-methylimidazole, because the free N-methylimidazole as an N-containing donor competed with the alkyne substrate to coordinate to Au-center. Moreover, Au-L1 exhibited good generality to a wide range of the substrates for the synthesis of 2,3-fused pyridine derivatives and 2-aryl(heteroaryl)-substituted pyridines.
A Ruthenium Catalyst with Unprecedented Effectiveness for the Coupling Cyclization of - Amino Alcohols and Secondary Alcohols
Pan, Bing,Liu, Bo,Yue, Erlin,Liu, Qingbin,Yang, Xinzheng,Wang, Zheng,Sun, Wen-Hua
, p. 1247 - 1253 (2016/02/18)
The ruthenium complex (8-(2-diphenylphosphinoethyl)aminotrihydroquinolinyl)(carbonyl)(hydrido)ruthenium chloride exhibited extremely high efficiency toward the coupling cyclization of -amino alcohols with secondary alcohols. The corresponding products, pyridine or quinoline derivatives, are obtained in good to high isolated yields. On comparison with literature catalysts whose noble-metal loading with respect to -amino alcohols reached 0.5-1.0 mol % for Ru and a record lowest of 0.04 mol % for Ir, the current catalyst achieves the same efficiency with a loading of 0.025 mol % for Ru. The mechanism of acceptorless dehydrogenative condensation (ADC) was proposed on the basis of DFT calculations; in addition, the reactive intermediates were determined by GC-MS, NMR, and single-crystal X-ray diffraction. The catalytic process is potentially suitable for industrial applications.
