- METHOD OF REDUCING AROMATIC NITRO COMPOUNDS
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A method for reducing a substrate selected from 2-methyl-5-nitropyridine and methyl 4-(2-fluoro-3-nitrobenzyl)piperazine-1-carboxylate is provided catalysed by a nitroreductase and a disproportionation agent.
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Paragraph 0332; 0345
(2022/02/26)
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- Palladium Immobilized on a Polyimide Covalent Organic Framework: An Efficient and Recyclable Heterogeneous Catalyst for the Suzuki–Miyaura Coupling Reaction and Nitroarene Reduction in Water
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An efficient and recyclable Pd nano-catalyst was developed via immobilization of Pd nanoparticles on polyimide linked covalent organic frameworks (PCOFs) that was facilely prepared through condensation of melamine and 3,3′,4,4′-biphenyltetracarboxylic dianhydride. The Pd nanoparticles (Pd NPs) catalyst was thoroughly characterized by FT-IR, XRD, SEM, TEM. Furthermore, the catalytic activity of Pd NPs catalyst was evaluated by Suzuki–Miyaura coupling reaction and nitroarene reduction in water, respectively. The excellent yields of corresponding products revealing revealed that the Pd NPs catalyst could be applied as an efficient and reusable heterogeneous catalyst for above two reactions. Graphical Abstract: [Figure not available: see fulltext.]
- Dong, Zhenhua,Pan, Hongguo,Gao, Pengwei,Xiao, Yongmei,Fan, Lulu,Chen, Jing,Wang, Wentao
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p. 299 - 306
(2021/05/10)
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- Industrial Cunninghamia lanceolata carbon supported FeO(OH) nanoparticles-catalyzed hydrogenation of nitroarenes
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The development of green and efficient methods for hydrogenation of nitroarenes is still highly demanding in organic synthesis. Herein, we report an industrial Cunninghamia lanceolata carbon supported FeO(OH) nanoparticles process for the synthesis of aryl amines with good yields via hydrogenation of nitroarenes. Nine key anti-cancer drug intermediates were successfully achieved with protocol. And Osimertinib intermediate 4m can be smoothly synthesized at a 2.67 kg-scale with >99.5% HPLC purity. This protocol features cheap carbon source, highly catalytic activity, simple operation, kilogram-scalable and recyclable catalysts (eight times without observable losing activity).
- Fu, Lihua,Li, Dingzhong,Lu, Hao,Qiu, Renhua,Sun, Tulai,Xing, Chen,Yang, Tianbao
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- Efficient and recyclable bimetallic Co–Cu catalysts for selective hydrogenation of halogenated nitroarenes
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Silica supported N-doped carbon layers encapsulating Co–Cu nanoparticles (Co1Cux@CN/SiO2) were prepared by a one-step impregnation of Co(NO3)2·6H2O, Cu(NO3)2·3H2O, urea and glucose, following in situ carbothermal reduction. Effects of Cu contents on the catalytic performance of the Co1Cux@CN/SiO2 catalysts were investigated for selective hydrogenation of p-chloronitrobenzene to p-chloroaniline. The Co1Cu0.30@CN/SiO2 with Cu/Co molar ratio of 0.30:1 presented much higher activity and stability than the monometallic Co@CN/SiO2 catalyst. The addition of Cu into Co1Cux@CN/SiO2 catalysts had favorable effects on the formation of highly active Co–N sites and N-doped carbon layer. The role of the N-doped carbon layer was to protect the Co from oxidation by air, and the Co1Cu0.30@CN/SiO2 could be reused for at least 12 cycles without decrease in catalytic efficiency. Mechanistic and in situ infrared studies revealed that the interaction effect between the Co and Cu atoms made the surface of Co highly electron rich, which decreased adsorption of halogen groups and resulting in the enhanced selectivity during chemoselective hydrogenation of halogenated nitroarenes for a wide scope of substrates.
- Lu, Xionggang,Ren, Jiaan,Sheng, Yao,Wang, Xueguang,Wu, Baoqin,Zou, Xiujing
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- Method for preparing 2, 3 -dichloropyridine from chlorination
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The invention relates to a method for preparing 2 and 3 - dichloropyridine from chlorination. The method introduces the graphene oxide catalyst in the traditional 3 - aminopyridine chlorination step, reduces the concentration and the dosage of hydrochloric acid and hydrogen peroxide, improves the selectivity of 2 -position chlorination, and reduces the generation of 2, 6 - dichloro -3 - aminopyridine. , The process enables high yield to obtain 2 - chloro -3 - aminopyridines of higher quality. , The method has good environmental friendliness and economical efficiency, and is suitable for being popularized and used in industry.
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Paragraph 0011; 0049-0054; 0057-0058
(2021/11/03)
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- NaI/PPh3-Mediated Photochemical Reduction and Amination of Nitroarenes
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A mild transition-metal- and photosensitizer-free photoredox system based on the combination of NaI and PPh3 was found to enable highly selective reduction of nitroarenes. This protocol tolerates a broad range of reducible functional groups such as halogen (Cl, Br, and even I), aldehyde, ketone, carboxyl, and cyano. Moreover, the photoredox catalysis with NaI and stoichiometric PPh3 provides also an alternative entry to Cadogan-type reductive amination when o-nitrobiarenes were used.
- Qu, Zhonghua,Chen, Xing,Zhong, Shuai,Deng, Guo-Jun,Huang, Huawen
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supporting information
p. 5349 - 5353
(2021/07/21)
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- Preparation method 2-chloro -3- aminopyridine
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The organic phase 2 - separates the organic phase and the aqueous phase in, steps: first and continuously pumps, aminopyridine hydrochloride in a hydrochloric acid solution and uniformly mixes; the organic phase containing 3 - aminopyridine hydrochloride solution, with an organic solvent 3 - chlorination reagent solution to obtain, chlorine - 3 3-aminopyridine solution, in a continuous pump in a sample stage extraction centrifuge as a sample stage extraction centrifuge; to extract a centrifuge. 2nd. The present invention uses ", continuous process; to prepare,aminopyridine as a present stage extraction centrifuge, in a continuous pump in a two-stage extraction centrifuge as a present stage extraction centrifuge, to extract a centrifuge, in a stage extraction, centrifuge as a. fourth present-stage extraction centrifuge, and continuously pump second the organic phase with the aqueous, phase separation, 2 - organic phase "; step. third by a continuous pump in a. stage extraction centrifuge as a present stage extraction centrifuge, to separate the organic phase and the organic phase.
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Paragraph 0070-0084; 0092; 0096-0098
(2020/03/29)
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- Preparation method of medical intermediate 2-chloro-3-aminopyridine
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The invention discloses a preparation method of a medical intermediate, namely 2-chloro-3-aminopyridine. The preparation method comprises the following steps: S1, preparation of nicotinamide; S2, preparation of 3-aminopyridine; S3, preparation of a crude product of 2-chloro-3-aminopyridine; and S4, refining. The method has the advantages of usage of easily available raw materials, low price, mildreaction conditions, easy product separation, high purity, high yield, less three wastes and small pollution, and is suitable for large-scale production. According to the method, dangerous and expensive raw materials such as chlorine and zinc powder are prevented from being used, so industrial application prospects are achieved; and ethyl acetate, toluene and dichloromethane are adopted as organicsolvents, and can be recycled.
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Paragraph 0025; 0032-0033; 0034; 0041-0042; 0043; 0047-0051
(2020/11/26)
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- Photochemical synthesis method of heteroarylamine compounds
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The invention provides a photochemical synthesis method of heteroarylamine compounds. The photochemical synthesis method comprises the following steps: S1, mixing raw materials including heteroaryl nitro compounds, a solvent and a photocatalyst to obtain a mixture; and S2, carrying out a photocatalytic reduction reaction on the mixture under an illumination condition to obtain a product system containing the heteroarylamine compounds. According to the photochemical synthesis method, photocatalytic reduction of various different heteroaryl nitro compounds is achieved under the illumination condition, and the high-yield heteroaryl amine compounds are obtained. The photocatalyst is an existing common catalyst, has no strict requirements on equipment and is easy to recover, and the safety riskof the heteroarylamine compound and the catalyst cost are reduced. Any metal reagent and reducing agent do not need to be added in the whole reaction process of photocatalysis, the reaction conversion rate is high, and post-treatment is simple and easy to operate, so the method is safer and more environmentally friendly.
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Paragraph 0067
(2020/10/14)
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- Method for reducing aromatic nitro into arylamine
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The invention relates to a method for reducing aromatic nitro to arylamine. The method comprises the following steps: (1) taking an aromatic nitro compound as a raw material, water as a hydrogen source, a palladium compound, cheap and easy to obtain, as a catalyst and tetrahydroxydiboron as an additive to reduce nitro to obtain a product; (2) taking the aromatic nitro compound as the raw material, a copper salt, cheap and easy to obtain, as the catalyst, the tetrahydroxydiboron as the additive to reduce the nitro to obtain a product; and (3) taking the aromatic nitro compound as the raw material, water as the hydrogen source, and the tetrahydroxydiboron as the additive, without needing a metal catalyst, to reduce the nitro to obtain a product. A preparation method for the arylamine, which is provided by the invention, is mild in reaction condition, low in costs, environment-friendly, high in yield, and suitable for industrial production.
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Paragraph 0181-0184
(2020/07/15)
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- In Situ Synthesized Silica-Supported Co@N-Doped Carbon as Highly Efficient and Reusable Catalysts for Selective Reduction of Halogenated Nitroaromatics
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Silica-supported Co@N-doped carbon (Co@CN/SiO2) catalysts were first prepared by a one-step impregnation with a mixed solution of cobalt nitrate, glucose and urea, followed by in situ carbonization and reduction. The Co@CN/SiO2 catalysts were investigated for the selective reduction of nitro aromatics to the corresponding anilines using hydrazine hydrate. The Co@CN/SiO2-500 carbonized at 500 °C exhibited the highest catalytic activity and excellent stability without any decay of activity after 6 cycles for the reduction of nitrobenzene. Both metallic Co atoms and Co?N species formed in the Co@CN/SiO2 catalysts were active, but the Co?N species were dominant active sites. The high activities of the Co@CN/SiO2 catalysts were attributed to the synergistic effect between the Co and N atoms, promoting heterolytic cleavage of hydrazine to form H+/H? pairs. Representative examples demonstrated that the Co@CN/SiO2-500 could completely transform various halogen-substituted nitro aromatics to the corresponding halogenated anilines with high TOFs and selectivity of '99.5 percent.
- Sheng, Yao,Wang, Xueguang,Yue, Shengnan,Cheng, Gonglin,Zou, Xiujing,Lu, Xionggang
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p. 4632 - 4641
(2020/07/30)
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- Highly selective hydrogenation of halogenated nitroarenes over Ru/CN nanocomposites by: In situ pyrolysis
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A highly chemoselective and recyclable ruthenium catalyst for the hydrogenation of halogenated nitroarenes has been prepared via the simple in situ calcination of a mixture of melamine, glucose and ruthenium trichloride. Superfine Ru particles (2.3 ± 0.3 nm) were obtained and highly dispersed in the nitrogen-doped carbon matrix. The Ru/CN catalyst smoothly transforms a variety of halogenated nitroarenes to the corresponding haloanilines with high intrinsic activity (e.g. TOF = 1333 h-1 for p-chloronitrobenzene) and selectivity of more than 99.6percent. Furthermore, through an analysis of the products in the reaction process, it was concluded that there are two parallel reaction pathways (a direct pathway and an indirect pathway) for the hydrogenation of aromatic nitro compounds over the Ru/CN catalyst, and the direct pathway was proved to be dominant in catalyzing the intermediates. This journal is
- Yue, Shengnan,Wang, Xueguang,Li, Shaoting,Sheng, Yao,Zou, Xiujing,Lu, Xionggang,Zhang, Chunlei
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p. 11861 - 11869
(2020/07/28)
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- BF3·SMe2 for Thiomethylation, Nitro Reduction and Tandem Reduction/SMe Insertion of Nitrogen Heterocycles
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Herein, a general, solvent-free and straightforward thiomethylation of electron deficient heterocycles using BF3·SMe2 as a dual thiomethyl source and Lewis acidic activator is presented. A range of heterocycles including pyrimidine, pyrazine, pyridazine, thiazole and purine derivatives were successfully substituted using this method. An unexpected reductive property of BF3·SMe2 towards nitropyridines was also discovered including an intriguing tandem reduction/SMe insertion process in certain substrates. Notable features of the present work include its convenience and use of a non-malodorous reagent while the discovery of novel chemical transformations using BF3·SMe2 provides fundamental new insights into the reactivity of this commonly employed reagent.
- S?derstr?m, Marcus,Zamaratski, Edouard,Odell, Luke R.
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p. 5402 - 5408
(2019/06/27)
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- Novel protocol for synthesis of 1,4-diiminocurcumin stabilized silver nanoparticles and application as heterogenous recyclable catalyst and antibacterial agent
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Abstract: Curcumin [(1E, 6E)-1,7-bis(4-hydroxy-3-methoxy-phenyl)-1,6-heptadiene-3,5-dione] is a low molecular weight yellow-orange polyphenolic pigment extracted from the powdered rhizome of Curcuma longa. Curcumin has wide medicinal applications as an antioxidant, anti-inflammatory, cancer chemopreventive, and potentially chemotherapeutic agents as well as stabilizer/reducing agent in silver nanoparticles (AgNPs) synthesis. However, the low solubility of curcumin in aqueous solutions limits its applications and also, many of AgNP synthetic processes lack a greener synthetic route. In the present work, a Schiff base of curcumin is synthesized condensing curcumin and 1,4-diaminobutane in 2:1 ratio. The resulting product shows improvement in solubility in water and favours the synthesis of AgNPs in aqueous medium at room temperature, acting as a self-reducing/stabilizing agent. This proposed synthetic route is simple, feasible and green. The size and morphology of AgNPs are analyzed by TEM, SEM, EDS and XRD techniques. The recyclable AgNPs as a heterogeneous catalyst in the reduction of nitroaromatics to amino compounds is environmentally benign and can be re-used up to 5th cycle without considerable loss of its catalytic activity. Moreover, both Cur-1,4 and AgNPs show bactericidal properties against bacterial strains (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa) which find medicinal importance in future. Graphic abstract: A greener approach has been proposed for the preparation of AgNPs stabilized on curcumin based Schiff base. The AgNPs finds applications as efficient, easily recyclable heterogenous catalyst in the reduction of nitroaromatics to environmentally benign aminoaromatics as well as an antibacterial agent.[Figure not available: see fulltext.].
- Gogoi, Nishi Gandha,Handique, Jyotirekha G
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- Utilization of a Hydrogen Source from Renewable Lignocellulosic Biomass for Hydrogenation of Nitroarenes
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Exploring of hydrogen source from renewable biomass, such as glucose in alkaline solution, for hydrogenation reactions had been studied since 1860s. According to proposed pathway, only small part of hydrogen source in glucose was utilized. Herein, the utilization of a hydrogen source from renewable lignocellulosic biomass, one of the most abundant renewable sources in nature, for a hydrogenation reaction is described. The hydrogenation is demonstrated by reduction of nitroarenes to arylamines in up to 95 % yields. Mechanism studies suggest that the hydrogenation occurs via a hydrogen transformation pathway.
- Tan, Fang-Fang,Tang, Kai-Li,Zhang, Ping,Guo, Yan-Jun,Qu, Mengnan,Li, Yang
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p. 4189 - 4195
(2019/03/07)
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- Rh Catalyzed Selective Hydrogenation of Nitroarenes under Mild Conditions: Understanding the Functional Groups Attached to the Nanoparticles
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Modifying the surface of metal catalyst is a crucial subject for improving the heterogeneous metal catalysts. It is still a great challenge to understand the structure-activity relationship (SAR) between the surface supporting groups and the metal particles. Herein, Rh NPs supported on the magnetic silica sphere with various functional groups (?NH2, ?SH, ?SO3H, ?N=CH2, ?Cl, ?NHCOCH3 and ?NHCH2Ph) have been prepared for catalytic hydrogenation of nitroarenes under atmospheric pressure at room temperature. We discover that the chemical state of Rh NPs depends on the supporting groups significantly. The electron-donating functionalities can effectively elevate the Rh0/Rh3+ ratio, which increase the catalytic performance both in conversion and selectivity. The amino group decorated catalyst has such a good selectivity that no dechlorination reaction is observable in the hydrogenation of 2-chloro-3-nitropyridine. What's more, by introducing magnetic Fe3O4 nuclei and mesoporous silica encapsulating layer, the catalyst can be recovered conveniently by an external magnet, and can be reused 10 cycles without any loss of activity.
- Tian, Haimeng,Zhou, Junjie,Li, Yunong,Wang, Yiming,Liu, Lei,Ai, Yongjian,Hu, Ze-Nan,Li, Jifan,Guo, Rongxiu,Liu, Zhibo,Sun, Hong-bin,Liang, Qionglin
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p. 5543 - 5552
(2019/11/03)
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- A halogenated nitrogen-containing unsaturated cyclic hydrocarbon preparation method
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The invention discloses a halogenated nitrogen-containing unsaturated cyclic hydrocarbon of the preparation method, the steps of: (1) the nitrogen-containing unsaturated cyclic hydrocarbon dissolved in hydrochloric acid or hydrobromic acid, addition of an oxidizing agent, the reaction system halogenated reaction, in the reaction process timing sampling detection, when detecting the target product quality of a halide accounted for is a reaction system in the total of the organic matter of 70% - 95% when, added to the reaction system in the terminator to terminate reaction, to obtain containing nitrogen-containing unsaturated cyclic hydrocarbon feed; (2) to the liquid mixed into the organic solvent extraction, extraction to obtain the organic phase, the organic phase temperature is reduced to make the solid precipitation or distilling the organic solvent to obtain a liquid product to be deducted, the resulting solid or liquid product is halogenated nitrogen-containing unsaturated cyclic hydrocarbon. The method solves the problem of the nitrogen-containing unsaturated cyclic hydrocarbon over [...] reaction problems.
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Paragraph 0019
(2018/05/16)
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- Preparation method of 2,3-dichloropyridine
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The invention provides a preparation method of 2,3-dichloropyridine. The 2,3-dichloropyridine is prepared by a one-pot method, pyridine alkyl ester serves as a raw material, and synthesis is conductedby a mode of performing chlorination, performing hydrolysis and performing chlorination again; the chlorination is substitution reaction, substitution on a benzene ring is relatively easy, the alkylester group can protect the site of the first-time chlorination reaction to be at 2 position, the hydrolysis reaction is mild in condition and rapid in reaction compared with the prior art, the second-time chlorination is to substitute the hydroxyl, the reaction is easy and the reaction condition is relatively mild. The preparation method provided by the invention is simple in operation, few threewastes are generated in the production process, requirements on equipment are low and the yield is high.
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Paragraph 0070
(2018/06/15)
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- Metal-free deoxygenation and reductive disilylation of nitroarenes by organosilicon reducing reagents
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A metal-free deoxygenation and reductive disilylation of nitroarenes was achieved using N,N’-bis(trime-thylsilyl)-4,4’-bipyridinylidene (1) under mild and neutral reaction conditions, and a broad functional group tolerance was possible in this reaction. Mono-deoxygenation, giving a synthetically valuable N,O-bis(trimethylsilyl)phe-nylhydroxylamine (7a) as a readily available and safe phenylnitrene source from nitrobenzene, and double-deoxy-genation, giving N,N-bis(trimethylsilyl)anilines 8, were easily controlled by varying the amounts of 1 and reaction temperature as well as adding dibenzothiophene (DBTP). Reaction of 2-arylnitrobenzenes with 1 resulted in the formation of the corresponding carbazoles 14 via in situ-gen-erated phenylnitrene species derived by thermolysis of N,O-bis(trimethylsilyl)phenylhydroxylamines 7, followed by their subsequent intramolecular C H insertion. In addition, the intramolecular N N coupling reaction proceeded in the reduction of 2,2’-dinitrobiphenyl derivatives by 1, giving the corresponding benzo[c]cinnolines.
- Bhattacharjee, Argha,Hosoya, Hiromu,Ikeda, Hideaki,Nishi, Kohei,Tsurugi, Hayato,Mashima, Kazushi
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supporting information
p. 11278 - 11282
(2018/10/20)
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- Metal-free Reduction of Nitro Aromatics to Amines with B 2 (OH) 4 /H 2 O
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A metal-free reduction of nitro aromatics mediated by diboronic acid with water as both the hydrogen donor and solvent under mild conditions has been developed. A series of aromatic amines were obtained with good functional group tolerance and in good yields.
- Chen, Danyi,Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Liu, Qixing,Zhang, Kaili,Uozumi, Yasuhiro
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supporting information
p. 1765 - 1768
(2018/06/26)
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- Nitrogen-Doped Graphene-Supported Iron Catalyst for Highly Chemoselective Hydrogenation of Nitroarenes
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A nitrogen-doped graphene-supported iron catalyst was used for the first time in the hydrogenation of a series of nitroarenes to give the corresponding amines with excellent activity and chemoselectivity under mild reaction conditions. Physicochemical characterization of the catalyst by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and M?ssbauer spectroscopy revealed the formation of iron particles with an iron oxide core and a metallic iron shell that were coated by a few layers of nitrogen-doped graphene. The unique structure of FeNx/C in the catalyst was proven to contribute to the hydrogenation activity.
- Wei, Zuojun,Hou, Yaxin,Zhu, Xinmiao,Guo, Liangyu,Liu, Yingxin,Zhang, Anyun
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p. 2009 - 2013
(2018/03/21)
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- A capping agent dissolution method for the synthesis of metal nanosponges and their catalytic activity towards nitroarene reduction under mild conditions
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We report a general strategy for the synthesis of metal nanosponges (M = Ag, Au, Pt, Pd, and Cu) using a capping agent dissolution method where addition of water to the M@BNHx nanocomposite affords the metal nanosponges. The B-H bond of the BNHx polymer gets hydrolysed upon addition of water and produces hydrogen gas bubbles which act as dynamic templates leading to the formation of nanosponges. The rate of B-H bond hydrolysis has a direct impact on the final nanostructure of the materials. The metal nanosponges were characterized using powder XRD, electron microscopy, XPS, and BET surface area analyzer techniques. The porous structure of these nanosponges offers a large number of accessible surface sites for catalytic reactions. The catalytic activity of these metal nanosponges has been demonstrated for the reduction of 4-nitrophenol where palladium exhibits the highest catalytic activity (k = 0.314 min?1). The catalytic activity of palladium nanosponge was verified for the tandem dehydrogenation of ammonia borane and the hydrogenation of nitroarenes to arylamines in methanol at room temperature. The reduction of various substituted nitroarenes was proven to be functional group tolerant except for a few halogenated nitroarenes (X = Br and I) and >99% conversion was noted within 30-60 min with high turnover frequencies (TOF) at low catalyst loading (0.1 mol%). The catalyst could be easily separated out from the reaction mixture via centrifugation and was recyclable over several cycles, retaining its porous structure.
- Ghosh, Sourav,Jagirdar, Balaji R.
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p. 17401 - 17411
(2019/01/03)
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- Highly chemoselective reduction of azides to amines by Fe(0) nanoparticles in water at room temperature
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A highly chemoselective reduction of aryl, heteroaryl, acyl and sulfonyl azides to the corresponding amines has been achieved by Fe(0) nanoparticles in water at room temperature in the absence of external hydride source. Several readily reducible functionalities including alkene, alkyne, S-S linkage, OTBDMS remain unaffected during reduction.
- Panja, Subir,kundu, Debasish,Ahammed, Sabir,Ranu, Brindaban C.
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supporting information
p. 3457 - 3460
(2017/08/10)
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- A two-chloro pyridine production process (by machine translation)
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Dichloro pyridine is an important raw material in the chemical industry. Dichloro pyridine production process flow is: (1) chlorinated reaction; the 3 - aminopyridine is added to the chlorination kettle in, add a certain amount of hydrogen peroxide, its jacket into the freezing brine cooling to 10 °C, then slowly dropping hydrochloric acid chloride the reaction, the reaction temperature is controlled 25 °C, the reaction pressure is normal pressure, after the end of the chlorination reaction, to obtain 2 - chloro -3 - aminopyridine. (2) the diazotization reaction; the 2 - chloro -3 - aminopyridine into diazonium cauldron in to, its jacket into the freezing brine cooling to -5 °C, then slowly dropping sodium nitrite solution diazo-reaction, the reaction temperature is controlled 5 °C, the reaction pressure is normal. The diazotization reaction is obtained after the end of the 2 - chloro -3 amino pyridine diazonium salt. (3) after treatment; in the crude product into to the kettle, add a certain amount of liquid alkali neutralized, adding chloroform extraction separation, the aqueous phase is filtered after the cuprous chloride recovery into a waste water processing. (by machine translation)
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Paragraph 0002
(2017/07/21)
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- Water as a hydrogen source in palladium-catalyzed reduction and reductive amination of nitroarenes mediated by diboronic acid
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An unprecedented palladium-catalyzed chemoselective reduction and reductive amination of nitroarenes with water as a hydrogen source mediated by diboronic acid have been discovered. A series of aryl amines containing various reducible functional groups were obtained in good to excellent yields.
- Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Pi, Danwei,Shen, Guanshuo
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p. 3898 - 3904
(2017/06/13)
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- PVP-Pd nanoparticles as efficient catalyst for nitroarene reduction under mild conditions in aqueous media
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The catalytic activity of PVP-Pd nanoparticles synthesized by electrochemical methods was explored in nitroaromatic hydrogenation reaction. In this transformation, the colloidal nanocatalyst proved to have outstanding catalytic activity under sustainable reaction conditions. This mild process efficiently reduced the nitroaromatic group at room temperature, without high pressure of molecular hydrogen and in aqueous medium. Furthermore, several functional groups were tolerated, given the corresponding substituted arylamines in excellent yields and with high TOF. In addition, one-pot reactions and tandem process were explored, in which nitroaromatic hydrogenation reaction was included in the synthesis of modified amines. This methodology was effectively incorporated in tandem reactions and one-pot procedures, achieving N-arylamines functionalized in good isolated yields. Finally, comparison of sustainable chemistry metrics analysis demonstrated that this methodology is a reliable approach to perform the nitro compound hydrogenation process.
- Uberman, Paula M.,García, Carolina S.,Rodríguez, Julieta R.,Martín, Sandra E.
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supporting information
p. 739 - 748
(2017/05/19)
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- MOF-derived Ni-based nanocomposites as robust catalysts for chemoselective hydrogenation of functionalized nitro compounds
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Porous graphitic carbon layers encapsulating Ni nanoparticles (Ni@C) were prepared by a facile thermolysis of a Ni-containing metal-organic framework, the structure of which were characterized by power X-ray diffraction (XRD), N2 adsorption-desorption, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) in detail. The resulting Ni@C nanocomposites served as highly efficient and magnetically recyclable catalysts for the hydrogenation of diverse functionalized nitro compounds to the corresponding anilines under relatively milder conditions. The high catalytic performance and the enhanced stability are ascribed to the synergistic effects and electron transfer between the metallic Ni and graphitic carbon as well as the unique encapsulation structure. The achieved success in the MOF-derived Ni@C nanocomposites may pave the way for designing environmentally benign catalytic hydrogenation processes for industrial applications.
- Tang, Bo,Song, Wei-Chao,Yang, En-Cui,Zhao, Xiao-Jun
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p. 1531 - 1539
(2017/01/21)
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- A metal-organic framework-templated synthesis of γ-Fe2O3 nanoparticles encapsulated in porous carbon for efficient and chemoselective hydrogenation of nitro compounds
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The γ-Fe2O3 nanoparticles well dispersed in porous carbon were fabricated via a Fe-based metal-organic framework-templated pyrolysis. The resultant product exhibits excellent catalytic activity, chemoselectivity and magnetic recyclability for the hydrogenation of diverse nitro compounds under mild conditions.
- Li, Yang,Zhou, Yu-Xiao,Ma, Xiao,Jiang, Hai-Long
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supporting information
p. 4199 - 4202
(2016/03/19)
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- Preparation of aniline derivatives
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In the present invention, provided is a novel manufacturing method of aniline derivative, which is more simple and eco-friendly and takes less cost compared with an existing synthesizing aniline method, comprising a step of manufacturing chemical formula 1 by making chemical formula 2 react with chemical formula 3 under catalyst, bases and solvents wherein the manufacturing method aniline derivative is manufactured through one pot in a simple manner and accordingly easily removes the solvent with use of distillation under reduced pressure after reaction.
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Paragraph 0087-0092
(2016/10/08)
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- Nitrogen-doped graphene-activated iron-oxide-based nanocatalysts for selective transfer hydrogenation of nitroarenes
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Nanoscaled iron oxides on carbon were modified with nitrogen-doped graphene (NGr) and found to be excellent catalysts for the chemoselective transfer hydrogenation of nitroarenes to anilines. Under standard reaction conditions, a variety of functionalized and structurally diverse anilines, which serve as key building blocks and central intermediates for fine and bulk chemicals, were synthesized in good to excellent yields.
- Jagadeesh, Rajenahally V.,Natte, Kishore,Junge, Henrik,Beller, Matthias
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p. 1526 - 1529
(2015/03/14)
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- Metal-Free Reduction of Aromatic and Aliphatic Nitro Compounds to Amines: A HSiCl3-Mediated Reaction of Wide General Applicability
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A new, mild, metal-free, HSiCl3-mediated reduction of both aromatic and aliphatic nitro groups to amines that is of wide general applicability, tolerant of many functional groups, and respectful of the stereochemical integrity of stereocenters is reported.
- Orlandi,Tosi,Bonsignore,Benaglia
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supporting information
p. 3941 - 3943
(2015/09/01)
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- Highly selective transfer hydrogenation of functionalised nitroarenes using cobalt-based nanocatalysts
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Anilines are important feedstock for the synthesis of a variety of chemicals such as dyes, pigments, pharmaceuticals and agrochemicals. The chemoselective catalytic reduction of nitro compounds represents the most important and prevalent process for the manufacture of functionalized anilines. Consequently, the development of selective catalysts for the reduction of nitro compounds in the presence of other reducible groups is a major challenge and is crucial. In this regard, herein we show that the cobalt oxide (Co3O4-NGr@C) based nano-materials, prepared by the pyrolysis of cobalt-phenanthroline complexes on carbon constitute highly selective catalysts for the transfer hydrogenation of nitroarenes to anilines using formic acid as a hydrogen source. Applying these catalysts, a series of structurally diverse and functionalized nitroarenes have been reduced to anilines with unprecedented chemo-selectivity tolerating halides, olefins, aldehyde, ketone, ester, amide and nitrile functionalities.
- Jagadeesh, Rajenahally V.,Banerjee, Debasis,Arockiam, Percia Beatrice,Junge, Henrik,Junge, Kathrin,Pohl, Marga-Martina,Radnik, J?rg,Brückner, Angelika,Beller, Matthias
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supporting information
p. 898 - 902
(2015/03/04)
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- A High-Throughput Assay for Arylamine Halogenation Based on a Peroxidase-Mediated Quinone-Amine Coupling with Applications in the Screening of Enzymatic Halogenations
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Arylhalides are important building blocks in many fine chemicals, pharmaceuticals and agrochemicals, and there has been increasing interest in the development of more "green" halogenation methods based on enzyme catalysis. However, the screening and development of new enzymes for biohalogenation has been hampered by a lack of high-throughput screening methods. Described herein is the development of a colorimetric assay for detecting both chemical and enzymatic arylamine halogenation reactions in an aqueous environment. The assay is based on the unique UV/Vis spectrum created by the formation of an ortho-benzoquinone-amine adduct, which is produced by the peroxidase-catalysed benzoquinone generation, followed by Michael addition of either a halogenated or non-halogenated arylamine. This assay is sensitive, rapid and amenable to high-throughput screening platforms. We have also shown this assay to be easily coupled to a flavin-dependent halogenase, which currently lacks any convenient colorimetric assay, in a "one-pot" workflow.
- Hosford, Joseph,Shepherd, Sarah A.,Micklefield, Jason,Wong, Lu Shin
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supporting information
p. 16759 - 16763
(2016/02/12)
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- Selective reduction of halogenated nitroarenes with hydrazine hydrate in the presence of Pd/C
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A large variety of halogenated nitroarenes have been selectively reduced with hydrazine hydrate in the presence of Pd/C to give the corresponding (halogenated) anilines in good yield.
- Li, Fang,Frett, Brendan,Li, Hong-Yu
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p. 1403 - 1408
(2014/06/23)
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- A radical thia-Brook rearrangement
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Geminal mercapto trialkyl- and trialkoxy-silanes undergo an efficient radical chain rearrangement, whereby the silyl group migrates from carbon to sulfur; the starting materials are readily obtained by exploiting the peroxide initiated radical addition of dithiocarbonates (xanthates) to trialkyl- or trialkoxy-vinylsilanes. the Partner Organisations 2014.
- Quiclet-Sire, Béatrice,Zard, Samir Z.
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supporting information
p. 5990 - 5992
(2014/05/20)
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- PROCESS FOR PREPARING DIHALOPYRIDINES
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Processes for manufacturing dihalopyridines without the use of copper salts are described. Additional processes for manufacturing dihalopyridines from niacinamide are described.
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Page/Page column 8; 9
(2014/01/07)
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- Design and evaluation of novel 8-oxo-pyridopyrimidine Jak1/2 inhibitors
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A highly ligand efficient, novel 8-oxo-pyridopyrimidine containing inhibitor of Jak1 and Jak2 isoforms with a pyridone moiety as the hinge-binding motif was discovered. Structure-based design strategies were applied to significantly improve enzyme potency and the polarity of the molecule was adjusted to gain cellular activity. The crystal structures of two representative inhibitors bound to Jak1 were obtained to enable SAR exploration.
- Labadie, Sharada,Barrett, Kathy,Blair, Wade S.,Chang, Christine,Deshmukh, Gauri,Eigenbrot, Charles,Gibbons, Paul,Johnson, Adam,Kenny, Jane R.,Kohli, Pawan Bir,Liimatta, Marya,Lupardus, Patrick J.,Shia, Steven,Steffek, Micah,Ubhayakar, Savita,Abbema, Anne Van,Zak, Mark
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p. 5923 - 5930
(2013/10/22)
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- One-pot conversion of phenols to anilines via Smiles rearrangement
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A convenient one-pot synthesis of phenols to anilines using 2-chloroacetamide/K2CO3/DMF system catalyzed by KI via Smiles rearrangement has been described. The synthesis of extensive amino aromatic products from phenols containing electron withdrawing group, has been performed in moderate to excellent yields to demonstrate the potentiality of this method in bio-medicinal and pharmaceutical applications.
- Xie, Yong-Sheng,Vijaykumar,Jang, Kiwan,Shin, Hong-Hyun,Zuo, Hua,Shin, Dong-Soo
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p. 5151 - 5154
(2013/09/02)
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- Pinacol as a new green reducing agent: Molybdenum-catalyzed chemoselective reduction of sulfoxides and nitroaromatics
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Pinacol is disclosed as a new chemoselective and environmentally benign reducing agent for sulfoxides and nitroaromatics assisted by readily available dichlorodioxomolybdenum(VI) complexes as catalysts. A wide range of substrates including those bearing challenging functional groups has been efficiently and selectively reduced with acetone and water being the only by-products of these reactions. Copyright
- Garcia, Nuria,Garcia-Garcia, Patricia,Fernandez-Rodriguez, Manuel A.,Rubio, Ruben,Pedrosa, Maria R.,Arnaiz, Francisco J.,Sanz, Roberto
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supporting information; experimental part
p. 321 - 327
(2012/04/11)
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- (2-Pyridyl)phenyl methanol: A new reagent for metal-free reduction of nitro aromatic compounds
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As previously reported for 1-(2-pyridyl)-2-propen-1-ol, (2-pyridyl)phenyl methanol is able to react as hydrogen donor towards nitro aromatic and heteroaromatic compounds. Operating in the presence of methyl acrylate as an aza-Michael acceptor, a domino process involving reduction and conjugate addition steps allows the one pot formation of β-amino esters. The crucial role of the pyridine nucleus in making this purely thermal reactivity of carbinols possible has been shown.
- Giomi, Donatella,Alfini, Renzo,Brandi, Alberto
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experimental part
p. 167 - 172
(2011/02/27)
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- Selective catalytic hydrogenation of nitro groups in the presence of activated heteroaryl halides
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Chemoselective reduction of nitro groups in the presence of activated heteroaryl halides was achieved via catalytic hydrogenation with a commercially available sulfided platinum catalyst. The optimized conditions employ low temperature, pressure, and catalyst loading (0.1 mol % Pt) to afford heteroaromatic amines with minimal hydrodehalogenation byproducts.
- Kasparian, Annie J.,Savarin, Cecile,Allgeier, Alan M.,Walker, Shawn D.
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experimental part
p. 9841 - 9844
(2012/01/06)
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- Rapid reduction of heteroaromatic nitro groups using catalytic transfer hydrogenation with microwave heating
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A method for the rapid, safe reduction of heteroaromatic and aromatic nitro groups to amines is described using catalytic transfer hydrogenation under microwave heating conditions. Commonly available Pd/C or Pt/C catalyst is extremely effective with 1,4-cyclohexadiene as the hydrogen transfer source. In the case of substrates containing potentially labile aromatic halogens, Pt/C is effective and results in little or no dehalogenation. In general, the reactions are complete within 5 min at 120 °C.
- Quinn, John F.,Bryant, Cole E.,Golden, Kathryn C.,Gregg, Brian T.
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experimental part
p. 786 - 789
(2010/03/24)
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- PROCESS FOR PRODUCING DIHALOPYRIDINES
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Disclosed herein an improved process for producing 2,3-dihalopyridine with high purity at industrial scale with minimum effluent.
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Page/Page column 4
(2010/07/04)
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- Iron-catalyzed selective reduction of nitroarenes to anilines using organosilanes
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The iron-catalyzed reduction of aromatic nitro compounds to the corresponding anilines applying organosilanes is reported. In the presence of FeX2-R3P catalysts a series of nitroarenes is selectively reduced tolerating a wide range of functional groups.
- Junge, Kathrin,Wendt, Bianca,Shaikh, Nadim,Beller, Matthias
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experimental part
p. 1769 - 1771
(2010/07/06)
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- HETEROCYCLIC HYDRAZIDE COMPOUND AND PESTICIDAL USE OF THE SAME
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A hydrazide compound represented by the formula (I), an N-oxide thereof or suitable salt thereof: has excellent pesticidal activity.
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Page/Page column 454-455
(2008/12/08)
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- New reactivity of 1-(2-pyridyl)-2-propen-1-ol with nitro derivatives
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1-(2-Pyridyl)-2-propen-1-ol showed an unprecedented reactivity behaving as Hantzsch ester 1,4-dihydropyridine mimic for the metal-free reduction of the nitro group of electron-deficient aromatic and heteroaromatic nitro compounds to the corresponding amino function. The redox mechanism is part of a domino process involving a direct trapping of the amino derivatives through aza-Michael addition to the vinyl ketone intermediate leading to the one-pot formation of new functionalised aminoacylpyridines.
- Giomi, Donatella,Alfini, Renzo,Brandi, Alberto
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scheme or table
p. 6977 - 6979
(2009/04/07)
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- Structure-activity studies of novel cyanoguanidine ATP-sensitive potassium channel openers for the treatment of overactive bladder
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A series of novel cyanoguanidine derivatives was designed and synthesized. Condensation of N-(1-benzotriazol-1-yl-2,2-dichloropropyl)-substituted benzamides with N-(substituted-pyridin-3-yl)-N′-cyanoguanidines furnished N-{2,2-dichloro-1-[N′-(substituted-pyridin-3-yl)-N′-cyanoguanidino] propyl}-substituted benzamide derivatives. These agents were glyburide-reversible potassium channel openers and hyperpolarized human bladder cells as assessed by the FLIPR membrane potential dye (KATP-FMP). These compounds were also potent full agonists in relaxing electrically stimulated pig bladder strips, an in vitro model of overactive bladder. The most active compound 9 was evaluated for in vivo efficacy and selectivity in a pig model of bladder instability. Preliminary pharmacokinetic studies in dog demonstrated excellent oral bioavailability and a t1/2 of 15 h. The synthesis, SAR studies, and biological properties of these agents are discussed.
- Perez-Medrano, Arturo,Brune, Michael E.,Buckner, Steven A.,Coghlan, Michael J.,Fey, Thomas A.,Gopalakrishnan, Murali,Gregg, Robert J.,Kort, Michael E.,Scott, Victoria E.,Sullivan, James P.,Whiteaker, Kristi L.,Carroll, William A.
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p. 6265 - 6273
(2008/04/05)
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- PROCESS FOR THE MANUFACTURE OF 2,3-DICHLOROPYRIDINE
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A method for preparing 2,3-dichloropyridine is disclosed in which 3-amino-2-chloropyridine is contacted with an alkali metal nitrite in the presence of aqueous hydrochloric acid to form a diazonium salt; and the diazonium salt is subsequently decomposed in the presence of copper catalyst wherein at least about 50% of the copper is the copper(II) oxidation state.
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Page/Page column 17-18
(2008/06/13)
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- A novel strategy for the preparation of arylhydroxylamines: Chemoselective reduction of aromatic nitro compounds using bakers' yeast
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Using bakers' yeast as a biocatalyst, the chemoselective reduction of aromatic nitro compounds bearing electron-withdrawing groups gave the corresponding hydroxylamines with good to excellent conversion under mild conditions.
- Li, Feng,Cui, Jingnan,Qian, Xuhong,Zhang, Rong
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p. 2338 - 2339
(2007/10/03)
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