- Chemoselective Transfer Hydrogenation of Nitroarenes Catalyzed by Highly Dispersed, Supported Nickel Nanoparticles
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A recyclable highly dispersed Ni/SiO2 catalyst was prepared by atomic layer deposition. Chemoselective reduction of nitroarenes was studied using the prepared Ni/SiO2 as the catalyst and hydrazine hydrate as a hydrogen donor. Different kinds of nitroarenes were converted to the corresponding anilines with high yields. The high activity of the catalysts could be a result of the highly dispersed Ni nanoparticles. (Chemical Presented).
- Jiang, Chengjun,Shang, Zeyu,Liang, Xinhua
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- Mild deprotection of the: N-tert -butyloxycarbonyl (N -Boc) group using oxalyl chloride
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We report a mild method for the selective deprotection of the N-Boc group from a structurally diverse set of compounds, encompassing aliphatic, aromatic, and heterocyclic substrates by using oxalyl chloride in methanol. The reactions take place under room temperature conditions for 1-4 h with yields up to 90percent. This mild procedure was applied to a hybrid, medicinally active compound FC1, which is a novel dual inhibitor of IDO1 and DNA Pol gamma. A broader mechanism involving the electrophilic character of oxalyl chloride is postulated for this deprotection strategy. This journal is
- Awuah, Samuel G.,George, Nathaniel,Ofori, Samuel,Parkin, Sean
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p. 24017 - 24026
(2020/07/23)
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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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- Cobalt in N-doped carbon matrix catalyst for chemoselective hydrogenation of nitroarenes
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Anilines as important intermediates for both organic synthesis and industrial manufactory are densely substituted with a variety of functional moieties, and the transformation of nitroarenes into corresponding anilines requires catalytically selective hydrogenation catalyst. Herein, we describe a simple pyrolysis strategy to prepare cobalt catalysts in nitrogen-doped carbon matrix applied in the selective hydrogenation of nitroarenes with molecular hydrogen. The Co/NC catalysts are obtained through thermal treatment of mixed precursors of cobalt phthalocyanine and melamine. The surface-modified Co particles with Co3O4 and CoNx sites are surrounded by N-doped carbon layers according to a series of structural characterization results. These Co/NC catalysts are capable of efficiently selective hydrogenation of nitrobenzene and various substituted nitroarenes into corresponding anilines under relatively mild reaction conditions. The optimal catalytic hydrogenation performance is contributed to the fast rate of H2 dissociated activation on the CoNx active sites and the facile adsorption of the reactant substances, which is verified by the isotopic H2-D2 exchange experiments, reactant adsorption and the ORR reaction tests. Furthermore, the heterogeneous Co/NC catalyst is highly stable without the Co leaching and deactivation issues during the recycling reaction runs.
- Dai, Yihu,Jiang, Chunyang,Xu, Min,Bian, Bo,Lu, Di,Yang, Yanhui
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p. 158 - 166
(2019/06/03)
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- Development and Scale-up of Continuous Electrocatalytic Hydrogenation of Functionalized Nitro Arenes, Nitriles, and Unsaturated Aldehydes
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Electrolysis flow reactors based on the filter-press architecture of redox flow batteries have proven to be effective and scalable toward the production of commercially relevant, pharmaceutical quantities of anilines (>500 kg/year) from halogen-, hydroxyl-, and carbonyl-substituted nitroarenes. Turbulent flow through the carbon felts on which the catalysts were supported facilitated scaling toward production levels because it conferred on the reactors scale-independent, plug flow-like residence time distributions and high mass transfer coefficients. Equipping the cells with microreference electrodes made it possible to transfer reaction conditions first developed in batch systems to the continuous flow reactors. The catalysts prepared by incipient wetness impregnation of metal salts into lightly oxidized carbon felt supports were readily generalizable.
- Egbert, Jonathan D.,Thomsen, Edwin C.,O'Neill-Slawecki, Stacy A.,Mans, Douglas M.,Leitch, David C.,Edwards, Lee J.,Wade, Charles E.,Weber, Robert S.
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p. 1803 - 1812
(2019/08/15)
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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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- Catalytic hydrogenation process of chlorine-containing nitro aromatic compound
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The invention discloses a catalytic hydrogenation process of a chlorine-containing nitro aromatic compound. The specific process comprises the following steps: adding a chlorine-containing nitrobenzene, water and an anti-dechlorination agent into a reactor, carrying out mixing by stirring, then adding a catalyst and a self-prepared cocatalyst, introducing nitrogen into the reactor for 5-10 min toreplace air in the reactor, then introducing hydrogen until the pressure is 18-26 kg, carrying out a reaction at 55-75 DEG C for 1-3 hours, carrying out cooling to room temperature after the reactionis finished, and detecting the content of the target product in the obtained product. The process conditions are mild, the effect of the reaction substrate on the catalyst is small, the catalytic activity is high, and the yield of the product is high.
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Paragraph 0036; 0037; 0038; 0039
(2018/11/27)
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- Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
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The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Alshammari, Ahmad S.,Pohl, Marga-Martina,Beller, Matthias,Jagadeesh, Rajenahally V.
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p. 8553 - 8560
(2018/11/30)
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- Development of a novel protocol for chemoselective deprotection of N/O-benzyloxycarbonyl (Cbz) at ambient temperature
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Abstract: A novel protocol for the deprotection of N-benzyloxycarbonyl and O-benzyloxycarbonyl groups by nickel boride generated in situ from NaBH4 and NiCl2·6H2O in methanol at room temperature has been developed to give the corresponding amines and phenols. This protocol is chemoselective as groups like chloro, bromo, amide, ester, pyridine, and tert-butyloxycarbonyl moiety are unaffected under these conditions. The deprotection has also been validated in gram scale reactions, to establish the wider appropriateness of this protocol. Graphical abstract: [Figure not available: see fulltext.].
- Saroha, Mohit,Aggarwal, Komal,Bartwal, Gaurav,Khurana, Jitender M.
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p. 2231 - 2235
(2018/10/02)
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- Preparation method of 4-fluoro-3-chloroaniline
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The invention discloses a preparation method of 4-fluoro-3-chloroaniline. The 4-fluoro-3-chloroaniline is prepared by adding fluorine to the amido para-position of the raw material 3-chloroaniline. The purity of the prepared 4-fluoro-3-chloroaniline is 99% or above; and the method has the advantages of accessible raw materials and low price, and is suitable for industrial production.
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Paragraph 0010
(2017/06/21)
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- Palladium-modified functionalized cyclodextrin as an efficient and recyclable catalyst for reduction of nitroarenes
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A palladium-modified functionalized cyclodextrin (DACH-Pd-β-CD) catalytic system was synthesized and characterised. It showed high catalytic performance in the reduction of different nitroarenes to the corresponding anilines with the presence of sodium borohydride in water at room temperature. The yields of the desired products are up to 99%. Furthermore, the catalyst can be easily separated and still could maintain high catalytic activity after five cycles and no leaching of Pd into solution occurred.
- Guo, Yafei,Li, Jiuling,Zhao, Fen,Lan, Guineng,Li, Liang,Liu, Yuqi,Si, Yunsen,Jiang, Yubo,Yang, Bo,Yang, Rui
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p. 7950 - 7954
(2016/02/09)
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- A norfloxacini pharmaceutical intermediate 3-chloro-4-fluoro aniline synthesis method (by machine translation)
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The invention discloses a pharmaceutical intermediate norfloxacini the 3 [...] -4 the method for the synthesis of aniline [...], the first powder is added into erbium chloride sodium bromide and 3 the amino- [...] the 3 [...] (4 the [...] b yl phenyl) propionic acid mixed solution, heating stirring, then dropwise 3 the [...] -4 the nitrobenzene [...], the adding, reflux reaction the 3 [...] 4h, then adding sulfurous acid monobasic potassium phosphate solution, vacuum distillation, molecular sieve decolourizations, recrystallization, to obtain crystal 3 the [...] -4 the aniline [...]. The present invention provides synthetic method, the reaction yield is compared with the traditional method is greatly improved, at the same time, the invention provides a new synthetic route, reaction yield in order to further enhance the basis of the good. (by machine translation)
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Paragraph 0023; 0024; 0025
(2016/10/24)
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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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- 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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- USE OF THERMALLY-TREATED SUPPORTED COBALT CATALYSTS COMPRISING A POLYCYCLIC AROMATIC STRUCTURE CONSISTING OF NITROGEN LIGANDS FOR HYROGENATING AROMATIC NITRO COMPOUNDS
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The invention relates to the use of thermally-treated supported cobalt catalysts for hydrogenating aromatic nitro compounds, the cobalt catalysts having been prepared by in situ immobilization of a cobalt-amine complex on an inorganic porous support and subsequent pyrolysis, and, in the cobalt-amine complex used, cobalt being present bonded to an aromatic or heterocyclic nitrogen ligand L, the nitrogen ligand being selected so as to form a polyaromatic structure with the cobalt atom.
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Paragraph 0031; 0032
(2015/11/16)
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- Dialkylimidazole inhibitors of Trypanosoma cruzi sterol 14α-demethylase as anti-Chagas disease agents
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New dialkylimidazole based sterol 14α-demethylase inhibitors were prepared and tested as potential anti-Trypanosoma cruzi agents. Previous studies had identified compound 2 as the most potent and selective inhibitor against parasite cultures. In addition, animal studies had demonstrated that compound 2 is highly efficacious in the acute model of the disease. However, compound 2 has a high molecular weight and high hydrophobicity, issues addressed here. Systematic modifications were carried out at four positions on the scaffold and several inhibitors were identified which are highly potent (EC50 1 nM) against T. cruzi in culture. The halogenated derivatives 36j, 36k, and 36p, display excellent activity against T. cruzi amastigotes, with reduced molecular weight and lipophilicity, and exhibit suitable physicochemical properties for an oral drug candidate.
- Suryadevara, Praveen Kumar,Racherla, Kishore Kumar,Olepu, Srinivas,Norcross, Neil R.,Tatipaka, Hari Babu,Arif, Jennifer A.,Planer, Joseph D.,Lepesheva, Galina I.,Verlinde, Christophe L.M.J.,Buckner, Frederick S.,Gelb, Michael H.
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supporting information
p. 6492 - 6499
(2013/11/19)
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- Chemoselective transfer hydrogenation to nitroarenes mediated by cubane-type Mo3S4 cluster catalysts
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Chemoselective cubes: Cubane-type [Mo3S4X 3(dmpe)3]+ clusters (dmpe=1,2-(bis) dimethylphosphinoethane), in combination with an azeotropic 5:2 mixture of HCOOH and NEt3 as the reducing agent, act as selective cluster catalysts (X=H) or precatalysts (X=Cl) for the transfer hydrogenation of functionalized nitroarenes, without the formation of hazardous hydroxylamines. Copyright
- Sorribes, Iván,Wienh?fer, Gerrit,Vicent, Cristian,Junge, Kathrin,Llusar, Rosa,Beller, Matthias
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experimental part
p. 7794 - 7798
(2012/10/08)
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- General and selective iron-catalyzed transfer hydrogenation of nitroarenes without base
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The first well-defined iron-based catalyst system for the reduction of nitroarenes to anilines has been developed applying formic acid as reducing agent. A broad range of substrates including other reducible functional groups were converted to the corresponding anilines in good to excellent yields at mild conditions. Notably, the process constitutes a rare example of base-free transfer hydrogenations.
- Wienhoefer, Gerrit,Sorribes, Ivan,Boddien, Albert,Westerhaus, Felix,Junge, Kathrin,Junge, Henrik,Llusar, Rosa,Beller, Matthias
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experimental part
p. 12875 - 12879
(2011/10/03)
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- Hydrous zirconia supported iridium nanoparticles: An excellent catalyst for the hydrogenation of haloaromatic nitro compounds
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Ir/ZrO2·xH2O was prepared by co-precipitation and characterized by TEM, XRD, and XPS. It showed an excellent catalytic performance for the hydrogenation of haloaromatic nitro compounds to the corresponding amines in the mixture solvent of ethanol and water. The catalyst gave both conversion and selectivity to be over 99.9% for the hydrogenation of p-chloronitrobenzene to p-chloroaniline. Besides the intrinsic characterization of iridium in the hydrogenation of haloaromatic nitro compounds, the high activity and selectivity of Ir/ZrO2·xH2O is probably attributed to the formation of hydrogen bond between substrate and the hydroxyl groups on the surface of the hydrous catalyst or solvent water to activate the N{double bond, long}O bond in nitro group. The activated N{double bond, long}O bond is easy to be attacked by the activated hydrogen, so the hydrogenation is promoted.
- Fan, Guang-Yin,Zhang, Lei,Fu, Hai-Yan,Yuan, Mao-Lin,Li, Rui-Xiang,Chen, Hua,Li, Xian-Jun
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scheme or table
p. 451 - 455
(2010/11/21)
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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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- Analogues of camptothecin, their use as medicaments and the pharmaceutical compositions containing them
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A compound of the formula wherein the substituents are defined as in the specification which compounds are useful in the treatment of cancer.
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- New analogues of camptothecin, their use as medicaments and the pharmaceutical compositions containing them
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A compound of the formula wherein the substituents are defined as in the specification which compounds are useful in the treatment of cancer.
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- SUBSTITUTED QUINAZOLINE DERIVATIVES AND THEIR USE AS INHIBITORS
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The use of a compound of formula (I) 1 or a salt, ester or amide thereof; where X is O, or S, S(O) or S(O)2, or NR6 where R6 is hydrogen or C1-6 alkyl,; R5 is an optionally substituted 5-membered heteroaromatic ring, R1, R2 ,R3, R4 are independently selected from various specified moieties, in the preparation of a medicament for use in the inhibition of aurora 2 kinase. Certain compounds are novel and these, together with pharmaceutical compositions containing them are also described and claimed
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- 4-(Phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives and process for preparing the same
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The present invention relates to 4-(phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives which inhibit tyrosine kinase of epidermal growth factor receptor (EGFR), and pharmaceutically acceptable salts, hydrates and solvates thereof, and a process for preparing the same. Since 4-(phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives of the invention have a high solubility in water and inhibit the activity of EGFR tyrosine kinase and the growth of cancer cells, they can be practically applied in the treatment of overproliferation-associated diseases such as cancer.
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- A simple and convenient method for the reduction of nitroarenes
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A variety of nitroarenes such as simple, electron rich and electron poor were reduced on A12O3 support in presence of sodium hydrogen sulphide under microwave condition to give the corresponding aromatic amines in high yields. It is found that the substituents at different positions on nitrobenzene have no influence except 2d on the rate of reaction and yields of product.
- Ravi Kanth,Venkat Reddy,Rama Rao,Maitraie,Narsaiah,Shanthan Rao
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p. 2849 - 2853
(2007/10/03)
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- Pyrrolopyrimidines and processes for the preparation thereof
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PCT No. PCT/EP96/02728 Sec. 371 Date Jan. 26, 1998 Sec. 102(e) Date Jan. 26, 1998 PCT Filed Jun. 24, 1996 PCT Pub. No. WO97/02266 PCT Pub. Date Jan. 23, 1997Described are 7H-pyrrolo[2,3-d]pyrimidine derivatives of formula I wherein the symbols are as defined in claim 1. Those compounds inhibit tyrosine protein kinase and can be used in the treatment of hyperproliferative diseases, for example tumour diseases.
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- The Bamberger reaction in hydrogen fluoride: the use of mild reductive metals for the preparation of fluoroaromatic amines
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The reduction of nitroaromatic compounds by various metals (tin, lead, bismuth) in liquid hydrogen fluoride under an inert atmosphere leads to fluoroaromatic amines, in accord with the Bamberger reaction.Generally, a co-solvent such as pentane or methylene chloride is used.Some non-fluorinated arylamines are also formed by a competitive direct reduction of the N-arylhydroxylamine intermediate.Of the mild reductive metals studied, bismuth was the most selective. - Keywords: Bamberger reaction; Hydrogen fluoride; Mild reductive metals; Fluoroaromatic amines; NMR spectroscopy
- Tordeux, Marc,Wakselman, Claude
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p. 251 - 254
(2007/10/03)
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