- 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 0328
(2022/02/26)
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- Method for synthesizing P-chloroO-toluidine
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The invention discloses a method for synthesizing p-chloroo-toluidine, which comprises the following steps: synthesizing o-toluidine and a protective agent in an organic solvent to obtain an amino-protected intermediate. The amino protected intermediate is added into hydrochloric acid, an oxidant is added for chlorination reaction, and a chlorination product is obtained. The chlorinated product is removed and the amino protecting group is removed to give p-chloroo-toluidine. The method for synthesizing p-chloroo-toluidine provided by the invention is high in yield, simple to operate, less in three wastes, high in product content and good in quality, and can be suitable for industrial mass production.
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Paragraph 0094; 0097
(2021/10/05)
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- Room-temperature copper-catalyzed electrophilic amination of arylcadmium iodides with ketoximes
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We started our study by preparation two ketoximes. Later, there were studies to reveal these ketoximes' effects in the electrophilic amination reaction with organocadmium reagents. Primarily, it was observed that arylcadmium iodides could not be reacted with ketoximes at room temperature in the absence of a catalyst. CuCN was a suitable catalyst for this electrophilic amination reaction of arylcadmium iodides and allowed the preparation of functionalized aniline derivatives in good yields under mild reaction conditions. We obtained the results indicated that the yield of primary arylamines was strongly dependent on the steric and electronic effects of organocadmium reagent and amination agent. In the case of both amination reagents, meta-substituted arylamines were obtained in higher yields than para-substituted arylamines. We observed that acetone O-(4-chlorophenylsulfonyl)oxime, 1, as an aminating agent, was more successful than acetone O-(2-Naphthylsulfonyl)oxime, 2, in the synthesis of functionalized arylamines by electrophilic amination of corresponding aryl cadmium iodides. In this method, there is no cadmium release to the environment.
- Korkmaz, Adem
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p. 3119 - 3125
(2021/05/10)
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- High yielding electrophilic amination with lower order and?higher order organocuprates: Application of acetone O-(4-Chlorophenylsulfonyl)oxime in the construction of the C?N bond at room temperature
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Electrophilic amination reaction was performed with lower order and?higher order organocuprates using acetone O-(4-Chlorophenylsulfonyl)oxime (1). It was proceeded smoothly at room temperature in the presence of organocuprates to provide the corresponding primary amines in good yields with 10 and 60 min, respectively. The primary amine yields of the electrophilic amination of bromomagnesium organocyanocuprates and dibromomagnesium diorganocyanocuprates were obtained 52–72% and 58–83%, respectively. We observed that higher order organocuprates were more successful than lower order organocuprates in the synthesis of functionalized arylamines by electrophilic amination.
- Duran, Serdar,Korkmaz, Adem
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p. 2077 - 2087
(2021/05/27)
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- Ultrasonic promoted synthesis of Ag nanoparticle decorated thiourea-functionalized magnetic hydroxyapatite: A robust inorganic-organic hybrid nanocatalyst for oxidation and reduction reactions
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In this research, ultrasonic synthesis is applied for the fabrication of a novel catalyst, based on immobilization of silver nanoparticles (AgNPs) on thiourea functionalized magnetic hydroxyapatite. A recoverable Ag nano-catalyst is constructed by decoration of AgNPs on the surface of thiourea modified magnetic hydroxyapatite. Magnetic hydroxyapatite is used as an organic-inorganic hybrid support for the catalyst. The organic-inorganic hybrid support is prepared by co-precipitation, followed by its surface modification through covalent functionalization of 1-(3,5-bis(trifluoromethyl)phenyl)-3-propyl)thiourea. The fabricated catalyst has been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET) analysis. The nanoparticles are mostly tubular in shape and their particle sizes are smaller than 100 nm. This nanocatalyst shows efficient and robust catalytic activity in different reactions, including selective reduction of 4-nitrophenol (4NP) and oxidation of primary amines by applying NaBH4and urea hydrogen peroxide (UHP) as reagents, respectively. The catalyst shows good reusability in 10 sequential reaction runs.
- Bahadorikhalili, Saeed,Arshadi, Hosein,Afrouzandeh, Zahra,Ma'mani, Leila
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p. 8840 - 8848
(2020/06/08)
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- Catalyst-Controlled Regioselective Chlorination of Phenols and Anilines through a Lewis Basic Selenoether Catalyst
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We report a highly efficient ortho-selective electrophilic chlorination of phenols utilizing a Lewis basic selenoether catalyst. The selenoether catalyst resulted in comparable selectivities to our previously reported bis-thiourea ortho-selective catalyst, with a catalyst loading as low as 1%. The new catalytic system also allowed us to extend this chemistry to obtain excellent ortho-selectivities for unprotected anilines. The selectivities of this reaction are up to >20:1 ortho/para, while the innate selectivities for phenols and anilines are approximately 1:4 ortho/para. A series of preliminary studies revealed that the substrates require a hydrogen-bonding moiety for selectivity.
- Dinh, Andrew N.,Maddox, Sean M.,Vaidya, Sagar D.,Saputra, Mirza A.,Nalbandian, Christopher J.,Gustafson, Jeffrey L.
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p. 13895 - 13905
(2020/11/03)
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- CHEMICAL COMPOUNDS AS ATF4 PATHWAY INHIBITORS
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The invention is directed to substituted bridged cycloalkane derivatives. Specifically, the invention is directed to compounds according to Formula (IIIQ): wherein X6', a, b, C8', D8', L82', L83', R81', R82', R83', R84', R85', R86', z82', z84', z85', and z86' are as defined herein; or salts thereof. The compounds of the invention are inhibitors of the ATF4 pathway. Accordingly, invention is further directed to pharmaceutical compositions comprising a compound of the invention. The invention is still further directed to methods of inhibiting the ATF4 pathway and treatment of disorders associated therewith using a compound of the invention or a pharmaceutical composition comprising a compound of the invention.
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Page/Page column 142
(2019/01/06)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
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Paragraph 0098; 0134; 0135; 0182
(2018/03/25)
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- Copper-Mediated monochlorination of anilines and nitrogen-containing heterocycles
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A simple and selective copper(II) chloride-mediated monochlorination of anilines and nitrogen-containing heterocycles has been developed. Stirring a mixture of aniline, copper(II) chloride, lithium chloride in EtOH under reflux condition produced 4-chloroaniline with high yield. Eighteen substrates including substituted anilines, N-substituted anilines, N,N-disubstituted anilines, 5-nitroindole and carbazole were all reactive and afforded desired products in moderate to excellent yields (52%–98%).
- Yang, Xue-Yan,Zhao, Hong-Yi,Mao, Shuai,Zhang, San-Qi
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supporting information
p. 2708 - 2714
(2018/10/15)
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- Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
- Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
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p. 681 - 688
(2017/06/30)
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- Magnetically separable core-shell iron oxide@nickel nanoparticles as high-performance recyclable catalysts for chemoselective reduction of nitroaromatics
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A magnetically separable core-shell iron oxide@nickel (IO@Ni) nanocatalyst was synthesized by reduction of Ni2+ ions in the presence of iron oxide (Fe2+, Fe3+) by a simple one-pot synthetic route using NaBH4 as a reducing agent and starch as a capping agent. The synthesized nanoparticles (NPs) were characterized by several techniques such as X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), and energy dispersive X-ray spectroscopy (EDS). The core-shell iron oxide@nickel nanoparticles (IO@NiNPs) were found to have excellent activity for the hydrogenation reactions of aromatic nitro compounds under mild conditions using water as a green solvent. Excellent chemoselectivity and recyclability up to 30 cycles for the nitro group reduction was demonstrated.
- Rathore, Puran Singh,Patidar, Rajesh,Shripathi,Thakore, Sonal
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p. 286 - 295
(2015/02/02)
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- Para-Selective Halogenation of Nitrosoarenes with Copper(II) Halides
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The para-selective direct bromination and chlorination of nitrosoarenes with copper(II) bromide and chloride is reported. Under mild reaction conditions, a range of halogenated arylnitroso compounds are obtained in moderate to good yields with high regioselectivity. Additionally, the versatility of the method is demonstrated by the development of a one-pot procedure to obtain the corresponding para-halogenated aniline- and nitrobenzene derivatives.
- Van Der Werf, Angela,Selander, Nicklas
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supporting information
p. 6210 - 6213
(2016/01/09)
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- PdCu nanoparticles supported on graphene: An efficient and recyclable catalyst for reduction of nitroarenes
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Graphene supported PdCu bimetallic nanoparticles were synthesized through coreduction of PdCl2and CuCl2·H2O. X-ray diffraction (XRD), X-ray photoelectron (XPS) and transmission electron microscopy (TEM) were performed to characterize the structures. The complex could be used as an efficient catalyst for reduction of nitroarenes to the corresponding anilines in the presence of NaBH4and recycled up to six runs without significant loss of activity.
- Feng, Yi-Si,Ma, Jing-Jing,Kang, Yu-Mei,Xu, Hua-Jian
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p. 6100 - 6105
(2014/12/10)
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- PdCu nanoparticles supported on graphene: An efficient and recyclable catalyst for reduction of nitroarenes
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Graphene supported PdCu bimetallic nanoparticles were synthesized through coreduction of PdCl2 and CuCl2·H2O. X-ray diffraction (XRD), X-ray photoelectron (XPS) and transmission electron microscopy (TEM) were performed to characterize the structures. The complex could be used as an efficient catalyst for reduction of nitroarenes to the corresponding anilines in the presence of NaBH4 and recycled up to six runs without significant loss of activity.
- Feng, Yi-Si,Ma, Jing-Jing,Kang, Yu-Mei,Xu, Hua-Jian
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p. 6100 - 6105
(2015/03/30)
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- Elusive metal-free primary amination of arylboronic acids: Synthetic studies and mechanism by density functional theory
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Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition-metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions, and, importantly, can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step.
- Zhu, Chen,Li, Gongqiang,Ess, Daniel H.,Falck, John R.,Kürti, László
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supporting information
p. 18253 - 18256
(2013/01/15)
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- Regioselective chlorination and bromination of unprotected anilines under mild conditions using copper halides in ionic liquids
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By using ionic liquids as solvents, the chlorination or bromination of unprotected anilines at the para-position can be achieved in high yields with copper halides under mild conditions, without the need for potentially hazardous operations such as supplementing oxygen or gaseous HCl.
- Wang, Han,Wen, Kun,Nurahmat, Nurbiya,Shao, Yan,Zhang, He,Wei, Chao,Li, Ya,Shen, Yongjia,Sun, Zhihua
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supporting information; experimental part
p. 744 - 748
(2012/06/30)
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- Regiospecific oxyhalogenation of aromatics over SBA-15-supported nanoparticle group IV-VI metal oxides
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TiOx, VOx, MoOx and WOx supported on SBA-15 exhibit efficient catalytic activity for oxyhalogenation of aromatics with the H2O2-halide ion system. Unlike the hitherto known solid catalysts, these reusable catalysts yield the para-halogenated product with 100% selectivity at 298 K and moderate acidic pH (3-5). The catalytic activity was enhanced by five orders of magnitude when supported on SBA-15. Springer Science+Business Media, LLC 2010.
- Saikia,Rajesh,Srinivas,Ratnasamy
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scheme or table
p. 190 - 201
(2010/11/05)
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- Effect of nitrogen-containing compounds on polychlorinated dibenzo-p-dioxin/dibenzofuran formation through de novo synthesis
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An experimental study was conducted to clarify the suppression effect of nitrogen-containing compounds, that is, ammonia and urea, on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) through the de novo synthesis reaction. In the experiment, graphite and copper chloride contained in a mixture were used as sources of carbon and chlorine, respectively. The granulated sample mixture was charged as a packed-bed in the glass tube and heated at 300 °C in the flow of Ar-O 2 gas mixture. In some cases, urea was added as aqueous solution to the sample, while ammonia was added to the gas flowed through the sample bed. The amount of PCDD/Fs formed decreases significantly by the addition of both ammonia and urea. Particularly, the addition of urea reduces the amount of PCDD/Fs discharged in the outlet gas by approximately 90%. The oxidation rate of carbon in the early stage of the experiment, that is, the heating period, is promoted by the addition of nitrogen-containing compounds. However, soon after the temperature reaches 300 °C, the formation rate becomes lower than that of the case without the addition of nitrogen-containing compounds. On the other hand, organic compounds containing amino (-NH2) or cyanide (-CN) groups and those containing nitrogen within the carbon ring frame were detected in the outlet gas in the case of urea addition. Typically observed aromatic compounds are chlorobenzonitriles, chlorobenzeneamines, and chloropyridines. This suggests a possibility that hydrogen and/or chlorine combined with PCDD/Fs are also substituted by such nitrogen-containing groups, and this decreases the formation rate of their frame of carbon rings. This phenomenon was also consistent with the fact that a significant reduction was observed in the amount of PCDD/Fs released to the outlet gas when urea was added.
- Kuzuhara, Shunsuke,Sato, Hiroshi,Tsubouchi, Naoto,Ohtsuka, Yasuo,Kasai, Eiki
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p. 795 - 799
(2007/10/03)
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- Co2(CO)8 as novel and water-tolerant reagent for the conversion of azides to amines in aqueous media
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Azides are readily converted into their corresponding amines using a catalytic amount of Co2(CO)8 under mild conditions. The method is highly chemoselective and compatible with a variety of functionalities such as halides, esters, acids, ethers, nitro, cyano and olefinic double bonds present in the molecule. Copyright
- Yadav,Reddy,Satheesh,Raghavender Rao
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p. 340 - 341
(2007/10/03)
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- Nitroarene reduction using Raney nickel alloy with ammonium chloride in water
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Aromatic nitroarenes are reduced in high yields using a user-friendly combination of Raney nickel alloy and ammonium chloride in water at 80-90°C.
- Bhaumik, Kankan,Akamanchi
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p. 197 - 198
(2007/10/03)
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- Halide ion trapping of nitrenium ions formed in the Bamberger rearrangement of N-arylhydroxylamines. Lifetime of the parent phenylnitrenium ion in water
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The data of p-aminophenol, the product of Bamberger rearrangement, Were analyzed by a mechanism involving rate-limiting formation of the appropriate arylnitrenium ion followed by product-determining steps in involving trapping by the solvent or by the added halide. The possibility that a portion of the halide-trapped products were derived from a pre-association mechanism was also include. Kinetic analyses then produced kBr:kw and kCl:kw ratios for two limiting cases, one involving pre-association with an equilibrium constant Kas = 0.3, and one ignoring pre-association. From an azide:water ratio (kAz:kw) previously determined for the 2,6-dimethylphenylnitrenium, kBr was concluded to lie in the range (4-5) × 109 M-1 s-1 for all of the nitrenium ions of this study. This range for kBr then led to kw values of (1-2) × 109 s-1 (2,5-Me2), (2-3) × 109 s-1 (2-Me), and (4-8) × 109 s-1 (parent and 2-Cl), where the ranges reflect uncertainties in the exact value of kBr and in the contribution from pre-association. The lifetime of the parent phenylnitrenium ion in water at one molar ionic strength is concluded to lie in the range 125-250 ps.
- Fishbein,McClelland
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p. 1321 - 1328
(2007/10/03)
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- 3-amino-5-methyl-1H-pyrazole-4-carboxylic acids and esters thereof as anticonvulsants, muscle relaxants and anxiolytics
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A novel method of controlling epilepsy, muscle tension, muscular spasticity, and anxiety in living animal bodies by administering compounds of the formula: STR1 wherein: R1 is hydrogen, loweralkyl or a pharmaceutically acceptable cation; R2 and R3, same or different, are hydrogen, loweralkyl, aryl, cycloalkyl, loweralkenyl, 1-adamantyl, heterocyclicaminoalkyl, diloweralkylaminoloweralkyl, or R2 with R3 and adjacent nitrogen may form a heterocyclic ring structure; and the pharmaceutical acceptable acid salts, and tautomeric isomers thereof; and novel pharmaceutical compositions therefor are disclosed.
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- Process for preparing aniline derivatives
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A process for the preparation of an aniline, which aniline is substituted at a 2- or the 4-position by a chlorine or bromine atom, from the corresponding nitrobenzene which is unsubstituted at the said 2- or the 4-position, which comprises passing an electric current through a divided electrochemical cell having a graphite cathode, which cell contains, in the cathode compartment, a solution of the nitrobenzene in a medium comprising an aqueous hydrohalic acid selected from hydrochloric acid and hydrobromic acid.
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- ONE-POT CHEMOSELECTIVE REDUCTIVE ALKYLATION OF NITROARENES: A NEW GENERAL METHOD OF SYNTHESIS OF ALKYLANILINES.
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A New facile and general synthesis of alkylanilines by one-pot reductive alkylation of nitroarenes is reported.This method is based on the "in situ" reduction by hydrides (LiAlH4 or NaBH4) in the presence of catalytic amounts of Pd/C, of nitronate adducts arising from the conjugate addition of Grignard reagents to mononitroarenes.LiAlH4 showed to be a more efficient but less selective reducing agent than NaBH4.The reaction can be successfully applied to mono, homo and hetero bicyclic systems and allows to introduce a large variety of alkyl chains without isomerisation phenomena.
- Bartoli, Giuseppe,Bosco, Marcella,Pozzo, Renato Dal,Petrini, Marino
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p. 4221 - 4226
(2007/10/02)
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- Succinimido azo dyestuffs
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The invention relates to water-insoluble azo dyestuffs of the formula SPC1 In which A represents the residue of a diazo component of the azobenzene series, R1 a hydrogen atom or an alkyl group which may be substituted which may be substituted, R2 an alkyl group which may be substituted, R3 represents a divalent organic residue which together with the grouping EQU1 may form a 5- to 7-membered heterocycle, and X represents a hydrogen atom or an alkyl, alkoxy, aryloxy or arylmercapto group. The dyestuffs dye polyester fibre in orange, red or blue shades with good fastness: the use of such succinimido containing azo dyestuffs in imparting blue to red color to fibers or fabrics of wool, cellulose triacetate, polyamides and polyesters. The dyeings display excellent fastness to light, sublimation and abrasion on polyester fibers.
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