- Selective Reduction of Nitroarenes to Arylamines by the Cooperative Action of Methylhydrazine and a Tris(N-heterocyclic thioamidate) Cobalt(III) Complex
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We report an efficient catalytic protocol that chemoselectively reduces nitroarenes to arylamines, by using methylhydrazine as a reducing agent in combination with the easily synthesized and robust catalyst tris(N-heterocyclic thioamidate) Co(III) complex [Co(κS,N-tfmp2S)3], tfmp2S = 4-(trifluoromethyl)-pyrimidine-2-thiolate. A series of arylamines and heterocyclic amines were formed in excellent yields and chemoselectivity. High conversion yields of nitroarenes into the corresponding amines were observed by using polar protic solvents, such as MeOH and iPrOH. Among several hydrogen donors that were examined, methylhydrazine demonstrated the best performance. Preliminary mechanistic investigations, supported by UV-vis and NMR spectroscopy, cyclic voltammetry, and high-resolution mass spectrometry, suggest a cooperative action of methylhydrazine and [Co(κS,N-tfmp2S)3] via a coordination activation pathway that leads to the formation of a reduced cobalt species, responsible for the catalytic transformation. In general, the corresponding N-arylhydroxylamines were identified as the sole intermediates. Nevertheless, the corresponding nitrosoarenes can also be formed as intermediates, which, however, are rapidly transformed into the desired arylamines in the presence of methylhydrazine through a noncatalytic path. On the basis of the observed high chemoselectivity and yields, and the fast and clean reaction processes, the present catalytic system [Co(κS,N-tfmp2S)3]/MeNHNH2 shows promise for the efficient synthesis of aromatic amines that could find various industrial applications.
- Ioannou, Dimitris I.,Gioftsidou, Dimitra K.,Tsina, Vasiliki E.,Kallitsakis, Michael G.,Hatzidimitriou, Antonios G.,Terzidis, Michael A.,Angaridis, Panagiotis A.,Lykakis, Ioannis N.
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supporting information
p. 2895 - 2906
(2021/02/27)
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- Electrochemically Tuned Oxidative [4+2] Annulation and Dioxygenation of Olefins with Hydroxamic Acids
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This work represents the first [4+2] annulation of hydroxamic acids with olefins for the synthesis of benzo[c][1,2]oxazines scaffold via anode-selective electrochemical oxidation. This protocol features mild conditions, is oxidant free, shows high regioselectivity and stereoselectivity, broad substrate scope of both alkenes and hydroxamic acids, and is compatible with terpenes, peptides, and steroids. Significantly, the dioxygenation of olefins employing hydroxamic acid is also successfully achieved by switching the anode material under the same reaction conditions. The study not only reveals a new reactivity of hydroxamic acids and its first application in electrosynthesis but also provides a successful example of anode material-tuned product selectivity.
- Wei, Bang-Yi,Xie, Dong-Tai,Lai, Sheng-Qiang,Jiang, Yu,Fu, Hong,Wei, Dian,Han, Bing
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supporting information
p. 3182 - 3188
(2020/12/11)
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- Practical bromination of arylhydroxylamines with SOBr2 towards ortho-bromo-anilides
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A facile approach for synthesizing ortho-bromoanilides from readily available aryhydroxylamines and thionyl bromide is demonstrated in this work. Mild reaction conditions and broad scope of substrates ranging from heterocyclic structures to pharmaceutics-potential motifs are used in the reactions of this paper. Efficient bromination of ortho C–H bonds of the aryhydroxylamines has been achieved. Ortho-bromoanilide products were obtained in good to excellent yields, and model scaled-up reactions of this synthetic approach are shown in this work.
- Du, Yuanbo,Feng, Lei,Gao, Hongyin,Guo, Lirong,Lu, Haifeng,Xi, Zhenguo
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supporting information
(2021/05/19)
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- Synthesis, anti-microbial, toxicity and molecular docking studies of N-nitroso-N-phenylhydroxylamine (cupferron) and its derivatives
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Bacterial resistance to antimicrobial agents is increasing at an alarming rate globally and requires new lead compounds for antibiotics. In this study, N-phenyl-N-nitroso hydroxylamine (cupferron) and its derivatives have been synthesised using readily available starting materials. The compounds were obtained in high yield and purity. They show activity towards a range of Gram-positive and Gram-negative pathogenic bacteria, with minimum inhibitory concentration (MIC) values as low as 2 μg.mL?1 against the tested organisms, especially for Gram-positive species. Toxicity studies on the lead compound 3b indicate insignificant effects on healthy cell lines. Molecular docking studies on the lead compound identify possible binding modes of the compound, and the results obtained correlate with those of in vitro and MIC studies. The lead compound shows excellent drug-likeness properties.
- Isa, Mustafa A.,Muller, Alfred,Sonopo, Molahlehi,Waziri, Ibrahim,Williams, D. Bradley G.
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supporting information
(2021/10/06)
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- Selective Photoinduced Reduction of Nitroarenes to N-Arylhydroxylamines
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We report the selective photoinduced reduction of nitroarenes to N-arylhydroxylamines. The present methodology facilitates this transformation in the absence of catalyst or additives and uses only light and methylhydrazine. This noncatalytic photoinduced transformation proceeds with a broad scope, excellent functional-group tolerance, and high yields. The potential of this protocol reflects on the selective and straightforward conversion of two general antibiotics, azomycin and chloramphenicol, to the bioactive hydroxylamine species.
- Kallitsakis, Michael G.,Ioannou, Dimitris I.,Terzidis, Michael A.,Kostakis, George E.,Lykakis, Ioannis N.
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supporting information
p. 4339 - 4343
(2020/06/08)
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- Tandem selective reduction of nitroarenes catalyzed by palladium nanoclusters
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We report a catalytic tandem reduction of nitroarenes by sodium borohydride (NaBH4) in aqueous solution under ambient conditions, which can selectively produce five categories of nitrogen-containing compounds: anilines, N-aryl hydroxylamines, azoxy-, azo- and hydrazo-compounds. The catalyst is in situ-generated ultrasmall palladium nanoclusters (Pd NCs, diameter of 1.3 ± 0.3 nm) from the reduction of Pd(OAc)2 by NaBH4. These highly active Pd NCs are stabilized by surface-coordinated nitroarenes, which inhibit the further growth and aggregation of Pd NCs. By controlling the concentration of Pd(OAc)2 (0.1-0.5 mol% of nitroarene) and NaBH4, the water/ethanol solvent ratio and the tandem reaction sequence, each of the five categories of N-containing compounds can be obtained with excellent yields (up to 98%) in less than 30 min at room temperature. This tunable catalytic tandem reaction works efficiently with a broad range of nitroarene substrates and offers a green and sustainable method for the rapid and large-scale production of valuable N-containing chemicals.
- Yan, Ziqiang,Xie, Xiaoyu,Song, Qun,Ma, Fulei,Sui, Xinyu,Huo, Ziyu,Ma, Mingming
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supporting information
p. 1301 - 1307
(2020/03/11)
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- Selective hydrogenation of nitroaromatics to: N -arylhydroxylamines in a micropacked bed reactor with passivated catalyst
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In this contribution, a protocol was established for the selective catalytic hydrogenation of nitroarenes to the corresponding N-arylhydroxylamines. The reduction of 1-(4-chlorophenyl)-3-((2-nitrobenzyl)oxy)-1H-pyrazole, an intermediate in the synthesis of the antifungal reagent pyraclostrobin that includes carbon-chlorine bonds, benzyl groups, carbon-carbon double bonds and other structures that are easily reduced, was chosen as the model reaction for catalyst evaluation and condition optimization. Extensive passivant evaluation showed that RANEY-nickel treated with ammonia/DMSO (1 : 10, v/v) afforded the optimal result, especially with a particle size of 400-500 mesh. To combine the modified catalyst with continuous-flow reaction technology, the reaction was conducted at room temperature, rendering the desired product with a conversion rate of 99.4% and a selectivity of 99.8%. The regeneration of catalytic activity was also studied, and an in-column strategy was developed by pumping the passivate liquid overnight. Finally, the generality of the method was explored, and 7 substrates were developed, most of which showed a good conversion rate and selectivity, indicating that the method has a certain degree of generality.
- Chen, Jian-Li,Cheng, Peng-Fei,Jiang, Zhi-Jiang,Su, Wei-Ke,Xu, Feng,Yu, Zhi-Qun
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p. 28585 - 28594
(2020/08/25)
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- Hydroxytriazene Derived from Sulphanilamide: Spectrophotometric and Biological Applications
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In this investigation, we report synthesis, spectrophotometric application and antimicrobial activities of 3-hydroxy-3-(4-chlorophenyl)-1-(4- sulphonamido)phenyltriazene(HCNT) and its Fe(III) complex [Fe(HCNT)2(H2O)2]. The complex has been synthesized by traditional as well as mechanochemical routes.These compounds have been characterized and screened for antimicrobial activity against bacterial strains i.e. E. coli, S. aureus, S. pyogenes, P. aeruginosa and fungal strains i.e. A.clavatus, A. niger, C. albicans using brothmicrodilution method. The results indicate that the compounds may serve as better bactericides compared to fungicides and the molar composition of iron(III) complex was found 1:2 (Fe:HCNT) by spectrophotometric study.
- Baroliya, Prabhat Kumar,Chauhan, Laxmi Kunwar,Goswami, Ajay Kumar,Nimodia, Kshipra,Ranawat, Pradhyuman Singh
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p. 855 - 862
(2020/11/25)
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- A general and scalable synthesis of polysubstituted indoles
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A consecutive 2-step synthesis of N-unprotected polysubstituted indoles bearing an electron-withdrawing group at the C-3 position from readily available nitroarenes is reported. The protocol is based on the [3,3]-sigmatropic rearrangement of N-oxyenamines generated by the DABCO-catalyzed reaction of N-arylhydroxylamines and conjugated terminal alkynes, and delivers indoles endowed with a wide array of substitution patterns and topologies.
- Diana-Rivero, Raquel,García-Tellado, Fernando,Tejedor, David
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- Highly Selective and Solvent-Dependent Reduction of Nitrobenzene to N-Phenylhydroxylamine, Azoxybenzene, and Aniline Catalyzed by Phosphino-Modified Polymer Immobilized Ionic Liquid-Stabilized AuNPs
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Gold nanoparticles stabilized by phosphine-decorated polymer immobilized ionic liquids (AuNP@PPh2-PIILP) is an extremely efficient multiproduct selective catalyst for the sodium borohydride-mediated reduction of nitrobenzene giving N-phenylhydroxylamine, azoxybenzene, or aniline as the sole product under mild conditions and a very low catalyst loading. The use of a single nanoparticle-based catalyst for the partial and complete reduction of nitroarenes to afford three different products with exceptionally high selectivities is unprecedented. Under optimum conditions, thermodynamically unfavorable N-phenylhydroxylamine can be obtained as the sole product in near quantitative yield in water, whereas a change in reaction solvent to ethanol results in a dramatic switch in selectivity to afford azoxybenzene. The key to obtaining such a high selectivity for N-phenylhydroxylamine is the use of a nitrogen atmosphere at room temperature as reactions conducted under an inert atmosphere occur via the direct pathway and are essentially irreversible, while reactions in air afford significant amounts of azoxy-based products by virtue of competing condensation due to reversible formation of N-phenylhydroxylamine. Ultimately, aniline can also be obtained quantitatively and selectively by adjusting the reaction temperature and time accordingly. Introduction of PEG onto the polyionic liquid resulted in a dramatic improvement in catalyst efficiency such that N-phenylhydroxylamine could be obtained with a turnover number (TON) of 100000 (turnover frequency (TOF) of 73000 h-1, with >99% selectivity), azoxybenzene with a TON of 55000 (TOF of 37000 h-1 with 100% selectivity), and aniline with a TON of 500000 (TOF of 62500 h-1, with 100% selectivity). As the combination of ionic liquid and phosphine is required to achieve high activity and selectivity, further studies are currently underway to explore whether interfacial electronic effects influence adsorption and thereby selectivity and whether channeling of the substrate by the electrostatic potential around the AuNPs is responsible for the high activity. This is the first report of a AuNP-based system that can selectively reduce nitroarenes to either of two synthetically important intermediates as well as aniline and, in this regard, is an exciting discovery that will form the basis to develop a continuous flow process enabling facile scale-up.
- Doherty, Simon,Knight, Julian G.,Backhouse, Tom,Summers, Ryan J.,Abood, Einas,Simpson, William,Paget, William,Bourne, Richard A.,Chamberlain, Thomas W.,Stones, Rebecca,Lovelock, Kevin R. J.,Seymour, Jake M.,Isaacs, Mark A.,Hardacre, Christopher,Daly, Helen,Rees, Nicholas H.
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p. 4777 - 4791
(2019/05/17)
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- Compositional Persistence in a Multicyclic Network of Synthetic Replicators
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The emergence of collections of simple chemical entities that create self-sustaining reaction networks, embedding replication and catalysis, is cited as a potential mechanism for the appearance on the early Earth of systems that satisfy minimal definitions of life. In this work, a functional reaction network that creates and maintains a set of privileged replicator structures through auto- A nd cross-catalyzed reaction cycles is created from the pairwise combinations of four reagents. We show that the addition of individual preformed templates to this network, representing instructions to synthesize a specific replicator, induces changes in the output composition of the system that represent a network-level response. Further, we establish through sets of serial transfer experiments that the catalytic connections that exist between the four replicators in this network and the system-level behavior thereby encoded impose limits on the compositional variability that can be induced by repeated exposure to instructional inputs, in the form of preformed templates, to the system. The origin of this persistence is traced through kinetic simulations to the properties and inter-relationships between the critical ternary complexes formed by the auto- A nd crosscatalytic templates. These results demonstrate that in an environment where there is no continuous selection pressure the network connectivity, described by the catalytic relationships and system-level interactions between the replicators, is persistent, thereby limiting the ability of this network to adapt and evolve.
- Huck, Jürgen,Kosikova, Tamara,Philp, Douglas
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supporting information
p. 13905 - 13913
(2019/09/30)
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- Compositional Persistence in a Multicyclic Network of Synthetic Replicators
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The emergence of collections of simple chemical entities that create self-sustaining reaction networks, embedding replication and catalysis, is cited as a potential mechanism for the appearance on the early Earth of systems that satisfy minimal definitions of life. In this work, a functional reaction network that creates and maintains a set of privileged replicator structures through auto- and cross-catalyzed reaction cycles is created from the pairwise combinations of four reagents. We show that the addition of individual preformed templates to this network, representing instructions to synthesize a specific replicator, induces changes in the output composition of the system that represent a network-level response. Further, we establish through sets of serial transfer experiments that the catalytic connections that exist between the four replicators in this network and the system-level behavior thereby encoded impose limits on the compositional variability that can be induced by repeated exposure to instructional inputs, in the form of preformed templates, to the system. The origin of this persistence is traced through kinetic simulations to the properties and inter-relationships between the critical ternary complexes formed by the auto- and crosscatalytic templates. These results demonstrate that in an environment where there is no continuous selection pressure the network connectivity, described by the catalytic relationships and system-level interactions between the replicators, is persistent, thereby limiting the ability of this network to adapt and evolve.
- Huck, Jürgen,Kosikova, Tamara,Philp, Douglas
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supporting information
p. 13905 - 13913
(2019/10/05)
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- A Modified System for the Synthesis of Enantioenriched N-Arylamines through Copper-Catalyzed Hydroamination
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Despite significant recent progress in copper-catalyzed enantioselective hydroamination chemistry, the synthesis of chiral N-arylamines, which are frequently found in natural products and pharmaceuticals, has not been realized. Initial experiments with N-arylhydroxylamine ester electrophiles were unsuccessful and, instead, their reduction in the presence of copper hydride (CuH) catalysts was observed. Herein, we report key modifications to our previously reported hydroamination methods that lead to broadly applicable conditions for the enantioselective net addition of secondary anilines across the double bond of styrenes, 1,1-disubstituted olefins, and terminal alkenes. NMR studies suggest that suppression of the undesired reduction pathway is the basis for the dramatic improvements in yield under the reported method.
- Ichikawa, Saki,Zhu, Shaolin,Buchwald, Stephen L.
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supporting information
p. 8714 - 8718
(2018/07/14)
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- FE NANOPARTICLES WITH PPM CONTENTS OF PD, CU AND/OR NI, REACTIONS IN WATER CATALYZED BY THEM
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The present application discloses a nanoparticle composition prepared from a mixture comprising: a) a transition metal salt; b) an iron salt; and c) a reducing agent; and methods for the use of such compositions, including the reduction of an organic compound comprising a nitro group to form an organic compound comprising an amine group, the Cu-catalyzed cyclization of an azide and an alkyne (click chemistry) and cross coupling reactions, notably Suzuki-Miyaura reactions. The transition metal salts are in particular Pd, Cu and Ni salts, the content of these metals being typically in the ppm range based on the major constituent Fe in the final products.
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Paragraph 0084
(2017/07/14)
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- Synthesis of N-aryl and N-heteroaryl hydroxylamines via partial reduction of nitroarenes with soluble nanoparticle catalysts
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Polystyrene-supported ruthenium nanoparticles enable the selective hydrazine-mediated reduction of nitroarenes to hydroxylamine products in high yield and selectivity. Key to obtaining the hydroxylamine product in good yield was the use of organic solvents capable of solubilizing the polystyrene-supported nanoparticle catalyst. N-aryl and N-heteroaryl hydroxylamines are generated under exceptionally mild conditions and in the presence of a various easily reduced functional groups.
- Tyler, Jefferson H.,Nazari, S. Hadi,Patterson, Robert H.,Udumula, Venkatareddy,Smith, Stacey J.,Michaelis, David J.
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supporting information
p. 82 - 86
(2016/12/23)
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- Sustainable and Scalable Fe/ppm Pd Nanoparticle Nitro Group Reductions in Water at Room Temperature
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An operationally simple and general process for the safe and selective reduction of nitro groups utilizing ppm Pd supported on Fe nanomaterials in aqueous solution of designer surfactant TPGS-750-M has been developed and successfully carried out at a 100 mmol scale. Preferred use of KBH4 as the hydride source, at ambient temperature and pressure, lends this process suitable for a standard reaction vessel alleviating the need for specialized hydrogenation equipment. Calorimetry data parallel those expected for a classical nitro group reduction when measuring the heat of reaction (-896 to -850 kJ/mol).
- Gabriel, Christopher M.,Parmentier, Michael,Riegert, Christian,Lanz, Marian,Handa, Sachin,Lipshutz, Bruce H.,Gallou, Fabrice
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p. 247 - 252
(2017/02/26)
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- Synthesis and Evaluation of Novel 5-cyclohexyl-2-(4″-substitutedphenyl)-3-(2″-substitutedphenyl)4H-2,3,3a,5,6,6a-hexahydropyrrolo[3,4-d]isoxazole-4,6-dione Derivatives for Their In Vitro Antioxidant and Antibacterial Activities
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1,3-Dipolar cycloaddition reactions of N-cyclohexyl maleimide (1) with azomethine N-oxide (2) have afforded novel isoxazolidine (3) in excellent yield. Their structures have been characterized from their IR,1H-NMR,13C-NMR,1H,1H-COSY, MS(ESI), and elemental analysis techniques. In vitro antibacterial activity of the synthesized compounds were investigated against a representative panel of pathogenic strains specifically two Gram-positive bacteria (Staphylococcus aureus and Streptococcus pyogenes) and two Gram-negative bacteria (Pseudomonas aeruginosa and Escherichia coli) using agar-well diffusion assay. Some of the compounds (3a, 3k, 3n, and 3o) exhibited promising antibacterial activities. All the synthesized compounds have also been screened for their antioxidant activities and were found to be significantly active.
- Kaur, Manpreet,Kaur, Anjandeep,Singh, Baldev,Singh, Baljit
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- Visible-Light, Photoredox-Mediated Oxidative Tandem Nitroso-Diels–Alder Reaction of Arylhydroxylamines with Conjugated Dienes
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Arylhydroxylamines were used in the nitroso-Diels–Alder reaction to generate in situ nitrosoarenes under visible-light, catalytic and aerobic conditions. Mixing a solution of aryl- or heteroarylhydroxylamines with conjuguated dienes in the presence of a catalytic amount of Ru(bpy)3Cl2 afforded 3,6-dihydro-1,2-oxazines in good yields under an oxygen atmosphere.
- Santacroce, Veronica,Duboc, Raphael,Malacria, Max,Maestri, Giovanni,Masson, Geraldine
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supporting information
p. 2095 - 2098
(2017/04/24)
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- Hydroxamic Acids as Chemoselective (ortho-Amino)arylation Reagents via Sigmatropic Rearrangement
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The use of readily available hydroxamic acids as reagents for the chemoselective (ortho-amino)arylation of amides is described. This reaction proceeds under metal-free, mild conditions, displays a very broad scope, and constitutes a direct approach for the metal-free attachment of aniline residues to carbonyl derivatives.
- Shaaban, Saad,Tona, Veronica,Peng, Bo,Maulide, Nuno
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supporting information
p. 10938 - 10941
(2017/08/30)
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- Controllable Synthesis of Mesoporous Iron Oxide Nanoparticle Assemblies for Chemoselective Catalytic Reduction of Nitroarenes
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Iron(III) oxide is a low-cost material with applications ranging from electronics to magnetism, and catalysis. Recent efforts have targeted new nanostructured forms of Fe2O3 with high surface area-to-volume ratio and large pore volume. Herein, the synthesis of 3D mesoporous networks consisting of 4-5 nm γ-Fe2O3 nanoparticles by a polymer-assisted aggregating self-assembly method is reported. Iron oxide assemblies obtained from the hybrid networks after heat treatment have an open-pore structure with high surface area (up to 167 m2 g-1) and uniform pores (ca. 6.3 nm). The constituent iron oxide nanocrystals can undergo controllable phase transition from γ-Fe2O3 to α-Fe2O3 and to Fe3O4 under different annealing conditions while maintaining the 3D structure and open porosity. These new ensemble structures exhibit high catalytic activity and stability for the selective reduction of aryl and alkyl nitro compounds to the corresponding aryl amines and oximes, even in large-scale synthesis.
- Papadas, Ioannis T.,Fountoulaki, Stella,Lykakis, Ioannis N.,Armatas, Gerasimos S.
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supporting information
p. 4600 - 4607
(2016/03/22)
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- TRIFLUOROMETHOXYLATION OF ARENES VIA INTRAMOLECULAR TRIFLUOROMETHOXY GROUP MIGRATION
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The present invention provides a process of producing a trifluoromethoxylated aryl or trifluoromethoxylated heteroaryl having the structure: (I), wherein A is an aryl or heteroaryl, each with or without subsutitution; and R1 is -H, -(alkyl), -(alkenyl), -(alkynyl), -(aryl), -(heteroaryl), - (alkylaryl), - (alkylheteroaryl), -NH-(alkyl), -N(alkyl)2, -NH-(alkenyl), -NH-(alkynyl) -NH-(aryl), -NH-(heteroaryl), -O-(alkyl), -O-(alkenyl), -O-(alkynyl), -O-(aryl), -O-(heteroaryl), -S-(alkyl), -S- (alkenyl), -S-(alkynyl), -S-(aryl), or -S-(heteroaryl), comprising: (a) reacting a compound having the structure: (II), with a trifluoromethylating agent in the presence of a base in a first suitable solvent under conditions to produce a compound having the structure: (III); and (b) maintaining the compound produced in step (a) in a second suitable solvent under conditions sufficient to produce the trifluoromethoxylated aryl or trifluormethoxylated heteroaryl having the structure: (I).
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Page/Page column 59
(2016/05/02)
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- Mechanistic studies on intramolecular C-H trifluoromethoxylation of (hetero)arenes via OCF3-migration
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The one-pot two-step intramolecular aryl and heteroaryl C-H trifluoromethoxylation recently reported by our group has provided a general, scalable, and operationally simple approach to access a wide range of unprecedented and valuable OCF3-containing building blocks. Herein we describe our investigations to elucidate its reaction mechanism. Experimental data indicate that the O-trifluoromethylation of N-(hetero)aryl-N-hydroxylamine derivatives is a radical process, whereas the OCF3-migration step proceeds via a heterolytic cleavage of the N-OCF3 bond followed by rapid recombination of a short-lived ion pair. Computational studies further support the proposed ion pair reaction pathway for the OCF3-migration process. We hope that the current study would provide useful insights for the development of new transformations using versatile N-(hetero)aryl-N-hydroxylamine synthons.
- Lee, Katarzyna N.,Lei, Zhen,Morales-Rivera, Cristian A.,Liu, Peng,Ngai, Ming-Yu
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supporting information
p. 5599 - 5605
(2016/07/06)
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- Synthesis and microbiological activities of novel acyclic nitrones
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In this article, the synthesis, antibacterial and antifungal activities of α-(5-(R)-2-thiophyl)-N-(4-R′) phenyl nitrones are reported. The synthesis was achieved by the condensation of N-substituted hydroxylamine [4-R′-phenylhydroxylamine] with 5-R-2-thiophenecarboxaldehyde in boiling absolute ethanol. The chemical structure of this nitrones was identified by spectroscopic techniques (IR and NMR). The antibacterial and antifungal activities were evaluated against bacteria: B. substilis, S. aureus, E. coli, S. enterica and fungus: M. ramannianus and F. oxysporium f.sp. albedinis. The reactivity of this reaction was making clear according the director condition.
- Mahieddine, Cherifa,Boukhechem, Mohamed Salah,Zerkout, Said,Zitouni, Abdelghani
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p. 1027 - 1030
(2016/03/01)
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- Titania-Supported Gold Nanoparticles Catalyze the Selective Oxidation of Amines into Nitroso Compounds in the Presence of Hydrogen Peroxide
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In this article, the catalytic activity of titania-supported gold nanoparticles (Au/TiO2) was studied for the selective oxidation of amines into nitroso compounds using hydrogen peroxide (H2O2). Gold nanoparticles deposited on Degussa P25 polymorphs of titania (TiO2) have been found to promote the selective formation of a variety of nitroso arenes in high yields and selectivities, even in a large-scale synthesis. In contrast, alkyl amines are oxidized to the corresponding oximes under the examined conditions. Kinetic studies indicated that aryl amines substituted with electron-donating groups are oxidized faster than the corresponding amines bearing an electron-withdrawing functionality. A Hammett-type kinetic analysis of a range of para-X-substituted aryl amines implicates an electron transfer (ET) mechanism (ρ=-1.15) for oxidation reactions with concomitant formation of the corresponding N-aryl hydroxylamine as possible intermediate. We also show that the oxidation protocol of aryl amines in the presence of 1,3-cyclohexadiene leads in excellent yields to the corresponding hetero Diels-Alder adducts between the diene and the in situ formed nitrosoarenes.
- Fountoulaki, Stella,Gkizis, Petros L.,Symeonidis, Theodoros S.,Kaminioti, Eleni,Karina, Athanasia,Tamiolakis, Ioannis,Armatas, Gerasimos S.,Lykakis, Ioannis N.
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supporting information
p. 1500 - 1508
(2016/05/19)
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- Synthesis, characterization, theoretical prediction of activities and evaluation of biological activities of some sulfacetamide based hydroxytriazenes
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Six new N [(4-aminophenyl)sulfonyl]acetamide based hydroxytriazenes have been synthesized and characterized using elemental analysis, IR, 1H NMR, 13C NMR and MASS spectral analysis. Further, their theoretical predictions for probable activities have been taken using PASS (Prediction of Activity Spectra for Substance). Although a number of activities have been predicted but specifically anti-inflammatory, antiradical, anti-diabetic activities have been experimentally validated which proves that theoretical predictions agree with the experimental results. The object of the Letter is to establish Computer Aided Drug Design (CADD) using our compounds.
- Agarwal, Shilpa,Baroliya, Prabhat K.,Bhargava, Amit,Tripathi,Goswami
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p. 2870 - 2873
(2016/06/06)
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- Influence of the side-group at C=N bridging bond of bis-aryl Schiff bases on the wavelength of absorption maximum of ultraviolet absorption spectra
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The compounds N-(benzylidene)-anilines XArCH=NArY (XBAY), N-(phenyl-ethylene)-anilines XArC(CH3)=NArY (XPEAY) and N-phenyl-α-phenylnitrones XArCH=N(O)ArY (XPNY) have bridging group CH=N, C(CH3)=N and CH=N(O) respectively, in which the C(CH3)=N has a side-group methyl CH3 at carbon end and the CH=N(O) has a side-group O atom at nitrogen end. In this work, a series of XPEAY and XPNY were synthesized, and their longest wavelength maximum λmax (nm) of ultraviolet absorption spectra were measured. Then the change regularity of the νmax (cm-1, νmax=1/λmax) of XPEAY and XPNY were investigated, and they were compared with that of XBAY (reported by ref.26). The results indicate: (1) There are no good linear relationships between the νmax of XBAYs and XPEAYs or XPNYs. (2) In case of a same set of X-Y group couples, the distribution of λmax of XPEAYs is larger than that of XPNYs. (3) The side-group CH3 makes the effect of σ(X) larger than that of σ(Y) on the νmax of XPEAYs, whereas the O atom makes the effect of σ(Y) larger than that of σ(X) on the νmax of XPNYs. (4) The cross-interaction between X and Y has important effect on the all νmax. However, the cross-interaction between CH3 and X/Y has not important effect on the νmax of XPEAY, and the cross-interaction between O and X/Y has not important effect on the νmax of XPNY. Copyright
- Luo, Qingqing,Cao, Chao-Tun,Cao, Zhongzhong,Cao, Chenzhong
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p. 406 - 413
(2016/07/28)
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- Hydrogenation of nitroarenes with palladium nanoparticles stabilized by alkyne derivatives in homogeneous phase
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Palladium nanoparticles stabilized by alkyne derivatives catalyzed the hydrogenation of nitroarenes to the aryl amines in homogeneous phase. The reaction of nitrobenzene proceeded smoothly with a substrate-to-palladium molar ratio (S/Pd) of 51,000 under 8 atm of H2. The reaction under 1 atm of H2 with an S/Pd of 1030 was completed in 4 h. A series of substituted nitroarenes, including 4-acetyl- and 4-formylnitrobenzenes, were converted to the aryl amines with high chemoselectivity.
- Arai, Noriyoshi,Onodera, Nozomi,Dekita, Atsushi,Hori, Junichi,Ohkuma, Takeshi
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supporting information
p. 3913 - 3915
(2015/06/08)
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- Selective conversion of nitroarenes using a carbon nanotube-ruthenium nanohybrid
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Ruthenium nanoparticles were assembled on carbon nanotubes and the resulting nanohybrid was used in the hydrazine-mediated catalytic hydrogenation of various nitroarenes, at room temperature. Depending on the solvent, a selective transformation occurred, giving either access to the corresponding aniline or hydroxylamine derivative.
- Jawale, Dhanaji V.,Gravel, Edmond,Boudet, Caroline,Shah, Nimesh,Geertsen, Valérie,Li, Haiyan,Namboothiri, Irishi N. N.,Doris, Eric
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supporting information
p. 1739 - 1742
(2015/03/03)
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- An asymmetric pericyclic cascade approach to 3-alkyl-3-aryloxindoles: Generality, applications and mechanistic investigations
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The reaction of L-serine derived N-arylnitrones with alkylarylketenes generates asymmetric 3-alkyl-3-aryloxindoles in good to excellent yields (up to 93%) and excellent enantioselectivity (up to 98% ee) via a pericyclic cascade process. The optimization, scope and applications of this transformation are reported, alongside further synthetic and computational investigations. The preparation of the enantiomer of a Roche anti-cancer agent (RO4999200) 1 (96% ee) in three steps demonstrates the potential utility of this methodology.
- Richmond, Edward,Ling, Kenneth B.,Duguet, Nicolas,Manton, Lois B.,elebi-?lcüm, Nihan,Lam, Yu-Hong,Alsancak, Sezen,Slawin, Alexandra M. Z.,Houk,Smith, Andrew D.
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supporting information
p. 1807 - 1817
(2015/02/19)
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- Metal fluoride promoted catalytic hydrogenation of aromatic nitro compounds over RANEY Ni
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The catalytic hydrogenation reactivity of aromatic nitro compounds over RANEY Ni was substantially improved when a moderate amount of metal fluoride (NaF, KF, MgF2, and CaF2) was added into the reaction system.
- Liu, Xia,Ma, Xuanxuan,Liu, Sujing,Liu, Ying,Xia, Chuanhai
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p. 36423 - 36427
(2015/05/06)
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- Rhodium(III)-catalyzed internal oxidative coupling of N-hydroxyanilides with alkenes via C-H activation
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Abstract Described herein is an efficient new method for ortho-olefination of anilides in the presence of AgSbF6 and NaOAc via rhodium(III)-catalyzed internal oxidative C-H bond activation based on hydroxyl as directing and oxidative group. A range of alkenes and functional groups on acetanilides is supported and a possible mechanism is proposed according to the experimental results.
- Wen, Jing,Wu, An,Chen, Pei,Zhu, Jin
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supporting information
p. 5282 - 5286
(2015/08/26)
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- Trifluoromethoxylation of arenes: Synthesis of ortho- Trifluoromethoxylated aniline derivatives by OCF3 migration
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Aryl trifluoromethoxylation by a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxylamine derivatives and intramolecular OCF3 migration is presented. This protocol allows easy access to a wide range of synthetically useful ortho-OCF3 aniline derivatives. In addition, it utilizes bench-stable reagents, is operationally simple, shows high functional-group tolerance, and is amenable to gram-scale as well as one-pot synthesis.Areaction mechanism of a heterolytic cleavage of the N-OCF3 bond followed by recombination of the resulting nitrenium ion and trifluoromethoxide is proposed for the OCF3-migration reaction.
- Hojczyk, Katarzyna N.,Feng, Pengju,Zhan, Chengbo,Ngai, Ming-Yu
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supporting information
p. 14559 - 14563
(2015/01/09)
-
- Synthesis and antibacterial properties of new phenothiazinyl-and phenyl-nitrones
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The synthesis of new phenothiazinyl-and phenyl-nitrones under classical versus microwave heating conditions is described. Better yields were obtained under microwave irradiation in the condensation reactions of phenothiazyl-carbaldehyde with hydro-xylamine derivatives. The structures of the new phenothiazinyl-nitrones were assigned on the basis of MS, FT-IR and NMR spectra. The new nitrones and some known phenylnitrones were screened for their antibacterial and antifungal activity against several Candida species, Gram negative bacteria, such as E. coli, Citrobacter spp, Morganella spp, Pseudomonas aeruginosa, Klebsiella pneumoniae (±ESBL), Proteus spp, Acinetobacter spp and the Gram positive bacterium Staphylococcus aureus, with moderate results.
- Petkes, Hermina Iulia,Gál, Emese,Gaina, Luiza,Sabou, Mihaela,Majdik, Cornelia,Silaghi-Dumitrescu, Lumini?a
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p. 1050 - 1056
(2014/12/11)
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- Pd0.01Ru0.01Ce0.98O2-δ: A highly active and selective catalyst for the liquid phase hydrogenation of p-chloronitrobenzene under ambient conditions
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Nanostructured bimetal ion substituted ceria, Pd0.01Ru 0.01Ce0.98O2-δ (PdRuC2), prepared for the first time by a novel solution combustion synthesis and characterized employing XRD, BET, HRTEM and XPS has been shown to be very active and selective than the monometal ion substituted analogue Pd0.02Ce0.98O 2-δ (PdC2), whereas Ru0.02Ce0.98O 2-δ (RuC2) is inactive towards liquid phase hydrogenation of p-chloronitrobenzene to p-chloroaniline under ambient conditions. Structural studies show metal ion substituted ceria as the predominant phase. The hydrogenation over PdRuC2 is completed beyond 75 min with 100% selectivity. Conversely, PdC2 hydrogenates ~40% of p-chloronitrobenzene with 82% selectivity. Increase of temperature from 35 C to 80 C showed a little higher activity of PdRuC2 but with a lower selectivity. The as-prepared and aged forms of PdRuC2 showed similar activity, whereas PdRuC2 heat-treated at 500 C increased the conversion and the 800 C heated catalyst reduced it (both ~2%) indicating high thermal stability. Maximum hydrogenation activity has been observed in ethanol as compared to methanol and butanol. The PdRuC2 catalyst also shows excellent hydrogenation activity towards o-, m-chloronitrobenzene and nitrobenzene. The enhancement of activity and selectivity of Pd in presence of Ru in the PdRu bimetal ionic catalyst for the hydrogenation reaction has been attributed to involvement of remarkable Ru4+-promotion in Pd0.01Ru 0.01Ce0.98O2-δ.
- Mistri, Rajib,Llorca, Jordi,Ray, Bidhan Chandra,Gayen, Arup
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p. 111 - 119
(2013/07/11)
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- Solid supported platinum(0) nanoparticles catalyzed chemo-selective reduction of nitroarenes to N-arylhydroxylamines
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Solid supported platinum(0) (SS-Pt) nanoparticles were developed as a heterogeneous catalyst following a reduction/deposition method and characterized by SEM, TEM, EDX and XRD analysis. The SS-Pt catalyst was applied in the chemo-selective reduction of nitroarenes to N-arylhydroxylamines using hydrazine hydrate as a hydrogen source. A wide variety of reducible functional groups such as halides, carboxylic acids, esters, amides, nitriles, keto, alkenes, alkynes and N-benzyl were well tolerated under the reaction conditions. This process was further successfully employed in 10 g scale reactions. N-Arylhydroxylamines were further applied for catalyst free synthesis of azoxybenzenes. Moreover, use of PEG-400 as cheap reaction medium, additive free methodology and the recyclability of SS-Pt catalyst up to ten times without significant loss of catalytic activity evidently follow the principles of green chemistry.
- Shil, Arun K.,Das, Pralay
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supporting information
p. 3421 - 3428
(2013/12/04)
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- Interrupted fischer-indole intermediates via oxyarylation of alkenyl boronic acids
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The oxyarylation of alkenyl boronic acids with N-arylbenzhydroxamic acids has been achieved under both copper-mediated and copper-catalyzed conditions to provide access to interrupted Fischer-indole intermediates. This transformation is believed to proceed through a copper-promoted C-O bond forming event followed by a [3,3] rearrangement. The scope of the method is described and mechanistic experiments are discussed.
- Wang, Heng-Yen,Anderson, Laura L.
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supporting information
p. 3362 - 3365
(2013/07/26)
-
- Selective reduction of nitroarenes to N-arylhydroxylamines by use of Zn in a CO2-H2O system, promoted by ultrasound
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The promoting effect of ultrasound on the selective reduction of nitroarenes to N-arylhydroxylamines by use of Zn in an environmentally benign CO2-H2O system has been demonstrated. The yield of N-phenylhydroxylamine reaches 95% when the reaction is carried out with a Zn-to-nitrobenzene molar ratio of 2.2 under ultrasound (40 kHz) at 25 °C and normal pressure of CO2 for 60 min. Application of ultrasound to the reaction has the advantages of higher yield of N-arylhydroxylamines, shorter reaction time, and consumption of less Zn. Springer Science+Business Media B.V. 2012.
- Liu, Shijuan,Wang, Yanhua,Yang, Xun,Jiang, Jingyang
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p. 2471 - 2478
(2013/02/25)
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- ISOXAZOLIDINE DERIVATIVES
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Anti-inflammatory and antiallergic compounds of the glucocorticosteroid series, according to formula (I) according to formula (I) defined herein are useful for treating diseases of the respiratory tract characterized by airway obstruction.
- -
-
Page/Page column 68
(2012/09/25)
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- ISOXAZOLIDINE DERIVATIVES
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The present invention relates to novel anti-inflammatory and antiallergic compounds of the glucocorticosteroid series, methods of preparing such compounds, pharmaceutical compositions comprising them, combinations and therapeutic uses thereof. More particularly, the invention relates to glucocorticosteroids that are derivatives of isoxazolidine.
- -
-
Page/Page column 136-137
(2012/10/07)
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- PROCESS FOR PREPARING SUBSTITUTED N-PHENYLHYDROXYLAMINES
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The present invention relates to a process for the preparation of 2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl] phenyl]-hydroxylamine from the correspondingly substituted nitrobenzene compound.
- -
-
Page/Page column 10
(2012/09/22)
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- Synthesis of N-arylhydroxylamines by Pd-catalyzed coupling
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Pd-catalyzed coupling of aryl halides with TeocNHOTBS, followed by treatment of the products with TBAF, provides effective access to a wide range of N-arylhydroxylamines by a route that produces stable doubly-protected intermediates and allows the protective groups to be removed under mild conditions that do not cause extensive degradation of the final product.
- Beaudoin, Daniel,Wuest, James D.
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experimental part
p. 2221 - 2223
(2011/05/05)
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- METHOD FOR PRODUCING ARYLHYDROXYLAMINE
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PROBLEM To provide a method for producing an arylhydroxylamine compound efficiently and safely under mild conditions. MEANS FOR SOLVING THE PROBLEM The present invention relates to a method for producing an arylhydroxylamine compound, which comprises contacting a nitroaryl compound with a hydrogen source in the coexistence of a platinum catalyst supported on amino group-coordinated silica and a poisoning agent.
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-
Page/Page column 23-24
(2010/03/04)
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- The selective reduction of nitroarenes to N-arylhydroxylamines using Zn in a CO2/H2O system
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Nitroarenes are reduced to the corresponding N-arylhydroxylamines with high selectivity using Zn dust in a CO2/H2O system under mild conditions. The yield of N-phenylhydroxylamine from nitrobenzene is 88% when the reaction is carried out at 25 °C for 1.5 hours with a Zn to nitrobenzene molar ratio equal to 3 under 0.1 MPa CO2. Other nitroarenes, which contain reducible functionality other than a nitro group, are also reduced to the corresponding N-arylhydroxylamines with yield from 88% to 99%. The process fully removes the need to use NH4Cl and is environmentally benign. The Royal Society of Chemistry 2009.
- Liu, Shijuan,Wang, Yanhua,Jiang, Jingyang,Jin, Zilin
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experimental part
p. 1397 - 1400
(2010/05/17)
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- Selective synthesis of N-aryl hydroxylamines by the hydrogenation of nitroaromatics using supported platinum catalysts
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Various substituted nitroaromatics were successfully hydrogenated to the corresponding N-aryl hydroxylamines in excellent yields (up to 99%) using supported platinum catalysts such as Pt/SiO2 under a hydrogen atmosphere (1 bar) at room temperature. The key to the fast and highly selective formation of hydroxylamines is the addition of small amounts of amines such as triethylamine and dimethyl sulfoxide; amines promote the conversion of nitroaromatics, while dimethyl sulfoxide inhibits further hydrogenation of hydroxylamines to anilines. The promotive effect depends on which type of amine and primary amine was most effective. The hydrogenation efficiently proceeded in common organic solvents, including isopropanol, diethyl ether, and acetone. This methodology should extend the application range of conventional solid catalysts to fine chemicals synthesis. The Royal Society of Chemistry 2009.
- Takenaka, Yasumasa,Kiyosu, Takahiro,Choi, Jun-Chul,Sakakura, Toshiyasu,Yasuda, Hiroyuki
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supporting information; experimental part
p. 1385 - 1390
(2010/05/18)
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- Solvent hydrogen bonding and structural influences on the CrVI oxidation of anilines in aqueous acetic acid medium
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The oxidation of meta- and para-substituted anilines by CrVI oxidant, imidazolium fluorochromate (IFC), in aqueous acetic acid mixtures of varying compositions in the presence of p-toluenesulfonic acid (PTS) is first order in IFC and PTS. Michaelis-Menten type kinetics is observed with all of the anilines. The IFC oxidation of 15 meta- and para-substituted anilines at 299-322 K complies with the isokinetic relationship but not to any of the linear free energy relationships. The isokinetic temperature lies within the experimental range. The rate data failed to correlate with macroscopic solvent parameters such as relative permittivity, εr, and ionizing power, Y, correlation of rate data with Kamlet-Taft solvatochromic parameters (hydrogen bond donor acidity, α, hydrogen bond acceptor basicity, β, and dipolarity/polarizability, π*) is linear which suggests that the specific solute-solvent interactions play a dominating role in governing the reactivity.
- Bhuvaneshwari,Elango
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experimental part
p. 242 - 249
(2010/04/26)
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- Kinetics and mechanistic study of acid-catalysed hydrolysis of p-chlorophenyl-2-furohydroxamic acid
-
The rate of hydrolysis of p-chlorophenyl-2-furohydroxamic acid [4-Cl-C 6H4N(OH)-C(O)-C4H3O] has been studied over a wide range of acidities in hydrochloric, sulphuric and perchloric acids in 20% (v/v) dioxane-water at 55°C. The kinetics has been analysed by Bunnett, Bunnett-Olsen and Cox-Yates excess acidity treatments. Solvent, salt and temperature effects has also been probed. The mechanism of acid-catalysed hydrolysis is postulated as involving two steps : a rapid protonation and a rate-determining A-2 nucleophilic attack by water.
- Rajput, Surendra K.,Raghavan, Vinita
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p. 588 - 592
(2008/12/20)
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- Effect of solvent on the rate of oxidation of substituted anilines with nicotinium dichromate in aqueous-acetic acid media
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Mechanistic studies on the oxidation of 15 para- and meta-substituted anilines by nicotinium dichromate in water-acetic acid medium of varying mole fractions have been performed. The reaction can be characterized by the experimental rate equation, -d[oxidizing agent]/dt = Kk [substrate] [HCrO 4-]/(1 + K [substrate]) The addition of p-toluenesulfonic acid enhances the reaction. The oxidation substituted anilines at 299-322 K complies with the isokinetic relationship but not to any of the linear free energy relationships, the isokinetic temperature lies within the experimental range. Correlation of rate data with Kamlet-Taft solvatochromic parameters (α, β, π*) suggests that the specific solute-solvent interactions play a major role in governing the reactivity.
- Bhuvaneshwari,Elango
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p. 999 - 1005
(2007/10/03)
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- Ultrasonically activated reduction of substituted nitrobenzenes to corresponding N-arylhydroxylamines
-
Arylhydroxylamines can be obtained by reduction of the corresponding nitroaromatic compounds. We report here an efficient preparation of arylhydroxylamines by a controlled reduction of nitro compounds using zinc metal and ammonium chloride under ultrasonic activation in very short reaction times.
- Ung, Stéphane,Falguières, Annie,Guy, Alain,Ferroud, Clotilde
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p. 5913 - 5917
(2007/10/03)
-
- Effect of substituents on the rate of oxidation of anilines with peroxomonosulfate monoanion (HOOSO3-) in aqueous acetonitrile: A mechanistic study
-
Mechanistic studies on the oxidation of 18 meta-, para-, and ortho-substituted anilines (Ans) by HOOSO3- in aqueous acetonitrile medium have been performed. The reaction can be characterized by the experimental rate equation, -d[HSO5-]/dt = k[An][HSO5-] The addition of p-toluenesulfonic acid (TsOH) retards the reaction. The increase in the reactivity of anilines as the medium is made more aqueous is interpreted. The reaction is enhanced by electron-donating groups on the amine in the series consistent with the rate-limiting nucleophilic attack of the amine on the persulfate oxygen. The proposed mechanism involves the conversion of phenylhydroxylamine to nitrosobenzene in a fast step. The ESR study reveals the absence of free radicals in the reaction. Various attempts have been made to analyze the experimental rate constants in terms of LFER plots. Improved correlations are obtained with σ- values and the σ- form of the Yukawa-Tsuno equation.
- Meenakshisundaram, Subbiah,Selvaraju,Made Gowda,Rangappa, Kanchugarakoppal S.
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p. 649 - 657
(2007/10/03)
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- 1,3-Dipolar cycloadditions: Part VII1 - Cycloaddition of C,N-diarylnitrones to ethyl crotonate
-
Cycloaddition of C, N-diarylnitrones to ethyl crotonate occurrs with high regio- and stereo-selectivity to furnish 3,4-trans-4,5-trans-22,3-diaryl-4- carbethoxy-5-methylisoxazolidine derivatives as the major cycloadducts. The 3,4-cis-4,5-trans stereoisomers are obtained as minor products.
- Banerji, Avijit,Dasgupta, Saugandha,Sengupta, Piyali,Prange, Thierry,Neuman, Alain
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p. 1925 - 1933
(2007/10/03)
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