104-96-1Relevant articles and documents
Highly selective reduction of nitroarenes to anilines catalyzed using MOF-derived hollow Co3S4 in water under ambient conditions
Xu, Yong,Lv, Xiao-Jun,Chen, Yong,Fu, Wen-Fu
, p. 31 - 35 (2017)
We developed a new strategy for the efficient reduction of nitroarenes using sodium sulfide as reducing agent with MOF-derived Co3S4 as catalyst in water and at room temperature. The introduction of sodium sulfite enhanced the reactant conversion and product selectivity, and the as-synthesized catalyst was used repeatedly five times and retained its activity and selectivity. A wide spectrum of reducible functional moieties kept unaffected under the reaction conditions, and isotope labeling experiment showed the hydrogen atom was derived from water.
Catalytic hydrogenation of sulfur-containing nitrobenzene over Pd/C catalysts: In situ sulfidation of Pd/C for the preparation of PdxSy catalysts
Zhang, Qunfeng,Xu, Wei,Li, Xiaonian,Jiang, Dahao,Xiang, Yizhi,Wang, Jianguo,Cen, Jie,Romano, Stephen,Ni, Jun
, p. 17 - 21 (2015)
The preparation of supported palladium sulfides catalysts has attracted much attention due to their good sulfur-resistant properties in the hydrogenation of sulfur-containing compounds. In this work, we unambiguously demonstrated that Pd/C catalyst could be in situ sulfided by organic sulfur-containing reactant molecules and the sulfidation was highly dependent on temperature. The in situ sulfidation of Pd/C catalyst was composed of a reaction of Pd with the sulfur derived from the cleavage of C-S bond of sulfur-containing reactant molecules, followed by a transformation to PdxSy at high temperatures (around 120 °C). The sulfided Pd/C catalyst could be used for at least 18 recycles without a significant loss in its activity during the hydrogenation of sulfur-containing nitrobenzene at 180 °C with 3 MPa H2, which could be attributed to the stable presence of Pd4S and Pd16S7.
Hexafluoro-2-propanol-assisted quick and chemoselective nitro reduction using iron powder as catalyst under mild conditions
Chen, Xu-Ling,Ai, Bai-Ru,Dong, Yu,Zhang, Xiao-Mei,Wang, Ji-Yu
, p. 3646 - 3649 (2017)
Hexafluoro-2-propanol as the promoter for the quick nitro reduction using a combination of iron powder and 2 N HCl aqueous solution is reported. This methodology has several positive features, as it is of room temperature, remarkably short reaction time. A wide range of substrates including those bearing reducible functional groups such as aldehyde, ketone, acid, ester, amide, nitrile, halogens, even allyl, propargyl and heterocycles are chemoselectively reduced in good to excellent yields, even on gram scale. Notably, the highly selective reduction of 3-nitrophenylboronic acid is achieved quantitatively. The reduction is also tolerant of common protecting groups, and aliphatic nitro compound, 1-nitrooctane can be reduced successfully.
Shape Engineering of Biomass-Derived Nanoparticles from Hollow Spheres to Bowls through Solvent-Induced Buckling
Chen, Chunhong,Li, Xuefeng,Deng, Jiang,Wang, Zhe,Wang, Yong
, p. 2540 - 2546 (2018)
The realization of asymmetric hollow carbonaceous nanostructures remains a great challenge, especially when biomass is chosen as the carbon resource through hydrothermal carbonization (HTC). Herein, a simple and straightforward solvent-induced buckling strategy is demonstrated for the synthesis of asymmetric spherical and bowl-like carbonaceous nanomaterials. The formation of the bowl-like morphology was attributed to the buckling of the spherical shells induced by the dissolution of the oligomers. The bowl-like particles prepared through this solvent-driven approach demonstrated a well-controlled morphology and a uniform particle size of approximately 360 nm. The obtained nanospheres and nanobowls were loaded with CoS2 nanoparticles to act as heterogeneous catalysts for the selective hydrogenation of aromatic nitro compounds. As expected, the CoS2/nanobowls catalyst showed good tolerance to a wide scope of reducible groups and afforded both high activity and selectivity in almost all the tested substrates.
Reduction of nitroarenes using CO and H2O in the presence of a nanostructured cobalt oxide/Nitrogen-Doped Graphene (NGr) catalyst
Westerhaus, Felix A.,Sorribes, Ivn,Wienh?fer, Gerrit,Junge, Kathrin,Beller, Matthias
, p. 313 - 317 (2015)
The most common route to anilines is based on the reduction of the corresponding nitroarenes. In general, hydrogen is preferred as reducing agent and numerous catalytic systems are known to achieve such transformations. Besides, the use of CO/H2O as hydrogen source offers interesting possibilities for reductions. Carbon monoxide is a cheap and abundant chemical used on industrial scale for a variety of transformations. Although the reduction of nitroarenes with CO/H2O is known in the presence of noble-metal catalysts, earth-abundant inexpensive catalysts showing high selectivity have not yet been developed. In this respect, herein we present the use of a heterogeneous cobalt oxide catalyst (Co3O4/NGr@C), which is modified by nitrogen-doped graphene layers. Using this non-noble metal catalyst nitroarenes are reduced in high yields and good chemoselectivities.
General and selective iron-catalyzed transfer hydrogenation of nitroarenes without base
Wienhoefer, Gerrit,Sorribes, Ivan,Boddien, Albert,Westerhaus, Felix,Junge, Kathrin,Junge, Henrik,Llusar, Rosa,Beller, Matthias
, p. 12875 - 12879 (2011)
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.
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Johnson,Hamilton
, p. 74 (1949)
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Defect-mediated selective hydrogenation of nitroarenes on nanostructured WS2
Sun, Yifan,Darling, Albert J.,Li, Yawei,Fujisawa, Kazunori,Holder, Cameron F.,Liu, He,Janik, Michael J.,Terrones, Mauricio,Schaak, Raymond E.
, p. 10310 - 10317 (2019)
Transition metal dichalcogenides (TMDs) are well known catalysts as both bulk and nanoscale materials. Two-dimensional (2-D) TMDs, which contain single- and few-layer nanosheets, are increasingly studied as catalytic materials because of their unique thickness-dependent properties and high surface areas. Here, colloidal 2H-WS2 nanostructures are used as a model 2-D TMD system to understand how high catalytic activity and selectivity can be achieved for useful organic transformations. Free-standing, colloidal 2H-WS2 nanostructures containing few-layer nanosheets are shown to catalyze the selective hydrogenation of a broad scope of substituted nitroarenes to their corresponding aniline derivatives in the presence of other reducible functional groups. Microscopic and computational studies reveal the important roles of sulfur vacancy-rich basal planes and tungsten-terminated edges, which are more abundant in nanostructured 2-D materials than in their bulk counterparts, in enabling the functional group selectivity. At tungsten-terminated edges and on regions of the basal planes having high concentrations of sulfur vacancies, vertical adsorption of the nitroarene is favored, thus facilitating hydrogen transfer exclusively to the nitro group due to geometric effects. At lower sulfur vacancy concentrations on the basal planes, parallel adsorption of the nitroarene is favored, and the nitro group is selectively hydrogenated due to a lower kinetic barrier. These mechanistic insights reveal how the various defect structures and configurations on 2-D TMD nanostructures facilitate functional group selectivity through distinct mechanisms that depend upon the adsorption geometry, which may have important implications for the design of new and enhanced 2-D catalytic materials across a potentially broad scope of reactions.
Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes
Westerhaus, Felix A.,Jagadeesh, Rajenahally V.,Wienhoefer, Gerrit,Pohl, Marga-Martina,Radnik, Joerg,Surkus, Annette-Enrica,Rabeah, Jabor,Junge, Kathrin,Junge, Henrik,Nielsen, Martin,Brueckner, Angelika,Beller, Matthias
, p. 537 - 543 (2013)
Molecularly well-defined homogeneous catalysts are known for a wide variety of chemical transformations. The effect of small changes in molecular structure can be studied in detail and used to optimize many processes. However, many industrial processes require heterogeneous catalysts because of their stability, ease of separation and recyclability, but these are more difficult to control on a molecular level. Here, we describe the conversion of homogeneous cobalt complexes into heterogeneous cobalt oxide catalysts via immobilization and pyrolysis on activated carbon. The catalysts thus produced are useful for the industrially important reduction of nitroarenes to anilines. The ligand indirectly controls the selectivity and activity of the recyclable catalyst and catalyst optimization can be performed at the level of the solution-phase precursor before conversion into the active heterogeneous catalyst.
Novel protocol for synthesis of 1,4-diiminocurcumin stabilized silver nanoparticles and application as heterogenous recyclable catalyst and antibacterial agent
Gogoi, Nishi Gandha,Handique, Jyotirekha G
, (2019)
Abstract: Curcumin [(1E, 6E)-1,7-bis(4-hydroxy-3-methoxy-phenyl)-1,6-heptadiene-3,5-dione] is a low molecular weight yellow-orange polyphenolic pigment extracted from the powdered rhizome of Curcuma longa. Curcumin has wide medicinal applications as an antioxidant, anti-inflammatory, cancer chemopreventive, and potentially chemotherapeutic agents as well as stabilizer/reducing agent in silver nanoparticles (AgNPs) synthesis. However, the low solubility of curcumin in aqueous solutions limits its applications and also, many of AgNP synthetic processes lack a greener synthetic route. In the present work, a Schiff base of curcumin is synthesized condensing curcumin and 1,4-diaminobutane in 2:1 ratio. The resulting product shows improvement in solubility in water and favours the synthesis of AgNPs in aqueous medium at room temperature, acting as a self-reducing/stabilizing agent. This proposed synthetic route is simple, feasible and green. The size and morphology of AgNPs are analyzed by TEM, SEM, EDS and XRD techniques. The recyclable AgNPs as a heterogeneous catalyst in the reduction of nitroaromatics to amino compounds is environmentally benign and can be re-used up to 5th cycle without considerable loss of its catalytic activity. Moreover, both Cur-1,4 and AgNPs show bactericidal properties against bacterial strains (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa) which find medicinal importance in future. Graphic abstract: A greener approach has been proposed for the preparation of AgNPs stabilized on curcumin based Schiff base. The AgNPs finds applications as efficient, easily recyclable heterogenous catalyst in the reduction of nitroaromatics to environmentally benign aminoaromatics as well as an antibacterial agent.[Figure not available: see fulltext.].
Metal–Organic-Framework-Derived Co3S4 Hollow Nanoboxes for the Selective Reduction of Nitroarenes
Yang, Shuliang,Peng, Li,Sun, Daniel T.,Oveisi, Emad,Bulut, Safak,Queen, Wendy L.
, p. 3131 - 3138 (2018)
MOF-derived Co3S4/CN hollow nanoboxes (CN=nitrogen-doped carbon) was used to catalyze the chemoselective reduction of nitroarenes to anilines under mild reaction conditions with H2 as the reducing agent. The catalyst provides high conversion efficiencies and selectivities for a variety of nitroarene substrates that contain electron-donating or electron-withdrawing substituents under mild reaction conditions (in methanol at 60 °C). Further, the nanobox inhibits both dehalogenation and vinyl hydrogenation reactions, which are common limitations of state-of-the-art Pd-based catalysts. Because the reactions result in pure aniline products, the need for separation by column chromatography is eliminated. The resulting anilines are easily separated from the methanolic reaction solution in just three simple steps (centrifugation, decantation, and drying). If employed in industrial processes, catalysts of this kind would significantly reduce the amount of waste organic solvent generated and thus satisfy the need for sustainable chemical processes.
Method for synthesizing heteroatom- substituted aromatic compound from styrene compound
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Paragraph 0169-0172, (2021/02/06)
The invention discloses a method for synthesizing a heteroatom-substituted aromatic compound from a styrene compound, which comprises the following steps of: mixing a styrene compound with a general formula (I) and a heteroatom-containing compound with a general formula (II), and reacting in the presence of an acid additive and an organic solvent to obtain a heteroatom-substituted compound with ageneral formula (III). According to the synthesis method disclosed by the invention, a large amount of styrene compounds are used as raw materials and react to generate aromatic amine or phenol compounds under the action of no metal catalysis; and compared with the traditional aromatic amine and phenol synthesis method, the method has the advantages of high yield, simple conditions, low waste discharge amount, no metal participation, simple reaction equipment, easiness in industrial production and the like.
Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?
Qiu, Xu,Wang, Yachong,Su, Lingyu,Jin, Rui,Song, Song,Qin, Qixue,Li, Junhua,Zong, Baoning,Jiao, Ning
, p. 3011 - 3016 (2021/09/13)
Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.
