106-50-3Relevant articles and documents
Cox,Lewin
, p. 350,352 (1935)
Efficiency of Radical-Cation Amination of Aromatic Compounds in Sulfuric Acid Solutions [5]
Lisitsyn,Kargin
, p. 829 - 830 (2003)
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Silver nanoparticles supported on P, Se-codoped g-C3N4 nanosheet as a novel heterogeneous catalyst for reduction of nitroaromatics to their corresponding amines
Elhampour, Ali,Heravi, Majid M.,Nemati, Firouzeh,Piri, Mohadese
, (2021)
P, Se-codoped g-C3N4 (PSeCN) nanosheet was in situ prepared by facile thermal polymerization of melamine, phosphonitrilic chloride trimer, and selenium black powder as the precursors. It was found as a suitable support for the immobilization of silver nanoparticles (Ag NPs). The prepared nanocatalyst was fully characterized via standard analysis methods including EDX, ICP-OES, XRD, FT-IR, SEM, TEM, and BET. This PSeCN/Ag nanocatalyst with a higher specific surface area compared with CN, showed excellent catalytic activity towards the reduction of several nitroaromatic compounds using sodium borohydride (NaBH4) in short reaction times with high efficiency and good selectivity in water as a green solvent. Significantly, the above-mentioned nanocomposite could be reused six times without appreciable loss of its catalytic activity.
Radical reactions in aqueous medium using (Me3Si)3SiH
Postigo, Al,Kopsov, Sergey,Ferreri, Carla,Chatgilialoglu, Chryssostomos
, p. 5159 - 5162 (2007)
(Chemical Equation Presented) (Me3Si)3SiH was used as a successful reagent in a variety of radical-based transformations in water. The system comprising substrate, silane, and initiator (ACCN) mixed in aqueous medium at 100°C worked well for both hydrophilic and hydrophobic substrates, with the only variation that an amphiphilic thiol was also needed in case of the water-soluble compounds.
Efficient hydrogenation catalyst designing via preferential adsorption sites construction towards active copper
Dai, Xingchao,He, Dongcheng,Li, Teng,Shi, Feng,Wang, Hongli,Wang, Tao,Wang, Xinzhi
, p. 397 - 406 (2021)
Based on the experimental and DFT calculation results, here for the first time we built preferential adsorption sites for nitroarenes by modification of the supported Cu catalysts surface with 1,10-phenathroline (1,10-phen), by which the yield of aniline via reduction of nitroarene is enhanced three times. Moreover, a macromolecular layer was in-situ generated on supported Cu catalysts to form a stable macromolecule modified supported Cu catalyst, i.e., CuAlOx-M. By applying the CuAlOx-M, a wide variety of nitroarene substrates react smoothly to afford the desired products in up to > 99% yield with > 99% selectivity. The method tolerates a variety of functional groups, including halides, ketone, amide, and C = C bond moieties. The excellent catalytic performance of the CuAlOx-M can be attributed to that the 1,10-phen modification benefits the preferential adsorption of nitrobenzene and slightly weakens adsorption of aniline on the supported nano-Cu surface.
Visible-light-induced photocatalytic hydrogenation of 4-nitroaniline over In2S3 photocatalyst in water
Wu, Weiming,Lin, Rui,Shen, Lijuan,Liang, Ruowen,Yuan, Rusheng,Wu, Ling
, p. 1 - 4 (2013)
Photocatalytic hydrogenation of 4-nitroaniline over the In 2S3 photocatalyst was investigated in water under visible light irradiation (λ ≥ 420 nm). After 90 min of visible light irradiation, 100% of 4-nitroaniline could be reduced t
Preparation and characterization of Ni/mZSM-5 zeolite with a hierarchical pore structure by using KIT-6 as silica template: An efficient bi-functional catalyst for the reduction of nitro aromatic compounds
Mazaheri, Omid,Kalbasi, Roozbeh Javad
, p. 34398 - 34414 (2015)
Ni/mZSM-5 and Ni/H-mZSM-5 were synthesized as hierarchical (micro/meso porous) ZSM-5 zeolites by an indirect template method for the first time. The resulting zeolite materials exhibited significantly enhanced diffusional properties in comparison to purely microporous zeolite materials. The structural and morphological characterization of the prepared catalysts was investigated using XRD, BET, atomic absorption spectroscopy, FT-IR, 27Al-MAS NMR, SEM, TEM, XPS and DRS-UV techniques. These hierarchical zeolites were used as acid-metal bi-functional heterogeneous catalysts for hydride transfer in the reduction of nitro aromatic compounds. In these reactions, NaBH4 was used as a reducing agent. Excellent yields at room temperature and very short reaction times in aqueous media conditions were obtained. Reusability experiments showed the excellent stability of Ni/mZSM-5 and Ni/H-mMZSM-5 and the catalysts could be reused 7 times without much loss of activity in reduction of nitro aromatic compounds. Surprisingly, the acid form of Ni/H-mZSM-5 showed much higher activity than that of Ni/mZSM-5. High yield, short reaction time, green solvent (water), room temperature, no by-product, the easy reusability of catalysts and the low amounts of catalyst required are some of the advantages of these catalysts.
Supported polymer magnets with high catalytic performance in the green reduction of nitroaromatic compounds
Safari,Gandomi-Ravandi,Haghighi
, p. 31514 - 31525 (2016)
Magnetic Fe3O4 nanoparticles (MNPs) were prepared by a simple co-precipitation method using molar ratios of Fe2+:Fe3+ = 1:2 in ammonia solution, and subsequently were modified with tetraethyl orthosilicate (TEOS
Starch functionalized creatine for stabilization of gold nanoparticles: Efficient heterogeneous catalyst for the reduction of nitroarenes
Gholinejad, Mohammad,Dasvarz, Neda,Shojafar, Mohammad,Sansano, José M.
, (2019)
Selective reduction of nitroaromatic pollutants into amines with recoverable and reusable heterogeneous catalysts is highly desirable. Herein, we prepared and characterized an efficient novel catalyst comprising 4 nm size Au nanoparticles supported on creatine modified starch. Using this catalyst, efficient reduction of nitroarenes into amines at room temperature in aqueous media was achieved. The presence of creatine in the structure of the catalyst plays important role in amount of Au loading, efficiency of the catalyst, recycling times, and leaching of Au compared to starch supported Au without creatine.
Hexafluoro-2-propanol Promotes para-Selective C–H Amination of Free Anilines with Azodicarboxylates
Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
, p. 4753 - 4757 (2017)
An effective, mild, and clean method for the C–H amination of free anilines with azodicarboxylates in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) without the need for any additional catalysts or reagents was developed. The reaction was found to be highly regioselective and provided a series of p-aminophenylhydrazine derivatives in excellent yields. Moreover, compatibility with a free amino group makes this protocol an attractive strategy in synthetic chemistry.
Comparison between Heterogeneous and Homogeneous Electron Transfer in p-Phenylenediamine Systems
Kapturkiewicz, Andrzej,Jaenicke, Walther
, p. 2727 - 2734 (1987)
The one-electron oxidation of selected p-phenylendiamines to form the corresponding radical cations has been studied at a Pt electrode in dimethylformamide and acetonitrile solutions containing 0.1 mol dm-3 NaClO4.The standard redox potentials, the diffusion coefficients and the standard rate constants have been evaluated in the range between room temperature and the melting point of the respective solvent using cyclic valtammetry.It has been shown that the dynamics of solvent reorientation affects the heterogeneous electron-transfer rate, as opposed to the homogeneous process.The free energies of activation are much greater in the heterogeneous than in the homogeneous case.Both results are explained by the different shape of the activated complexes, consisting of one or two ellipsoidal molecules.
REDUCTION OF NITRO COMPOUNDS BY CARBON MONOXIDE ON PALLADIUM COMPEXES
Min'kov, A. I.,Eremenko, N. K.,Merkur'eva, S. E.,Efimov, O. A.
, p. 1223 - 1226 (1986)
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Peculiarities of azobenzene catalytic hydrogenation in 2-propanol aqueous solutions with acid or base additives
Lefedova,Kha, Nguen Tkhi Tkhu,Komarov,Budanov
, p. 32 - 35 (2012)
It is shown experimentally that the hydrogenation of azobenzenes over a nickel skeleton catalyst in 2-propanol aqueous solutions proceeds selectively with the formation of aniline. It is pointed out that during the reaction, considerable participation of hydrogen bonded with active centers of a catalyst surface was observed. The competitive character of adsorption between the initial azo compound and aniline formed as a result of reaction is established. It is concluded that purposeful change of the azo group hydrogenation rate is possible by introducing acid or base additives into 2-propanol aqueous solution.
Bio-waste chitosan-derived N-doped CNT-supported Ni nanoparticles for selective hydrogenation of nitroarenes
Advani, Jacky H.,Bajaj, Hari C.,Biradar, Ankush V.,Gawande, Manoj B.,Naikwadi, Dhanaji R.,Ravi, Krishnan
, p. 10431 - 10440 (2020)
In this study, a facile method for the synthesis of leach proof and earth-abundant non-noble Ni nanoparticles on N-doped carbon nanotubes is reported. The catalyst was synthesized by an impregnation-carbonization method, wherein a Ni-chitosan complex upon carbonization in a 5% H2/N2 atmosphere at 800 °C yielded Ni-containing N-doped CNTs. Chitosan served as a single source of carbon and nitrogen, and the nanotube growth was facilitated by the in situ formed Ni nanoparticles. The nanocatalyst was thoroughly characterized by several techniques; elemental mapping by SEM and TEM analysis confirmed the uniform distribution of Ni nanoparticles on the surface of N-doped CNTs with an average size in the range of 10-15 nm. The catalyst efficiently reduced a variety of nitroarenes (>99%) into their corresponding amines at a moderate pressure (5 bar) and a comparatively lower temperature (80 °C). Furthermore, the easy recovery of the catalyst using an external magnetic field along with high activity and easy recyclability makes the protocol eco-friendly.
Facile reduction of aromatic nitro compounds to aromatic amines catalysed by support-free nanoporous silver
Li, Zhiwen,Xu, Xiaohong,Jiang, Xiaojian,Li, Yingchun,Yu, Zhixin,Zhang, Xiaomei
, p. 30062 - 30066 (2015)
Nanoporous silver was used as the catalyst for the reduction of aromatic nitro compounds even in the presence of some sensitive functional groups under mild conditions with excellent yields. A reduced amount of NaBH4 was used. The reaction kine
Kinetics of the hydrogenation of 2-chloro-4-nitroaniline over skeletal nickel and supported palladium catalysts in an aqueous solution of 2-propanol
Krasnov,Latypova,Lefedova,Sharonov, N. Yu.
, p. 455 - 459 (2017)
The kinetics of the liquid-phase hydrogenation of 2-chloro-4-nitroaniline in an aqueous solution of 2-propanol over skeletal nickel and supported palladium catalysts is studied. The selectivity of the reaction with respect to 2-chloro-1,4-phenylenediamine is determined. It is found that samples of supported palladium catalysts differ with respect to the amount of the active component and the nature of the support. Some of their structural characteristics are provided.
Sustainable and recyclable palladium nanoparticles–catalyzed reduction of nitroaromatics in water/glycerol at room temperature
Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhao, Yongde,Zhou, Yang
, p. 540 - 544 (2021)
Palladium nanoparticles with unique catalytic activity and high stability are synthesized. These nanoparticles exhibit excellent catalytic reduction activity for nitroaromatics in green solvents in the presence of H2 at ambient pressure and temperature. The prominent advantages of this nanotechnology include low consumption of catalyst, excellent chemoselectivity, high reusability of the catalyst, and environmentally green solvents.
Immobilized iron oxide nanoparticles as stable and reusable catalysts for hydrazine-mediated nitro reductions in continuous flow
Moghaddam, Mojtaba Mirhosseini,Pieber, Bartholom?us,Glasnov, Toma,Kappe, C. Oliver
, p. 3122 - 3131 (2014)
An experimentally easy to perform method for the generation of alumina-supported Fe3O4 nanoparticles [(6±1)nm size, 0.67 wt%]and the use of this material in hydrazine-mediated heterogeneously catalyzed reductions of nitroarenes to anilines under batch and continuous-flow conditions is presented. The bench-stable, reusable nano-Fe3O4@Al2O3 catalyst can selectively reduce functionalized nitroarenes at 1 mol% catalyst loading by using a 20 mol% excess of hydrazine hydrate in an elevated temperature regime (150°C, reaction time 2-6 min in batch). For continuous-flow processing, the catalyst material is packed into dedicated cartridges and used in a commercially available high-temperature/-pressure flow device. In continuous mode, reaction times can be reduced to less than 1 min at 150°C (30 bar back pressure) in a highly intensified process. The nano-Fe3O4@Al2O3 catalyst demonstrated stable reduction of nitrobenzene (0.5 m in MeOH) for more than 10 h on stream at a productivity of 30mmolh-1 (0.72 mol per day). Importantly, virtually no leaching of the catalytically active material could be observed by inductively coupled plasma MS monitoring.
Cox
, p. 3,9 (1934)
The Anodic Oxidation of 1,4-Diaminobenzene: an Electron Spin Resonance and Electrochemical Study
Albery, W. John,Compton, Richard G.,Kerr, Ian S.
, p. 825 - 829 (1981)
The electrochemical e.s.r. of 1,4-diaminobenzene, 1,4-diamino-2-chlorobenzene, and 1,4-diamino-2-methylbenzene has been studied in aqueous methanol using an apparatus in which a tube electrode is linked to the e.s.r. cavity.Laminar flow transports species from the electrode into the cavity.The distribution of species in the cavity can be described theoretically and from the variation of e.s.r. signal with current, flow rate, concentration, and pH the protonation and kinetic stability of the 1,4-diaminobenzene cation radical is established.From the electrochemistry, the protonation of the unstable benzoquinone di-imide is deduced.The kinetics and the mechanism of its substitution reaction with water leading to benzoquinone are deduced from the behaviour of the e.s.r. signal from the radical cation with which the benzoquinone di-imide is in equilibrium.
Unprotected and interconnected Ru0 nano-chain networks: Advantages of unprotected surfaces in catalysis and electrocatalysis
Anantharaj,Jayachandran,Kundu, Subrata
, p. 3188 - 3205 (2016)
Seedless, surfactantless and support-free unprotected, metallic, interconnected nano-chain networks of ruthenium nanoparticles (NPs) were successfully synthesized via the reduction of ruthenium(iii) chloride (RuCl3) with sodium borohydride (NaBH4) at three different temperatures, viz. 30 °C, 45 °C and 60 °C. The molar ratio of RuCl3 solution and borohydride was optimized to be 1:1.5 to produce stable colloids with the optimum final solution pH of 9.7 ± 0.2. Average diameters of the interconnected nano-chain networks prepared at 30 °C (Ru-30), 45 °C (Ru-45) and 60 °C (Ru-60) were 3.5 ± 0.5 nm, 3.0 ± 0.2 nm and 2.6 ± 0.2 nm respectively. The morphology and composition dependent catalytic and electrocatalytic activities of these unprotected Ru nano-chain networks (Ru-30, Ru-45 and Ru-60) were studied in detail. The catalysis study was performed by investigating the transfer hydrogenation of several substituted aromatic nitro compounds. It was observed that Ru-60 was relatively more active compared to Ru-30 and Ru-45, which was reflected in their rate constant values. The electrocatalytic activities of Ru-30, Ru-45 and Ru-60 were screened for anodic water splitting in alkaline medium (0.1 M NaOH) and it was found that all of them showed almost the same activity which required an over-voltage of 308 ± 2 mV to obtain an anodic current density of 10 mA cm-2. The catalytic and electrocatalytic performances of these unprotected Ru0 networks were compared with Ru0 nanomaterials prepared under similar conditions with three different surfactants, viz. CTAB, SDS and TX-100, which revealed that unprotected Ru0 networks are better catalysts than those stabilized with surfactants. The superior catalytic and electrocatalytic performance is due to the availability of unprotected Ru0 surfaces. The present route may provide a new possibility of synthesizing other surfactant-free, unprotected metal colloids for enhanced catalytic and electrocatalytic applications.
Binuclear half-sandwich ruthenium(II) Schiff base complexes: Synthesis, characterization, DFT study and catalytic activity for the reduction of nitroarenes
Nandhini, Raja,Krishnamoorthy, Bellie Sundaram,Venkatachalam, Galmari
, (2019)
The binuclear ruthenium(II) p-cymene complexes containing Schiff base ligands of general composition [(Ru(p-cymene)Cl)2L1-6] (1-6) have been synthesized. The complexes were characterized by analytical and spectral (FT?IR, UV–Vis & 1H NMR) methods. The molecular structure of the representative complex [(Ru(p-cymene)Cl)2(L6)] (6) was determined by single-crystal X-ray diffraction and density functional theory (DFT) calculations. Further, these half-sandwich ruthenium complexes are active catalysts for the mild hydrogenation of nitroarenes to aromatic anilines in the presence of NaBH4 in ethanol. The most efficient catalyst 6, was found be compatible with nitroarenes of various functional groups.
Wilson, R. F.,Henry, G.
, p. 1005 - 1012 (1963)
Braun
, p. 1511,1512 (1932)
Hydrogenation of Substituted Benzenes Containing Nitro and Azo Groups over Skeletal Nickel in Aqueous Solutions of 2-Propanol
An’, Khoang,Belova, A. V.,Lefedova, O. V.,Nemtseva, M. P.
, p. 720 - 724 (2020)
Abstract: An analysis is made of the kinetic characteristics of the hydrogenation of 4-nitro- and 2-nitro-2'-hydroxy-5'-methylazobenzenes, 4-nitroaniline and 4-aminoazobenzene over skeletal nickel in neutral azeotropic 2-propanol–water mixture and in the same solvent in the presence of acetic acid or sodium hydroxide. It is found that the selectivity of the hydrogenation of these isomers to the intermediate products depends on the composition and nature of the solvent, and is determined by the rate of reactive group conversion. Compared to the process in the presence of sodium hydroxide, which suppresses the route leading to the predominant hydrogenation of the nitro group, the contribution from the transformation of azo group is considerably greater in the hydrogenation of 4-nitro-2'-hydroxy-5'-methylazobenzene in the presence of acetic acid. Adding a base to the solvent during the hydrogenation of 2-nitro-2'-hydroxy-5'-methylazobenzene accelerates the rate of nitro group conversion and the intramolecular cyclization of the intermediate compound, increasing the selectivity towards the products containing the benzotriazole cycle (particularly 2-(2-hydroxy-5-methylphenyl)benzotriazole-N-oxide). The almost linear correlation between the selectivity of the catalytic hydrogenation of isomers of nitro-2'-hydroxy-5'-methylazobenzene and the kinetic characteristics of the hydrogenation of nitro and azo groups in compounds containing a single reactive substituent at different values of medium’s pH is estimated.
Yeast supported gold nanoparticles: an efficient catalyst for the synthesis of commercially important aryl amines
Krishnan, Saravanan,Patel, Paresh N.,Balasubramanian, Kalpattu K.,Chadha, Anju
supporting information, p. 1915 - 1923 (2021/02/06)
Candida parapsilosisATCC 7330 supported gold nanoparticles (CpGNP), prepared by a simple and green method can selectively reduce nitroarenes and substituted nitroarenes with different functional groups like halides (-F, -Cl, -Br), olefins, esters and nitriles using sodium borohydride. The product aryl amines which are useful for the preparation of pharmaceuticals, polymers and agrochemicals were obtained in good yields (up to >95%) using CpGNP catalyst under mild conditions. The catalyst showed high recyclability (≥10 cycles) and is a robust free flowing powder, stored and used after eight months without any loss in catalytic activity.
Highly efficient N-doped carbon supported FeSx-Fe2O3 catalyst for hydrogenation of nitroarenes via pyrolysis of sulfurized N,Fe-containing MOFs
Li, Xuewei,She, Wei,Wang, Jing,Li, Weizuo,Li, Guangming
, (2021/05/18)
Integrating MOFs as precursor, especially for employing N-containing organic linkers, with sulfides is an effective method to prepare the highly efficient N-doped carbon supported metal-based catalysts for hydrogenation of nitroarenes. In this work, a N,Fe-containing metal organic frameworks (MOFs; termed as MIL88-HMTA) with spindle-like structure was prepared via self-assembly method, in which hexamethylenetetramine (HMTA) linker was introduced as N source. Subsequently, N-doped carbon supported FeSx-Fe2O3 catalyst (named FeSx-Fe2O3@CN) was fabricated upon the pyrolysis of sulfurized MIL88-HMTA. Catalytic experiments reveal that the FeSx-Fe2O3@CN delivered excellent performance for hydrogenation of nitroarenes in comparison with those of catalyst without sulfidation process (Fe2O3@CN) and conventional MIL88 derived catalyst (Fe2O3@C). The XRD, TEM, SEM/EDX, Raman, UV, and XPS analyses have revealed that the developed FeSx-Fe2O3@CN catalyst exhibited outstanding catalytic efficiency was ascribed to synergistic effect between FeSx and Fe2O3 species, abundant structural defects, more Fe-Nx species, and strengthened decomposition ability of hydrazine hydrate (N2H4?H2O). Furthermore, the effect of sulfidation ratio (the mass ratio between thioacetamide and MIL88-HMTA) towards preparation of the developed FeSx-Fe2O3@CN on the catalytic activity of hydrogenation reaction was also systematically performed. Notably, the optimized catalyst (denoted as FeSx-Fe2O3@CN-8) exhibited unexpected performance and recyclability for hydrogenation of nitroarenes under mild condition. The pyrolysis of sulfurized N-containing MOFs may present a facile approach for fabricating MOFs-derived N-doped carbon supported catalysts, which provides a potential application in heterogeneous catalytic reactions.