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106-47-8Relevant articles and documents
Chemoselective hydrogenation of 4-nitrostyrene to 4-aminostyrene by highly efficient TiO2 supported Ni3Sn2 alloy catalyst
Yamanaka, Nobutaka,Hara, Takayoshi,Ichikuni, Nobuyuki,Shimazu, Shogo
, p. 811 - 816 (2019)
Ni3Sn2 alloy catalysts supported on various metal oxides (TiO2, Al2O3, ZrO2, SnO2, and CeO2) were successfully prepared by simple hydrothermal method and then applied to the hydrogenation of 4-nitrostyrene under H2 3.0 MPa at 423 K. All the supported catalysts hydrogenated the nitro group more preferentially than the olefin group from the initial reaction stages, showing 100% chemoselectivities towards the desired 4-aminostyrene. This may be attributed to -interaction between the oxygen lone pairs in the nitro group and Sn atoms in Ni3Sn2 alloy. By prolonging the reaction times, the 4- aminostyrene yields increased and finally reached the maximum yields. Among the catalysts, Ni3Sn2/TiO2 alloy catalyst showed the highest catalytic activity with remarkably high chemoselectivity towards 4-aminostyrene. The conversion and chemoselectivity were 100% and 79%, respectively, at a reaction time of only 2.5 h. From the physical and chemical characterization of the supported catalysts, it was clear that the catalytic activity was correlated with H2 uptake. The application of the best catalyst for the hydrogenation of a wide variety of substituted nitroarenes resulted in the chemoselective formation of the corresponding aminoarenes.
Polymeric PEG35k-Pd nanoparticles: Efficient and recyclable catalyst for reduction of nitro compounds
Yadav, Veena,Gupta, Shweta,Kumar, Rupesh,Singh, Gajendra,Lagarkha, Rekha
, p. 213 - 222 (2012)
The small size polymeric PEG35k-Pd nanoparticles are key attractions for catalysis due to their large surface to volume ratio, non-toxicity, inexpensive, thermal stability, and recoverability. Polymeric PEG35k-Pd nanoparticles in the absence of phosphine ligands are insensitive to the air and moisture and act as an active heterogeneous catalyst for the reduction of nitroarenes. Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file. Taylor & Francis Group, LLC.
A nonmetal catalyst for molecular hydrogen activation with comparable catalytic hydrogenation capability to noble metal catalyst
Li, Baojun,Xu, Zheng
, p. 16380 - 16382 (2009)
(Chemical Equation Presented) Fullerene can activate molecular hydrogen and is a novel nonmetal hydrogenation catalyst. The hydrogenation of aromatic nitro compounds to amino aromatics is achieved on this catalyst with high conversion and selectivity under 1 atmospheric pressure of H2 and light irradiation at room temperature or under conditions of 120-160°C and 4-5 MPa H2 pressure without light irradiation, which is comparable to the case with a noble metal catalyst.
Amination-Oxidation Strategy for the Copper-Catalyzed Synthesis of Monoarylamines
Thomas, Christopher,Wu, Marvin,Billingsley, Kelvin L.
, p. 330 - 335 (2016)
A novel approach for the synthesis of monoarylamines from aryl halides is presented. This method employs an inexpensive, nontoxic metal source (copper) and incorporates a stable ammonia surrogate (α-amino acids), obviating the need for special experimental setup or handling of ammonia reagents. This process, which is proposed to proceed via an amination-oxidation sequence, selectively promotes the transformation of a range of aryl and heteroaryl iodides as well as bromides to the corresponding monoarylamines.
HIGH SITE-SELECTIVITY IN THE CHLORINATION OF ELECTRON-RICH AROMATIC COMPOUNDS BY N-CHLORAMMONIUM SALTS.
Smith, John R. Lindsay,McKeer, Linda C.
, p. 3117 - 3120 (1983)
N-Chlorammonium salts are efficient and very site-selective monochlorinating agents for electron-rich aromatic compounds.
Ultrasound-assisted diversion of nitrobenzene derivatives to their aniline equivalents through a heterogeneous magnetic Ag/Fe3O4-IT nanocomposite catalyst
Taheri-Ledari, Reza,Rahimi, Jamal,Maleki, Ali,Shalan, Ahmed Esmail
, p. 19827 - 19835 (2020)
A heterogeneous magnetic catalytic system is fabricated and suitably applied for the fast and direct conversion of nitrobenzene (NB) derivatives to their aniline forms. For this purpose, different conditions and methods have been checked with numerous catalytic amounts of the nanocatalyst composite, which was constructed of iron oxide and silver nanoparticles and possessed an isothiazolone organic structure. Herein, the mechanistic aspect of the catalytic functioning of this highly efficient nanocatalyst is highlighted and discussed. Firstly, a convenient preparation route assisted by ultrasonication for this metal and metal oxide nanocomposite is presented. Further, a fast and direct reduction strategy for NBs is investigated using ultrasound irradiation (50 kHz, 200 W L-1). As two great advantages of this catalyst, high magnetic property and excellent reusability are also mentioned. This report well reveals that a really convenient conversion of NBs to anilines can be achieved with a high yield during the rapid reaction time in presence of mild reaction conditions. This journal is
Sustainable and Scalable Fe/ppm Pd Nanoparticle Nitro Group Reductions in Water at Room Temperature
Gabriel, Christopher M.,Parmentier, Michael,Riegert, Christian,Lanz, Marian,Handa, Sachin,Lipshutz, Bruce H.,Gallou, Fabrice
, p. 247 - 252 (2017)
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).
A phosphorus-carbon framework over activated carbon supported palladium nanoparticles for the chemoselective hydrogenation of para-chloronitrobenzene
Lu, Chunshan,Wang, Mengjun,Feng, Zhenlong,Qi, Yani,Feng, Feng,Ma, Lei,Zhang, Qunfeng,Li, Xiaonian
, p. 1581 - 1589 (2017)
A novel Pd-P-C framework structure was fabricated by supporting Pd on a P-doped carbon layer coated with activated carbon. A P-doped carbon layer was generated via calcination of sodium hypophosphite and ethanediol under inert gas atmosphere. The catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) and were evaluated in the selective hydrogenation of p-CNB to p-CAN. The results indicate that the carbon layer generated via calcination of ethanediol presents a higher disordered structure and then the P-doped carbon layer becomes more ordered due to the formation of a P-C framework. Some electrons were transferred from C atoms adjacent to the P atoms to P atoms, which favors the formation of stable Pd-P species such as the Pd15P2 phase. Pd in the Pd-P-C framework structure possesses electron-rich properties resulting from electron transfer from C atoms to Pd atoms via P atoms, which induces the formation of electron-rich hydrogen (H-) when hydrogen was absorbed on the Pd particles. The produced electron-rich H- might prefer the nucleophilic attack on the nitro group rather than the electrophilic attack on the C-Cl bond. We suggest that it is responsible for the superior selectivity of up to 99.9% to p-CAN for the hydrogenation of p-CNB. The catalytic performance of the Pd particles supported on the P-doped carbon layer remains unchanged after five cycles indicating excellent stability.
Sustainable Hydrogenation of Nitroarenes to Anilines with Highly Active in-situ Generated Copper Nanoparticles
Kinik, F. Pelin,Nguyen, Tu N.,Mensi, Mounir,Ireland, Christopher P.,Stylianou, Kyriakos C.,Smit, Berend
, p. 2833 - 2839 (2020)
Metal nanoparticles (NPs) are usually stabilized by a capping agent, a surfactant, or a support material, to maintain their integrity. However, these strategies can impact their intrinsic catalytic activity. Here, we demonstrate that the in-situ formation of copper NPs (Cu0NPs) upon the reduction of the earth-abundant Jacquesdietrichite mineral with ammonia borane (NH3BH3, AB) can provide an alternative solution for stability issues. During the formation of Cu0NPs, hydrogen gas is released from AB, and utilized for the reduction of nitroarenes to their corresponding anilines, at room temperature and under ambient pressure. After the nitroarene-to-aniline conversion is completed, regeneration of the mineral occurs upon the exposure of Cu0NPs to air. Thus, the hydrogenation reaction can be performed multiple times without the loss of the Cu0NPs’ activity. As a proof-of-concept, the hydrogenation of drug molecules “flutamide” and “nimesulide” was also performed and their corresponding amino-compounds were isolated in high selectivity and yield.
Deficient copper decorated platinum nanoparticles for selective hydrogenation of chloronitrobenzene
Li, Xin,Wang, Yue,Li, Liqun,Huang, Wenqing,Xiao, Zicheng,Wu, Pingfan,Zhao, Wenbo,Guo, Wei,Jiang, Peng,Liang, Minghui
, p. 11294 - 11300 (2017)
Two types of model Pt-Cu catalysts are designed and prepared to explore the contribution of the geometric and electronic effects from copper to the catalytic performance of Pt nanoparticles in the selective hydrogenation of p-chloronitrobenzene (p-CNB). One model Pt-Cu catalyst (called Cu/C-Pt) is Pt nanoparticles deposited on ultra-small copper particle-decorated activated carbon, and the other is copper particle-decorated Pt/C catalyst (called Pt/C-Cu). Cu/C-Pt catalyst has an activity lower than that of Pt/C, but the selectivity of the desired product p-chloroaniline (p-CAN) on the Cu/C-Pt catalyst is much higher than that on Pt/C. On the Pt/C-Cu catalyst, p-CNB cannot be completely converted into p-CAN. The dechlorination rates of p-CAN on Cu/C-Pt catalysts are three orders of magnitude lower than that on Pt/C. More interestingly, the dechlorination reaction of p-CAN on Pt/C-Cu cannot be observed. High resolution TEM images of our Pt-Cu catalysts show that Pt nanoparticles keep their crystalline structure after incorporation with copper. The dispersions of Pt in 2Pt/C, 5Cu/C-2Pt, and 2Pt/C-5Cu reach 0.106, 0.083 and 0.027, respectively (the numbers before Pt and Cu represent their percentages), revealing that Pt nanoparticles in Cu/C-Pt have a larger exposed surface than those in Pt/C-Cu. It can be deduced that copper mainly exerts an electronic effect on the catalytic performance of Pt nanoparticles in Cu/C-Pt. On the other hand, the geometric effect on Pt from copper in Pt/C-Cu leads to not only a low dispersion of Pt nanoparticles but a weak activity in catalytic hydrogenation of p-CNB and dechlorination of p-CAN. The interaction between Pt nanoparticles and Cu nanoparticles at room temperature is also discussed.
