367-21-5Relevant articles and documents
Chemoselective Transfer Hydrogenation of Nitroarenes Catalyzed by Highly Dispersed, Supported Nickel Nanoparticles
Jiang, Chengjun,Shang, Zeyu,Liang, Xinhua
, p. 4814 - 4818 (2015)
A recyclable highly dispersed Ni/SiO2 catalyst was prepared by atomic layer deposition. Chemoselective reduction of nitroarenes was studied using the prepared Ni/SiO2 as the catalyst and hydrazine hydrate as a hydrogen donor. Different kinds of nitroarenes were converted to the corresponding anilines with high yields. The high activity of the catalysts could be a result of the highly dispersed Ni nanoparticles. (Chemical Presented).
Mild deprotection of the: N-tert -butyloxycarbonyl (N -Boc) group using oxalyl chloride
Awuah, Samuel G.,George, Nathaniel,Ofori, Samuel,Parkin, Sean
, p. 24017 - 24026 (2020/07/23)
We report a mild method for the selective deprotection of the N-Boc group from a structurally diverse set of compounds, encompassing aliphatic, aromatic, and heterocyclic substrates by using oxalyl chloride in methanol. The reactions take place under room temperature conditions for 1-4 h with yields up to 90percent. This mild procedure was applied to a hybrid, medicinally active compound FC1, which is a novel dual inhibitor of IDO1 and DNA Pol gamma. A broader mechanism involving the electrophilic character of oxalyl chloride is postulated for this deprotection strategy. This journal is
Utilization of a Hydrogen Source from Renewable Lignocellulosic Biomass for Hydrogenation of Nitroarenes
Tan, Fang-Fang,Tang, Kai-Li,Zhang, Ping,Guo, Yan-Jun,Qu, Mengnan,Li, Yang
, p. 4189 - 4195 (2019/03/07)
Exploring of hydrogen source from renewable biomass, such as glucose in alkaline solution, for hydrogenation reactions had been studied since 1860s. According to proposed pathway, only small part of hydrogen source in glucose was utilized. Herein, the utilization of a hydrogen source from renewable lignocellulosic biomass, one of the most abundant renewable sources in nature, for a hydrogenation reaction is described. The hydrogenation is demonstrated by reduction of nitroarenes to arylamines in up to 95 % yields. Mechanism studies suggest that the hydrogenation occurs via a hydrogen transformation pathway.
Cobalt in N-doped carbon matrix catalyst for chemoselective hydrogenation of nitroarenes
Dai, Yihu,Jiang, Chunyang,Xu, Min,Bian, Bo,Lu, Di,Yang, Yanhui
, p. 158 - 166 (2019/06/03)
Anilines as important intermediates for both organic synthesis and industrial manufactory are densely substituted with a variety of functional moieties, and the transformation of nitroarenes into corresponding anilines requires catalytically selective hydrogenation catalyst. Herein, we describe a simple pyrolysis strategy to prepare cobalt catalysts in nitrogen-doped carbon matrix applied in the selective hydrogenation of nitroarenes with molecular hydrogen. The Co/NC catalysts are obtained through thermal treatment of mixed precursors of cobalt phthalocyanine and melamine. The surface-modified Co particles with Co3O4 and CoNx sites are surrounded by N-doped carbon layers according to a series of structural characterization results. These Co/NC catalysts are capable of efficiently selective hydrogenation of nitrobenzene and various substituted nitroarenes into corresponding anilines under relatively mild reaction conditions. The optimal catalytic hydrogenation performance is contributed to the fast rate of H2 dissociated activation on the CoNx active sites and the facile adsorption of the reactant substances, which is verified by the isotopic H2-D2 exchange experiments, reactant adsorption and the ORR reaction tests. Furthermore, the heterogeneous Co/NC catalyst is highly stable without the Co leaching and deactivation issues during the recycling reaction runs.
Development and Scale-up of Continuous Electrocatalytic Hydrogenation of Functionalized Nitro Arenes, Nitriles, and Unsaturated Aldehydes
Egbert, Jonathan D.,Thomsen, Edwin C.,O'Neill-Slawecki, Stacy A.,Mans, Douglas M.,Leitch, David C.,Edwards, Lee J.,Wade, Charles E.,Weber, Robert S.
, p. 1803 - 1812 (2019/08/15)
Electrolysis flow reactors based on the filter-press architecture of redox flow batteries have proven to be effective and scalable toward the production of commercially relevant, pharmaceutical quantities of anilines (>500 kg/year) from halogen-, hydroxyl-, and carbonyl-substituted nitroarenes. Turbulent flow through the carbon felts on which the catalysts were supported facilitated scaling toward production levels because it conferred on the reactors scale-independent, plug flow-like residence time distributions and high mass transfer coefficients. Equipping the cells with microreference electrodes made it possible to transfer reaction conditions first developed in batch systems to the continuous flow reactors. The catalysts prepared by incipient wetness impregnation of metal salts into lightly oxidized carbon felt supports were readily generalizable.
Nitrogen-Doped Graphene-Supported Iron Catalyst for Highly Chemoselective Hydrogenation of Nitroarenes
Wei, Zuojun,Hou, Yaxin,Zhu, Xinmiao,Guo, Liangyu,Liu, Yingxin,Zhang, Anyun
, p. 2009 - 2013 (2018/03/21)
A nitrogen-doped graphene-supported iron catalyst was used for the first time in the hydrogenation of a series of nitroarenes to give the corresponding amines with excellent activity and chemoselectivity under mild reaction conditions. Physicochemical characterization of the catalyst by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and M?ssbauer spectroscopy revealed the formation of iron particles with an iron oxide core and a metallic iron shell that were coated by a few layers of nitrogen-doped graphene. The unique structure of FeNx/C in the catalyst was proven to contribute to the hydrogenation activity.
Catalytic hydrogenation process of chlorine-containing nitro aromatic compound
-
Paragraph 0036; 0037; 0038; 0039, (2018/11/27)
The invention discloses a catalytic hydrogenation process of a chlorine-containing nitro aromatic compound. The specific process comprises the following steps: adding a chlorine-containing nitrobenzene, water and an anti-dechlorination agent into a reactor, carrying out mixing by stirring, then adding a catalyst and a self-prepared cocatalyst, introducing nitrogen into the reactor for 5-10 min toreplace air in the reactor, then introducing hydrogen until the pressure is 18-26 kg, carrying out a reaction at 55-75 DEG C for 1-3 hours, carrying out cooling to room temperature after the reactionis finished, and detecting the content of the target product in the obtained product. The process conditions are mild, the effect of the reaction substrate on the catalyst is small, the catalytic activity is high, and the yield of the product is high.
Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Alshammari, Ahmad S.,Pohl, Marga-Martina,Beller, Matthias,Jagadeesh, Rajenahally V.
, p. 8553 - 8560 (2018/11/30)
The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
Development of a novel protocol for chemoselective deprotection of N/O-benzyloxycarbonyl (Cbz) at ambient temperature
Saroha, Mohit,Aggarwal, Komal,Bartwal, Gaurav,Khurana, Jitender M.
, p. 2231 - 2235 (2018/10/02)
Abstract: A novel protocol for the deprotection of N-benzyloxycarbonyl and O-benzyloxycarbonyl groups by nickel boride generated in situ from NaBH4 and NiCl2·6H2O in methanol at room temperature has been developed to give the corresponding amines and phenols. This protocol is chemoselective as groups like chloro, bromo, amide, ester, pyridine, and tert-butyloxycarbonyl moiety are unaffected under these conditions. The deprotection has also been validated in gram scale reactions, to establish the wider appropriateness of this protocol. Graphical abstract: [Figure not available: see fulltext.].
Preparation method of 4-fluoro-3-chloroaniline
-
, (2017/06/21)
The invention discloses a preparation method of 4-fluoro-3-chloroaniline. The 4-fluoro-3-chloroaniline is prepared by adding fluorine to the amido para-position of the raw material 3-chloroaniline. The purity of the prepared 4-fluoro-3-chloroaniline is 99% or above; and the method has the advantages of accessible raw materials and low price, and is suitable for industrial production.
