دانلود رایگان مقاله لاتین انتقال هیدروژن از نیتروآرنس به آریلامینس از سایت الزویر
عنوان فارسی مقاله:
انتقال هیدروژن از نیتروآرنس به آریلامینس کاتالیز شده توسط کاتالیزور اکسیژن MoS2
عنوان انگلیسی مقاله:
Transfer hydrogenation of nitroarenes to arylamines catalysed by an oxygen-implanted MoS2 catalyst
سال انتشار : 2016
برای دانلود رایگان مقاله انتقال هیدروژن از نیتروآرنس به آریلامینس اینجا کلیک نمایید.
مقدمه انگلیسی مقاله:
1. Introduction
Functionalized arylamines prepared from its corresponding nitroarenes are very important industrial intermediates for pharmaceuticals, functional polymers, herbicides, dyestuffs and other fine chemicals [1]. Previous studies onnitroarene reductionmajorly focused on oxide-supported catalysts containing d6–d10 metals [2–16]. Besides their oxidizable nature in the air, the selectivity of the corresponding amines was not high enough when other reducible functional groups were present in the same molecules. Regarding the storage and availability, robust non-precious metal oxides have attracted attentions for nitroarene reduction, but oxide catalysts with high activity are still rarely used [17–23]. So, researches on new catalytic methods and the intrinsic mechanism should be done. Recently, in the nitroarenes catalytic transformation, numbers of effective and selective approaches with various oxide-supported Au [24–33], Pt [34] and Ag [35] catalysts have been developed. Besides the catalytic approaches exploitation, Corma and co-workers found the cooperative effects between gold and thesupport played crucial roles in the selective activation of substrates [26] and hydrogenation route control [36]. Kaneda and co-workers found thatthe metal-oxide interfacial structure played crucial roles in the hydrogenation of nitro and alkynyl groups with active hydrogen species in polar electronic states [35,37,38]. The metal-oxide interfacial structure can dynamically stabilize the in-situ generated hydride and proton via a cooperative effect of metallic and basic sites [35]. Since most of the pure metal oxides lack the required metallic properties, the redox character of central metal plays crucial roles in the catalysis [19]. Itis understandable that most pure metal oxide catalysts are inactive in nitroarenes catalytic reduction. Recently, Beller and co-workers found that Fe2O3 and CoOx particles surrounded by nitrogen-doped carbon layers were efficient catalysts for the selective hydrogenation [39–41] and transfer hydrogenation [42–44] of nitroarenes to anilines. The nitrogen-doped carbon layers and MNx (M = Co, Fe) species of the oxide catalysts account for the high activity. Without doping or other modification methods, we recently found that the crystalline MoO2, with inherent bifunctional metallic-basic character, was an effective catalyst for the transfer hydrogenation of nitrobenzene with N2H4 [23]. Density functional theory (DFT) calculations suggestthatthe stepwise hydrogen transfer via the prior cleavage of N H bond than N N bond is the keystep to create the dissociated hydride and proton species on the surface MoIVOx center. However,the MoO2 surface can be oxidized, and the adsorbed ammonia can prevent the oxidized sites reduction with N2H4, which causes the catalyst deactivation. The used catalyst needs calcination regeneration in recycle using. In this work, we prepared an oxygen-implanted MoS2 catalyst (O-MoS2) via an incomplete sulfidation and reduction method. The ammonium molybdate was used as the precursor, and some MoIVOx structure was left to O-MoS2. The O-MoS2 can efficiently catalyse nitroarenes reduction to the corresponding arylamines with N2H4 under air condition, and the used catalyst can be easily recovered and reused four times without any significant loss of activity. Different from previous MoS2-based catalysts with MoS2 skeleton as the active center for the nitroarenes reduction [45–50], results of this work propose that the MoIVOx structure implanted in O-MoS2 works as the active center. The O-MoS2 can catalyse the N2H4 selective decomposition to the active hydrogen species in polar electronic states (H− and H+), which show high chemoselectivity toward the nitro reduction. The MoS2 skeleton with metallic character around the MoIVOx structure can also catalyse N2H4 decomposition to create active H*, which has the potential ability to promote the antioxidant properties of MoIVOx structure. This cooperative effect makes O-MoS2 an effective and robust catalyst.
برای دانلود رایگان مقاله انتقال هیدروژن از نیتروآرنس به آریلامینس اینجا کلیک نمایید.
کلمات کلیدی:
PDF]Reduction of Nitroarenes into Aryl Amines and N-Aryl hydroxylamines ... www.mdpi.com/2079-4991/6/3/54/pdf by D Andreou - 2016 - Cited by 3 - Related articles Mar 22, 2016 - Keywords: silver nanoparticles; nitroarenes; aryl amines; N-aryl ... Furthermore, a detailed mechanistic route for the AgNP-catalyzed reduction of nitroarenes .... transfer hydrogenation reagent such as the 1,1,3,3-tetramethyl ... Amino Group Chemistry: From Synthesis to the Life Sciences https://books.google.com/books?isbn=352762127X Alfredo Ricci - 2008 - Science Scheme 9.5 Synthesis of aniline hydrochloride by transfer hydrogenation. ... Transition Metal-Catalyzed Arylamination 9.2.1 Reduction of Nitroarenes Arylamine ... Chemoselective Transfer Hydrogenation to Nitroarenes Mediated by ... onlinelibrary.wiley.com/doi/10.1002/anie.201202584/abstract by I Sorribes - 2012 - Cited by 81 - Related articles Jun 18, 2012 - ... (X=H) or precatalysts (X=Cl) for the transfer hydrogenation of functionalized nitroarenes, without the formation of hazardous hydroxylamines. Science of Synthesis: Houben-Weyl Methods of Molecular ... https://books.google.com/books?isbn=3131720719 2014 - Science ... cross coupling with styrenes, palladium catalyzed, 4-(arylvinyl)diaryldiazene ... 1463 fi Diazenes, diaryl-, from condensation of nitroarenes with arylamines, using ... from reduction of nitroarenes, using catalytic transfer hydrogenation 1471, ... Transfer hydrogenation of nitroarenes with hydrazine at near-room ... pubs.rsc.org/-/content/articlehtml/2016/gc/c5gc02460a by C Zhang - 2016 - Cited by 2 - Related articles Dec 8, 2015 - Transfer hydrogenation of nitroarenes with hydrazine at near-room temperature ... results in hydrogenation reactions, such as nitroarenes to arylamines. ..... in hydrogen transfer reactions catalyzed with Mo-cluster catalysts. Aromatic Compounds: A Modern Comprehensive Treatise https://books.google.com/books?isbn=0080880983 Malcolm Sainsbury - 1995 - Science ... 1983, 24, 4121) for the homogeneous metal catalysed reduction of a variety of nitroarenes. ... Catalytic transfer-hydrogenation has been further studied. ... J. Org. Chem., 1982, 47, 3018) allows selective reduction of nitroarenes to aromatic amines. Primary arylamines are also prepared by hydrogenolysis of aryl azides by ... Amine synthesis by nitro compound reduction - Organic Chemistry Portal www.organic-chemistry.org › Reactions › Organic Synthesis Search Palladium-catalyzed reduction of aromatic nitro groups to amines can be ... of nitroarenes and reductive cleavage of azo compounds by catalytic transfer ...
