- Biomass Sucrose-Derived Cobalt@Nitrogen-Doped Carbon for Catalytic Transfer Hydrogenation of Nitroarenes with Formic Acid
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Fabrication of non-noble metal-based heterogeneous catalysts by a facile and cost-effective strategy for ecofriendly catalytic transfer hydrogenation (CTH) is of great significance for organic transformations. A cobalt@nitrogen-doped carbon (Co@NC) catalyst was prepared from renewable biomass-derived sucrose, harmless melamine, and earth-abundant Co(AcO)2 as the precursor materials by hydrothermal treatment and carbonization. Co nanoparticles (NPs) were coated with NC shells and uniformly embedded in the NC framework. The as-obtained Co@NC-600 (carbonized at 600 °C) catalyst exhibited excellent catalytic efficiency for CTH of various functionalized nitroarenes with formic acid (FA) as hydrogen donor in aqueous solution. The uniformly incorporated N atoms in the C matrix and the encapsulated Co NPs showed synergistic effects in the CTH reactions. A mechanistic analysis indicated that the protons from FA were activated by Co sites after being captured by N atoms, and then reacted with nitroarenes adsorbed on the surface of the catalysts to generate the corresponding aromatic amines. Moreover, the catalyst showed excellent durability and reusability without obvious decrease in activity even after five reaction cycles. Thus, the study reported herein provides a cost-effective, sustainable strategy for fabrication of biomass-derived non-noble metal-based catalysts for green and efficient catalytic transformations.
- Yuan, Man,Long, Yu,Yang, Jin,Hu, Xiwei,Xu, Dan,Zhu, Yangyang,Dong, Zhengping
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Read Online
- Fabrication of Pd/Mg2P2O7 via a Struvite-Template Way from Wastewater and Application as Chemoselective Catalyst in Hydrogenation of Nitroarenes
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A highly efficient heterogeneous catalyst Pd/Mg2P2O7 was fabricated by combining palladium nanoparticles (PdNPs) and mesoporous Mg2P2O7 fibers/rods. Mg2P2O7 fibers with ultra-high specific surface area were prepared from struvite as templates, which were synthesized from waste water containing N- and P-containing pollutants. This strategy provided a novel pathway for developing advanced catalysts from eutrophication-polluted water. The composite Pd/Mg2P2O7 showed brilliant performance in selective hydrogenation of nitro aromatics to give anilines. As an example of nitrobenzene hydrogenation, the conversion to aniline and selectivity were found to reach almost 100 % at a temperature of T=90 °C and under a pressure of P (Formula presented.) =2.0 MPa. The superior performance was found to originate from PdNPs, which were boosted by electron transfer afforded by the nanofiber Mg2P2O7 supports. The favorable adsorption of withdrawing groups (?NO2) was realized by synergistic effects between Pd and oxygen vacancies provided by pyrolysis of struvite. The catalyst remained stable after cycles of reuse with little degradation in catalytic performance.
- Zhang, Peng,Xu, Shaonan,Wang, Yan,Zhang, Wei,Li, Wenqing,Wei, Cundi,Zhang, Peiping,Miao, Shiding
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Read Online
- In situcreation of multi-metallic species inside porous silicate materials with tunable catalytic properties
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Porous metal silicate (PMS) material PMS-11, consisting of uniformly distributed multi-metallic species inside the pores, is synthesized by using a discrete multi-metal coordination complex as the template, demonstrating high catalytic activity and selectivity in hydrogenation of halogenated nitrobenzenes by synergistically activating different reactant moleculesviaNi and Co transition metal centers, while GdIIILewis acid sites play a role in tuning the catalytic properties.
- Liu, Yang-Yang,Wu, Chuan-De,Zhan, Guo-Peng
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supporting information
p. 6185 - 6188
(2021/06/30)
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- Rhodium nanoparticles supported on 2-(aminomethyl)phenols-modified Fe3O4 spheres as a magnetically recoverable catalyst for reduction of nitroarenes and the degradation of dyes in water
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A magnetic nanostructured catalyst (Fe3O4@SiO2-Amp-Rh) modified with 2-(aminomethyl)phenols (Amp) was designed and prepared, which is used to catalyze the reduction of aromatic nitro compounds into corresponding amines and the degradation of dyes. The 2-aminomethylphenol motif plays a vital role in the immobilization of rhodium nanoparticles to offer extraordinary stability, which has been characterized by using various techniques, including transmission electron microscopy (TEM), thermal gravimetric analyzer (TGA), X-Ray Diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). A variety of nitroaromatic derivatives have been reduced to the corresponding anilines in water with up to yields of 99% within 1?h at room temperature. In addition, the catalyst system is effective in catalyzing the reduction of toxic pollutant 4-nitrophenol and the degradation of MO, MB and RhB dyes. Importantly, this catalyst Fe3O4@SiO2-Amp-Rh can be easily recovered by an external magnetic field because of the presence of magnetic core of Fe3O4, and the activity of Fe3O4@SiO2-Amp-Rh does not decrease significantly after 7 times’ recycling, which indicates that the catalyst performed high reactivity as well as stability. Graphical abstract: [Figure not available: see fulltext.]
- Chen, Tian,Chen, Zhangpei,Hu, Jianshe,Lv, Kexin,Reheman, Aikebaier,Wang, Gongshu
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- Minimization of Back-Electron Transfer Enables the Elusive sp3 C?H Functionalization of Secondary Anilines
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Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N-Dialkyl-derivatives enable radical generation α to the N-atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back-electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α-anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp3 C?H functionalization.
- Zhao, Huaibo,Leonori, Daniele
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supporting information
p. 7669 - 7674
(2021/03/08)
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- METHOD AND CATALYST FOR PREPARING ANILINE COMPOUNDS AND USE THEREOF
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The present invention provides a method for preparing aniline compounds, and also provides a kind of catalyst and use thereof. This method for synthesizing an aniline compound in the invention includes following steps: use molybdenum oxide and activated carbon as catalyst, hydrazine hydrate as reducing agent, then reduce aromatic nitro compounds to aniline compounds. This method is green and high efficiency, and easy to be applied in industry.
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Paragraph 0048-0049
(2019/04/18)
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- Method for synthesizing aniline compound, catalyst and application thereof
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The invention provides a method for synthesizing an aniline compound, and further provides a catalyst and an application thereof. The method for synthesizing the aniline compound includes the following steps: taking molybdenum-based oxide and activated carbon as catalysts; taking hydrazine hydrate as a reducing agent; and reducing an aromatic nitro compound to the aniline compound. The method forsynthesizing the aniline compound has the characteristics of green and high efficiency, easy industrial application and the like.
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Paragraph 0051; 0052
(2019/04/17)
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- A visible-light-responsive metal-organic framework for highly efficient and selective photocatalytic oxidation of amines and reduction of nitroaromatics
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Photocatalysis is a green synthetic method for organics transformation. We present here the synthesis of a novel visible-light-responsive metal-organic framework and its photocatalytic application. The prepared MOF is highly efficient for the self-coupling of primary amines and oxidative dehydrogenation of secondary amines to selectively produce imines assisted by the green and economic oxidant of molecular oxygen. Studies reveal that both energy transfer and electron transfer from the photoexcited MOF to molecular oxygen are important for amine oxidation, where the highly reactive species of superoxide radicals and singlet oxygen together account for the high catalytic performance. The photogenerated electrons of the MOF have also been utilized for the reduction of aromatic nitroarenes. Results show that they are highly selective for the reduction of nitroarenes to produce anilines in the presence of hydrazine hydrate. The work demonstrates the enormous potential of photoactive MOFs for converting organic substrates into valuable chemicals.
- Chen, Peiqi,Guo, Zhifen,Liu, Xin,Lv, Hui,Che, Yan,Bai, Rong,Chi, Yanhong,Xing, Hongzhu
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p. 27074 - 27080
(2019/12/11)
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- COMPOUNDS FOR THIOL-TRIGGERED COS AND/OR H2S RELEASE AND METHODS OF MAKING AND USING THE SAME
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Disclosed herein are embodiments of a compound that is capable of releasing COS and/or H2S upon reaction with a thiol-containing compound. The compound embodiments also can produce a detectable signal (e.g., a fluorescent signal) substantially concomitantly with COS and/or H2S release and/or can release an active agent, such as a therapeutic agent. Methods of making and using the compound embodiments also are disclosed.
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Page/Page column 35
(2019/12/25)
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- Ru-Catalyzed Deoxygenative Transfer Hydrogenation of Amides to Amines with Formic Acid/Triethylamine
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A ruthenium(II)-catalyzed deoxygenative transfer hydrogenation of amides to amines using HCO2H/NEt3 as the reducing agent is reported for the first time. The catalyst system consisting of [Ru(2-methylallyl)2(COD)], 1,1,1-tris(diphenylphosphinomethyl) ethane (triphos) and Bis(trifluoromethane sulfonimide) (HNTf2) performed well for deoxygenative reduction of various secondary and tertiary amides into the corresponding amines in high yields with excellent selectivities, and exhibits high tolerance toward functional groups including those that are reduction-sensitive. The choice of hydrogen source and acid co-catalyst is critical for catalysis. Mechanistic studies suggest that the reductive amination of the in situ generated alcohol and amine via borrowing hydrogen is the dominant pathway. (Figure presented.).
- Pan, Yixiao,Luo, Zhenli,Xu, Xin,Zhao, Haoqiang,Han, Jiahong,Xu, Lijin,Fan, Qinghua,Xiao, Jianliang
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supporting information
p. 3800 - 3806
(2019/07/12)
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- Highly efficient reduction of nitro compounds: Recyclable Pd/C-catalyzed transfer hydrogenation with ammonium formate or hydrazine hydrate as hydrogen source
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Herein, we described a highly efficient heterogeneous Pd/C-catalyzed transfer hydrogenation of nitro compounds for the synthesis of primary amines, using ammonium formate and hydrazine hydrate as hydrogen source independently. The products were obtained with up to >99% yield. Furthermore, gram scale and recycling of catalyst had been tested with well results.
- Chen, Xia,Zhou, Xiao-Yu,Wu, Hong,Lei, Yi-Zhu,Li, Jin-Hui
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supporting information
p. 2475 - 2484
(2018/10/25)
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- Visible-Light-Driven Chemoselective Hydrogenation of Nitroarenes to Anilines in Water through Graphitic Carbon Nitride Metal-Free Photocatalysis
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Green and efficient procedures are essential for the chemoselective hydrogenation of functionalized nitroarenes to form industrially important anilines. Herein, it is shown that visible-light-driven, chemoselective hydrogenation of functionalized nitroarenes with groups sensitive to forming anilines can be achieved in good to excellent yields (82–100 %) in water under relatively mild conditions and catalyzed by low-cost and recyclable graphitic carbon nitride. The process is also applicable to gram-scale reaction, with a yield of aniline of 86 %. A study of the mechanism reveals that visible-light-induced electrons are responsible for the hydrogenation reactions, and thermal energy can also promote the photocatalytic activity. A study of the kinetics shows that this reaction possibly occurs through one-step hydrogenation or stepwise condensation routes. A wide range of applications can be expected for this green, efficient, and highly selective photocatalysis system in reduction reactions for the synthesis of fine chemicals.
- Xiao, Gang,Li, Peifeng,Zhao, Yilin,Xu, Shengnan,Su, Haijia
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p. 1950 - 1955
(2018/07/31)
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- Preparing method of Barasertib
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The invention discloses a preparing method of Barasertib. The chemical name of Barasertib is 2-5{-[(7-{3-[ethyl(2-hydroxyethyl)amino]propoxy}quinazoline-4-group)amino]-1H-pyrazole-3-group}-N-(3-fluorophenyl)acetamide, and the chemical formula of Barasertib is C26H30FN7O3. According to the preparing method of Barasertib, the preparing process is simple, raw materials are easy to obtain, the preparing method is economical and environmentally friendly, industrialization is easy to achieve, the economic technology development of Barasertib raw material medicine can be promoted, the production costis lowered, and the preparing method is suitable for large-scale production.
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Paragraph 0013; 0014
(2018/03/26)
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- Shape Engineering of Biomass-Derived Nanoparticles from Hollow Spheres to Bowls through Solvent-Induced Buckling
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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.
- Chen, Chunhong,Li, Xuefeng,Deng, Jiang,Wang, Zhe,Wang, Yong
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p. 2540 - 2546
(2018/08/01)
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- Ethyl 6-Hydroxyfulvene-1-Carboxylate: A Reagent Discriminating Primary Amines from Secondary Amines
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A highly chemo-selective reaction was observed when ethyl 6-hydroxyfulvene-1-carboxylate 1 was treated with different nucleophiles such as primary amines, secondary amines, alcohols, and thiols. Among them, only primary amines are reactive toward 1 to afford the condensation products 3, which exhibit good stability under both weakly acidic and basic conditions. The condensation process proved to be reversible between different primary amines. On the basis of this observation, the chemical selectivity of typical primary aromatic amines was evaluated quantitatively by determining equilibrium constants of the condensation reactions with aniline as a reference. Moreover, the primary amines of 3 can be readily released upon treatment with aqueous ammonia, making 6-hydroxyfulvene-1-carboxylate 1 a promising protecting reagent for primary amines.
- Yang, Sen,Lu, Dengfu,Zhu, Yuequan,Shi, Mei,Luo, Fan,Gong, Yuefa
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p. 6681 - 6689
(2018/06/11)
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- AgPd Nanoparticles Deposited on WO2.72 Nanorods as an Efficient Catalyst for One-Pot Conversion of Nitrophenol/Nitroacetophenone into Benzoxazole/Quinazoline
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We report a seed-mediated growth of 2.3 nm AgPd nanoparticles (NPs) in the presence of 40 × 5 nm WO2.72 nanorods (NRs) for the synthesis of AgPd/WO2.72 composites. The strong interactions between AgPd NPs and WO2.72 NRs make the composites, especially the Ag48Pd52/WO2.72, catalytically active for dehydrogenation of formic acid (TOF = 1718 h-1 and Ea = 31 kJ/mol) and one-pot reactions of formic acid, 2-nitrophenol, and aldehydes into benzoxazoles in near quantitative yields under mild conditions. The catalysis can also be extended to the one-pot reactions of ammonium formate, 2-nitroacetophenone, and aldehyde for high yield syntheses of quinazolines. Our studies demonstrate a new catalyst design to achieve a green chemistry approach to one-pot reactions for the syntheses of benzoxazoles and quinazolines.
- Yu, Chao,Guo, Xuefeng,Xi, Zheng,Muzzio, Michelle,Yin, Zhouyang,Shen, Bo,Li, Junrui,Seto, Christopher T.,Sun, Shouheng
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supporting information
p. 5712 - 5715
(2017/05/04)
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- Unconventional Pd@Sulfonated Silica Monoliths Catalysts for Selective Partial Hydrogenation Reactions under Continuous Flow
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Doubly functionalized, hierarchical-porosity silica monoliths were synthesized by postgrafting of sulfonic groups and in situ growth of Pd nanoparticles in that order. PdNP of 3.1 nm size located in the mesopores of the material showed to be evenly distributed within 4.6 % wt Pd monoliths. The system was explored in the continuous-flow, catalytic partial hydrogenation reaction of 3-halogeno-nitrobenzenes and 3-hexyn-1-ol in the liquid phase, showing remarkable conversion, selectivity, and resistance under very mild conditions.
- Liguori, Francesca,Barbaro, Pierluigi,Said, Bilel,Galarneau, Anne,Santo, Vladimiro Dal,Passaglia, Elisa,Feis, Alessandro
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p. 3245 - 3258
(2017/08/29)
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- Direct Hydrogenation of a Broad Range of Amides under Base-free Conditions using an Efficient and Selective Ruthenium(II) Pincer Catalyst
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The ruthenium(II) complex, [fac-PNHN]RuH(η1-BH4)(CO) (B; PNHN=8-(2-diphenylphosphinoethyl)aminotrihydroquinoline), is a highly versatile and effective catalyst (loadings of 0.1–1 mol %) for the hydrogenation of a multitude of amides, which include primary, secondary, and tertiary amides, to give their corresponding alcohols and amines in high yields under base-free conditions. All products were confirmed by using GC and GC–MS.
- Wang, Zheng,Li, Yong,Liu, Qing-Bin,Solan, Gregory A.,Ma, Yanping,Sun, Wen-Hua
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p. 4275 - 4281
(2017/12/02)
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- Direct Catalytic Hydrogenation of Simple Amides: A Highly Efficient Approach from Amides to Amines and Alcohols
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A highly chemoselective and reactive direct catalytic reduction of various amides to amines and alcohols was developed by using a tetradentate ruthenium complex. The catalytic system showed excellent activity (turnover numbers up to 19 600) and great functional group tolerance under mild reaction conditions, compared to several bidentate and tridentate ruthenium-catalyzed systems.
- Shi, Liyang,Tan, Xuefeng,Long, Jiao,Xiong, Xiong,Yang, Song,Xue, Peng,Lv, Hui,Zhang, Xumu
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supporting information
p. 546 - 548
(2017/01/18)
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- Electrophilic amination of aromatics with sodium azide in BF3-H2O
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Boron trifluoride monohydrate is an excellent Br?nsted acid catalyst system for a wide range of reactions. It is a non-oxidizing acid catalyst prepared easily by bubbling BF3 into water. We have found boron trifluoride monohydrate/sodium azide combination to be an efficient reagent system for aromatic electrophilic amination. The present method avoids the use of expensive superacids such as trifluoromethanesulfonic acid and provides a facile access to aromatic amines directly from aromatics.
- Prakash, G.K. Surya,Gurung, Laxman,Marinez, Eric R.,Mathew, Thomas,Olah, George A.
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supporting information
p. 288 - 291
(2016/01/12)
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- Boron Lewis Acid Promoted Ruthenium-Catalyzed Hydrogenation of Amides: An Efficient Approach to Secondary Amines
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The hydrogenation of amides to amines has been developed by using the catalyst [Ru(H)2(CO)(Triphos)] (Triphos=1,1,1-tri(diphenylphosphinomethyl)ethane) and catalytic boron Lewis acids such as B(C6F5)3 or BF3?Et2O as additives. The reaction provides an efficient method for the preparation of secondary amines from amides in good yields with high selectivity.
- Yuan, Ming-Lei,Xie, Jian-Hua,Zhou, Qi-Lin
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p. 3036 - 3040
(2016/10/11)
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- Deoxygenative Hydrogenation of Amides Catalyzed by a Well-Defined Iridium Pincer Complex
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The iridium-catalyzed highly chemoselective hydrogenation of amides to amines has been developed. Using a well-defined iridium catalyst bearing a P(O)C(O)P pincer ligand combined with B(C6F5)3, the C-O cleavage products are formed under mild reaction conditions. The reaction provides a new method for the preparation of amines from amides in good yield with high selectivity.
- Yuan, Ming-Lei,Xie, Jian-Hua,Zhu, Shou-Fei,Zhou, Qi-Lin
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p. 3665 - 3669
(2016/07/06)
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- Reduction of aromatic nitro compounds catalyzed by biogenic CuO nanoparticles
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Synthesis of CuO nanoparticles using the peel of Musa balbisiana and its application in reduction of nitro aryl compounds are reported here. CuO nanoparticles were characterized by using XRD, XPS, PL, SEM and TEM techniques. In XRD analysis, significant peaks appeared at 18.3, 24.4, 33.6, 34.6, 35.2, 38.2 and 42.7 respectively. The BET surface area and total pore volume of CuO were found to be 7.479 m2 g-1 and 0.1259 m3 g-1, respectively. The generated CuO nanoparticles exhibited interplanar lattice fringe spacings of 0.16 nm. SEM images indicate the formation of flower-like CuO architecture. The hierarchical CuO architecture is found to be made up of nanosheets which were self assembled to form flower-like nanostructures. The synthesized CuO nanoparticles show efficient catalytic activity in reduction of nitro aryl compounds to corresponding amino compounds with a high yield of conversion (74-96%). The reaction was carried out in a green solvent i.e. water. The catalyst was found to be active for several runs. It was further confirmed by several pieces of experimental evidence.
- Tamuly, Chandan,Saikia, Indranirekha,Hazarika, Moushumi,Das, Manash R.
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p. 53229 - 53236
(2015/02/05)
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- METHODS FOR PREPARING ALKYLFURANS
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Provided herein are methods for preparing alkylfurans, such as 2,5-dialkylfurans and 2-alkylfurans. Furfural or 5-alkylfurfural can be reacted with aniline or diaminobenzene, or derivatives thereof, to form the corresponding imine, which can be reduced to form alkylfurans and to regenerate the aniline or diaminobenzene, or derivatives thereof. The alkylfuran may be, for example, 2,5-dimethylfuran or 2-methylfuran.
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Paragraph 0158-0160
(2014/10/04)
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- Pd/C-mediated depropargylation of propargyl ethers/amines in water
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Propargyl ethers and amines are effectively depropargylated to the parent alcohols or amines via a C-O/C-N bond cleavage catalyzed by 10% Pd/C in water. This simple, facile, and inexpensive methodology could be utilized for the selective removal of propargyl groups from a variety of aryl ethers and amines.
- Rambabu,Bhavani,Swamy, Nalivela Kumara,Basaveswara Rao,Pal, Manojit
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p. 1169 - 1173
(2013/04/10)
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- Highly selective hydrogenation of halonitroaromatics to aromatic haloamines by ligand modified Ni-based catalysts
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Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics. The selectivity of above 99.9% to aromatic haloamines can be achieved at the conversion of 100%. The results of H2-TPD and FT-IR experiments show that Ni-H+ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation. When Raney Ni was treated by dicyandiamide, Ni -H+ species interacted with N atom from the dicyandiamide. This interaction was stable even at reaction temperature, which reduced the possibility to form the intermediate state of ArCl?H+Ni -. And then CCl bond could not be polarized and activated. The hydrodechlorination process was suppressed effectively.
- Lu, Chun Shan,Lv, Jing Hui,Ma, Lei,Zhang, Qun Feng,Feng, Feng,Li, Xiao Nian
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experimental part
p. 545 - 548
(2012/06/16)
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- A new class of heterogeneous platinum catalysts for the chemoselective hydrogenation of nitroarenes
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A new series of nanostructured platinum catalysts able to catalyze the selective reduction of nitroarenes has been developed. The materials, made of organosilica physically doped with nanostructured platinum(0), are stable and efficient. Reactions in general proceed with high yield and often go to completion, while the catalysts can be reused in further reaction runs. This establishes a new class of relevant solid catalysts for synthetic organic chemistry named SiliaCat Platinum-Hydrogel.
- Pandarus, Valerica,Ciriminna, Rosaria,Beland, Francois,Pagliaro, Mario
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scheme or table
p. 1306 - 1316
(2011/06/25)
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- Synthesis and in vitro activity of novel 1,2,4-triazolo[4,3-a]pyrimidine oxazolidinone antibacterial agents. Part II
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The synthesis and antibacterial activity of 1,2,4-triazolo[4,3-a]pyrimidine oxazolidinones is reported. Compound 3e with a 2,4-disubstituted thiophene ring was found to be a potent inhibitor of Gram-positive pathogens and was 4-16-fold more potent than Linezolid.
- Khera, Manoj Kumar,Cliffe, Ian A.,Prakash, Om
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scheme or table
p. 5266 - 5269
(2011/10/02)
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- Simple and efficient CuI/PEG-400 system for amination of aryl halides with aqueous ammonia
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The cross-coupling reaction between aryl halides with aqueous ammonia was efficiently catalyzed in CuI/PEG-400 System with high yield. A range of electron-withdrawing or electron-donating aryl iodides and bromides were found to be applicable to the environmentally benign system. The process allows assembly of primary arylamines in great diversity which bear a wide range of functional groups including cyano, nitro, acetyl, ether, or amino moiety.
- Chen, Junmin,Yuan, Tangjun,Hao, Wenyan,Cai, Mingzhong
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experimental part
p. 3710 - 3713
(2011/08/06)
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- Silver-catalysed protodecarboxylation of ortho-substituted benzoic acids
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Catalytic amounts of Ag(i) salts in DMSO have been found to promote the protodecarboxylation of a wide variety of ortho-substituted benzoic acids under mild conditions and in excellent yields, highlighting a possible role for silver in decarboxylative cross-couplings. The Royal Society of Chemistry 2009.
- Cornella, Josep,Sanchez, Carolina,Banawa, David,Larrosa, Igor
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supporting information; experimental part
p. 7176 - 7178
(2010/03/25)
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- Palladium-catalyzed silane/siloxane reductions in the one-pot conversion of nitro compounds into their amines, hydroxylamines, amides, sulfonamides, and carbamates
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A combination of palladium(II) acetate, aqueous potassium fluoride, and polymethylhydrosiloxane (PMHS) facilitates the room-temperature reduction of aromatic nitro compounds to anilines. These reactions tend to be quick (30 min), high-yielding, and tolerate a range of other functional groups. Replacement of PMHS/KF with triethylsilane allows for the reduction of aliphatic nitro compounds to their corresponding hydroxylamines. Depending on the substrate, both conditions can allow for the in situ conversion of the product amines into amides, sulfonamides, and carbamates. Georg Thieme Verlag Stuttgart.
- Rahaim Jr., Ronald J.,Maleczka Jr., Robert E.
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p. 3316 - 3340
(2008/09/17)
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- Pd-catalyzed silicon hydride reductions of aromatic and aliphatic nitro groups
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(Chemical Equation Presented) Room-temperature reduction of aromatic nitro groups to amines can be accomplished in high yield, with wide functional group tolerance and short reaction times (30 min) using a combination of palladium(II) acetate, aqueous potassium fluoride, and polymethylhydrosiloxane (PMHS). Replacing PMHS/KF with triethylsilane allows aliphatic nitro groups to be reduced to their hydroxylamines.
- Rahaim Jr., Ronald J.,Maleczka Jr., Robert E.
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p. 5087 - 5090
(2007/10/03)
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- Electrophilic aromatic fluorination with fluorine: meta-Directed fluorination of anilines
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Anilines are mainly or selectively fluorinated in the meta-position with F2 when dissolved in triflic acid, sometimes in the presence of small quantities of antimony pentafluoride. The regioselectivity is increased when an electron-donating substituent is present at the para-position.
- Alric,Marquet,Billard,Langlois
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p. 661 - 667
(2007/10/03)
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- SUBSTITUTED QUINAZOLINE DERIVATIVES AND THEIR USE AS INHIBITORS
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The use of a compound of formula (I) 1 or a salt, ester or amide thereof; where X is O, or S, S(O) or S(O)2, or NR6 where R6 is hydrogen or C1-6 alkyl,; R5 is an optionally substituted 5-membered heteroaromatic ring, R1, R2 ,R3, R4 are independently selected from various specified moieties, in the preparation of a medicament for use in the inhibition of aurora 2 kinase. Certain compounds are novel and these, together with pharmaceutical compositions containing them are also described and claimed
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- The thermodynamics of m-fluoroaniline and of the proton ionization of m-fluoroanilinium ion: A solvent extraction study
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The distribution coefficients of m-fluoroaniline between a petroleum ether fraction and aqueous sodium chloride solutions were determined at different temperatures. The activity coefficients of the amine in aqueous sodium chloride solutions, and the salting coefficients were determined at different temperatures. The results agree with the Debye theory of salt effects. The effect of sodium chloride on the proton ionization of m-fluoroanilinium was studied at different temperatures, by a modified distribution method. Attention was directed to the choice of the extracting solvent, the purity of the amine, and the analytical method. Km, Ko, (Kb)m, (Kb)o, ΔGo, ΔHo and ΔSo were evaluated for the proton ionization of the m-fluoroanilinium ion.
- Aboul-Seoud,Salama
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- Optionally substituted pyrido[2,3-d]pyridine-2,4(1H,3H)-diones and pyrido[2,]pyrimidine-2(1H,3H)-ones
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The present invention relates to optionally substituted pyrido[2,3-d]pyrimidine-2,4(1H,3H)-diones or optionally substituted pyrido[2,3-d]pyrimidine-2(1H,3H)-ones, i.e., compounds of Formula I: STR1 wherein: Y is --CH2 -- or --C(O)--; R1 is hydrogen or --(CH2)n --R7, wherein: R7 is aryl or heteroaryl, and n is 1 or 2, provided that when Y is --C(O)--, R7 is heteroaryl; and R2, R3, R4, R5 and R6 are hydrogen, or one is selected from lower alkyl, halo, carboxy, methoxycarbonyl, carbamoyl, methylcarbamoyl, di-methylcarbamoyl, methylcarbonyl, methylthio, methylsulfinyl, methylsulfonyl, hydroxymethyl, amino, trifluoromethyl, cyano or nitro; or R2, R3, R4 and R5 are independently selected from hydrogen, lower alkyl, nitro, chloro, fluoro, methoxycarbonyl or methylcarbonyl, provided at least one is hydrogen, and R6 is hydrogen; or a pharmaceutically acceptable ester, ether or salt thereof.
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- A Study of the Ferrous Ion-initiated SRN1 Reactions of Halogenoarenes with tert-Butyl Acetate and N-Acylmorpholine Enolates
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A detailed preparative study is reported of the ferrous ion-initiated SRN1 reactions of a range of halogenoarenes with the sodium enolates of tert-butyl acetate, n-acetylmorpholine and a number of higher N-acylmorpholines.Smooth and rapid substitution occurs in many cases, and good to excellent yields were obtained of arylacetic esters or acids, arylacetamides and arylalkanamides.The broad scope and limitations of the process have been defined, and the possible role of the ferrous ion is discussed.
- Leeuwen, Milko van,McKillop, Alexander
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p. 2433 - 2440
(2007/10/02)
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- KINETICS OF ALKALINE HYDROLYSIS AND CORRELETION STUDIES OF m- AND p-SUBSTITUTED PIPERIDINOETHYL PHENYLCARBAMATES
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Kinetics of alkaline hydrolysis have been studied with a series of 15 m- and p-substituted piperidinoethyl phenylcarbamates.The rate constants have been determined at 70, 60, 50, and 40 deg C and the activation parameters have been calculated.These values have been correlated with the substituent constants ?, , , F, R, ?.Validity of the Hammett equation and the Swain-Lupton equation has been confirmed in the series studied and for the p-derivatives, respectively.The lipophilicity parameter ? does not correlate with the values found.
- Stankovicova, Maria,Cizmarik, Jozef
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p. 1846 - 1853
(2007/10/02)
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- NONCATALEPTIC NEUROLEPTIC AGENTS: 4-SUBSTITUTED 1-(2-CHLORO-7-FLUORO-10,11-DIHYDRODIBENZOTHIEPIN-10-YL)PIPERAZINES AND RELATED COMPOUNDS
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1-(2-chloro-7-fluoro-10,11-dihydrodibenzothiepin-10-yl)piperazine (VI) was used to prepare a new group of potential noncataleptic neuroleptic agents.Addition of acrylonitrile and acrylamide gave the nitrile VII and the amide X.Further transformations of the nitrile VII led to the phenone VIII and the amidoxime IX.Alkylations of compound VI with 2-(2-chloroethyl)-1,3-dioxolane and 2-(2-chloroethyl)-1,3-dioxane resulted in the cyclic acetals XII and XIII.Several improvements of the synthesis of compound VI are reported.Out of the compounds prepared, the amide X (methanesulfonate VUFB-15496) proved most interesting: it has low acu te toxicity, is noncataleptic and has significantly higher antidopaminergic activity than clozapine.
- Protiva, Miroslav,Jilek, Jiri,Cervena, Irena,Pomykacek, Josef,Bartl, Vaclav,et al.
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p. 2598 - 2616
(2007/10/02)
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- Bis(salicylaldehyde)ethylenedi-iminecobalt(II)-catalysed Oxidation of Aromatic Amins with Oxygen
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N-n-Butylanilines undergo N-dealkylation to give a primary amine and butyrylaldehyde by oxidation with oxygen in the presence of bis(salicylaldehyde)ethylenedi-iminecobalt(II) (CoIIsalen) as a catalyst.High conversions are obtained with high catalyst concentrations and low / ratios (r).Inspection of the effect of catalyst and substrate concentrations on initial reaction rates (Vin) shows poor sensitivity to the electronic effect of the nuclear substituent.Some anilines give azo derivatives at a lower rate in the same conditions.
- Benedini, Francesca,Galliani, Guido,Nali, Micaela,Rindone, Bruno,Tollari, Stefano
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p. 1963 - 1968
(2007/10/02)
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- Certain phenoxy-benzyloxy ether derivatives and an insecticidal and/or acaricidal composition containing the same and methods of use
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Ether compounds of the general formula, STR1 wherein W represents CH group or nitrogen atom, and (1) when W is the CH group, R1 represents hydrogen atom, fluorine atom, chlorine atom, bromine atom or methyl group, R2 represents hydrogen atom or fluorine atom, R3 and R4 are same or different and represent hydrogen atom, a halogen atom, a C1-4 alkyl, a C1-4 alkoxyl, difluoromethoxy or 2,2,2-trifluoroethoxy group, or represent, taken together, methylenedioxy group, A represents oxygen atom, methylene group or imino group, and when the A represents oxygen atom or methylene group, X and Y represent, taken together, ethylene group or 1,1-difluoroethylene group and when the A represents imino group, both X and Y represent methyl group or represent, taken together, ethylene group or 1,1-difluoroethylene group, and (2) when W is the nitrogen atom, both R1 and R2 represent hydrogen atom, R3 and R4 are as define above, A represents oxygen atom, and both X and Y represent methyl group or represent, taken together, ethylene group or 1,1-difluoroethylene group. The ether compounds of the present invention are useful as an active ingredient of an insecticidal and/or acaricidal composition.
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- Polar Effects in Free Radical Reactions. Homolytic Aromatic Amination by the Amino Radical Cation, +NH3: Reactivity and Selectivity
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Small amounts of Fe(II) salt initiate redox chains with hydroxyamino-O-sulfonic acid (HSA) and aromatic compounds leading to the amination of the aromatic ring.The positional and substrate selectivity with a variety of substituted benzenes show the important role of the electrophilic character of the radical +NH3.Hammett relationships with ? and ?+ are roughly observed.The lower sensitivity to polar effects of the radical +NH3 compared with (CH3)2+NH is explained by the different reaction enthalpies.The different positional selectivity obtained with anisole and the redox system +NH3OH/Ti(III) is discussed.
- Citterio, Attilio,Gentile, Anna,Minisci, Francesco,Navarrini, Valter,Serravalle, Marco,Ventura, Susanna
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p. 4479 - 4482
(2007/10/02)
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- Effect of Meta and Para Substituents on the Stannous Chloride Reduction of Nitrobenzenes in Aqueous Ethanol
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The rate of reduction of 24 meta- and para-substituted nitrobenzenes with SnCl2 catalyzed by HCl in ethanol-water (90 : 10 v/v) at 30 degC has been measured iodometrically.The rate is expressed as υ = kst0.5, suggesting that the sole active reducing species is SnCl3- and the dissociation of HCl is very small.The effect of meta and para substituents in which the solvation of the substituent is taken into account was examined with the Hammett equation, which gave a ρ value of 2.1 +/- 0.1.Yukawa-Tsuno and Taft equations, in which resonance and inductive effects are separated, are also discussed.
- Xing, Wen-Kang,Ogata, Yoshiro
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p. 2515 - 2520
(2007/10/02)
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- Pyridazine urea plant growth regulators
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Plant growth regulators of the N-(4-pyridazinyl)urea and thiourea type are disclosed which exhibit excellent cytokinin-like activities and are useful for regulating plant growth in various manners, such as acceleration and suppression.
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- Method for the preparation of fluoroaniline
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A process for the preparation of fluoroaniline compounds comprises the steps of (A) reacting an ammonium fluorophthalamate or a fluorophthalamic acid of the formula STR1 where n is 1 or 2 with an alkali or an alkali earth metal hypochlorite to form the corresponding fluoroanthranilic acid; and (B) decarboxylating the fluoroanthranilic acid by reaction with a mineral acid to form the corresponding fluoroaniline of the formula STR2 where n is as previously defined.
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