- A New Route to Cyclohexanone using H2CO3 as a Molecular Catalytic Ligand to Boost the Thorough Hydrogenation of Nitroarenes over Pd Nanocatalysts
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Carbon dioxide has been important in green chemistry, especially in catalytic and chemical engineering applications. While exploring CO2 to produce cyclohexanone for nylon or nylon 66 that is currently produced with low yields using harsh catalytic methods, we made the exciting discovery that carbonic acid, generated from dissolved CO2 in water, was utilized as molecular catalytic ligand to produce cyclohexanone via the hydrogenation of nitrobenzene in aqueous solution that uses Pd catalysts with a total yield higher than 90 %. Importantly, the gaseous nature of catalytic ligand H2CO3 profoundly simplifies post-catalysis cleanup unlike liquid or solid catalysts. This new green catalysis strategy demonstrated the universality for hydrogenation of aromatic compounds like aniline and N-methylaniline and could be broadly applicable in other catalytic field like artificial photosynthesis and electrocatalytic organic synthesis.
- Zhao, Tian-Jian,Zhang, Jun-Jun,Zhang, Bing,Liu, Yong-Xing,Lin, Yun-Xiao,Wang, Hong-Hui,Su, Hui,Li, Xin-Hao,Chen, Jie-Sheng
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- Coordination or Oxidative Addition? Activation of N-H with [Tp′Rh(PMe3)]
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A thermal reaction of amines, anilines, and amides with Tp′Rh(PMe3)(CH3)H (1, Tp′ = tris(3,5-dimethyl-pyrazolyl)borate) is described in this report. No N-H bond cleavage was observed for reactions between ammonia or unsubstituted aliphatic amines with the reactive fragment [Tp′Rh(PMe3)]. Instead, amine coordination products (κ2-Tp′)Rh(PMe3)(NHR1R2) (R1 = H, R2 = H, nPr, iPr, octyl; R1 = R2 = Et; R1, R2: pyrrolidine) were observed, and the crystal structure of (κ2-Tp′)Rh(PMe3)(NH2iPr) is reported. No coordination products were observed when 1 was reacted with 1,1,1,3,3,3-hexafluoropropan-2-amine, anilines, and amides. Instead, the oxidative addition products (κ3-Tp′)Rh(PMe3)(NHR)H (R = CH(CF3)2, C6H5, 3,5-dimethylbenzyl, C6F5, C(O)CH3, C(O)CF3) were observed. Both RhI-N coordination products (κ2-Tp′)Rh(PMe3)(NH2CH2CF3) and RhIII N-H addition products (κ3-Tp′)Rh(PMe3)(NHCH2CF3)H were generated when 1 was reacted with 2,2,2-trifluoroethylamine. Coordination products dissociate ammonia and amines in benzene much faster than oxidative addition products eliminate anilines and amides. The relative metal-nitrogen bond energies were studied using established kinetic techniques. Analysis of the relationship between the relative M-N bond strengths and N-H bond strengths showed a linear correlation with a slope = RM-N/N-H of 0.91 (10), indicating that the Rh-N bond strength varies in direct proportion to the N-H bond strength.
- Yuwen, Jing,Brennessel, William W.,Jones, William D.
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- Encapsulation of bimetallic metal nanoparticles into robust zirconium-based metal–organic frameworks: Evaluation of the catalytic potential for size-selective hydrogenation
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The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored. Sufficient stabilization can be achieved by confinement of NPs in porous support materials. In this sense, metal–organic frameworks (MOFs) in particular have gained a lot of attention during the last years; however, encapsulation of bimetallic species remains challenging. Herein, the exclusive embedding of preformed core–shell PdPt and RuPt NPs into chemically robust Zr-based MOFs is presented. Microstructural characterization manifests partial retention of the core–shell systems after successful encapsulation without harming the crystallinity of the microporous support. The resulting chemically robust NP@UiO-66 materials exhibit enhanced catalytic activity towards the liquidphase hydrogenation of nitrobenzene, competitive with commercially used Pt on activated carbon, but with superior size-selectivity for sterically varied substrates.
- R?sler, Christoph,Dissegna, Stefano,Rechac, Victor L.,Kauer, Max,Guo, Penghu,Turner, Stuart,Ollegott, Kevin,Kobayashi, Hirokazu,Yamamoto, Tomokazu,Peeters, Daniel,Wang, Yuemin,Matsumura, Syo,van Tendeloo, Gustaaf,Kitagawa, Hiroshi,Muhler, Martin,Llabrés I Xamena, Francesc X.,Fischer, Roland A.
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- Ligand compound for copper catalyzed aryl halide coupling reaction, catalytic system and coupling reaction
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The invention provides a ligand compound capable of being used for copper catalyzed aryl halide coupling reaction, the ligand compound is a three-class compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group, and the invention also provides a catalytic system for the aryl halide coupling reaction. Thecatalytic system comprises a copper catalyst, a compound containing a 2-(substituted or non-substituted) aminopyridine nitrogen-oxygen group adopted as a ligand, alkali and a solvent, and meanwhile, the invention also provides a system for the aryl halide coupling reaction adopting the catalyst system. The compound containing the 2-(substituted or non-substituted) aminopyridine nitrogen oxygen group can be used as the ligand for the copper catalyzed aryl chloride coupling reaction, and the ligand is stable under a strong alkaline condition and can well maintain catalytic activity when being used for the copper-catalyzed aryl chloride coupling reaction. In addition, the copper catalyst adopting the compound as the ligand can particularly effectively promote coupling of copper catalyzed aryl chloride and various nucleophilic reagents which are difficult to generate under conventional conditions, C-N, C-O and C-S bonds are generated, and numerous useful small molecule compounds are synthesized. Therefore, the aryl halide coupling reaction has a very good large-scale application prospect by adopting the copper catalysis system of the ligand.
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Paragraph 0111-0119
(2021/05/29)
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- Selective Reduction of Nitroarenes to Arylamines by the Cooperative Action of Methylhydrazine and a Tris(N-heterocyclic thioamidate) Cobalt(III) Complex
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We report an efficient catalytic protocol that chemoselectively reduces nitroarenes to arylamines, by using methylhydrazine as a reducing agent in combination with the easily synthesized and robust catalyst tris(N-heterocyclic thioamidate) Co(III) complex [Co(κS,N-tfmp2S)3], tfmp2S = 4-(trifluoromethyl)-pyrimidine-2-thiolate. A series of arylamines and heterocyclic amines were formed in excellent yields and chemoselectivity. High conversion yields of nitroarenes into the corresponding amines were observed by using polar protic solvents, such as MeOH and iPrOH. Among several hydrogen donors that were examined, methylhydrazine demonstrated the best performance. Preliminary mechanistic investigations, supported by UV-vis and NMR spectroscopy, cyclic voltammetry, and high-resolution mass spectrometry, suggest a cooperative action of methylhydrazine and [Co(κS,N-tfmp2S)3] via a coordination activation pathway that leads to the formation of a reduced cobalt species, responsible for the catalytic transformation. In general, the corresponding N-arylhydroxylamines were identified as the sole intermediates. Nevertheless, the corresponding nitrosoarenes can also be formed as intermediates, which, however, are rapidly transformed into the desired arylamines in the presence of methylhydrazine through a noncatalytic path. On the basis of the observed high chemoselectivity and yields, and the fast and clean reaction processes, the present catalytic system [Co(κS,N-tfmp2S)3]/MeNHNH2 shows promise for the efficient synthesis of aromatic amines that could find various industrial applications.
- Ioannou, Dimitris I.,Gioftsidou, Dimitra K.,Tsina, Vasiliki E.,Kallitsakis, Michael G.,Hatzidimitriou, Antonios G.,Terzidis, Michael A.,Angaridis, Panagiotis A.,Lykakis, Ioannis N.
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p. 2895 - 2906
(2021/02/27)
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- Sustainable and recyclable palladium nanoparticles–catalyzed reduction of nitroaromatics in water/glycerol at room temperature
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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.
- Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhao, Yongde,Zhou, Yang
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p. 540 - 544
(2020/07/14)
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- Synthesis of Substituted Anilines from Cyclohexanones Using Pd/C-Ethylene System and Its Application to Indole Synthesis
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The synthesis of anilines and indoles from cyclohexanones using a Pd/C-ethylene system is reported. A simple combination of NH4OAc and K2CO3 under nonaerobic conditions was found to be the most suitable to perform this reaction. Hydrogen transfer between cyclohexanone and ethylene generates the desired products. The reaction tolerates a variety of substitutions on the starting cyclohexanones.
- Maeda, Katsumi,Matsubara, Ryosuke,Hayashi, Masahiko
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supporting information
p. 1530 - 1534
(2021/03/08)
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- Porous polymeric ligand promoted copper-catalyzed C-N coupling of (hetero)aryl chlorides under visible-light irradiation
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A porous polymeric ligand (PPL) has been synthesized and complexed with copper to generate a heterogeneous catalyst (Cu@PPL) that has facilitated the efficient C-N coupling with various (hetero)aryl chlorides under mild conditions of visible-light irradiation at 80 °C (58 examples, up to 99% yields). This method could be applied to both aqueous ammonia and substituted amines, and is compatible to a variety of functional groups and heterocycles, as well as allows tandem C-N couplings with conjunctive dihalides. Furthermore, the heterogeneous characteristic of Cu@PPL has enabled a straightforward catalyst separation in multiple times of recycling with negligible catalytic efficiency loss by simple filtration, affording reaction mixtures containing less than 1 ppm of Cu residue. [Figure not available: see fulltext.]
- Wang, Erfei,Chen, Kaixuan,Chen, Yinan,Zhang, Jiawei,Lin, Xinrong,Chen, Mao
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- C-H Amination of Arenes with Hydroxylamine
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This Letter describes the development of a TiIII-mediated reaction for the C-H amination of arenes with hydroxylamine. This reaction is applied to a variety of electron-rich (hetero)arene substrates, including a series of natural products and pharmaceuticals. It offers the advantages of mild conditions (room temperature), fast reaction rates (30 min), compatibility with ambient moisture and air, scalability, and the use of inexpensive commercial reagents.
- See, Yi Yang,Sanford, Melanie S.
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supporting information
p. 2931 - 2934
(2020/04/09)
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- The immobilized Cu nanoparticles on magnetic montmorillonite (MMT?Fe3O4?Cu): As an efficient and reusable nanocatalyst for reduction and reductive-acetylation of nitroarenes with NaBH4
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In this study, the immobilization of copper nanoparticles on superparamagnetic montmorillonite, MMT?Fe3O4?Cu, was studied. Magnetically nanoparticles (MNPs) of iron oxide (Fe3O4) were primarily prepared by a chemical co-precipitation method. Next, the prepared Fe3O4 MNPs were intercalated within the interlamellar spaces and external surface of sodium-exchanged montmorillonite. Finally, Cu NPs were immobilized on magnetic montmorillonite by a simply mixing of an aqueous solution of CuCl2·2H2O with MMT?Fe3O4 followed by the reduction with NaBH4. Characterization of MMT?Fe3O4 clay system represented that through the immobilization of Fe3O4 MNPs, disordered-layers structure of MMT was easily reorganized to an ordered-layers arrangement. The synthesized composite systems were characterized using FT-IR, SEM, EDX, XRD, VSM, BET and ICP-OES analyses. SEM analysis exhibited that dispersion of Cu NPs, with the size distribution of 15–25 nm, on the surface of magnetic clay was taken place perfectly. BET surface analysis indicated that after the immobilization of Fe3O4 and Cu species, the surface area and total pore volume of MMT?Fe3O4?Cu system was decreased. Next, the Cu-clay nanocomposite system showed a perfect catalytic activity towards reduction of nitroarenes to anilines as well as reductive-acetylation of nitroarenes to acetanilides using NaBH4 and Ac2O in water as a green and economic solvent. The copper magnetic clay catalyst can be easily separated from the reaction mixture by an external magnetic field and reused for six consecutive cycles without the significant loss of its catalytic activity.
- Zeynizadeh, Behzad,Rahmani, Soleiman,Tizhoush, Hengameh
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- Simple reversible fixation of a magnetic catalyst in a continuous flow system: Ultrafast reduction of nitroarenes and subsequent reductive amination using ammonia borane
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Continuous reductive amination of aldehydes with nitroarenes over a Pd-Pt-Fe3O4 catalyst was performed. We used NH3BH3 as not only a hydrogen source for nitro reduction, but also a reductant for imine reduction. Secondary aromatic amines were obtained in the continuous flow reaction in good to excellent yields.
- Byun, Sangmoon,Cho, Ahra,Kang, Dong Yun,Kim, B. Moon,Kim, Ha Joon,Kim, Hong Won,Kim, Seong Min,Lei, Cao,Park, Jin Kyoon
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p. 944 - 949
(2020/03/11)
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- Superhydrophobic nickel/carbon core-shell nanocomposites for the hydrogen transfer reactions of nitrobenzene and N-heterocycles
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In this work, catalytic hydrogen transfer as an effective, green, convenient and economical strategy is for the first time used to synthesize anilines and N-heterocyclic aromatic compounds from nitrobenzene and N-heterocycles in one step. Nevertheless, how to effectively reduce the possible effects of water on the catalyst by removal of the by-product water, and to further introduce water as the solvent based on green chemistry are still challenges. Since the structures and properties of carbon nanocomposites are easily modified by controllable construction, a one step pyrolysis process is used for controllable construction of micro/nano hierarchical carbon nanocomposites with core-shell structures and magnetic separation performance. Using various characterization methods and model reactions the relationship between the structure of Ni?NCFs (nickel-nitrogen-doped carbon frameworks) and catalytic performance was investigated, and the results show that there is a positive correlation between the catalytic performance and hydrophobicity of catalysts. Besides, the possible catalytically active sites, which are formed by the interaction of pyridinic N and graphitic N in the structure of nitrogen-doped graphene with the surfaces of Ni nanoparticles, should be pivotal to achieving the relatively high catalytic performance of materials. Due to its unique structure, the obtained Ni?NCF-700 catalyst with superhydrophobicity shows extraordinary performances toward the hydrogen transfer reaction of nitrobenzene and N-heterocycles in the aqueous state; meanwhile, it was also found that Ni?NCF-700 still retained its excellent catalytic activity and structural integrity after three cycles. Compared with traditional catalytic systems, our catalytic systems offer a highly effective, green and economical alternative for nitrobenzene and N-heterocycle transformation, and may open up a new avenue for simple construction of structure and activity defined carbon nanocomposite heterogeneous catalysts with superhydrophobicity.
- Duan, Zhiying,Liu, Fangfang,Pang, Shaofeng,Su, Qiong,Wang, Yanbin,Xie, Xin,Zhang, Ping,Zhang, Yujing,Zhou, Feng
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p. 1996 - 2010
(2020/04/07)
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- One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols
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Benzynes were selectively generated in situ from phenols and trapped regioselectively with potassium hexamethyldisilazide to form primary anilines following acidic workup. The direct conversion of a phenolic hydroxyl group into a free amino group is a useful method for the preparation of primary aryl amines that are hard to synthesize by using coupling reactions involving phenol derivatives with ammonia. Whereas reactions of ortho- and meta-substituted phenols produced meta-substituted anilines exclusively, those of para-substituted phenols provided ortho-silylanilines.
- Akai, Shuji,Ikawa, Takashi,Masuda, Shigeaki
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- Method for synthesizing 3,5 -dimethylaniline (by machine translation)
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3,5 - Dimethylphenol is used as a raw material, toluene is used as a solvent, and 3,5 -dimethylaniline is obtained through indirect amination reaction of fixed bed catalysis, hydrogenation, amination and dehydrogenation 3,5 . To the invention, through the indirect hydrogenation method of hydrogenation, amination and dehydrogenation, the reaction conditions are mild, the service life of the catalyst is prolonged. (by machine translation)
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Paragraph 0103-0138
(2020/07/12)
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- Superfine CoNi alloy embedded in Al2O3 nanosheets for efficient tandem catalytic reduction of nitroaromatic compounds by ammonia borane
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Aromatic amino compounds are important and universally used chemical intermediates in a wide range of industrial fields. Thus, their production with high efficiency and selectivity under ambient conditions is expected and demanded in modern industry. Herein, a series of superfine CoNi alloy nanoparticles embedded in Al2O3 nanosheet (CoxNi1-x/Al2O3, where x represents the content of Co in the precursor) catalysts was fabricated from CoNiAl-LDH and used to catalyze the tandem dehydrogenation of ammonia borane (AB) and hydrogenation of nitroaromatics to the corresponding amines. Systematic experiments indicate that the composition, size, morphology and catalytic performance of the CoxNi1-x/Al2O3 catalysts can be easily controlled by changing the content of Ni in the CoNiAl-LDH precursor. Particularly, Co0.67Ni0.33/Al2O3 exhibited the best tandem catalytic performance among the six samples. This as-prepared catalyst not only showed a moderate turn-over-frequency value (TOF: 34.5 molH2 molCo0.67Ni0.33-1 min-1 at 298 K without base or additives) and relatively low activation energy (32.4 kJ mol-1) for the dehydrogenation of AB, but also superior catalytic activity (conversion yield reaching up to 100%) and selectivity (>99%) for the tandem reductive transformation of in excess of sixteen types of nitroaromatics to aromatic amines. Density functional theory (DFT) calculations suggest that the construction of the CoNi alloy optimized the electronic structure with respect to the pure component, promoting its activity for AB hydrolysis and nitroaromatics hydrogenation. Finally, the catalyst could be easily recycled using a magnet due to the magnetic properties of the Co0.67Ni0.33 alloy.
- Cheng, Sihang,Liu, Yanchun,Zhao, Yingnan,Zhao, Xinyu,Lang, Zhongling,Tan, Huaqiao,Qiu, Tianyu,Wang, Yonghui
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p. 17499 - 17506
(2019/12/23)
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- Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium
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Primary anilines are essential building blocks to synthesize various pharmaceuticals, agrochemicals, pigments, electronic materials, and others. To date, the syntheses of primary anilines mostly rely on the reduction of nitroarenes or the transition-metal-catalyzed Ullmann, Buchwald-Hartwig and Chan-Lam cross-coupling reactions with ammonia, in which non-renewable petroleum-based chemicals are typically used as feedstocks via multiple step syntheses. A long-standing scientific challenge is to synthesize various primary anilines directly from renewable sources. Herein, we report a general method to directly convert a broad range of phenols into the corresponding primary anilines with the cheap and widely available hydrazine as both amine and hydride sources with simple Pd/C as the catalyst.
- Qiu, Zihang,Lv, Leiyang,Li, Jianbin,Li, Chen-Chen,Li, Chao-Jun
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p. 4775 - 4781
(2019/05/16)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
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Paragraph 0098; 0134; 0135; 0153
(2018/03/25)
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- Synthesis of magnetic Fe3O4@SiO2@Cu–Ni–Fe–Cr LDH: an efficient and reusable mesoporous catalyst for reduction and one-pot reductive-acetylation of nitroarenes
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Abstract: Magnetically recoverable Fe3O4@SiO2@Cu–Ni–Fe–Cr LDH was prepared under co-precipitation conditions. Characterization of the mesoporous catalyst was confirmed using Fourier-transformed infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, vibration sample magnetometer, Brunauer–Emmett–Teller, thermogravimetric, differential thermogravimetric analyses and transmission electron microscopy. Reduction of nitroarenes to the corresponding arylamines and one-pot reductive-acetylation of nitroarenes to acetanilides were carried out successfully by nanoparticles of the immobilized Cu–Ni–Fe–Cr layered double hydroxide on silica-coated Fe3O4 in water as a green solvent. All reactions were carried out within 6–22?min affording arylamines and N-arylacetamides in high-to-excellent yields. Reusability of the core–shell nanocatalyst was examined six times without significant loss of its catalytic activity.
- Gilanizadeh, Masumeh,Zeynizadeh, Behzad
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p. 2821 - 2837
(2018/10/31)
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- Magnetically nano core–shell Fe3O4@Cu(OH)x: a highly efficient and reusable catalyst for rapid and green reduction of nitro compounds
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Magnetically separable nano core–shell Fe3O4@Cu(OH)x with 22?% Cu content was prepared by the addition of sodium hydroxide to a mixture of CuCl2·2H2O and nano Fe3O4 in water. Characterization of the impregnated copper hydroxide was carried out by X-ray fluorescence (XRF), X-ray diffraction (XRD) atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM), value stream mapping (VSM) and Brunauer–Emmett–Teller (BET) analysis. The core–shell nanocatalyst exhibited the excellent catalytic activity toward reduction of various nitro compounds to the corresponding amines with NaBH4. All reactions were carried out in H2O (55–60?°C) within 3–15?min to afford amines in high to excellent yields. Reusability of core–shell Cu(OH)x catalyst was examined 9?times without significant loss of its catalytic activity.
- Shokri, Zahra,Zeynizadeh, Behzad,Hosseini, Seyed Ali,Azizi, Behrooz
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p. 101 - 109
(2017/01/05)
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- Selective synthesis of primary anilines from cyclohexanone oximes by the concerted catalysis of a Mg-Al layered double hydroxide supported Pd catalyst
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Although the selective conversion of cyclohexanone oximes to primary anilines would be a good complement to the classical synthetic methods for primary anilines, which utilize arenes as the starting materials, there have been no general and efficient methods for the conversion of cyclohexanone oximes to primary anilines until now. In this study, we have successfully realized the efficient conversion of cyclohexanone oximes to primary anilines by utilizing a Mg-Al layered double hydroxide supported Pd catalyst (Pd(OH)x/LDH) under ligand-, additive-, and hydrogen-acceptor-free conditions. The substrate scope was very broad with respect to both cyclohexanone oximes and cyclohexenone oximes, which gave the corresponding primary anilines in high yields with high selectivities (17 examples, 75% to >99% yields). The reaction could be scaled up (gram-scale) with a reduced amount of the catalyst (0.2 mol %). Furthermore, the one-pot synthesis of primary anilines directly from cyclohexanones and hydroxylamine was also successful (five examples, 66-99% yields). The catalysis was intrinsically heterogeneous, and the catalyst could be reused for the conversion of cyclohexanone oxime to aniline at least five times with keeping its high catalytic performance. Kinetic studies and several control experiments showed that the high activity and selectivity of the present catalyst system were attributed to the concerted catalysis of the basic LDH support and the active Pd species on LDH. The present transformation of cyclohexanone oximes to primary anilines proceeds through a dehydration/dehydrogenation sequence, and herein the plausible reaction mechanism is proposed on the basis of several pieces of experimental evidence.
- Jin, Xiongjie,Koizumi, Yu,Yamaguchi, Kazuya,Nozaki, Kyoko,Mizuno, Noritaka
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p. 13821 - 13829
(2017/11/06)
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- Dibenzothiophene Sulfoximine as an NH3 Surrogate in the Synthesis of Primary Amines by Copper-Catalyzed C?X and C?H Bond Amination
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Readily accessible dibenzothiophene sulfoximine is an NH3 surrogate allowing the preparation of free anilines by copper-catalyzed cross-coupling reactions with aryl iodides or amides followed by radical S?N bond cleavage. The one-pot/two-step r
- Li, Zhen,Yu, Hao,Bolm, Carsten
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supporting information
p. 9532 - 9535
(2017/08/01)
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- Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
- Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
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p. 681 - 688
(2017/06/30)
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- Synthetic method for 1,5-bis(chloromethyl)-3-fluorobenzene
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The invention discloses a synthetic method for 1,5-bis(chloromethyl)-3-fluorobenzene, which belongs to the field of chemical synthesis. The synthetic method comprises the following steps: adding concentrated sulfuric acid and fuming nitric acid into 3,5-dimethylchlorobenzene and carrying out a reaction in an ice bath so as to obtain 3,5-dimethylnitrobenzene; then adding ethanol and palladium charcoal and introducing hydrogen so as to obtain 3,5-dimethylaniline; allowing 3,5-dimethylaniline and tetrafluoroboric acid to undergo an ice bath and adding a sodium nitrite solution drop by drop; carrying out filtering after completion of addition and drying obtained filter residue; and placing the filter residue in a flask for decomposition, adding water and petroleum ether and carrying out distillation so as to obtain 1,5-bis(chloromethyl)-3-fluorobenzene.
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Paragraph 0007
(2017/02/17)
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- A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines
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A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments.
- Ohtsuka, Naoya,Okuno, Moriaki,Hoshino, Yujiro,Honda, Kiyoshi
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p. 9046 - 9054
(2016/10/05)
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- A 3,5-dimethyl aniline method for the preparation of
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The invention discloses a preparation method of 3, 5-dimethylaniline. The preparation method is used for preparing the target product 3, 5-dimethylaniline through a reaction of chlorination, nitration and catalytic reductive dechlorination of a ring by taking m-xylene as a raw material. Compared with existing processes, the method disclosed by the invention is few in reaction step and simple in technological process. The yield of 3, 5-dimethylaniline based on m-xylene can reach over 75% of a theoretical amount. The cost of the 3, 5-dimethylaniline can be greatly lowered.
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Paragraph 0037
(2016/10/08)
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- A circulating aqueous phase system method of synthesizing aromatic primary amine
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The invention discloses a method for synthesizing an aromatic primary amine in a circulating water phase system. According to the method, an aryl halide and ammonia water are taken as raw materials, water is taken as a solvent, a carbonate, a fluoride, a phosphate or a hydroxide of an alkali metal or an alkaline-earth metal or a compound which can be converted to a corresponding alkali in water is taken as the alkali, polyamine carboxylic acid and a salt type compound thereof are taken as ligands, and a copper source catalyst is adopted for catalyzing the formation of the aromatic primary amine from the aryl halide and the ammonia water. According to the method disclosed by the invention, the water is used as the solvent, any phase transfer of the catalyst is not required, and the catalyst, the ligands and the reaction solvent, namely the water, can be recycled, so that the environment-friendly property of reaction is effectively improved, the method is more in line with requirements of green chemical development, a substrate particularly has a wide range of applications, and the method further has broad prospects in the aspects of preparation of natural products, medicaments and pesticides.
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Paragraph 0055; 0056
(2016/10/20)
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- N-(1-Oxy-2-picolyl)oxalamic Acid as an Efficient Ligand for Copper-Catalyzed Amination of Aryl Iodides at Room Temperature
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N-(1-Oxy-pyridin-2-ylmethyl)oxalamic acid was identified as efficient ligand for CuI-catalyzed amination of aryl halides at room temperature. In our catalytic system, N-arylation of cyclic secondary amines, primary amines, amino acids, and ammonia proceeded with moderate to excellent yields and high functional group tolerance.
- Wang, Yongbin,Ling, Jing,Zhang, Yu,Zhang, Ao,Yao, Qizheng
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p. 4153 - 4161
(2015/07/01)
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- BIO-ORTHOGONAL DRUG ACTIVATION
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Disclosed is a kit for the administration and activation of a Prodrug. The kit comprises a Masking Moiety linked, directly or indirectly, to a Trigger moiety, which in turn is linked to a Drug, and an Activator for the Trigger moiety. The Trigger moiety comprises a dienophile and the Activator comprises a diene, whereby the dienophile is an eight-membered non- aromatic cyclic alkenylene group, preferably a cyclooctene group, and more preferably a trans-cyclooctene group. The Trigger and the Activator undergo a fast, bio-orthogonal reaction resulting in the release of the Masking Moiety, and activation of the drug.
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Page/Page column 89-90; 92
(2014/06/11)
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- CHEMICALLY CLEAVABLE GROUP
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Disclosed is the use of the reactive components of the inverse electron-demand Diels Alder reaction for chemical masking and unmasking in vitro. This can be applied in complex chemical reactions and, particularly in the synthesis of biomolecules, e.g. on solid supports. The reactice components are a dienophile, particularly a trans-cyclooctene, and a diene, particularly a tetrazine.
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Page/Page column 98-102
(2014/06/11)
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- CHANNEL PROTEIN ACTIVATABLE LIPOSOMES
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Disclosed is a liposome, comprising a lipid bilayer enclosing a cavity, wherein the bilayer comprises a channel protein releasably linked to an eight-membered non-aromatic cyclic alkenylene group, preferably a cyclooctene group, and more preferably a trans-cyclooctene group. The liposomes are used in a kit comprising the liposome, the liposomal membrane of which comprises a channel protein linked to a Trigger, and an Activator for the Trigger, wherein the Trigger comprises the eight- membered non-aromatic cyclic alkenylene group, and the Activator comprises a diene.
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Page/Page column 114; 116
(2014/06/11)
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- ACTIVATABLE LIPOSOMES
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Disclosed are reactive liposome, comprising a lipid bilayer enclosing a cavity, wherein the bilayer comprises a linkage to an eight-membered non-aromatic cyclic alkenylene group, preferably a cyclooctene group, and more preferably a trans-cyclooctene group. The liposomes are use in a kit comprising the liposome linked, directly or indirectly, to a Trigger, and an Activator for the Trigger, wherein the Trigger comprises an eight-membered non-aromatic cyclic alkenylene group, and the Activator comprises a diene.
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Page/Page column 131; 132
(2014/06/11)
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- A simple and recyclable copper/DTPA catalyst system for amination of aryl halides with aqueous ammonia in water
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Commercially available CuO/DTPA (diethylenetriaminepentaacetic acid) was established to be a low-cost, recyclable, and environmentally benign homogeneous catalyst system for direct amination of aryl halides with ammonia. Primary aryl amines can be readily prepared from both electron-withdrawing and electron-donating aryl halides in good yields in water without the addition of surfactants.
- Yang, Bo,Liao, Lihao,Zeng, Yongheng,Zhu, Xinhai,Wan, Yiqian
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p. 100 - 103
(2014/01/06)
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- ORGANIC COMPOUNDS
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The present invention provides compounds of the following structure; [in-line-formulae]A-L1-B-C-D[/in-line-formulae] that are useful for treating or preventing conditions or disorders associated with DGAT1 activity in animals, particularly humans.
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Page/Page column 60
(2011/04/14)
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- Novel redox photocatalyst Pt-TiO2 for the synthesis of 2-Methylquinolines from nitroarenes
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An eco-friendly and efficient procedure for synthesis of 2-methylquinoline derivatives from nitroarenes has been developed by a simple one-pot reaction on the surface of platinum-loaded TiO2 with neat ethanol under UV irradiation without any harsh reagent according to green chemistry. TiO 2 catalysts with various amounts of Pt loadings were prepared by photodeposition using chloroplatinic acid solution and characterized by XRD, BET, AFM, HR-TEM, XPS, and DRS. XRD patterns showed that the crystal structure of Pt-TiO2 still remained as anatase phase. The UV-vis spectra indicated that Pt promoted the absorption of visible light. The XPS measurements reveal that platinum particles are present mainly in metallic form. AFM and HR-TEM analysis revealed the presence of nonspherical shaped platinum nanoparticles of the diameter 312 nm. Pt-TiO2 on irradiation induces a combined redox reaction with nitroarene and alcohol and this is followed by condensationcyclization of aniline and oxidation products to give 2-methylquinolines
- Selvam, Kaliyamoorthy,Swaminathan, Meenakshisundaram
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experimental part
p. 953 - 959
(2011/10/18)
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- An efficient copper-catalyzed synthesis of anilines by employing aqueous ammonia
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Under the catalysis of CuI/2-carboxylic acid-quinoline-N-oxide, the cross coupling reactions between aryl iodides or bromides and aqueous ammonia proceed very well to afford N-unprotected aniline derivatives in excellent yields. This inexpensive catalytic system shows great functional group tolerance and excellent reaction selectivity. The Royal Society of Chemistry 2011.
- Zeng, Xin,Huang, Wenming,Qiu, Yatao,Jiang, Sheng
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supporting information; experimental part
p. 8224 - 8227
(2012/04/04)
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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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- Copper/oxalohydrazide/ketone catalyzed synthesis of primary arylamines via coupling of aryl halides with aqueous ammonia in water
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The coupling reaction of aryl halides with aqueous ammonia was catalyzed by copper/oxalohydrazide/ketone system in water to yield primary arylamines without inert atmosphere. This method was fast and facile. The coupling reaction proceeded at 90 °C for 20-80 min, or at room temperature for a prolonged reaction time. A variety of aryl bromides and iodides were found to be applicable to this three-component catalytic system, which afforded good to excellent isolated yields.
- Li, Ying,Zhu, Xinhai,Meng, Fei,Wan, Yiqian
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experimental part
p. 5450 - 5454
(2011/08/06)
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- Efficient copper-catalyzed direct amination of aryl halides using aqueous ammonia in water
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The N2,N2′-diisopropyloxalohydrazide/CuO system efficiently catalyzed the direct amination of aryl bromides andiodides with aqueous ammonia in water at 60 °C in 24 h or at 120 °C in only 20-30 min. Both activated and unactivated aryl and heteroaryl bromides and iodides were readily aminated in good to excellent yields. A highly efficient N 2,N2′-diisopropyloxalohydrazide/CuO system was developed for the direct amination of aryl halides with aqueous ammonia in water at 60 °C for24 h or at 120 °C for 20-30 min. The resulting aromatic primary amines were obtained in good to excellent yields.
- Meng, Fei,Zhu, Xinhai,Li, Ying,Xie, Jianwei,Wang, Bo,Yao, Junhua,Wan, Yiqian
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supporting information; experimental part
p. 6149 - 6152
(2010/12/29)
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- Efficient copper-catalyzed coupling of aryl chlorides, bromides and iodides with aqueous ammonia
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The copper(i)-catalyzed synthesis of a range of primary anilines from electron-rich and electron-deficient aryl halides including aryl chlorides has been achieved with aqueous ammonia, avoiding the need for inert atmosphere, expensive catalysts and ligands, anhydrous solvents, and additional base or other additives. The Royal Society of Chemistry 2009.
- Xu, Hanhui,Wolf, Christian
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supporting information; experimental part
p. 3035 - 3037
(2009/12/01)
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- An efficient copper-catalyzed amination of aryl halides by aqueous ammonia
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The copper(I) bromide/1-(5,6,7,8-tetrahydroquinolin-8-yl)-2-methylpropan-l- one (CuBr-LS) combination catalyzed the cross-coupling reactions between aryl or heteroaryl halides and aqueous ammonia with high yields to produce primary aromatic or heteroaromatic amines at room temperature or under mild conditions.
- Wang, Deping,Cai, Qian,Ding, Ke
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supporting information; experimental part
p. 1722 - 1726
(2011/02/25)
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- Ammonium salts as an inexpensive and convenient nitrogen source in the Cu-catalyzed amination of aryl halides at room temperature
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Convenient and inexpensive ammonium salts such as NH4Cl and aqueous NH3 solution are found to be readily utilized in the Cu-catalyzed room temperature N-arylation of aryl halides, providing N-unprotected aniline derivatives in high yields. The Royal Society of Chemistry.
- Kim, Jinho,Chang, Sukbok
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supporting information; scheme or table
p. 3052 - 3054
(2009/02/04)
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- Triarylamine-based compound for organic electroluminescent device and organic electroluminescent device employing the same
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A triarylamine-based compound represented by Formula (1), and an organic electroluminescent device using an organic layer including the triarylamine-based compound are provided: where each of Ar1 to Ar8 is independently a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2-C30 heteroaryl group. The triarylamine-based compound has superior electric properties and charge transport abilities, and thus is useful as a hole injection material and a hole transport material which are suitable for fluorescent and phosphorescent devices of all colors, including red, green, blue, and white colors. The organic electroluminescent device manufactured using the triarylamine-based compound has high efficiency, low voltage, high luminance, and a long lifespan.
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- 4-(Phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives and process for preparing the same
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The present invention relates to 4-(phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives which inhibit tyrosine kinase of epidermal growth factor receptor (EGFR), and pharmaceutically acceptable salts, hydrates and solvates thereof, and a process for preparing the same. Since 4-(phenylamino)-[1,4]dioxano[2,3-g]quinazoline derivatives of the invention have a high solubility in water and inhibit the activity of EGFR tyrosine kinase and the growth of cancer cells, they can be practically applied in the treatment of overproliferation-associated diseases such as cancer.
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- Direct Aromatic Amination by Azides: Reactions of Hydrazoic Acid and Butyl Azides with Aromatic Compounds in the Presence of Both Trifluoromethanesulfonic Acid and Trifluoroacetic Acid
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Reactions of hydrazoic acid with aromatic compounds in the presence of both trifluoromethanesulfonic acid (TFSA) and trifluoroacetic acid (TFA) efficiently gave primary arylamines without diamine contaminants.The reactions provide mainly the ortho- and para-monoamines wven for readily oxidised aromatic compounds such as cumene, mesitylene, durene, isodurene and anisole.The mechanistic investigation demonstrates that the reactions proceed via a concerted process involving both arene attack on a conjugate acid of the azide and elimination of N2 from the conjugate acid.The reaction of butyl azide with benzene and mesitylene in the presence of both TFSA and TFA produced N-butylarylamines in low yields together with high yields of butanal via a butylnitrenium ion intermediate; a similar reaction with tert-butyl azide gave no tert-butylarylamines.
- Takeuchi, Hiroshi,Adachi, Taki,Nishiguchi, Hideaki,Itou, Katsutaka,Koyama, Kikuhiko
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p. 867 - 870
(2007/10/02)
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- Process for the preparation of 3,5-dimethylaniline (sym. m-xylidine)
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The invention provides a process for the preparation of 3,5-dimethylaniline by catalytically dehydrogenating 3,5-dimethyl-cyclohexenone oxime in the gaseous phase. The catalyst contains at least one noble metal of the 8th subgroup of the Periodic Table.
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- Dinuclear Palladium(II) Complexes Containing Anilide Anions as Bridging Ligands
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The reactions of with aniline and its derivatives (L) in benzene at room temperature afforded 3)L>, (hfac), and (hfac)2 depending on the reactants mole ratio.On the other hand, the reactions of various complexes with L in refluxing benzene (in most cases) gave rise to the anilide-bridged dinuclear complexes 2, which in turn reacted with primary amines and pyridine (L') to produce 2(β-dik)2.
- Okeya, Seichi,Yoshimatsu, Hisako,Nakamura, Yukio,Kawaguchi, Shinichi
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p. 483 - 491
(2007/10/02)
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