排序方式: 共有157条查询结果,搜索用时 31 毫秒
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在苯、乙醚等溶剂中,CF_2Br_2与 PhSNa不反应或反应极慢.加入催化量的二苯并-18-冠-6,则反应在数分钟内完成,主产物 PhSCF_2Br 的产率提高至75~85%,副产物 PhSCF_2H 及 PhSSPh受到显著抑制.本体系明显优于最近文献报道的其他反应体系.讨论了反应机理,给出了表明反应主要是阴离子型链式机理的进一步证据:反应速度和产物分布对水、醇等给质子性杂质敏感,对氢原子供体型溶剂及光、氧、自由基捕获剂不敏感;在以 CCl_4为溶剂的反应中,得到 PhSCF_2Cl 和属于~-CCl_3的产物,而未检测到自由基型机理所预期的 CCl_3CCl_3. 相似文献
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[TPPFe(III)]~2O的合成及其对细胞色素P-450的模拟 总被引:3,自引:0,他引:3
TPPFe(III)Cl通过中性Al~2O~3色谱柱得到一个新化合物, 它在HPLC中的保留时间比TPPFe(III)Cl大得多, IR、UV-Vis和元素分析表明, 这个新化合物是[TPPFe(III)]~2O. 同TPPFe(III)Cl一样, 它具有在常温常压下催化碳氢化合物单充氧化的性质。[TPPFe(III)]~2O催化下PhIO氧化环己烷的反应, 在CH~2Cl~2和环己烷介质中, 氧化产率分别为14.97和62.6%, 高于TPPFe(III)Cl作催化剂时的产率。在环己烷溶剂中, 反应产率与反应时间呈线性关系, 且反应有大约3小时诱导期。但在CH~2Cl~2溶剂中不存在反应产物与时间的线性关系, 也不存在诱导期。与TPPFe(III)Cl比较,[TPPFe(III)]~2O对氧化剂更稳定。上述事实表明, [TPPFe(III)]~2O能够作为细胞色素P-450的模型化合物。 相似文献
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Jaromir Dmytrzyk Andrzej Kotarba Hanna Grabowska Roman Klimkiewicz 《Research on Chemical Intermediates》2004,30(3):337-342
The influence of gas-phase methylation of phenol on the state of the Fe-Si-Cr-K oxide catalyst surface was investigated by thermodesorption of K atoms and ions. Changes in potassium desorption energies, as determined from Arrhenius-like plots, varied from 3.07 eV to 1.21 eV for the atoms and from 2.59 eV to 2.89 eV for ion desorption from the active and deactivated samples, respectively. The results were discussed in terms of transformation of the catalyst surface and formation of β-ferrite. 相似文献
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We report a new structure-based strategy for the identification of novel inhibitors. This approach has been applied to Bacillus stearothermophilus alanine racemase (AlaR), an enzyme implicated in the biosynthesis of the bacterial cell wall. The enzyme catalyzes the racemization of l- and d-alanine using pyridoxal 5-phosphate (PLP) as a cofactor. The restriction of AlaR to bacteria and some fungi and the absolute requirement for d-alanine in peptidoglycan biosynthesis make alanine racemase a suitable target for drug design. Unfortunately, known inhibitors of alanine racemase are not specific and inhibit the activity of other PLP-dependent enzymes, leading to neurological and other side effects.This article describes the development of a receptor-based pharmacophore model for AlaR, taking into account receptor flexibility (i.e. a `dynamic' pharmacophore model). In order to accomplish this, molecular dynamics (MD) simulations were performed on the full AlaR dimer from Bacillus stearothermophilus (PDB entry, 1sft) with a d-alanine molecule in one active site and the non-covalent inhibitor, propionate, in the second active site of this homodimer. The basic strategy followed in this study was to utilize conformations of the protein obtained during MD simulations to generate a dynamic pharmacophore model using the property mapping capability of the LigBuilder program. Compounds from the Available Chemicals Directory that fit the pharmacophore model were identified and have been submitted for experimental testing.The approach described here can be used as a valuable tool for the design of novel inhibitors of other biomolecular targets. 相似文献
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一类新型的双β-氨基醇的合成及催化硼烷对芳酮的不对称还原反应 总被引:7,自引:0,他引:7
以L-半胱氨酸盐酸盐出发,经与二卤代烷偶联,成酯和格氏反应制得三种双手性β-氨基醇,1,2-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]乙烷(4a),1,3-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丙烷(4b),1,4-双[R-2-氨基-3-羟基-3,3-二苯基丙硫基]丁烷(4c)。将此类双手性β-氨基醇与硼烷在THF溶液中反应,in situ制备双手性恶唑硼烷催化硼烷对芳酮的不对称还原,产物苯乙醇的光学收率达72.8%、α-溴代苯乙醇的光学收率达91.4%。 相似文献
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Styrene-2-(methylsulfinyl)ethyl methacrylate copolymer-supported MCl3 complexes, where M = La, Pr, Nd, Eu, Ho, Er, Tm, and Yb, were prepared and characterized by IR spectroscopy. The catalytic activity of the polymer-supported NdCl3-(iso-Bu)3Al system towards stereospecific polymerisation of butadiene was 2-3 times higher than that of NdCl3-(iso-Bu)3Al-DMSO system. The cis-1,4 content of polybutadiene formed was >98%. 相似文献
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采用程序升温还原技术(TPR)研究CuO-Ag2O/γ-Al2O3双组分及其单组分催化剂的还原特性以及热处理温度对其还原性能的影响。发现不同负载量的Cuo-Ag2O/γ-Al2O3催化剂的还原特性有明显差异, 反映出催化剂表面存在着不同种类的铜物种。Ag2O的存在, 使催化剂的TPR峰位与单组分CuO/γ-Al2O3的TPR曲线产生明显差异, 还原峰发生位移, 随Ag2O添加量的增加, 位移增大。对苯的完全氧化反应结果表明, 催化剂的氧化活性次序为:CuO-Ag2O/γ-Al2O3>CuO/γ-Al2O3>Ag2O/γ-Al2O3。热处理温度升高, 使催化剂表面铜物种分散状态及其还原性能发生变化。从500~900℃, 存在一个使铜物种达到最佳分散态的温度。讨论了负载于γ-Al2O3载体上的CuO-Ag2O双组分及其单组分催化剂在还原过程中金属与载体, 金属与金属间的相互作用以及热处理温度对其还原性能的影响。 相似文献
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