吲哚及其衍生物合成的研究进展

吲哚及其衍生物是重要的精细化工原料和化工产品,评述了吲哚及其衍生物的化学合成方法.     

吲哚、二氢吲哚的研究进展

本文介绍了吲哚及其衍生物的用途,应用前景,研究现状.综述了利用Heck反应合成吲哚衍生物的方法.     

固体酸SO4/ZrO2区域选择性催化合成吲哚3位酰基化衍生物

研究了固体酸SO4/ZrO2区域选择性催化吲哚3位傅-克酰基化的反应.实验结果确定了吲哚及其衍生物在固体酸催化下的酰基化反应条件.通过吲哚衍生物和酰氯的酰基化反应合成出了一系列高区域选择性的吲哚系化合物,实验均取得了良好的效果.此方法为吲哚及其同系物的合成提供一条较为优化、绿色的合成新途径.     

异吲哚啉衍生物的合成及应用进展

作为一类结构特殊且具有多种用途的重要含氮杂环化合物,异吲哚啉衍生物在医药化工等行业发挥着重要作用,尤其在药物分子设计合成及染料领域有着重要的应用。近年来,异吲哚啉及其衍生物的合成得到了快速的发展,各种异吲哚啉衍生物被合成,尤其是多取代异吲哚啉衍生物的合成及活性研究得到了广泛的关注。本文综述了异吲哚啉衍生物的合成方法,并对其在医药和化工领域的应用进行了介绍。     

吲哚化合物合成研究进展

吲哚及其衍生物是一类重要的杂环化合物和化工产品中间体,由于它性质独特,使得在医药、农药和香精香料等领域中具有广泛的应用,鉴于吲哚及其衍生物的广泛应用,人们对这类化合物的合成方法展开了一系列较为深入的研究工作,目前关于吲哚类衍生物已有多种有效的合成方法,本文主要综述了近年来吲哚衍生物较为有效的合成方法。     

吲哚衍生物合成方法研究新进展

吲哚及其衍生物具有非常重要的生物和药理活性,广泛应用于农业、医药等领域中。因此对吲哚及其衍生物合成方法的研究也越来越多。近年来经过化学家的努力,以2-炔基芳香胺分子内环化和芳香胺类化合物与炔反应来合成吲哚衍生物都取得了很大的进展,成为了重要的合成方法。主要对近十年来这两类方法即2-炔基芳香胺在各种不同催化条件下的分子内环化和各种不同取代的芳香胺类化合物与炔反应合成吲哚衍生物的研究进展进行了综述。     

RuCl_3催化下一锅化合成双吲哚甲烷

吲哚及其衍生物具有各种药理学和生物学特性,包括:抗菌,细胞毒性,抗氧化,及杀虫活性。本文报道了一种简便的合成双吲哚甲烷衍生物的方法:在室温条件下,乙二醇二甲醚溶剂,RuCl_3·3H_2O作用下苄醇和吲哚反应来生成双吲哚甲烷衍生物。     

医药化工中的一些重要吲哚化合物

介绍了吲哚及十几种吲哚化合物的性质、合成方法以及在医药领域中的应用简况,这些吲哚衍生物如：3-醛基吲哚-5-甲酸乙酯,5-甲氧基吲哚,3,3,-二吲哚甲烷（DIM）等。许多吲哚及其衍生物在治疗癌症．艾滋病、心血管疾病以及骨风湿性疾病、消炎、镇痛等医药治疗方面取得了显著成就,故对其相关化合物作了重点叙述。例如：MCM-41负载Lewis酸催化合成2-甲基吲哚,5-甲氧基吲哚,吲哚甲基海英的合成等。已经表明,吲哚及其衍生物在医药化工领域中的应用具有很好的前景,值得引起关注和进-步研究和开发。     

医药化工中的一些重要吲哚化合物

介绍了吲哚及十几种吲哚化合物的性质、合成方法以及在医药领域中的应用简况,这些吲哚衍生物如：3-醛基吲哚-5-甲酸乙酯,5-甲氧基吲哚,3,3,-二吲哚甲烷（DIM）等。许多吲哚及其衍生物在治疗癌症,艾滋病、心血管疾病以及骨风湿性疾病、消炎、镇痛等医药治疗方面取得了显著成就,故对其相关化合物作了重点叙述。例如：MCM-41负载Lewis酸催化合成2-甲基吲哚,5-甲氧基吲哚,吲哚甲基海英的合成等。已经表明,吲哚及其衍生物在医药化工领域中的应用具有很好的前景,值得引起关注和进一步研究和开发。     

表面活性剂和盐酸高效催化二吲哚甲烷的合成

二吲哚甲烷及其衍生物是很多生理活性分子的重要构成部分,我们开发了一种新的合成二吲哚甲烷及其衍生物的方法。在10mol%的十二烷基苯磺酸钠和盐酸的共同催化下,吲哚和醛、酮在60℃下能顺利、高效的发生反应得到二吲哚甲烷衍生物。在最优的反应条件下,我们对醛和酮的适用范围进行了考察。催化剂循环使用研究表明,该催化体系在循环使用五次后仍能保持很好的催化活性。     

Heterogeneous Palladium Catalysts Applied to the Synthesis of 2‐ and 2,3‐Functionalised Indoles

Heterogeneous palladium catalysts ([Pd(NH₃)₄]²⁺/NaY and [Pd]/SBA‐15) were applied to the synthesis of 2‐functionalised indoles, giving generally high conversions and selectivities (>89% yield) using only 1 mol % [Pd]‐catalyst under standard reaction conditions (polar solvent, 80 °C). For the synthesis of 2,3‐functionalised indoles by cross‐coupling arylation, the [Pd]/SBA‐15 catalyst was found to be particularly interesting, producing the expected compound with =35% yield after 12 days of reaction, which is comparable to the homogeneous catalyst, Pd(OAc)₂ (=48% yield). In the course of the study, the dual reactivity of the indole nucleus was demonstrated: aryl bromides gave clean C C coupling while aryl iodides led to a clean C N coupling.     

Heterogeneous hydrogenation of nitrobenzenes over recyclable Pd(0) nanoparticle catalysts stabilized by polyphenol-grafted collagen fibers

A novel heterogeneous palladium (Pd) nanoparticle catalyst stabilized by collagen fibers (CF) was synthesized. Epigallocatechin-3-gallate (EGCG), a typical natural polyphenol, was grafted onto the CF surface to improve the stabilization and immobilization of Pd(0) nanoparticles. The main physical and chemical properties of the catalyst were characterized by means of Scanning Electron Microscopy, Fourier Transform-Infrared Spectroscopy, X-ray Photoelectron Spectroscopy, X-ray Diffraction and Transmission Electron Microscopy. This catalyst is in an ordered fibrous state with high flexibility. The Pd(0) nanoparticles with diameters of 3–4 nm are homogeneously dispersed onto the outer surfaces of CF, and they are stabilized by the coordinative interactions between the surface Pd atoms of nanoparticle and the surrounding oxygen and nitrogen atoms of the EGCG-grafted CF. These stabilized Pd(0) nanoparticles were found to be active and selective catalysts for nitrobenzene and its derivatives, directly hydrogenating to the correspondingly reductive anilines under mild conditions. Both Pd particle size and activity of the catalyst showed a marked dependence on the grafting degree of EGCG on CF. These catalysts can be easily recovered, reused multiple times, and stored for two months in air while maintaining high catalytic efficiencies. All these facts suggest that the EGCG-grafted CF can be used as an effective stabilizer for the preparation of Pd(0) nanoparticle catalysts.     

A study on the dispersion and catalytic activity of gamma alumina-supported palladium catalysts

Electron spectroscopy for chemical analysis (ESCA) and carbon monoxide adsorption techniques have been applied to study the percent exposed (i.e., dispersion) and Pd deposition in the pores of highly porous gamma alumina-supported Pd catalysts. A correlation has been found between Pd dispersion and its extent of penetration into the pores: more edge-coated catalysts are less dispersed. The dispersion of Pd is controlled by a carrier-catalyst interaction that originates in part from electron transfer from the support to the supported Pd. This electronic interaction is demonstrated by the broadening of the ESCA peaks. The activity of the catalysts, measured by the hydrogenation of nitrobenzene to aniline, is dependent on the dispersion of palladium.     

氢氧直接合成过氧化氢贵金属催化剂的研究

采用浸渍法制备了一系列负载型钯催化剂，用于催化氢气和氧气直接合成过氧化氢的反应。分别考察了钯负载节、溶剂、载体预处理对反应的影响；结合XPS分析推断了催化剂活性组分价态。结果发现钯最佳负载量为1．88％（质量分数）；氢气在溶剂中的溶解度越大其反应转化率也越高，其中甲醇和丙酮都是良好的溶剂；载体经过卤化铵预处理可大幅度地提高催化剂的选择性；金属态钯为具有催化活性的价态。     

苯甲酸加氢用钯碳催化剂的制备、失活及再生研究

研究了苯甲酸加氢用钯碳催化剂的制备、失活及再生。提出了钯碳催化剂的制备关键、加入甲烷化助剂可以延长钯碳催化剂寿命、利用超临界流体再生方法可以有效再生失活钯碳催化剂。     

Supported Pd Nanoparticles for Carbon–Carbon Coupling Reactions

We intent to present an overview of the available catalysts for the carbon–carbon cross-coupling reactions based on supported palladium (Pd) nanoparticles (NPs). We begin this perspective with a brief introduction about the cross-coupling reactions and the mechanistic implications of using Pd NPs as catalyst, i.e. heterogeneous versus homogeneous catalysis, then we summarize some of the most versatile Pd supported catalysts as a function of its nature. The supported catalysts have been classified in inorganic, organic and hybrid supports. Finally we outline the perspectives for the development of new Pd supported catalysts.     

One‐Pot/Four‐Step/Palladium‐Catalyzed Synthesis of Indole Derivatives: The Combination of Heterogeneous and Homogeneous Systems

One‐pot, four‐step syntheses of indoles using both solid‐supported heterogeneous and homogeneous palladium catalysts and reagents were carried out. Such a combination of these two‐phase catalysts and reagents causes a dramatic increase in yield, and it is a simple process. The presented methodology is effective for four‐step reactions to provide various functionalized indoles.     

对称四取代钯酞菁的合成及其对氯苯气相加氢脱氢的催化作用

1 INTRODUCTION Catalytic hydrodechlorination is an elegant reaction for disposal of environmentally hazardous chlorocarbons,such as chloro-benzene[1].Development of a new catalyst with excellent stability is necessary due to the deactivation of supported noble metal catalysts[1].However the modification of catalytic properties of catalysts in hydrodechlorination reaction by introducing stable ligands to noble metals has been the least studied.Here the synthesis of Pd(Ⅱ) 2,9,16,23-symetrically tetrasubstituted phthalocyanines PdPTX4 (where X=-H,-NO2,-NH2 respectively) from phthalimide derivatives is reported,and their application as catalysts in hydrodechlorination of chlorobenzene,which is a representative environmentally hazardous materials is discussed.     

Tungsten–palladium selective hydrogenation catalysts

Steady-state, steam-reforming rates for methane were measured on model and high-surface-area, ceria-supported Pd catalysts and compared to rates on Pd/silica between 600 and 825 K. Specific rates on Pd/ceria were higher than those on Pd/silica by a factor of 10 ⁵ and were higher even than rates reported in the literature for Ni catalysts. Model catalysts prepared with Pt or Rh on ceria also showed very high rates, essentially identical to rates for Pd/ceria. However, catalysts prepared by addition of Pd to ceria which had been calcined to high temperatures (>1175 K) before the addition of Pd were not active. Based on these results, we suggest that steam reforming on ceria-supported catalysts occurs through a bifunctional mechanism in which oxygen from ceria reacts with dissociated methane on the precious metal. High-temperature calcination of ceria significantly changes its reducibility, so that the reaction is not enhanced. This revised version was published online in August 2006 with corrections to the Cover Date.     

废催化剂中Pd的回收及循环利用

在六苄基六氮杂异伍兹烷(HBIW)的催化氢解反应中，所用催化剂是Pd(OH)2／C，而Pd属于贵金属，它的回收利用直接影响着最终产品的成本核算。对HB研的催化氢解反应中产生的废催化剂进行了回收，并将回收所得金属钯重新制备成催化剂。再次用于HBIW的催化氢解反应，其活性与以PdCl2为前体制备的催化剂活性相当。回收的金属钯纯度为99．6％，回收率为92％-94％。