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关键词： 3-苯基丙烯酸甲酯   对轻基苯甲酸乙酯   TiO2/SO42-   硫酸锆   双缩醛(酮)   微波辐射   合成  

摘要： 本文共分3章: 第1章:综述了近年来MxOy/SO42-（M=Zr,Ti,Fe）型催化剂在有机合成中的应用,并对其今后的发展趋势作了预测。MxOy/SO42-是一种新型固体超强酸催化剂,因其具有独特的酸性、高活性、高选择性、不怕水、耐高温、制备方便、无三废污染、简化产品分离程序等优点,是一类对环境友好的催化剂,有着广泛的应用前景,倍受人们的关注和重视。 第2章:近年来,固体超强酸已经被广泛的应用在有机合成中。固体超强酸是一类比无机酸还强的酸。它有许多优点,如,高活性、无毒、无味、无腐蚀、无污染、不挥发、高稳定性。我们用此类催化剂催化了一些有机反应,得到了较好的结果。如,用固体超强酸催化,合成了3-苯基丙烯酸甲酯和对羟基苯甲酸乙酯。该方法具有反应条件温和、反应时间短、操作简单、对环境友好等特点,优化了反应条件。 第3章:季戊四醇双缩醛和双缩酮化合物广泛用作高分子材料的增塑剂、固化剂、抗氧化剂等树脂的添加剂,亦可用作杀虫剂和阴离子表面活性剂清洗液的消泡剂。此外,季戊四醇双缩醛和双缩酮化合物在稀酸性条件下经水解生成原来的醛和酮,因而,又可用于醛、酮羰基的保护。 微波辐射是近十几年来新兴的一种实验技术,已广泛地应用于有机合成反应。微波技术与常规加热方法相比,具有反应体系受热均匀、促进反应分子间的碰撞几率、缩短反应时间、提高反应收率等特点。我们将微波辐射硫酸锆-硅胶催化用于该反应,取得了令人满意的结果,本文方法未见文献报道。

关键词： 充氢   烯烃   脂肪族不饱和烃   有机合成   化学合成   高级醇   一元醇   锂电池  

关键词： .high yield   primary alcohols   Phosphonium   Mitsunobu reaction   uoromethanesulfonate   phosphine oxide   ic anhydride   useful reagent   tetraphenyl oxa   polymer-supported triphenylphosphine   use of azodicarboxylates  

摘要： Two novel dehydrating reagents 3 and 4, based on a phosphonium anhydride and an oxyphosphonium triflate respectively, were prepared by reaction of the corresponding polymer-supported phosphine oxides with triflic anhydride. Reagent 3, based on the novel phosphorus heterocycle 1,1,3,3-tetraphenyl-2-oxa-1,3-diphospholanium bis(trifluoromethanesulfonate), was found to be a useful reagent for ester and amide formation. A wide range of coupling/dehydration-type reactions, such as ester, amide, anhydride, peptide, ether and nitrile formation, were performed in high yield using the more readily prepared polymer-supported triphenylphosphine ditriflate 4, which was easily recovered and re-used several times without loss of efficiency. With primary alcohols, both reagents 3 and 4 provide an alternative to the Mitsunobu reaction, where the use of azodicarboxylates and chromatography to remove the phosphine oxide by-product can be avoided. The use of 4-dimethylaminopyridine allowed the esterification of secondary alcohols with 4 to proceed in high yield but with retention of configuration.

关键词： Catalysis  

摘要： Biocatalysis offers mild reaction conditions, an environmentally attractive catalyst-solvent system, high activities, and chemo-, regio-, and stereoselectivities, while the use of enzymes generally circumvents the need for functional group activation and avoids protection/deprotection steps required in traditional organic syntheses. This review, using beta-lactam antibiotics as an example, discusses recent advances in biocatalysis research towards the goal of 'green' methodologies for the manufacture of (fine) chemicals and the emulation of a cell's enzymatic cascade processes.

关键词： 催化   合成   1，1一二乙酸酷   芳香磺酞亚胺类化合物   香豆素  

摘要： 本文共分三部分： 第一部分：硅胶负载四水硫酸锆催化1，1—二乙酸酯的合成及裂解。四水硫酸锆是一种酸性催化剂，由于它价廉易得且反应过程中无腐蚀、无污染，已应用于有机合成中。第一节介绍了硅胶负载的四水硫酸锆为催化剂由醛与乙酸酐反应合成1，1—二乙酸酯。此方法的特点在于醛与酮同时存在时，只有醛反应生成1，1—二乙酸酯，而酮不发生反应。该方法具有反应时间短、操作简单、收率高、催化剂易回收等特点。第二节介绍了硅胶负载的四水硫酸锆为催化剂由1，1—二乙酸酯发生裂解反应生成相应的醛，反应的收率较高。传统的方法是使用硫酸或盐酸为催化剂，但这些催化剂不能回收、易腐蚀设备、污染环境且产率较低。而以硅胶负载四水硫酸锆催化裂解1，1—二乙酸酯，其方法具有反应时间短、收率高、环境友好、易操作等特点。 第二部分：固体超强酸酸催化芳香磺酰亚胺类化合物的合成。该部分分别介绍了TiO2／SO42-催化及微波辐射zrO2／S282-催化，芳香醛与对甲苯磺酰胺或苯磺酰胺作用合成芳香磺酰亚胺类化合物的方法。这两种方法均具有操作简单、收率高、催化剂价廉易得且可回收重复使用等优点。 第三部分：该部分介绍了微波辐射硅胶负载的四水硫酸锆催化，酚与乙酰乙酸甲酯或乙酰乙酸乙酯作用合成香豆素的方法。该方法具有速率快、产率高，催化剂价廉易、腐蚀小、对环境友好、可回收重复使用等优点。

关键词： 相转移催化剂   聚乙二醇400   三甲基硅睛   三甲硅基拟卤类化合物   二氧化氯   芳酞睛   乙酞睛   硫代乙酸醋   间澳苯甲醚  

摘要： 本文研究了相转移催化剂聚乙二醇400在无水条件下的固—液相有机合成反应中的应用，全文共分为五章。 第一章：室温、搅拌条件下，以三甲基氯硅烷和氰化钾为反应原料，聚乙二醇400为相转移催化剂，碘化锌为助催化剂，合成了三甲基硅腈。碘化钠，碘化钾，碘化锌作为助催化剂的选择中，以碘化锌的助催化效果最佳。反应在乙腈中进行2小时，GC检测产物比例92％，但溶剂与产物形成共沸物，不能分离。二氯甲烷作溶剂时反应时间为24小时，产物可以与溶剂分离，且纯度较高。超声波条件下反应时间大大缩短至6小时。 第二章：在聚乙二醇400和碘化锌作用下，三甲基氯硅烷、三乙基氯硅烷分别与氰酸钠、硫氰酸钾、氰化钠、叠氮化钠、乙酸钠、丙酸钠、苯甲酸钠在二氯甲烷中反应，较高收率地制备了两类重要的有机合成试剂—三烷硅基类卤化物和三甲硅基羧酸酯类化合物。并且首次研究了聚乙二醇400催化下三甲基氯硅烷与无机含氧酸盐硝酸钠、亚硝酸钠、碳酸钠、亚硫酸钠和氯酸钾的反应，其中与氯酸钾的反应生成了二氧化氯。 第三章：室温搅拌条件下，以二氯甲烷作溶剂，芳酰氯与氰化钾在聚乙二醇400和碘化锌催化下合成出了九种芳酰腈，条件温和，二聚物生成较少。并且进行了三甲基硅腈与乙酰氯一锅法制备乙酰腈的研究，除得到乙酰腈外，还意外地制得了α—三甲基硅氧基丙烯腈。 第四章：室温搅拌条件下，卤代烷与硫代乙酸和碳酸钠在聚乙二醇400催化下在二氯甲烷中反应，高产率地制备了硫代乙酸烃酯。反应条件温和，时间短，操作简便，溶剂可回收利用，具有应用于大规模生产的开发前景。 第五章：以硝基苯为原料，经溴代，还原，重氮化，重氮盐水解和醚化反应合成了间溴苯甲醚。醚化反应在聚乙二醇400催化和无溶剂条件下进行。

关键词： 有机合成化学   苯磺酰胺   1,2,4-三唑   小麦叶锈病  

摘要： 由1-(甲)氨基-2-(1H-1,2,4-三唑-1-基)-4,4-二甲基-3-戊酮和苯磺酰氯类化合物发生取代反应合成了6个未见文献报道的三唑化合物,其化学结构经IR,1HNMR,MS和元素分析确证.目标化合物的生物活性数据表明,该类化合物对小麦叶锈病有良好的防治效果.

关键词： Salts   Purification   Ethers   Chemical reactions   Solvents  

摘要： [GRAPHICS] The efficiency of ionic liquid supported synthesis was demonstrated by the Suzuki reaction of ionic liquid supported iodobenzoate compounds with arylboronic acids in aqueous media to give, after cleavage with ammonia/methanol, biaryl products in good yields and high purities, without the need for chromatographic purification.

关键词： epoxides   oxidations   catalysis   bismuth   oxygen  

摘要： This article focuses on stoichiometric and catalytic epoxide oxidations and their scope in organic synthesis. The work on Bi/O-2-catalysed oxidation, developed in our group over the last last ten years, is presented with various reactions leading to several oxidised compounds. 1 Introduction 2 Epoxide Oxidations Involving C-C Bond Cleavage 2.1 Stoichiometric Oxidations 2.2 Catalytic Oxidations 3 Epoxide Oxidations Without C-C Bond Cleavage 3.1 Stoichiometric Oxidations 3.2 Catalytic Oxidations 4 Conclusion.

关键词： automated synthesis   combinatorial chemistry   flow-through processes   monolithic materials   polymers   reactors  

摘要： As part of the dramatic changes associated with the need for preparing compound libraries in pharmaceutical and agrochemical research laboratories, the search for new technologies that allow automation of synthetic processes has become one of the main topics. Despite this strong trend for automation high-throughput chemistry is still carried out in batches, whereas flow-through processes are rather restricted to production processes. This is far from understandable because the main advantages of that approach are facile automation, reproducibility, safety, and process reliability, because constant reaction parameters can be assured. Indeed, methods and technologies are missing that allow rapid transfer from the research level to process development without time-consuming adaptation and optimization of methods from the laboratory scale to production plant scale. Continuous-flow processes are considered as a universal lever to overcome these restrictions and, only recently, joint efforts between synthetic and polymer chemists and chemical engineers have resulted in the first continuous-flow devices and microreactors;these allow rapid preparation of compounds with minimum workup. Many of these approaches use immobilized reagents and catalysts, which are embedded in a structured flow-through reactor. It is generally accepted, that for achieving best reaction and kinetic parameters for convective-flow processes monolithic materials are ideally suited as solid phases or polymer supports. In addition, immobilization techniques have to be developed that allow facile regeneration of the active species in the reactor.