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关键词： SELECTIVE DIRECT FLUORINATION   TOTAL ANALYSIS SYSTEMS   PROCESSINTENSIFICATION   HEAT-TRANSFER   USER ACCEPTANCE   MICRO REACTORS   PLANT CONCEPTS   ELEMENTAL FLUORINE   HELICAL FLOWS   IONIC LIQUIDS  

摘要： Micro-reaction technology is entering more and more into chemical process engineering and chemistry, complementing existing technologies. The benefits of microstructured reactors such as enhanced mass and heat transfer, defined residence time setting, and known, highly regular flow profiles give process intensification following standard chemical protocols. These unique features, however, can achieve more, namely to enable process chemistry with novel features. This includes handling of instable intermediates, safe processing in the explosive regime, setting reaction temperature at unusually high level, and more. In this way, the engineering benefits change the chemistry;thus, it has been termed novel chemistry here. While this has been done in a heuristic manner in the past, first deductive approaches were recently developed based on diffusion-reaction calculations and potential energy profiles which provide a mechanistic understanding what the new tool can do. In this context, many examples for organic reactions in microstructured reactors are described to underline the possible means of novel chemistry by using microstructured reactors.

关键词： transformations   carbon-hydrogen   carbonylation reactions   oxidative coupling   anti-markovnikov product   toluene   phenylation   palladium-catalyzed oxidative coupling   anilides  

摘要： Catalytic carbon-carbon bond formation using transition metal complexes typically incorporates the use of an aryl halide or triflate compound (electrophile) in combination with an organometallic reagent (nucleophile). Versatile synthetic methods that allow C-C bond formation of aromatic compounds that proceed through transformation of C-H bonds would be of substantial value. Potential routes for C-C bond formation with aromatic substrates include the hydroarylation of unsaturated compounds (e.g., olefins or alkynes) and oxidative coupling of aromatic compounds and olefins or alkynes. Such reactions can proceed through metal-mediated transformation of C-H bonds. The range of reported catalysts and catalytic cycles for these classes of reactions have been reviewed herein.

关键词： Hydrocarbons   Aromatic compounds   Alcohols   Crystal cleavage   Organic polymers  

摘要： A new, robust tert-butyldiarylsilyl (TBDAS) linker has been developed for solid-phase organic synthesis. This linker is stable to both protic and Lewis acidic reaction conditions, overcoming a significant limitation of previously reported silyl linkers. Solid-phase acetal deprotection, olefination, asymmetric allylation, and silyl protecting group cleblocking reactions have been demonstrated with TBDAS-linked substrates.

关键词： NUCLEOPHILIC-SUBSTITUTION REACTION   MICROEMULSIONS   SURFACTANT   COPOLYMERS   SILICA  

摘要： A common problem in synthetic organic chemistry is attaining proper contact between lipophilic organic compounds and inorganic salts. Various strategies, for example, phase transfer catalysis (Starks, C. M.;Liotta, C. L.;Halpern, M. Phase Transfer Catalysis: Fundamentals, Applications and Industrial Perspectives;Chapman & Hall: New York, 1994) or use of a microheterogeneous medium such as a microemulsion (Hager, M.;Currie, F.;Holmberg, K. Organic Reactions in Microemulsions. In Colloid Chemistry 11;Antonietti, M., Ed.;Topics in Current Chemistry 227;Springer-Verlag: Heidelberg, 2003;p 53) have been worked out to tackle the issue. Here, we report that mesoporous solid materials made from surfactant self-assembly can be used as medium for such reactions. The material is made from silica, and the pore size is large, relatively uniform, and can be controlled with a high degree of precision by the choice of surfactant that is being used as template (Palmqvist, A. E. C. Curr. Opin. Colloid Interface Sci. 2003 8, 145). The pores are hydrophilic and are filled with an aqueous solution containing the inorganic salt. The porous material is dispersed in the lipophilic organic substrate that is 4-tent-butylbenzyl bromide, or in a hydrocarbon solution of this substrate. The reaction occurs at the hydrophilic/lipophilic interface, and, because the interface is large, the reaction is fast. A considerable advantage with this new reaction medium is that the workup procedure is extremely facile. After the reaction is completed, the solid is simply removed by filtering or centrifugation.

关键词： diazo compounds   hydrazones   Bamford-Stevens reaction   epoxidation   aziridination   cyclopropanation   olefination   pyrazoles   homologation   ether synthesis  

摘要： Diazo compounds are useful synthetic intermediates in organic synthesis but, due to their toxicity and unpredictable explosive behaviour, their unique reactivity has not been fully exploited and their use on large scale has been avoided. We have developed a reliable method that generates diazo compounds in situ. Our approach is based on the Bamford-Stevens reaction, which utilizes tosylhydrazone salts as diazo precursors. In the presence of phase-transfer-catalysts (PTC), we found that tosylhydrazone salts can be cleanly converted to diazo compounds under mild reaction conditions and in a wide range of solvents. These diazo compounds can then be induced to react directly with alkenes or alkynes to synthesize pyrazoles or with aldehydes to generate ketones. Alternatively, diazo compounds can react with transition metals capable of carbene transfer reactions. We have shown the usefulness of this chemistry in a number of different transformations, such as Wittig olefination reactions and the sulfur ylide mediated epoxidation, as well as aziridination and cyclopropanation chemistry as applied toward the synthesis of more complicated molecules. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

关键词： 环氧烷   开环反应   微波反应   亲核试剂   生物活性   芳氧甲基  

摘要： 本文研究的主要目的是以环氧烷为原料，利用其与各种亲核试剂的亲核开环反应，探讨新的反应条件，合成新的具有潜在生物活性的化合物，并进而研究这些化合物的生物活性。本论文的研究工作大体分成了四个部分：\n　　1.以3-芳氧基-1，2-环氧丙烷与伯醇、仲醇及酚为原料，通过碱催化开环反应，区域选择性地合成1-烷氧基-3-芳氧基-2-丙醇以及1，3-二芳氧基-2-丙醇化合物，收率为79～98％。产物结构经过IR和1HNMR验证。\n　　2.在氧化铝催化下，以3-芳氧基-1，2-环氧丙烷和芳胺为原料，区域选择性地合成了一系列1-芳氧基-3-芳氨基异丙醇衍生物。收率为50～80％。产物结构均由IR、MS和1HNMR进行表征。\n　　3.以3-芳氧基-1，2-环氧丙烷和芳胺为原料，在无溶剂微波照射的条件下进行位置选择性反应，得到了15个1-芳氧基-3-芳氨基异丙醇化合物。收率50～80％。产物结构由IR、MS和1HNMR进行表征。\n　　4.以合成的1-芳氧基-3-芳氨基异丙醇衍生物为原料，首先与氯乙酰氯在碳酸钾存在下进行酰化反应，制备2-氯-N-(2-羟基-3-苯氧基丙基)-N-苯基乙酰胺，收率69～82％。然后得到的2-氯-N-(2-羟基-3-苯氧基丙基)-N-苯基乙酰胺在氢化钠存在下通过自身关环反应得到N-芳基-6-芳氧甲基-3-吗啉酮衍生物，收率76～92％。\n　　5.

关键词： 中国石油大连石化分公司   双向拉伸聚丙烯   助剂   生产能力   技术改革  

摘要： 由中国石油大连石化分公司有机合成厂开发的双向拉伸聚丙烯(BOPP)树脂专用料项目，通过了中国石油公司的验收。该项目于2003年11月开发，大连石化有机合成厂针对该产品的特殊性，选用了新型助剂，先后4次在70kt／a聚丙烯装置上进行试生产，形成了较完整的生产工艺。在汕头全国单线生产能力最大的德国高速双向拉伸薄膜机上试用结果表明，产品主要技术指标在同类产品中居领先水平。

关键词： 含钼催化剂   杂多酸   有机合成及应用  

摘要： 概述含钼杂多酸催化剂在有机合成中的应用,对这类杂多酸作为酸催化反应和氧化反应催化剂在烯烃水合、酯化、异构化、环氧化、醇类脱水、氧化等反应中的应用以及对可能的反应机理进行了讨论,并预测了该领域今后的发展方向。

关键词： 苯甲醛   绿色合成   缩醛   丁二醇   缩羰基化合物   反应中间体   废水排放量   后处理工艺   缩合反应   食品工业   日用化工   有机合成   无机强酸   反应时间   硫酸催化   设备腐蚀   催化剂   副反应   产物   香料  

摘要： 缩羰基化合物是由醛或酮与醇发生缩合反应的产物，近年来作为新型香料在日用化工和食品工业中均有广泛应用，也可用在有机合成的羰基保护或作为反应中间体，其中苯甲醛系列缩醛由于具有独特的新鲜果香香气、留香持久而占据着重要地位。工业上一般采用无机强酸如硫酸作为催化剂来合成，由于硫酸催化反应时间长，副反应多，对反应设备腐蚀严重，废水排放量大，后处理工艺复杂，

关键词： 有机合成化学   创新精神   素质教育   动手能力   实践教学   高校  

摘要： 传授新知识的同时,开发与培养学生的创新精神与创新能力是加强素质教育的核心。本文就有机合成化学教学环节中如何提高教学效果、切实加强学生的动手能力,开发与培养学生的创新精神与创新能力等问题进行了一些探讨。