萘并呋喃类化合物的合成研究进展

萘并呋喃是一类重要的有机芳杂环,其分子骨架不仅是许多天然产物、药物分子的核心结构,而且还是重要的有机合成中间体,在材料化学中也具有广泛的应用价值。因此,萘并呋喃及其衍生物的合成一直是有机合成的研究热点之一。本文将对已有的萘并呋喃类化合物的主要合成策略、方法,结合笔者课题组的部分研究工作进行综述,包括如下几个方面:(1)碱或酸促进的环化反应;(2)过渡金属催化的串联环化反应;(3)自由基引发的环化反应;(4)其他非金属催化的环化反应。最后展望了萘并呋喃衍生物合成的研究和发展方向。     

有机化学实验的新模式

现行的一些高等学校有机化学实验教材的编写模式承袭了几十年前的方式,由基本操作、性质实验、合成实验和部分鉴定实验等几部分组成.即使新版教材有所改进,仍然大体保留上述几部分内容[1,2].当前,基础教育课程改革正在深入进行,如果高等学校开设的实验还是较旧的内容,滞后于课程改革的形势,将会影响义务教育与普通高中的课程改革.下面对有机化学实验课程谈谈我们的设想与实践.     

对卤代烃消去反应实验修订的理解与思考

对苏教版高中化学教材选修5《有机化学基础》中卤代烃消去反应实验的3次修订做了比较研究。结合卤代烃消去反应的原理,进行了实验反应物用量、反应装置、反应条件、产物检验的分析与思考。提出在教材实验改进中应使操作更规范、现象更明确、指导更具针对性,及对反应条件选择和实验装置创新的改进建议。     

谈溴苯的制备实验

高中化学实验中溟苯的制备在有机化学中具有十分重要的地位,是讨论苯的取代反应的重要依据和基础。而按教材中该实验方案演示,存在如下不足之处。     

有机染料靛蓝的合成与应用——介绍一个国外本科生实验并讨论其相关问题

介绍一个国外大学有机化学实验——有机染料靛蓝(Indigo)的合成,及后续比较其对于不同的合成织物或天然纤维的染色情况。对实验中3方面问题进行了分析讨论,而这在国外的实验教材中并没有涉及到,即靛蓝合成过程的反应机理、靛蓝对纤维织物染色的原理以及关于靛蓝对纤维织物染色过程的讨论。该实验的设计值得借鉴于国内本科生有机化学实验。     

有效合成5—硝基呋喃烯衍生物

报道了一种有效合成５－硝基呋喃烯衍生物的方法。在常温、弱碱Ｋ２ＣＯ３存在下（ｔｒａｃｅＨ２Ｏ），５－硝基呋喃亚甲基溴化钾盐与芳醛反应，高产率、高立体选择性地得到５－硝基呋喃烯衍生物。     

金催化的环化反应与钯催化的炔醇偶联/环化反应相结合用于合成多取代呋喃衍生物:串联反应的应用范围(英文)

开发了一种由金和钯催化π-活化由炔醇合成呋喃衍生物的集成方法.该合成策略是最显著的特点适用于带环辛基的底物,其适用范围比之前报道的有很大扩展.在Sonogashira反应条件下,由相应底物可直接得到环辛基呋喃.Pd在这些反应中起到2个重要作用:底物发生偶联反应的关键催化剂;通过π-活化促进炔醇中间体成环反应.该方法在一步合成3-碘呋喃反应中作用很突出,使通过偶联法进一步官能团化成为可能.我们还将AuBr_3用于多米诺成环/C-H键活化反应和无环前体的成环反应.本文结果表明,在该类成环反应中金和钯催化剂相辅相成.     

微型化有机合成实验的实践

１前言微型化有机化学实验有降低学生实验费用、节约时间、减少实验的污染物排放、有利于学生实验技能提高等诸多好处，因此，有机化学实验教学工作者一直为微型化有机实验在努力，比较有机化学实验的新老教材，许多有机合成实验的试剂用量都已大大减少［’，’］，但是，真正毫克级的微型化实验对学生来说因操作难度过大而不易实用化。但随着实验技术的发展，在科研中毫克级的合成己广泛应用，因此，对学生进行毫克级的合成反应实验训练已是迫切需要。本文建立了一套在学生实验中实用的薄层色谱操作，并用之于分析、监测反应、判断产物纯度…     

4′-{2-[5-(4-羧基苯基)呋喃基]}-2,2′:6′,2″-三联吡啶的合成——推荐一个大学有机化学实验

介绍一个面向大学高年级本科生的综合性有机化学实验——4′-{2-[5-(4-羧基苯基)呋喃基]}-2,2′:6′,2″-三联吡啶的合成与结构表征。以糠醛、对氨基苯甲酸为原料经低温条件下的偶联反应制备5-(4-羧基苯基)呋喃-2-甲醛,并以其和2-乙酰基吡啶为原料,在碱性条件下以氨水为氮源合成目标产物。通过熔点测定、红外光谱和核磁共振氢谱对其结构进行表征。该实验合成路线成熟,包括芳环偶联、α,β-不饱和酮的合成、Michael加成等内容,能达到多方面对学生进行锻炼之目的,是一个值得推荐的有机化学实验。     

取代呋喃的合成新方法

本文提供了一种合成2-取代呋喃和2,5-二取代呋喃的方法,即通过碘代烃与末端炔丁醇发生Sonogashira偶联反应,生成3-炔-1-醇,再在Dess-Martin Periodinane的作用下发生异构环化得到一系列2-取代呋喃和2,5-二取代呋喃类化合物。通过该方法得到4种目标物,其结构经~1H NMR、~(13)C NMR和HRMS得到确证。     

Covalent Organic Frameworks for Photocatalytic Organic Transformation

Photocatalytic organic transformation is an efficient, energysaving and environmentally friendly strategy for organic synthesis. The key to developing a green and economical route for photocatalytic organic synthesis lies in the construction of optimal photocatalysts. Covalent organic frameworks(COFs), a kind of porous crystalline materials with characteristics of high surface area, excellent porosity, and superior thermo-chemical stability, have driven people to explore their potential as photocatalysts in photocatalytic organic transformations by virtue of their structural versatility and designability. Furthermore, the insolubility of COFs makes it possible to recycle the catalysts by simple technical means. In recent years, researchers have made great efforts to develop both the design strategies of COFs as heterogeneous photocatalysts and the reaction types of photocatalytic organic transformations. In this review, we focus on the design of COF-based photocatalytic materials and analyze the influence factors of photocatalytic performance. Moreover, we summarize the application of COFbased photocatalysts in photocatalytic organic conversion. Finally, the perspectives on new opportunities and challenges in the field are discussed.     

Binding of Organic Pollutants to Soil Organic Matter

Abstract

Binding of organic pollutants to water-soluble, low-molecular weight humic substances increases their mobility in soil and their leaching, whereas binding to high-molecular weight humic substances results in unextractable residues. Water-soluble pollutants in leachate may be bound to low-molecular weight humic material, or may be free water-soluble conversion products that are slowly released from a soil-bound form, as shown for a conversion product of the insecticide aldrin. Unextractable soil-bound 4-chloroaniline was isolated by supercritical methanol extraction 16 years after application of the phenylurea herbicide buturon to soil. Biodegradation and bioavailability of unextractable soil-bound residues are greatly reduced as compared to the free compounds. For some chlorinated anilines and phenols, biomineralization and plant uptake was shown to be highest for residues bound in fulvic acids and lowest for those in humic acids. Model experiments demonstrate that chlorinated anilines form covalent bonds with humic acid precursors.     

Organic optocouplers

Organic optocoupler(OOC) or organic photocoupler,optical coupler is a novel and one of the most promising organic optoelectronic devices for its well electrical isolation and anti-jamming ability in long-distance and real-time digital communications.The performance parameters of OOC were greatly raised during the past decade,and its development was strongly associated with basic organic devices such as organic light emitting diodes(OLED),organic photodiodes(OPD) and organic phototransistors(OPT) etc.Here we...     

Organic superconductors

The present status of organic superconductors of charge‐transfer (CT) type based on donor molecules is reviewed. Along with the superconducting phases of such materials and also of oxide superconductors, reside spin‐ordered phases such as spin‐density wave (SDW) and antiferromagnetic (AF) phases. We briefly describe the recent development of superconductors having a superconducting phase next to a spin‐disorder state (quantum spin liquid state). In addition to the CT type superconductors, there are a few single‐component superconductors under high pressure. DOI 10.1002/tcr.201000039     

Organic Superhalogens

Using first‐principles calculations with predictive capability we show that organic molecules having negative electron affinity can be transformed to superhalogens with electron affinities far exceeding that of chlorine, once its core and ligand atoms are suitably replaced. The discovery of organic superhalogens could have significant impact in chemistry, allowing the synthesis of new materials and compounds.     

有机复合光电导材料及器件研究进展

有机光电导复合材料已经成为当前国际上有机光电材料科学研究的前沿与热点之一。复合化是大幅度提高有机半导体材料光电导性能的有效手段,本文主要从有机光电导材料的复合化角度,综述了新型高效的多种有机复合光电导材料体系的制备及其光电导性能,初步解释了其相应的复合原理和光电导机理,并介绍了其在单层型光电导器件中的研究进展。最后提出了制备高性能有机光电导复合材料及单层型光电导器件的几点建议。