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Chemical Modifications of Furan-Based Calixarenes by Diels-Alder Reactions

机译:Diels-Alder反应对呋喃基杯芳烃的化学修饰

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摘要

The simple chemical modification by Diels-Alder reacrtions of the cyclic hexamer of furan and acetone, utilising two readily accessible dienophiles, benzyne and dimethylacetylenedicarboxylate (DMAD),is described. The studies have explored the ease with which different furan units within the macrocycle can be converted into either naphthalenes, o-phthalic ester residues or 3,4-furandicarboxylate units. The cycloaddition products are shown to differ as a function of stoichiometry, regiochemistry and stereochemistry. The problems encountered in the attempts to aromatise the benzyne adducts to their corresponding naphthafurophanes hamper the exploitation of these compounds as acenophane precursors. Similarly, the DMAD adduts are not suitable precursors for derivatives containing phthalic acid units. On the other hand, they readily provide access to furanophanes contianing carboxyl substituents. The X-ray crstal structures of a variety of key derivatives have been determined and their conformations analysed and compared.
机译:本文描述了利用两种易得的亲二烯体,苯并炔和二甲基乙酰二羧酸二甲酯(DMAD),通过呋喃酮和丙酮的环状六聚体的狄尔斯-阿尔德反应简单地化学修饰。研究已经探索了大环中不同呋喃单元可以轻松转化为萘,邻苯二甲酸酯残基或3,4-呋喃二甲酸酯单元的难易程度。所示的环加成产物根据化学计量,区域化学和立体化学而不同。在将苯并加合物加成芳烃相应的萘并呋喃的尝试中遇到的问题阻碍了将这些化合物开发为oph庚烷前体。类似地,DMAD添加物也不是含有邻苯二甲酸单元的衍生物的合适前体。另一方面,它们很容易获得包含羧基取代基的呋喃呋喃。已经确定了各种关键衍生物的X射线地壳结构,并对其构象进行了分析和比较。

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