【作者】 李家星；

【导师】 王官武；

【作者基本信息】 中国科学技术大学 ， 有机化学， 2008， 博士

【摘要】 在富勒烯化学中,化学修饰一直是富勒烯研究的主要领域之一。至今,人们已经合成了大量的功能富勒烯衍生物。它们在材料科学,生物医药等方面具有巨大的潜在应用价值。对新型富勒烯衍生物的合成及其性能研究一直都具有重要的意义。在富勒烯的众多反应中,亲核加成反应是属于研究最早的一类反应。本文所述工作主要包括富勒烯化学修饰的四种新型的亲核环加成方法,并以这些方法合成了几类新型的富勒烯衍生物。1.在三乙胺的作用下,CS₂和氨基酸丙二酸二乙酯的加成产物进一步转化成负离子,与C₆₀反应高产率的得到富勒烯并硫代吡咯酮。得到的硫代吡咯酮作为一个很好的中间体可以发生进一步的衍生化反应。在含水的溶液中可以定量水解成吡咯酮衍生物,在碱的作用下很容易和各种卤代物反应,定量转化成硫醚,与酰氯反应也几乎定量生成酰胺衍生物。2.研究了在有机碱DBU的作用下硫氰酸酯衍生物生成的负离子与C₆₀的亲核环加成反应,合成了一系列新型的富勒烯并四氢噻吩衍生物,并且研究了不同的取代基和碱的当量对该反应的影响。随后研究了这类化合物的乙酰化和水解反应,通过二次衍生化增加了这类化合物的溶解度和稳定性。同时研究了此反应的机理。3.通过异喹啉或喹啉与丁炔二酸二甲酯反应先生成的1,4偶极子,然后再对C₆₀双键进行亲核环加成反应,得到了一系列的富勒烯并氮杂六元环衍生物。反应中异喹啉的活性远高于喹啉的活性。4.研究了高频振荡（HSVM）条件下二氰基烯烃衍生物与C₆₀的亲核环加成反应,得到了一系列含有氨基和氰基的富勒烯并环己二烯衍生物,并研究了不同的碱在此反应中的效果,在与不同底物的反应中,三乙胺和N,N-二甲基吡啶作用下的反应产物及其产率不同。更多还原

【Abstract】 Chemical modification is one of the most important research fields in the fullerene chemistry.Many functionalized fullerene derivatives have been synthesized hitherto,and have potential applications in material and medicine science.Among these various functionalization methods,nucleophilic reactions are among the pioneering reactions investigated in fullerene chemistry.In this dissertation,we synthesized several new types of fullerene derivatives through four new types of nucleophilic cycloaddition reactions.1.It was found that the novel reaction of C₆₀with diethyl aminomalonate hydrochloride and CS₂ in the presence of Et₃N afforded C₆₀-fused thiopyrrolidone derivative with high yield.The C=S group in the heterocycle fused to C₆₀could easily be hydrolyzed to C=O group.And the derivative with the C=S group could react with halides to give thioethers or amides with high yields under basic condition.2.Nucleophilic cycloaddition of thiocyanates with C₆₀in the presence of DBU afforded C₆₀-fused 3-imino-thiophene derivatives and methanofullerenes.The product distributions were highly sensitive to the employed substrates.And the products were further manipulated by hydrolysis and acetylation to give more stable 3-oxo-thiophene derivatives and 3-acetamido-thiophene derivatives.The possible reaction mechanism for the formation of products was also proposed.3.The novel multicomponent cycloaddition reaction of C₆₀with 1,4-dipolar reagents generated from DMAD and isoquinoline,quinolines or substituted quinolines giving a new type of C₆₀-fused isoquinoline or quinoline derivatives was investigated.And the isoquinoline had higher activity than quinoline in this reaction.4.The solvent-free cycloadditions of alkylidene malononitrile derivatives with C₆₀ were realized in the presence of Et₃N or DMAP under the HSVM conditions, which led to the formation of C₆₀-fused cyclohexadiene derivatives.更多还原