【作者】 黄涛；

【导师】 魏俊发；

【作者基本信息】 陕西师范大学 ， 有机化学， 2006， 硕士

【摘要】 富勒烯及相关问题的研究开辟了全新的学科领域,它不但涉及到化学,物理学,生物学,而且还涉及到天体物理学,地质科学,医药科学,纳米技术科学等几乎所有学科。它的发现向有机合成化学家提出了艰巨的合成挑战,用逐步合成法,能得到每一个中间体,则对于富勒烯的形成机理研究相当有价值。因此从理论和实验两方面探索化学合成富勒烯片段成为当前世界各国科学家研究的焦点和热点之一。本文设计了从六氯环戊二烯,联五氯环戊二烯和全氯富烯合成富勒烯片段的新方法,并指出了其中的全氯富烯是具有研究前景的一种化合物。在综述了目前富勒烯及其片段国内外研究现状的基础上,通过六氯环戊二烯,联五氯环戊二烯,全氯富烯合成富勒烯片段的研究,为合成更大的C₆₀片段提供合成方面的实验基础。 综述了C₆₀及富勒烯家族的合成方法,如激光法、电阻加热法、电弧法、高频诱导加热法、太阳能聚焦加热法等,特别是在有机合成的基础上,提出了合理的合成路线,并综合分析了这些路线的合理性和优缺点。根据原料便宜易得、实验操作易行,产物易分离,反应易于控制等原则,设定了从六氯环戊二烯、联五氯环戊二烯,全氯富烯通过金属来脱氯合成富勒烯片段的合成路线。 六氯环戊二烯与金属的脱氯反应,考察了反应温度、催化剂的用量等因素对反应活性的影响。结果表明,N,N-二甲基甲酰胺对六氯环戊二烯用铜粉脱氯有很好的催化作用。考察了联五氯环戊二烯在金属下脱氯、加热脱氯、碘化钾脱氯,硫代硫酸钠脱氯聚合的反应。结果表明,在二价铜的催化下,铜在80%的乙醇中可以高效地对联五氯环戊二烯进行脱氯,生成全氯富烯。考察了全氯富烯在金属钠、金属铜的脱氯反应,生成了新的化合物,结构在确定中。 实验过程中对所设计的合成路线进行了深入的研究,讨论了影响反应的各种因素,各种中间体和目标化合物的分离方法等;对实验现象和实验结果进行了详细的分析和讨论。详细叙述了合成多个化合物的具体操作步骤和提纯方法,并根据IR;¹³C NMR图谱、X-单晶衍射图谱等确定了各化合物的结构;对于化合物2,3,5,6,7-五氯-1-茚酮-4-甲酸乙酯,给出了用硅胶柱色谱的分离方法和结果。对于中间体全氯代-2,6-二茚酮代提供了最佳合成时间和分离方法,并通过IR、¹³C NMR确定了其结构。用硅胶柱色谱分离出的化合物2,3,5,6,7-五氯-1-茚酮-4-甲酸乙酯和全氯代-2,6-二茚酮,经过单晶培养,得到了它们的X-单晶衍射图谱,确定其结构的正确性。 其中一些重要的化合物均采用新的合成方法,联五氯环戊二烯,全氯富烯的更多还原

【Abstract】 The fuilerene and the correlation question’s research opened the brand-new discipline domain. It not only relates to chemistry, physics and biology, but also relates to astrophysics, geological science, medicopharmaceutical science, nanotechnology science and so on. Its discovery proposed the arduous synthesis challenge to the organic synthesis chemists. If fuilerene fragment can be synthesized by chemical methods, important evidences can be provide to explain the mechanism on formation of fuilerene. Therefore, it becomes focus of many scientists’ researches to exploit the chemical methods of synthesizing fuilerene fragment from theory and experiment. This thesis designs to synthesize fuilerene fragment from hexachloro-cyclopentadiene, bis-（pentachlorocyclopentadienyl） and perchlorofulvalene. The result shows that perchlorofulvalene is a compound of research foreground. In our research, fuilerene fragment is synthesized from hexachlorocyclopentadiene, bis-（pentachlo rocyclo pen tadienyl）, perchlorofulvalene on the basis of summarizing the present development on synthesis of fuilerene fragment, which can provide experimental foundation to synthesize the bigger fuilerene fragments.In this dissertation, reasonable routes to synthesis of fuilerene fragments are discussed. After analyzing the classical synthesis of fuilerene fragments, especially on the basis of organic synthesis, proposed the reasonable process of synthesis. We designs the synthesis route of fuilerene fragments from cheap and available raw materials. The procedure of synthesis is simpler and the quality of the product can be easily controlled. We researched on the synthesis method and mainly discussed the effect of reaction conditions. It is studied that how to follow the reaction by purify the products. The concrete operation steps, the method of purification and the yield of reactions are explained. In addition, the intermediates have been confirmed by the spectra of IR, ¹³C NMR. The purities of intermediates, such as 2,3,5,6,7-hexachloro-l-indenone-4-ethyl formylate and 1,6-dioxoperchlorobisindenone were separated by column chromatography. In order to identify the structure of intermediates, the dissertation provided the spectra of IR, ¹³C NMR and X-ray diffraction.The purities of several important intermediate compounds were detected by column chromatography. As for 2,3,5,6,7-hexachloro-l-indenone-4-ethyl formylate and1,6-dioxoperchlorobisindenone, methods of synthesis and purification were improved. The yield was better than those reported, because the column chromatography was avoided in purification. Thus, the product could be synthesized in larger scale.The synthesis of perchlorofulvalene used in the dissertation has good repeat ability, stability and dependability. Using this method in the lab, the intermdiate compounds were accumulated and gram’s perchlorofulvalene was achieved. It provides stable foundation for preparation of perchlorofulvalene. The experiment provided a ference method for synthesis of fuilerene fragment from pyrolysis of perchlorofulvalene.更多还原