【作者】 杨海涛；

【导师】 王官武；

【作者基本信息】 中国科学技术大学 ， 有机化学， 2006， 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潜在的巨大应用价值。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。本文主要工作是找到富勒烯化学修饰的三种新方法，合成了几类新型的富勒烯衍生物以及研究了C₇₀单加成反应的区域选择性。 1．研究了两类环氧化合物反式-2-苯基-2-苯甲酰基环氧和反式-2-氰基-2-乙氧基羰基-3-芳基环氧在热引发下原位生成的羰基叶立德与C₆₀的1，3-偶极加成反应，合成了一系列新型的四氢呋哺环合C₆₀衍生物，成功引入了羰基、氰基和酯基等官能团，有利于其进一步的衍生化。该反应表现了很强的立体选择性，C₆₀与反式-2-苯基-2-苯甲酰基环氧反应只得到了顺式产物；与反式-2-氰基-2-乙氧基羰基-3-芳基环氧的反应得到了顺式为主的产物或单一的顺式产物并且异构体的分布受到苯环上取代基的电子效应极大的影响。 2．通过2，5-二氢-1，1-二氧-1，2，3-硫二氮唑加热脱SO₂原位生成的1，3-二取代-1，2-二氮杂丁二烯与C₆₀的杂Diels-Alder反应，合成了一类新型的四氢哒嗪环合C₆₀衍生物，并研究了不同的取代基对反应的影响。 3．研究了三价醋酸锰引发的烯胺酮类化合物与C₆₀的自由基环加成反应，合成了一系列氮原子直接和C₆₀相连的新型二氢吡咯环合C₆₀生物，发现了一种全新的合成二氢吡咯化合物的方法，这种方法可能在合成吡咯环类的化合物中有着重要的应用。 4．研究了两种N-取代-4-硝基苯甲亚胺酰氯在碱性条件下原位生成的腈叶立德和C₆₀的1，3-偶极加成反应，分别得到两种[6，6]闭环的异构体，证实了并不存在[6，5]开环的异构体，反应温度对两种异构体的分布有巨大影响。 5．通过研究不同的底物与C₇₀的加成反应，并对所得到的不同单加成异构体的含量及结构进行确定，我们确定了C₇₀的单加成反应的区域选择性，首先是选择性的加成到C1-C2和C5-C6上，然后是C7-C8，再次之是C7-C21，证明了C7-C8的[6，5]键是除C1-C2和C5-C6以外最优先的选择加成位置，而不是长期以来人们一直所认为的C7-C21。更多还原

【Abstract】 Chemical modification is one of the most important research fields in the fullerene chemistry. Many functional fullerene derivatives have been synthesized to this day, and have potential applications in material and medicinal science. In this dissertation, we synthesized three types of new fullerene derivatives and investigated the regioselectivity of the mono-addition reactions of C₇₀.1. The thermal reaction of C₆₀ with the carbonyl ylides generated in situ from epoxides to give a new type of C₆₀-fused tetrahydrofuran derivatives has been investigated. There was a strong stereoselectivity in this reaction. The reaction of C₆₀ with trans-2-benzoy1-3-aryl oxiranes afforded cis-products, while the reaction of C₆₀ with 2-cyano-2-ethoxycarbonyl-3-aryl oxiranes gave only cis-isomer or a mixture of cis-and trans-isomers, for which the isomer distribution was drastically affected by the substituent on the phenyl ring.synthesized2. The hetero-Diels-Alder reaction of C₆₀ with 1,2-diaza-1,3-butadienes generated in situ by the thermal extrusion of SO₂ from 2,5-dihydro-1,2,3-thiadiazole-1,1-dioxides has been realized for the first time, and led to the formation of a new type of stable C₆₀-fused tetrahydropyridazine derivatives. We also investigated the influence of the substituted groups.3. Mn（OAc）₃·2H₂O has been successfully utilized in the radical reactions of C₆₀ with β-enamino carbonyl compounds to give C₆₀-fused pyrroline derivatives, of which the nitrogen atom is directly connected to fullerene cage. It was a brand-new method for the synthesis of 4,5-dihydropyrrole compounds.4. The reaction of C₆₀ with the nitrile ylides generated in situ from two kinds of N-substituted-4-nitro-benzimidoyl chlorides gave two types of [6,6]-closed C₆₀-fused 1,2-dihydropyrrole derivatives, respectively. There was not [6,5]-opened isomer formed at all. We also explored the influence of reaction temperature to the distribution of the two isomers.5. We investigated the regioselectivity of the mono-addition reactions of C₇₀ through the reactions of different substrates with C₇₀ and characterization of the structures and distributions of the isomers. We proved that the [6,5]-bond on the C7-C8 but not the [6,6]-bond on the C7-C21 is the most active site besides for C1-C2 double bond and C5-C6 double bond.更多还原