【作者】 杨艳丽；

【导师】 曾和平；

【作者基本信息】 华南师范大学 ， 有机化学， 2003， 硕士

【摘要】 Buckminsterfullerene-C₆₀（简称fullerene，中文简称“富勒烯”）具有独特的球网状结构。理论上认为富勒烯C₆₀具有三个能量较低的LUMO轨道，可以接受6个电子在它的LUMO轨道上，循环伏安法和电子亲和性测定C₆₀却是个中等程度的电子接受体。在光的激发下，C₆₀吸收能量跃迁到单线激发态。由于富勒烯C₆₀单线激发态寿命短暂，很快从单线态转为亚稳态的三线态。在光化学还原反应和电化学还原反应中，C₆₀可以形成阴离子自由基，又是一个很好的电子接受体（acceptor）。 近年来，对C₆₀进行化学修饰成为化学界研究的热门，环加成反应是比较有效的修饰方法，研究发现：加成反应主要是[6／6]环加成。目前环加成产物主要有三元环，四元环，五元环，六元环，其中以三元和五元杂环居多。其中著名的Diels-Alder环加成反是对C₆₀重要的修饰方式。在Diels-Alder环加成反应中，C₆₀作为亲双烯体参与反应，作为双烯体的化合物可以带有给电子基团，也可以带吸电子基团。由于独特的网装结构，在化学反应中，C₆₀有30个具有等同的化学活性的[6／6]双键可以参加反应。其单加成衍生物只有一种，但是多加成反应可以生成8种不同结构的异构体：cis-1,cis-2,cis-3,e,trans-1,trans-2,trans-3,trans-4。近几年来，关于C₆₀的双加成和多加成也相应成为科学界研究的热门。 本文设计以C₆₀为亲双烯体，以2-（哌啶-硫代磺酸酯）-1,3-丁二烯为亲双烯体，通过Diels-Alder环加成反应得到带2-（哌啶-硫代磺酸酯）基团的六元环C₆₀衍生物。并且采用PM3和AM1半经验方法对产物的轨道能进行了计算。在分离过程中，我们还分离得到相应的双加成和三加成C₆₀衍生物，采用PM3半经验方法，从热力学和动力学上理论推测了双加成取代基可能加成的位置。对其产物的相关谱图进行了分析。由于双加成和三加成产物异构体多而且比较复杂，也由于时间有限，所以就没有进行进一步分离和鉴定。更多还原

【Abstract】 the Diels-Alder reaction of 2-(piperidine-carbodithioate)-l,3-Butadiene withCeo-fullerene.Organic functionalization of fullernene is fascinating and promising for new material chemistry because of its unique spherical structure and feasibility in bulk production. According to theoretical calculations,C60 exhibits a LUMO(t1u) comparatively low in energy. Consequently, C60 behaves like an electronegative molecule which reversibly accepts up to six electrons in solution. The Cyclic voltammetry and the electron affinity measured for C60 confirm that it is a moderate electron acceptor. Upon light excitation, C60 can form singlet because of absording energy, quickly transfers the triplet state with near unit efficiency.Addition reactions instead of substitution reactions are therefore typically undergone by Ceo molecule. Among these reactions, cycloaddition reactions are the most reliable methods, For example , cyclopropanation, [2+2] cycloaddition, [3+2] cycloaddition, [4+2] cycloaddition ,the Diels-Alder reaction being particularly successful. Addition reactions occurs on the [6/6] junction bonds between the two six-membered rings on C60 surface.Recently, multiple addition to C60 becomes of increasing interest.In principle, the bisaddition reaction can form eight different regioisomers:cis-l, cis-2, cis-3, e, trans-1, trans-2, trans-3,and trans-4. Usuallly, the bisadditions take place without sufficient regioselectivity and the separation chromatographic techniques.In this paper, we will introduce the Diels-Alder reaction of 2-(piperidine-carbodithioate)-1,3-Butadiene with C60-fullerene. Semi-empirical methods(AM1 and PM3) were carried out to calculate the electronic structure and front orbits of monoadduct and bisadducts. The stability of bisadducts were discussed by energies of heat of conformation.The result implies that the type e is the most stable one.更多还原