基于富勒烯杂环化合物和新模式的四加成产物和六加成产物的电化学合成研究

By utilizing controlled potential electrolysis, [60]fullerene-fused heterocycles including [60]fullerene-fused indolines, dihydrofurans, and lactones, which have been synthesized by our own developed methods, can be reduced to the corresponding dianions. The dianions will react with diaryl halomethanes, triaryl halomethanes, and 2-halomalonate esters to give tetra-adducts with a new addition pattern, i.e., 1,4,9,25-adducts. In comparison, when the dianions react with diiodomethane, 1,2-dihaloethanes, 1,3-dihalopropanes, 1,4-dihalobutanes, 2,2-dihalomalonate esters, and 1,2-bis(halomethyl)benzenes, another type of tetra-adducts, i.e., 1,2,4,17-adducts, a unique “cis-2” adducts fused with a [5,6]-bond and [6,6]-bond, would be generated. In addition, the above-mentioned tetra-adducts can be further electrochemically reduced to the corresponding dianions, and then react with electrophiles to provide hexa-adducts. It is expected that these hexa-adducts would also have new addition patterns. These multiadducts will behave as organic functional materials such as the receptors in solar cells.

利用本课题组开发合成的富勒烯杂环化合物包括富勒烯并吲哚啉衍生物、富勒烯并苯并二氢呋喃衍生物、富勒烯并内酯衍生物等，通过恒电位电解还原为相应的二价负离子，然后与二芳基卤甲烷、三芳基卤甲烷、2-卤代丙二酸酯等亲电试剂反应，预期将生成新加成模式的四加成产物，即1,4,9,25-四加成产物；与二碘甲烷、1,2-二卤乙烷、1,3-二卤丙烷、1,4-二卤丁烷、2,2-二卤代丙二酸酯、二（卤甲基）芳烃等亲电试剂反应，预期将获得另一新加成模式的四加成产物，即1,2,4,17-四加成产物，也是一类加成到[5,6]-键和[6,6]-键的特殊"cis-2"产物。进一步将上述获得的新加成模式的四加成产物电化学还原为相应的二价负离子，然后与亲电试剂反应，可以获得相应的六加成产物，预期也将是新的加成模式。这些多加成产物将可用作有机功能材料如太阳能电池受体。

富勒烯及其衍生物具有缺电子性质，在电化学条件下转化为富勒烯负离子后发生极性反转变为亲核性，能与一系列亲电试剂发生反应，从而拓展了富勒烯化学。本项目研究了[60]富勒烯并吲哚啉衍生物、[60]富勒烯并苯并二氢呋喃衍生物、[60]富勒烯并内酯衍生物、[60]富勒烯并3,4-二氢吡啶酮[1,6-a]吲哚等富勒烯杂环化合物通过恒电位电解还原为相应的二价负离子，再与苄溴、酰氯、氯甲酸酯、邻二溴苄、邻苯二甲酰氯、二溴代丙二酸二乙酯等一系列亲电试剂反应，高区域选择性、高产率地获得富勒烯多取代产物包括1,4,9,25-四加成产物及尚未见文献报道的富勒烯新型加成模式的cis-3’-型1,2,4,17-四加成产物和“S”-型1,2,3,4,9,10-六加成产物、内酯开环苄基化产物、环丙烷化产物等。富勒烯并内酯二负离子在乙酸作用下意外地转化为富勒烯并环酮，实现了逆向Baeyer–Villiger反应。获得的部分富勒烯衍生物被应用于太阳能电池器件中，获得了良好的光电转化效率。