单加成环丙烷富勒烯膦酸酯衍生物的合成与电化学性能  

Synthesis and Electrochemical Properties of Mono-methano[60]fullerene Organophosphonates

作　　者：杨新林[1] 乔新歌[1] 朱张广[1] 程福永[2] 朱鹤孙[2] 范楼珍[3] 

机构地区：[1]北京理工大学生命科学与技术学院,北京100081 [2]北京理工大学材料科学研究中心,北京100081 [3]北京师范大学化学系,北京100875

出　　处：《有机化学》2006年第11期1557-1561,共5页Chinese Journal of Organic Chemistry

基　　金：高等学校博士学科点专项科研基金(No.20030007011);北京理工大学基础研究基金(No.000Y06)资助项目.

摘　　要：在Mn(OAc)3·2H2O催化下,C60分别和亚甲基二膦酸四乙酯、氰基亚甲基膦酸二乙酯或乙氧羰基亚甲基膦酸二乙酯在氯苯中回流,生成3个单加成环丙烷富勒烯膦酸衍生物C60C(R)PO(OEt)2[1,R=PO(OEt)2;2,R=COOEt;3．R= CN]．与以前报道的Bingel反应法相比,该方法副产物少并且缩短了反应时间．采用循环伏安法发现1,2的还原电位相对于C60发生负移,而3的还原电位相对于C60却正移40mV,表明引入象氰基一样具有很强吸电子能力的取代基团,可以改善富勒烯球的电化学性能,合成电子接受能力较强的富勒烯衍生物．In the presence of manganese（Ⅲ） acetate dihydrate [Mn（OAc）3.2H2O], the reaction of [60]fullerene with tetraethyl methylenediphosphonate, diethyl cyanomethylphosphonate or diethylphosphonoacetic acid ethyl ester in refluxing chlorobenzene afforded the corresponding methano[60]fullerene organophosphonates C60C（R）PO（OEt）2 [1, R=PO（OEt）2; 2, R=COOEt; 3, R=CN], respectively. This reaction produced fewer by-products and needed less reaction time. Therefore it is superior to the Bingel reaction for the preparation of compounds 1, 2 and 3. In addition, compared with C60, compounds 1 and 2 had negative shifts but 3 had a posive shift of 40 mV in reduction half-wave potentials （E1/2） determined by cyclic voltammetry. These data indicate that the introduction of electro-attracting groups such as cyano-group to fullerene ball might improve the electrochemical properties and synthesize fullerene derivatives with strong electron-accepting ability.

关 键 词：单加成环丙烷富勒烯膦酸衍生物 合成 电化学性能 循环伏安法 

分 类 号：O627.51[理学—有机化学]