杯芳烃与NO_2硝化反应的研究  

Study on the Nitration of Calix[n]arenes with Nitrogen Dioxide

作　　者：于付江[1] 杨海军[1] 李勇[1] 

机构地区：[1]清华大学化学系生命有机磷化学及化学生物学教育部重点实验室,北京100084

出　　处：《有机化学》2006年第4期482-486,共5页Chinese Journal of Organic Chemistry

基　　金：国家973(No.2002CB211803)资助项目

摘　　要：系统地研究了羟基杯[n]芳烃、甲氧基杯[n]芳烃和对特丁基杯[n]芳烃(n=4,6,8)与NO2气体的硝化反应,发现可以成功地得到25,26,27,28-四羟基杯[4]芳烃、37,38,39,40,41,42-六羟基杯[6]芳烃以及25,26,27,28-四甲氧基杯[4]芳烃的对位全硝化产物,产率分别为90%,70%和40%;尤其是25,26,27,28-四羟基杯[4]芳烃与NO2的反应20min即可完成.认为共振式酚氧负离子结构是影响该类硝化反应的关键,并对反应机理进行了探讨.Syntheses of p-nitrocalix[n]arenes were carded out under different reaction conditions by using nitrogen dioxide as nitration agent. It was found that only p-nitrocalix[4]arene, p-nitrocalix[6]arene and 25,26,27,28-tetramethoxy-5,11,17,23-tetranitrocalix[4]arene were obtained from the corresponding calix[4]arene, calix[6]arene and 25,26,27,28-tetramethoxycalix[4]arene in yields of 90%, 70% and 40% respectively. Especially, the reaction of calix[4]arene with NO2 could be finished in 20min. The reaction mechanism based on resonance structures of phenoxy anion in calixarene is discussed.

关 键 词：杯芳烃 NO2 硝化反应 

分 类 号：O621.25[理学—有机化学]