杯芳烃与NO_2硝化反应的研究

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

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.