杯[4]芳烃咪唑盐的微波合成及在氟化反应中的应用

Microwave-assisted Synthesis of Calix[4] arene Imidazolium Salts and Application in Fluoridation

以杯[4]芳烃为起始原料,首先制得中间体杯[4]芳烃双溴代烷基衍生物,然后经微波辐射和阴离子交换,共得9种杯[4]芳烃咪唑盐衍生物,化合物的结构与构象经元素分析、IR、~1HNMR、^(19)FNMR、^(31)PNMR表征。研究了它们在对氯硝基苯氟化反应中的催化性能以及对K+的萃取性能。结果表明,这9种化合物在氟化反应中的催化效果良好,对氟硝基苯的收率为80.89%~92.67%;同时化合物对K+具有较好的萃取效果,其中以化合物25,27-二[4-(3-甲基咪唑)乙氧基]-26,28-二羟基-5,11,17,23-四叔丁基杯[4]芳烃六氟磷酸盐的萃取效果最好,萃取率可达75.45%。

O-Alkylated calix [4]arene derivatives were synthesized by using calix[4]arene as a starting material. Nine calix[4]arene imidazolium salts were obtained by microwave-assisted synthesis and anion complexation. The structures were confirmed by elemental analyses,IR,^1HNMR,^19FNMR,^31PNMR. The compounds were used as phase transfer catalysis in the fluoridation of p-chloronitrobenzene. And their extraction properties of K＋was evaluated. The results showed that all compounds possessed excellent catalytic properties for the fluoridation. The yields of p-fluoronitrobenzene were between 80. 89% ～ 92. 67%. And these compounds have good extraction efficiency of K～＋. 25,27-Bis[4-（ 3-methylimidazolium） ethoxy]-26,28-dihydroxy-5,11,17,23-tetra-tertbutylcalix [4] a-rene hexafluorophosphate has the best extraction performance,the extracted percentage was as high as 75. 45%.