杯4芳烃衍生物的合成及其晶体结构

摘要

A novel phenomenon about calix[4]arenes was observed that there were two discrete conformational isomers observed in single crystals of tetra-O-alkylated calix[4]arenes. Four calix[4] arene derivatives （2, 3, 4 and 5 ） were synthesized with 1 as the precursor, and their single crystals were prepared to disclose reasons for this novel phenomenon. It was found that the introduced alkyl groups inhibited the oxygen-through-the-annulus rotation of phenyl rings, and there was enough space for the forth phenyl ring to randomly position in cone conformation or upside down in partial-cone conformation, leading to the coexistence of two discrete conformational isomers in single crystals of calix[4]arenes.%通过向杯[4]芳烃下沿引入不同基团,合成得到四种杯[4]芳烃衍生物（2,3,4和5）,并采用NMR、ESI-MS和EA对所合成的化合物进行结构表征.同时培养得到化合物2,3和4的单晶,解析出晶体结构,发现在化合物3和4的晶体中同时存在杯[4]芳烃的两种主要构象：锥型和部分锥型.通过分析研究,把产生这种现象的原因归结为：当下沿的保护基团具有适度大的尺寸时,就能够阻止苯环的翻转,并且提供足够的空间.当杯芳烃从溶液中析出时,第四个苯环随机地定位,从而使得两种构象并存于同一晶体中.