杯芳烃的研究 Ⅰ.三乙酰氧基羟基杯[4]芳烃的合成及其与乙腈形成的包合物的晶体结构

The Study of Calixarene——I. Synthesis of Triacetoxyhydroxycalix [4] arene and Crystal Structure of Its Acetonitrile Clathrate

本文报道了25,26,27-三乙酰氧基-28-羟基杯[4]芳烃的合成,并通过~1H NMR,^(13)C NMR,IR以及元素分析对它进行了表征。三乙酰氧基羟基杯[4]芳烃在乙腈中重结晶可得到1:1包合物的单晶。X射线结构分析确定它为单斜晶系,其空间群为P2_1/n,属分子间包合物。在晶体中,三乙酰氧基羟基杯[4]芳烃呈“内式”的部分锥形构象,残留羟基处在分子中央,被苯环和乙酰氧基所包围,这种构象不利于对残留羟基的进攻。

25, 26, 27-triacetoxy-28-hydroxycalix [4] arene was synthesized and characterized by ~1H NMR, ^(13)C NMR, IR, and elemental analysis. A single crystal of its (1∶1) acetonitrile clathrate was obtainted by recrystallizing the compound from acetonitrrile. The results of Xray analysis show that the crystal is moncelinic and its space group belongs to P2_1/n and the clathrate is an intermolecular one. In the crystal, triacetoxy- hydroxycalix [4] arene exists in an 'inside' partial cone conformation and a residual OH group lies in the centre of the molecule, which is surrounded with three OAc groups and four benzene rings. Thus, the conformation is unfavorable for attacking the OH group.