杯芳烃的分子设计(Ⅵ)——一种新的杯[4]磺胺衍生物的合成及晶体结构

Molecular Design of Calixarenes(VI)- Synthesis and Crystal Structure of a Novel Sulfonamino Calix[4]arene Derivative

杯芳烃是由酚单体通过亚甲基在羟基邻位桥连而成的环状低聚物, 它具有可调的杯状疏水空腔, 结构柔性较大, 构象可变, 并对中性分子和有机、无机离子具有选择性配位能力. 因此, 在其上下缘进行化学修饰所得到的杯芳烃衍生物可广泛应用于萃取分离、离子选择性电极、色谱分析、功能材料、催化及模拟酶等研究领域[1～4].

A novel calix[4]arene derivative (2), 5,11,17, 23-tetra-tert-butyl--25, 26-dihydroxy-27, 28-[bis(p-toluenesulfonylaminoethoxy) ]calix [4]arene was synthesized in a 90% yield by the reaction of 5,11, 17, 23-tetra-tert-butyl-25, 2 6-dihydroxy-27, 28- [bis (β-aminoethoxy) ]-calix [4] arene (1) and p-tolue-nesulfonyl chloride in dry CH2C12 in the presence of NEt3. compound 2 crystallizes in triclinic space groupP1, with a = 1.20444(11) nm, b = 1.61735(14) nm, c = 1.773 16(15) nm, a=80. 050(2)°, β=76.644(2) °,γ = 82. 084(2) °, V = 3.292 9(5) nm3, Dc=1.135 g/cm3, Z=2, R = 0.0683. Theresult shows the flatted cone conformation with the distorted sulfonamido substituents attached to the low-er rim of compound 2 resulted from the dipole-dipole repulsive interaction. The structure of 2-acetonitrilecomplex shows that the acetonitrile lies on the pseudo crystallgraphic fourfold axis with the nitrogen atomdirecting exo and the methyl pointing inside the intramolecular cavity, which is attributed to the specificCH-π interaction between the acetonitrile CH3 group and the aromatic nuclei of host 2.