四乙氧羰基甲氧基杯[4]芳烃的合成与性质

Synthesis and Property of Tetraethoxy- carbonylmethoxy calix[4]arene

通过杯 [4]芳烃与溴乙酸乙酯的反应制得了 2 5 ,2 6,2 7,2 8-四乙氧羰基甲氧基杯 [4]芳烃 ,并经元素分析、IR、UV、1H NMR、13 C NMR和 MS等分析证实了产物的结构。用荧光光谱法研究了产物与稀土 ( )硝酸盐在乙腈溶液中的配位作用 ,由 Hilderbrand-Benesi公式计算出配合物的稳定常数和配位反应的 Gibbs自由能变化。结果表明 ,所得环芳烃与稀土 ( )硝酸盐在乙腈溶液中具有较强的配位能力 ,对苦味酸钠具有很强的液膜传递能力和配位选择性。

Tetraethoxycarbonylmethoxy calixarene(3) was synthesized by reacting calixarene(2) with ethyl bromoacetate using K 2CO 3 as base in acetone. The structure of (3) was characterized by elmenetal analysis, IR, UV, MS, 1H and 13 C NMR spectra. Compound 3 exist in 'partial cone' conformations. The coordination behavior of the compound with four rare earth metal(Ⅲ) nitrates in acetonitrile were studied by fluorescence spectrometry. The stability constants(lg K s) of the complexes of 3 with rare earth metal(Ⅲ) nitrates and Gibbs free energy change( -Δ G 0) of the coordination reactions were calculated according to the modified Hilderbrand Benesi equation. The calixarene obtained exhibited a strong coordination ability with rare earth nitrates and good transportability for alkali metal ions throungh liquid membrane in order of Na +>K +>Li +.