四氨羰甲基对-叔丁基杯[4]芳烃的合成及聚集行为

四氨羰甲基对-叔丁基杯[4]芳烃的合成及聚集行为 Synthesis of p-tert-Butylcalix[4]arene Tetraamide and Its Aggregating Behavior 龚淑玲 GONG Shuling 1 2 first-author 王巍 WANG Wei 1 2 杨伟平 YANG Weiping 1 2 李艳 LI Yan 1 2 陈远荫 CHEN Yuanyin 1 2 武汉大学化学与分子科学学院 武汉大学化学与分子科学学院 College of Chemistry and Molecular Sciences,Wuhan University College of Chemistry and Molecular Sciences,Wuhan University 武汉大学化学与分子科学学院,湖北,武汉,430072 武汉大学化学与分子科学学院,湖北,武汉,430072 对-叔丁基杯[4]芳烃与溴乙酸乙酯反应,得到锥式、1,2-交替、1,3-交替和部分锥式构象的四取代衍生物;将锥式、1,2-交替和1,3-交替构象的四乙酸乙酯取代衍生物在氨的甲醇溶液中进行氨解得到相应的酰胺产物.通过核磁研究比较了氨解产物的自聚集情况.锥式构象四氨羰甲基对-叔丁基杯[4]芳烃分子在氯仿溶剂中的分子间作用力很弱,容易溶剂化,溶剂中核磁谱图不能观察到分子聚集;而1,2-交替构象的四氨羰甲基对-叔丁基杯[4]芳烃分子间存在相当强的作用力,在氯仿中的溶解性较差,核磁谱图表明分子在氯仿溶剂中有分子聚集的现象.1,3-交替构象的四氨羰甲基对-叔丁基杯[4]芳烃分子可以形成一定的聚集体,在高浓度时是聚集体的形式;在浓度较低或者加入酸予以破坏时,溶液中是以单体的形式存在. All the conformers（cone,partial cone,1,2-alternate and 1,3-alternate） of tetrakis（ethoxycarbonylmethyl）-p-tert-butylcalix[4]arene were synthesized by the reaction of p-tert-butylcalix[4]arene with ethyl bromoacetate.Their tetraamide derivatives were obtained in quantitative yields by aminolysis of corresponding p-tert-butylcalix[4]arene tetraethylacetate with NH3 in the solution of methanol.The aggregating behavior of calixarene amide derivatives in different conformations was studied by 1H NMR.The conic p-tert-butylcalix[4]arene tetraamide is very soluble in CHCl3,all proton resonance signals of the compound were clear and sharp peaks in 1H NMR spectrum in pure CDCl3;1,2-alt p-tert-butylcalix[4]arene tetraamide was sparingly soluble in CHCl3,after minor CF3COOH being added,the obvious signals appeared.This indicated that there was strong intermolecular interaction between the molecules.1,3-alt p-tert-butylcalix[4]arene tetraamideis could aggregete in high concentration;when in low concentration or after minor CF3COOH being added,it existed in monomer. 杯芳烃 氨解 聚集 自组装 calixarene aminolysis aggregate self-assemble O625 国家自然科学基金（20772092）;湖北省自然科学基金（2007ABB021）资助项目 2008-02-01 2021-04-01 2