CONSTRUCTION OF SELF-ASSEMBLY CAPSULE TYPE HOST COMPOUND : METAL ION PROMOTED CAPTURE AND RELEASE OF THE GUEST.

以一种简便的方法合成了具有不同侧臂的氮杂杯芳烃。对位取代的2，6-二(羟甲基)-苯酚衍生物与胺的缩合反应得到环状三聚物，六高三氮杂[3]芳烃，产率较高。从2，2-methylene-bis(4-methyl-6-hydroxymethylphenol)和胺出发，以中等到很好的产率得到了四高重氮杯[4]芳烃。环化过程非常简单：双羟甲基苯酚衍生物和胺在回流的甲苯或二甲苯中反应，这种环化方法不需要高稀释技术，因为在非质子化溶剂中存在酚羟基和胺之间的氢键模板效应。用X-射线单晶衍射法研究了对二甲苯桥联化合物的结构。用动态核磁共振和MM3计算研究了溶液中的结构。Azacalix[4]骨架被固定在浅锥形构象中，桥连二甲苯单元(p-和In-)位于环状骨架的空腔中。OH和N原子之间的腔内氢键在低温下发生局域化。对二甲苯和间二甲苯桥联化合物的局域化自由能分别为10.8kcal和11.2kcal摩尔比~(-1)~(Gt)。甲胺、福尔马林和苯酚一锅反应得到N-甲基氮杂杯芳烃混合物，N-甲基氮杂杯[4]芳烃经N-烷基化得到甜菜碱型大环分子。

Azacalixarenes which have various side arms were synthesized in a convenient method. The condensation reaction of para-substituted 2,6-bis(hydroxymethyl)-phenol derivatives and amines gave cyclic trimers, hexahomotriazacalix[3]arenes in good yields. Starting from 2,2-methylene-bis(4-methyl-6-hydroxymethylphenol) and amines, tetrahomodiaza-calix[4]arenes, were obtained in moderate to excellent yields. The cyclization procedure is very simple : bis(hydroxymethyl)phenol derivatives and amines are reacted in refluxing toluene or xylene, In this cyclization method, the high dilution technique is not required since the template effect of hydrogen bonds between phenolic OH groups and amines is present in the aprotic solvents.Novel self-filled azacalixarenes were synthesized following a simple method. The structure of a p-xylylene-bridged compound was investigated by X-ray crystallographic analysis. Dynamic NMR and MM3 calculations were also employed to study the structures in solution. Azacalix [4] skeletons are rigidly fixed in shallow cone conformations and bridging xylylene units (p- and in-) are located in the cavities of the cyclic skeletons. Intra-cavity hydrogen bonds between OH and N atoms localize at low temperatures. The free energy of the localization was estimated to be 10.8 and 11.2kcal mol^<-1> for p- and m-xylylene-bridged compounds, respectively.A new synthetic method of N-methylazacalixarenes was developed. One-pot reaction employing methylamine, formaline, and phenol afforded the mixture of N-methylazacalixarenes.N-alkylation of N-Me-azacalix[4]arene afforded betain-type macrocyclic molecule.