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多种侧臂的阿扎卡萼芳烃。对取代的2,6-二（羟甲基）苯酚衍生物与胺的缩合反应得到了六同型三氮杂环芳烃，收率高。以2,2-亚甲-双（4-甲基-6-羟甲基酚）和胺为原料，以中高收率制备了四异质杯芳烃。环化过程非常简单：双（羟甲基）苯酚衍生物和胺在回流甲苯或二甲苯中反应，在这种环化方法中，由于酚羟基和胺之间的氢键在非质子溶剂中存在模板效应，因此不需要高稀释技术。采用简单的方法合成了一种新颖的自填杜鹃花芳烃。用x射线晶体学方法研究了对二甲苯桥接化合物的结构。采用动态核磁共振和MM3计算对溶液中的结构进行了研究。杜鹃花[4]骨架刚性固定为浅锥形构象，桥接二甲苯单元（p-和in-）位于循环骨架的空腔中。在腔内氢键之间的OH和N原子局部化在低温。对二甲苯和间二甲苯桥接化合物的定位自由能分别为10.8和11.2kcal mol^<-1>。提出了一种合成n -甲基二叉杯芳烃的新方法。甲胺、福尔马林和苯酚一锅反应得到n -甲基杯芳烃的混合物。n- me -杜鹃花[4]芳烃的n-烷基化得到了β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.