THE DEVEROPMENT OF ARMED-MACROCYCLES WHICH MANIFESTS THE NEW HOST FUNCTION BY SELF-ASSEMBLING

答：通过曼尼希反应，将一些苯酚用于合成大环臂环，得到副产物。用11种苯酚进行了该反应，并通过pH测量和酚类化合物的p-碳的静电荷电的结果阐明了反应机理。结果表明，当使用2，6-二取代苯酚时，可通过pH测量和静态电荷势的计算来估算酚类化合物的Mannich反应活性。B：化合物2和3在苯酚上含有i-Pr和x-Bu的RbSCN配合物的X-射线结构分析。结果表明，侧臂带有t-Bu基团的3-RbSCN形成1：1的络合物，而具有i-Pr基团的2-RbSCN形成1：1络合物和聚合物(1：1)_n络合物交替的结构。当考虑含有Me基团为聚合物(1：1)_n络合物的1-RbSCN络合物时，揭示了CoMP-…的结构在这一系列化合物中，更多的Lexes通过依赖于引入到侧臂中的大量烷基而系统地改变。C：在武装大环的RbSCN络合物中，将F引入侧臂羟基的两个邻位，Rb~(++)离子与冠环上的五个杂原子和SCN盐的S原子配位，形成2：2的络合物。另外，另一个分子侧臂的F原子配位形成了8配位结构。在该络合物中，Rb+离子与F原子结合，而不是与酚羟基结合。D：研究表明，侧链上的苯酚与其他分子中的苯酚以2：2的构型结合到钾离子上形成二次包结场，在侧臂羟基两侧引入MeO基团的臂大环KSCN络合物中形成二次包含场。结果表明，侧臂上可能引入了对金属离子具有较强配位能力的官能团，从而促进了大环的络合作用。较少

A : The by-products were obtained, when some phenols were used for the synthesis of the armed-macrocycles using the Mannich reaction. The reaction was carried out using 11 kinds of phenol, and the reaction mechanism was clarified from the results of pH measurements and static potential charging of p-carbon of the phenols. It is reveals that the reactivity for the Mannich reaction of the phenols would be estimated by pH measurement and the calculation of the static potential charge when 2,6-disubstituted phenols were used. B : The X-ray structural analysis for the RbSCN complexes of compounds 2 and 3 having i-Pr and x-Bu on phenol. As the results, 3-RbSCN having t-Bu groups in the side arm forms 1 : 1 complex, while 2-RbSCN having i-Pr groups forms the structure in which 1 : 1 complexes and polymeric (1 : 1)_n complex become alternate. When it was considered including 1-RbSCN complex with the Me groups being the polymeric (1 : 1)_n complex, it is revealed that the structures of the comp … More lexes systematically changed in these a series of the compounds by being dependent on the bulk of alkyl group introduced in to the side arm. C : In the RbSCN complex of the armed macrocycle which introduced F into both neighbors of hydroxyl group of the side arm, Rb^+ ion was coordinated by five hetero atoms on the crown ring and S atom of SCN salt, and 2 : 2 complex was formed. In addition, 8 coordinated structure was formed by the coordinating in F atom of the side arm of the other molecule. In this complex, the Rb+ ion was bounded by the F atom not the phenolic OH grotrp. D : It is revealed that 2 : 2 complexes are formed by the configuration to the potassium ion that the phenol of the side-chain was incorporated in other molecule, and the secondary inclusion field is formed in the KSCN complex of the armed-macrocycle in which MeO group was introduced in both neighbors of hydroxyl group of the side arm. The results suggested that functional groups which have stronger coordination ability toward metal ions may be introduced in the side arm in order to development of the host complexation by armed macrocycles. Less