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

通过自组装体现新主机功能的武装大循环的开发

基本信息

批准号：
09640698
负责人：
HABATA Yoichi
金额：
$ 1.86万
依托单位：
TOHO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640698/
关键词：
crown ether complex alkali metal polymer host guest supramolecule

项目摘要

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

答：当使用一些苯酚通过曼尼希反应合成武装大环时，获得了副产物。该反应使用 11 种苯酚进行，并且根据 pH 测量结果阐明了反应机理。酚类曼尼希反应的反应活性可以通过 pH 测量和静电荷计算来估计。使用2,6-二取代苯酚B：对苯酚上具有i-Pr和x-Bu的化合物2和3的RbSCN配合物进行X射线结构分析。结果，3-RbSCN在苯酚上具有t-Bu基团。侧臂形成 1 : 1 复合物，而具有 i-Pr 基团的 2-RbSCN 形成 1 : 1 复合物和聚合 (1 : 1)_n 的结构当考虑包含 1-RbSCN 络合物时，Me 基团是聚合 (1 : 1)_n 络合物，结果表明，在这一系列化合物中，该络合物的结构发生了系统性的变化。取决于引入到侧臂C的烷基的体积：在将F引入到侧臂的两个相邻羟基的臂大环的RbSCN络合物中，Rb^+离子由五个杂原子配位。其冠环与SCN盐的S原子形成2:2配合物，另外，该配合物中的Rb+离子与另一分子侧臂的F原子配位形成8配位结构。由F原子而不是酚OH基团连接：表明侧链的苯酚与钾离子构型形成2:2络合物。侧臂羟基两侧均引入MeO基团，在臂大环KSCN配合物中形成二次包合物，表明官能团对金属离子具有较强的配位能力。可以在侧臂中引入，以便通过武装大环较少发展主体络合。