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

• 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

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：当使用某些苯酚使用Mannich反应用于武装大环的合成时，获得了副产品。使用11种苯酚进行反应，并从pH测量结果和苯酚P碳的静态电势充电的结果中阐明了反应机理。据表明，当使用2,6-二取代的苯酚时，将通过pH测量估算苯酚的Mannich反应的反应性，并计算静态电荷。 B：具有I-pr和X-BU的苯酚上的RBSCN复合物的X射线结构分析。结果，在侧臂中具有T-BU组的3-RBSCN形成1：1复合物，而具有I-PR组的2-RBSCN形成了1：1复合物和聚合物（1：1）_n _n复合物的结构。当被认为包括1-RBSCN复合物时，ME组为聚合物（1：1）_n络合物时，据揭示了COMP的结构……在这些化合物中，由于依赖于引入到侧臂引入的大部分烷基基团而有系统地改变了这些化合物。 C：在武装大环的RBSCN复合物中，将F引入了侧臂羟基的两个邻居，RB^+离子由冠状环和SCN盐的S原子上的五个杂原原子协调，并形成了2：2络合物。此外，在另一个分子的侧臂的F原子中协调形成了8个协调结构。在该复合物中，Rb+离子由F原子而不是苯酚OH GrotRP界定。 D：据表明，由钾离子的构型形成2：2的复合物，即侧链的苯酚在其他分子中掺入，并且在武装大环的KSCN复合物中形成了次级夹杂物，在该武装大环的KSCN络合物中形成了MEO组，其中MEO组在该侧臂的两个邻居中都引入了MEO组。结果表明，可以在侧臂中引入具有更强协调能力的官能团，以通过武装大环形成宿主的络合。较少的

项目成果

Y.Habata: "Syntheses of armed-azecrown ethers by the manrich reaction" J.Heterocyclic Chem. (印刷中).

Y.Habata：“通过曼里奇反应合成武装氮冠醚”J.Heterocyclo Chem。

M.Sato, Y.Kawata, H.Shintate, Y.Habata, S,Akabori, and K.Unoura: "Novel structural rearrengements induced by metal-metal interactions in (pentamethylruthenocenyl) acetylide complexes, RcC * CRuL_2(eta^5-C_5R_5) and Rc' * CruCRuL_2(eta^5-C_5R_5)[Rc = ruthe

M.Sato、Y.Kawata、H.Shintate、Y.Habata、S、Akabori 和 K.Unoura：“（五甲基钌烯基）乙炔络合物中金属-金属相互作用诱导的新型结构重排，RcC * CRuL_2(eta^5-

Y.Habata: "Molecular structure of RbSCN complex with H-(4′hydroxy-3′-5′-drisopropylbenzyl)monoagza-15-crown-5" Supramolecular Chem.(印刷中).

Y. Habata：“RbSCN 与 H-(4′羟基-3′-5′-二异丙基苄基)monoagza-15-crown-5 复合物的分子结构”超分子化学（出版中）。

Z.Chen, J.S.Bradshaw, Y.Habata, and M.L.Lee: "A built-in route leading to a self-inclusion complexe of 6^A,6^B-(bis-O-p-allyloxyphenyl) hexakis (2,3-di-O-methyl)- -cyclodextrin" J.Heterocyclic Chem.34. 983-987 (1997)

Z.Chen、J.S.Bradshaw、Y.Habata 和 M.L.Lee：“一种导致 6^A,6^B-(双-O-对烯丙氧基苯基) 六基 (2,3-

Y.Habata: "Unusual one substitution-one dechlorination product of 1,8-dichloroanthraquinone with(s)-(-)-2-tetraturomyloxy)prepanol" Tetrahedron. 53. 4179-4184 (1997)

Y.Habata：“1,8-二氯蒽醌与(s)-(-)-2-四酰氧基)异丙醇的不寻常的一取代一脱氯产物”四面体。