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：当用一些酚类化合物用曼尼希反应合成手臂大环时，得到了副产物。用11种苯酚进行了反应，并通过测定苯酚的pH值和对碳的静电位电荷来阐明反应机理。结果表明，当使用2,6-二取代苯酚时，可通过测定pH值和计算静电位来估计苯酚的曼尼希反应活性。B：苯酚上含有i-Pr和x-Bu的化合物2和3的RbSCN配合物的x射线结构分析。结果表明，在侧臂上含有t-Bu基团的3-RbSCN形成1:1配合物，而含有i-Pr基团的2-RbSCN形成1:1配合物和聚合物（1:1）_n配合物交替的结构。当考虑含有1- rbscn配合物，其中Me基团为聚合物（1:1）_n配合物时，揭示了这一系列化合物的结构系统地改变了更多的链，这依赖于引入到侧臂的烷基的体积。C：在将F引入到侧臂羟基的两个邻基上的旋臂大环RbSCN配合物中，Rb^+离子被冠环上的5个杂原子和SCN盐的S原子配位，形成了2:1的配合物。另外，另一分子侧臂F原子的配位形成了8个配位结构。在这个配合物中，Rb+离子被F原子束缚，而不是被酚羟基束缚。D：研究发现，侧链上的苯酚与钾离子结合在其他分子中的构型形成了2∶2配合物，并且在侧链上的羟基的两个邻域都引入MeO基团的臂大环的KSCN配合物中形成了二级包合场。结果表明，可以在侧臂中引入对金属离子具有较强配位能力的官能团，以促进臂形大环与宿主络合的发展。少

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。