SYNTHESES AND CHIRAL RECOGNITlON ABILITIES OF THE PODANDS THAT ARE ORGANIZED BY

所组织的 Podand 的合成和手性识别能力

基本信息

批准号：
12640566
负责人：
HABATA Yoichi
金额：
$ 2.11万
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：
2000
资助国家：
日本
起止时间：
2000 至 2001
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640566/
关键词：
podand hydrogen bonding alkali metal molecular modeling X ray crystallography NMR titration intramolecular hydrogen bonding hydroxy group ホスト-ゲスト超分子組織化包接錯体ポーダンド配位子擬似環状

项目摘要

[part 1] In order to develop podands which form intramolecular hydrogen bonding, new pordands 1, 2 and 3 having OH group in both ends have been synthesized. Bis(2'-hydroxyethyl) 2,6-pyridinedicarboxylate (1) was prepared by the reaction of pyridinedicarboxy acid and ethylene glycol and the structure was characterized in solid (fourier trans form-ir and X-ray analyses), in liquid (^1H and ^<13>C nmr titrations), and in the gas-phase (fast atom bombardment (fab) ms). Two bis(2'-hydroxyethy) 2,6-pyridinedicarboxylate molecules each with an included water molecule are bound together through hydrogen bonding to give a pseudo-macrocycle in the solid state and in chloroform solution. The FAB mass spectrum also suggested that ligand 1 forms a dimer in the gas-phase. In this part, we have demonstrated that ligand 1 forms apseudo-crown ether-like structure in the solid state and in solution. Also, ligand 1 forms a 1:1 complex with water and a dimer in gas phase. Complexalion studies of metal cat … More ions and organic guests by the new ligand are in progress.[part 2] New podands capable of having intramolecular hydrogen bonding (2 and 3) have been synthesized. Molecular modeling (conformer search, AMI optimization and 3-21G(*) calculations) suggest that podand 2, which was prepared by the reaction of pyridinedimethanol dilosylate with catechol, and podand 3, which was prepared by the reaction of pyridinedimethanol with salicylic acid, form cyclic and non-cyclic structures, respectively. Podand 2 was prepared by the reaction of pyridinedimethanol ditosylate with catechol in the presence of Na_2C0_3 in acetonitrile in 41% yield. Dimerizalion product 4 was also isolated as a by-product in 3% yield. Podand 3 was prepared from pyridinedimethanol and salicylic add in the presence of DCC/DMAP in CH_2Cl_2 in 41% yield. Structures of new podands 2 and 3 were confirmed by ^1H and ^<13>C NMR, MS, FT-IR, elemental analyses, and X-ray crystallography. In this part, we have demonstrated that a podand which forms a pseudo-cyclic structure by hydrogen bonding shows higher affinity for metal ions than a podand which forms a non-cyclic structure. The X-ray crystal structure of the 2-NaSCN complex is also reported. Less

[第1部分] 为了开发形成分子内氢键的化合物，合成了两端具有OH基团的新化合物1、2和3，合成了双(2'-羟乙基)2,6-吡啶二甲酸酯(1)。吡啶二甲酸和乙二醇的反应，并在固体中表征了结构（傅立叶反式红外和 X 射线分析），液体(^ 1 H和^ 13 C nmr滴定)和气相(快原子轰击(fab)ms) 两个双(2'-羟基乙基)2，6-吡啶二甲酸分子，每个分子包含水分子。通过氢键结合在一起，在固态和氯仿溶液中形成假大环。FAB 质谱还表明配体 1 在溶液中形成二聚体。在这一部分中，我们证明了配体 1 在固态和溶液中形成假冠醚状结构，并且配体 1 在气相中与水和二聚体形成 1:1 络合物。新配体对金属猫… 更多离子和有机客体的研究正在进行中。[第 2 部分] 已经合成了能够具有分子内氢键（2 和 3）的新荚体。 (构象搜索、AMI优化和3-21G(*)计算)表明，由吡啶二甲醇二甲磺酸酯与儿茶酚反应制备的podand 2和由吡啶二甲醇与水杨酸反应制备的podand 3形成环状结构。 Podand 2 是由吡啶二甲醇二甲苯磺酸酯与儿茶酚反应分别制备的。在Na_2CO_3的存在下，在乙腈中，以41%的收率还分离出二聚产物4，以3%的收率在DCC/DMAP的存在下，从吡啶二甲醇和水杨酸在CH_2Cl_2中以41%的收率制备。新podands 2和3的结构由^1H和确认。 ^ 13 C NMR、MS、FT-IR、元素分析和X射线晶体学在这一部分中，我们已经证明通过氢键形成假环结构的荚体比金属离子表现出更高的亲和力。形成非环状结构的 2-NaSCN 配合物的 X 射线晶体结构也有报道。