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

[part为了开发形成分子内氢键的配体，已经合成了在两端具有OH基团的新配体1、2和3。以吡啶二甲酸和乙二醇为原料，合成了2，6-吡啶二甲酸双（2 '-羟乙基）酯（1），并对其结构进行了固相（傅立叶变换红外光谱和X射线分析）、液相（~ 1H和~ <13>1C核磁共振滴定）和气相（快原子轰击质谱）表征。两个2，6-吡啶二甲酸双（2 ′-羟乙基）酯分子各自与一个水分子通过氢键结合在一起，在固态和氯仿溶液中得到一个假大环。FAB质谱还表明配体1在气相中形成二聚体。在这一部分中，我们证明了配体1在固态和溶液中都形成了类邻位冠醚结构。此外，配体1在气相中与水和二聚体形成1：1的络合物。金属催化剂的配合物研究 ...更多信息 离子和有机客体的新配体的研究正在进行中。[part 2]已经合成了能够具有分子内氢键的新的豆荚化合物（2和3）。分子模拟（构象搜索、AMI优化和3- 21 G（*）计算）表明，吡啶二甲醇二对甲苯磺酸酯与邻苯二酚反应生成的podand 2和吡啶二甲醇与水杨酸反应生成的podand 3分别形成环状和非环状结构。吡啶二甲醇二对甲苯磺酸酯与邻苯二酚在碳酸钠存在下于乙腈中反应制得Podand 2，产率41%。二聚体产物4也作为副产物以3%产率分离。以吡啶二甲醇和水杨酸为原料，DCC/DMAP为催化剂，二氯甲烷为溶剂合成了荚状配体3，产率41%。新豆荚化合物2和3的结构经^1H和11 <13>C NMR、MS、FT-IR、元素分析和X射线晶体学确证。在这一部分中，我们证明了通过氢键形成假环状结构的荚状配体比形成非环状结构的荚状配体对金属离子具有更高的亲和力。还报道了2-NaSCN配合物的X-射线晶体结构。少

[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