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Application of Artificial Polyamides, Having Cyclobutane Rings in the Main Chain, as Chiral Stationary Phases for Hplc

主链带有环丁烷环的人造聚酰胺作为 HPLC 手性固定相的应用

基本信息

批准号：
01850200
负责人：
SAIGO Kazuhiko
金额：
$ 3.07万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B).
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

项目摘要

The phenolic hydroxyl groups in optically active polyamides, which consist of anti head-to-head coumarin dimer, were easily carbamoylated with several kinds of isocyanates in high yield and conversion. HPLC coumns were prepared by coating the polyamides on silica gel surface. The carbamoylated polyamides showed a chiral recognition ability for the racemates, which could not be recognized by the parent polyamides. Consequently, the carbamoylated and parent polyamides showed complementary recognition ability.The chiral recognition ability of polyamides, consisting of anti head-to-head coumarin dimer and alpha, omega-alkanediamine, depended on the methylene number of the diamine component and showed odd-even dscrimination. The X-ray diffraction and DSC analyses revealed that the chiral recognition ability appeared only for the polyamides, which could crystallize on the surface of silica gel and that the higher crystallinity resulted in the higher chiral recognition ability. This result is … More the first example for the elucidation of the correlation between chiral recognition ability, crystallinity, and odd-even discrimination.Polyamides, derived from anti head-to-head umbelliferone dimer, showed steep decrease of their viscosity in an alkaline solution, whereas polyamides consisting of anti head-to-head coumarin dimer were rather stable in an alkaline solution. This phenomenon was found to result from the scission of the main chian via a quinoid from of dihydroxyphenyl groups in the side chain.Anti head-to-head umbelliferone dimer was successfully resolved into enantiomers with high optical purities. The ring-opening polyaddition reaction of the optically active dimer with diamines proceeded very smoothly to give the corresponding, optically active polyamides. Some of them existed in ordered conformation in a solution and/or film state. The polyamides, however, unfortunately showed no chiral recognition ability, which would come from the strong hidrogen bonding between the hydroxyl group at C7 and a solute. Less

光学活性聚酰胺中的酚羟基由反头对头香豆素二聚体组成，可以很容易地与几种异氰酸酯进行氨甲酰化反应，产率和转化率都很高。将聚酰胺包覆于硅胶表面，制得高效液相色谱柱。氨基甲酰化聚酰胺对外消旋体具有一定的手性识别能力，而母体聚酰胺则不能识别。由反头对头香豆素二聚体和α，omega-烷二胺组成的聚酰胺的手性识别能力依赖于二胺组分的亚甲基数，表现为奇偶数差异。X-射线衍射和DSC分析表明，只有在硅胶表面结晶的聚酰胺才具有手性识别能力，结晶度越高，手性识别能力越强。此结果为…更多的是解释手性识别能力、结晶度和奇偶识别之间关系的第一个例子。由反伞形内酯二聚体衍生的聚酰胺在碱性溶液中粘度急剧下降，而由反香豆素二聚体组成的聚酰胺在碱性溶液中相当稳定。这一现象是由于侧链上的二羟基苯基中的一种奎宁类化合物使主链断裂所致。反头对头伞形内酯二聚体被成功拆分成光学纯度较高的对映体。光学活性二聚体与二胺的开环多加成反应进行得非常顺利，得到了相应的光学活性聚酰胺。它们中的一些在溶液和/或薄膜状态下以有序构象存在。然而，不幸的是，聚酰胺没有显示出手性识别能力，这可能来自于C7上的羟基与溶质之间的强氢键。较少