Synthesis of Optically Active Polyamides and Their Application as Stationary Phases for Optical Resolution

为了获得合成光学活性聚酰胺的有用组分，我们首次建立了反式头对头香豆素二聚体的光学拆分方法。此外，还实现了一种新的高效拆分1，2-二苯基乙二胺的方法：将光学活性的反头-头香豆素二聚体与各种二胺通过开环加成反应合成光学活性聚酰胺。CD光谱研究的基础上，有人建议，这些聚酰胺中的一些存在于一个有序的构象在溶液中取决于刚性和共轭的二胺组分。例如，由柔性的六亚甲基二胺组分组成的光学活性聚酰胺在溶液中以无规构象存在，而由刚性的可共轭的1，4-苯二胺组分组成的光学活性聚酰胺在碱性介质中以有序构象存在。 ...更多信息 用二苯基硅烷偶联剂处理，制备了高效液相色谱拆分外消旋体的色谱柱。含有己二胺或1，4-苯二胺组分的聚酰胺对外消旋体具有很好的光学拆分能力。薄膜态聚酰胺的CD光谱研究表明，聚酰胺的手性识别能力强烈依赖于聚酰胺与溶质之间的相互作用和/或聚酰胺的有序构象. 1，2-二苯基乙二胺与二甲酰氯的低温溶液聚合反应顺利进行，得到了相应的光学活性聚酰胺.含芳香族二元酸的聚酰胺比含脂肪族二元酸的聚酰胺具有更强的手性识别能力。其原因被认为如下：由芳香族二羧酸组分组成的聚酰胺在重复单元中具有与pirkle型类似的关键结构，pirkle型是众所周知的有效的光学活性固定相。研究结果为开发高性能、适用范围广的光学活性固定相提供了重要信息。少

To obtain the useful components for the synthesis of optically active polyamides, we developed for the first time a method for the optical resolution of anti head-to-head coumarin dimer. Moreover, a new and efficient method for the optical resolution of 1,2-diphenylethylenediamine was achieved.Optically active anti head-to-head coumarin dimer easily reacted with various kinds of diamines to give optically active polyamides by ring-opening polyaddition. On the basis of CD spectral studies, it was suggested that some of these polyamides exsist in an ordered conformation in a solution depending on the rigidity and conjugatability of the diamine components. For examples, optically active polyamide consisting of flexible hexamethylenediamine component exists in a random conformation in solutions although that consisting of rigid and conjugatable 1,4-phenylenediamine component exists in an ordered conformation in basic media.These optically active polyamides were coated on the silica gel, pr … More etreated with diphenylsilane coupler, to prepare columns for high-performance liquid chromatographic resolution of racemates. The polyamide having hexamethylenediamine or 1,4-phenylenediamine component showed high ability for the optical resolution of racemates. The CD spectral sudies of the polyamides in film state indicated that the chiral recognition ability depends strongly on the simultanious interaction between the polyamide and the solute and/or on the ordered conformation of the polyamide.The low temperature solution polymerization of 1,2-diphenylethylenediamine with dicarbonyl chlorides proceeded smoothly to give the corresponding optically active polyamides. The polyamides having aromatic dicarboxylic acid component showed higher ability for chiral recognition than those having aliphatic dicarboxylic acid component. The reason is considered as follows: The polyamides consisting of aromatic dicarboxylic acid component have a similar key structure to pirkle type, which is well-known to be effective as an optically active stationary phase, in the repeating units. Moreover, high-ordered comformation would contribute the high ability.It is concluded that the results in this work offer important informations for the development of high-performance and wide-applicable optically active stationary phases for optical resolution. Less