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，我们首次建立了一种光学拆分反头对头香豆素二聚体的方法。此外，还获得了一种新的高效的光学拆分1，2-二苯乙二胺的方法，即光学活性的反头对头香豆素二聚体很容易与各种二胺通过开环多加成反应得到光学活性的聚酰胺。根据CD光谱研究表明，某些聚酰胺在溶液中以有序的构象存在，这取决于二胺组分的刚性和共轭能力。例如，由柔性六亚甲二胺组成的光学活性聚酰胺在溶液中以随机构象存在，而在碱性介质中由刚性和可共轭的1，4-苯二胺组成的光学活性聚酰胺以有序构象存在。这些光学活性聚酰胺被包覆在硅胶上，Pr…更多的是用二苯基硅烷偶联剂来制备高效液相色谱拆分外消旋体的柱。含有六亚甲二胺或1，4-苯二胺的聚酰胺对外消旋体具有较高的光学拆分能力。薄膜状态下聚酰胺的圆二色谱研究表明，手性识别能力强烈地依赖于聚酰胺与溶质的同时相互作用和/或聚酰胺的有序构象。1，2-二苯乙二胺与二羰基氯的低温溶液聚合顺利地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高的手性识别能力。原因被认为是：由芳香族二元酸组成的聚酰胺在重复单元中具有与Pirkle类型相似的关键结构，众所周知，Pirkle类型作为光学活性固定相是有效的。研究结果为开发高性能、广泛应用的光学活性固定相提供了重要的信息。较少

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