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，我们首次开发了一种反头对头香豆素二聚体的光学分辨方法。此外，还获得了一种新的、高效的1,2-二苯乙二胺的光学分辨方法。具有旋光性的抗头对头香豆素二聚体通过开环加成容易与多种二胺反应得到旋光性聚酰胺。在CD光谱研究的基础上，提出了一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性。例如，由柔性六亚二胺组分组成的光学活性聚酰胺在溶液中以随机构象存在，而由刚性和可共轭的1,4-苯二胺组分组成的聚酰胺在基本介质中以有序构象存在。将这些光学活性聚酰胺包被在硅胶上，再用二苯基硅烷偶联剂处理，制备高效液相色谱分离外消旋物的色谱柱。含有六亚二胺或1,4-苯二胺成分的聚酰胺对外消旋物具有较高的光学分辨能力。膜态聚酰胺的CD谱研究表明，手性识别能力主要取决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化物的低温溶液聚合进展顺利，得到了相应的光学活性聚酰胺。具有芳香二羧酸成分的聚酰胺比具有脂肪二羧酸成分的聚酰胺具有更高的手性识别能力。其原因是：芳香族二羧酸组成的聚酰胺在重复单元中具有与旋光固定相相似的键结构，而旋光固定相是众所周知的有效的旋光固定相。此外，高序构象有助于提高能力。本文的研究结果为开发高性能和广泛应用的光学分辨光学主动固定相提供了重要的信息。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