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

抗头对头香豆素二聚体组成的光学活性聚酰胺的酚羟基易于与几种异氰酸酯进行氨基甲酰化，收率高，转化率高。将聚酰胺包覆在硅胶表面制备了高效液相色谱柱。氨基甲酰化聚酰胺对外消旋体具有手性识别能力，而对外消旋体具有手性识别能力。因此，氨基甲酰化聚酰胺和亲本聚酰胺表现出互补的识别能力。由抗头对头香豆素二聚体和- ω -烷二胺组成的聚酰胺的手性识别能力取决于二胺组分的亚甲基数，并表现出奇偶识别。x射线衍射和DSC分析表明，只有聚酰胺具有手性识别能力，聚酰胺可以在硅胶表面结晶，结晶度越高，手性识别能力越强。该结果是第一个阐明手性识别能力、结晶度和奇偶辨别之间关系的例子。在碱性溶液中，由抗头对头伞形素二聚体制成的聚酰胺粘度急剧下降，而由抗头对头香豆素二聚体制成的聚酰胺在碱性溶液中粘度相当稳定。发现这种现象是由于侧链上的二羟基苯基的一个醌类基团使主链断裂。反头对头伞形酮二聚体成功地分离成光学纯度高的对映体。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。它们中的一些以溶液和/或膜态的有序构象存在。然而，不幸的是，聚酰胺没有手性识别能力，这可能是由于C7羟基与溶质之间的强氢键。少

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