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Rationalization of Chiral Discrimination upon Crystallization of Diastereomeric Salt and Development of Novel Practical Resolving Reagent

非对映盐结晶手性判别的合理化及新型实用拆分试剂的开发

基本信息

批准号：
07555581
负责人：
SAIGO Kazuhiko
金额：
$ 1.28万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555581/
关键词：
Optical Resolution Diastereomeric Method Mandelic Acid 1-Phenylethylamine Enantiomer

项目摘要

In order to understand the mechanism of chiral discrimination upon crystallization of diastereomeric salt and to develop novel resolving reagents, the resolution of 1-arylalkylamines by mandelic acid was studied. As a result, it was found that the position of a substituent on the aromatic group of the amines was correlated with the resolution efficiency to a considerable extent. A substituent, which elongated the molecular length of the amine, diminished the resolution efficiency. The crystal structures of less-soluble diastereomeric salts revealed that a characteristic hydrogen-bond layr, consisting of hydrogen-bond columns and having planar boundary surfaces, was commonly formed ; these crystals were considered to be stable from the viewpoint of both hydrogen-bonding and van der Waals interactions. Such a stable layr would be necessary for efficient resolution, and in order to realize such a stable hydrogen-bond layr, the molecular length of a racemate should be similar to or a little shorter than that of the resolving reagent. In contrast, in the cases of the corresponding more-soluble salts and diastereomeric salts, which could not be separated by crystallization, such a stable crystal structure was not realized in all cases. On the basis of these results, (S)-p-methylmandelic acid and (R)-p-methoxymandelic acid were selected as new resolving reagents for 1-arylalkylamines ; these resolving reagents were found to have a higher resolving ability for 1-arylalkylamines than mandelic acid.

为了了解非对映体盐结晶时的手性识别机制，开发新型拆分试剂，研究了扁桃酸拆分1-芳烷基胺的方法。结果发现，胺的芳族基团上的取代基的位置在相当大的程度上与拆分效率相关。取代基延长了胺的分子长度，降低了拆分效率。不太可溶的非对映体盐的晶体结构显示，通常形成由氢键柱组成并具有平面边界表面的特征性氢键层;从氢键和货车范德华相互作用的观点来看，这些晶体被认为是稳定的。这种稳定的层对于有效的拆分是必要的，并且为了实现这种稳定的氢键层，外消旋体的分子长度应该与拆分试剂的分子长度相似或稍短。相反，在不能通过结晶分离的相应的更可溶的盐和非对映异构体盐的情况下，在所有情况下都不能实现这种稳定的晶体结构。在此基础上，选择了（S）-对甲基扁桃酸和（R）-对甲氧基扁桃酸作为1-芳烷基胺类化合物的新拆分试剂，发现这两种拆分试剂对1-芳烷基胺类化合物的拆分能力高于扁桃酸。