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Synthesis of salicylideneamines-inclusion compounds and elucidation of their chromotropism

水杨胺包合物的合成及其向色性的阐明

基本信息

批准号：
07640725
负责人：
KAWATO Toshio
金额：
$ 1.47万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
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

项目摘要

Chiral N-salicylidene-1-phenylethylamine derivatives and achiral N-salicylidenebenzylamine derivatives were prepared by the condensation of 1-phenylethylamine and benzylamine derivatives with salicylaldehyde or 3,5-di-tert-butylsalicylaldehyde. From the chiral salicylideneamines (R)-and (S)-enantiomers, racemic compounds, and racemic mixtures were obtained. Photo-colored species were obtained by irradiating the crystalline salicylidencamines powder with 365 nm light. The thermal fading reaction of the photochrome was followed by reflectance spectrophotometry by measuring the optical density at the wavelength at which a maximal decrease occurred in the dark. The photochromicity of the (R)-and (S)-enantiomers and the racemic mixture was identical and differed from that of the racemic compound. Introduction of bulky t-butyl substituents to salicylideneamines was effective to prepare photosensitive Schiff base crystals.Each (R)-and (S)-isomer of the salicylidencamines without tert-butyl substituent was incroporated in the crystal lattice cavities formed by chiral deoxycholic acid (DCA) to give diastereomeric crystals.Most of the obtained definite clathrate compounds were photosensitive but the rate constants of the diastereomeric crystals were different each other. These results clearly show that the photoinduced framework alteration is not entirely independent from nonbonding interaction with the neighboring chiral molecules and that unimolecular asymmetric motion in the crystals is influenced by the neighboring asymmetric crystal environments.Trying to develop a new series of functional ligands, we introduced steroidal subunits derived from 3beta-cholesterol and 3beta-cholestanol to a pyridine ring at the 2- and 6-positions. The Pd (II) complexes of the resultant ligands were recrystallized from ordinary organic solvents with some Schiff bases to fail to include the Schiff bases between the steroidal substituents to prepare clathrate compounds.

以水杨醛或3，5-二叔丁基水杨醛与1-苯乙胺和苄胺反应，合成了手性N-亚水杨基-1-苯乙胺衍生物和非手性N-亚水杨基苄胺衍生物。从手性水杨醛胺得到（R）-和（S）-对映体、外消旋化合物和外消旋混合物。通过用365 nm光照射结晶水杨醛胺粉末获得光着色物质。通过反射分光光度法测量在黑暗中发生最大降低的波长处的光密度，跟踪光致变色剂的热褪色反应。（R）-和（S）-对映异构体和外消旋混合物的光致变色性相同且不同于外消旋化合物的光致变色性。在水杨醛缩胺上引入大体积叔丁基取代基是制备光敏席夫碱晶体的有效方法，不含叔丁基取代基的水杨醛缩胺的（R）-和（S）-异构体均被引入手性脱氧胆酸（DCA）形成的晶格空腔中所得到的包合物大部分具有光敏性，但各非对映体晶体的速率常数不同其他.这些结果清楚地表明，光诱导的骨架变化并不完全独立于与相邻手性分子的非键相互作用，晶体中的单分子不对称运动受到相邻不对称晶体环境的影响。我们将衍生自3 β-胆固醇和3 β-胆甾烷醇的甾体亚基在2-和6-位引入吡啶环。将所得配体的Pd（II）配合物从普通有机溶剂中与一些Schiff碱重结晶，以不包括在甾体取代基之间的Schiff碱，从而制备笼形化合物。