Synthesis of salicylideneamines-inclusion compounds and elucidation of their chromotropism

以1-苯乙胺和苯甲胺为原料，分别与水杨醛或3，5-二叔丁基水杨醛缩合，合成了手性N-水杨基-1-苯乙胺衍生物和非手性N-水杨醛-1-苯乙胺衍生物。从手性水杨亚胺(R)-和(S)-对映体得到外消旋化合物和外消旋混合物。用365 nm光照射结晶水杨酸亚胺粉末，得到光致变色物种。用反射分光光度法跟踪光致变色反应，测量在黑暗中光致变色最大的波长的光密度。(R)和(S)对映体和外消旋混合物的光致变色性相同，但与外消旋化合物不同。在水杨亚胺中引入大量的叔丁基取代基可以有效地制备光敏性席夫碱晶体。不含叔丁基的水杨亚胺的每个(R)-和(S)-异构体都被嵌入到由手性脱氧胆酸形成的晶格空腔中，得到非对映异构体晶体。这些结果清楚地表明，光诱导的骨架改变并不完全独立于与邻近手性分子的非键相互作用，并且晶体中的单分子不对称运动受到邻近不对称晶体环境的影响。为了开发一系列新的功能配体，我们在2-和6-位将3-β-胆固醇和3-β-胆甾醇衍生的甾体亚基引入了一个吡啶环。合成的配体的Pd(II)络合物在普通有机溶剂中与一些席夫碱重结晶，不能将席夫碱包含在取代基之间，以制备笼状化合物。

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.