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Study on Dynamic Molecular Behaviors in Crystal

晶体动态分子行为研究

基本信息

批准号：
09044091
负责人：
TODA Fumio
金额：
$ 4.35万
依托单位：
Okayama University of Science (1999)Ehime University (1997-1998)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

When crystals of diallene derivative (A) is heated for 1h, dimethylencecyclobutene derivative (B) is produced by a cyclization reaction. Since A has a s-trans structure on crystal, isomenzation reaction from the s-trans configuration to a s-cis one should be occurred before the cyclization reaction. It is very interesting that such the big molecular motion occurs in a small space of crystal. It was also confirmed that the thermal conversion proceeds stereoselectively.When a prochiral molecule is included in a chiral host compound, the former is arranged in a chiral form in its inclusion crystal and its inadiation gave optically active photoreaction product. In most cases of the photoreaction in crystal, crystalline lattice of the inclusion compound is destroyed as the reaction proceeds. On the contrary, photodimerzation of cyclohexenone, coumarin, and thiocoumarin in inclusion complex crystal with optically active host compound proceeded from single-crystal-to-single-crystal and enantioselectively to give corresponding optically active dimer. These reactions were studied by X-ray analysis.Some other organic solid state reactions were also developed. For example, Dieckmann reaction, azomethine formation reaction, and Michael addition reaction were found to proceed efficiently in the solid state. Of these reactions, azomethine formation reaction was studied carefully by AFM method.Solvent-free reactions were also clarified to proceed selectively. For example, treatment of stilibene and chalcone with pyridine-HBr-BrィイD22ィエD2 salt in the solid state gave meso- and erythro- addition product, respectively. These data clearly show that molecules in crystal move easily and that reaction occurs selectively and efficiently in the solid state.

当将二联烯衍生物（A）的晶体加热1小时时，通过环化反应生成二亚甲基环丁烯衍生物（B）。由于A在晶体上具有s-反式结构，因此在环化反应之前，应该发生从s-反式构型到s-顺式构型的异构化反应。如此大的分子运动发生在晶体的一个小空间里，这是非常有趣的。当前手性分子被包含在手性主体化合物中时，前手性分子以手性形式排列在包合晶体中，其辐照得到光学活性的光反应产物。在晶体中的光反应的大多数情况下，包合物的晶格随着反应的进行而被破坏。与此相反，环己烯酮、香豆素和硫代香豆素在光学活性主体化合物的包合物晶体中的光二聚反应则是从单晶到单晶，并对映选择性地生成相应的光学活性二聚体。用X-射线衍射分析研究了这些反应，并发展了其他一些有机固相反应。例如，发现迪克曼反应、甲亚胺形成反应和迈克尔加成反应在固态下有效地进行。在这些反应中，甲亚胺的生成反应用原子力显微镜（AFM）进行了详细的研究，并阐明了无溶剂反应的选择性。例如，在固态下，用吡啶-HBr-Br-Br-D22-Br-D2盐处理芪和查耳酮分别得到内消旋和外消旋加成产物。这些数据清楚地表明，晶体中的分子容易移动，并且反应在固态下选择性地和有效地发生。