Study on Dynamic Molecular Behaviors in Crystal

当crystals of diallene derivative (A) is heated for 1h，dimethylencecyclobutene derivative is produced by a cyclization reaction.自a has a -transstructure on crystalisomenzation reaction from the s-trans configuration to a -cis one should be occurred before thecyclization reaction It is very interesting that such the big molecular motion occurs in a smallspace of crystal.它也可以确认thermal conversion proceeds stereoselectively.Whena prochiral molecule is included in a chiral host compoundformer is arranged ina chiral form in its inclusion crystal and its inadiation gave opticallyactive photoreaction product. In most cases of the photoreaction In crystalcrystalline lattice of the inclusion compound is destroyed as the反应协议. On thecontrary, photodimerzation of cyclohexenone, coumarinthiocoumarin in inclusion complex crystal with optically active host compound proceeded fromsingle-crystal-to-single-crystal and enantioselectively to give corresponding optically activedimer. These reactions were studied by X-ray analysis.Some other organic solid state reactions werealso developed. For example, Dieckmann reaction, azomethine formation reactionMichael addition reaction found to proceed efficiently in the solid state. Of thesereactions,azomethine formation reaction was studied carefully by AFM method.Solvent-free reactions were alsoclarified to proceed selectively. For example，treatment of stilibene and chalcone with pyridine- hbre - br D22 - D2 salt in the solid state gave meso-erythro- addition product这些数据很清楚地显示了在crystal move easily and that reaction occurs的秘密活动和反应occursselectively and efficiently in the solid state

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.