1999 Fiscal Year Final Research Report Summary
Study on Dynamic Molecular Behaviors in Crystal
| Project/Area Number |
09044091
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| Research Category |
Grant-in-Aid for Scientific Research (B).
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Okayama University of Science (1999)
Ehime University (1997-1998) |
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Principal Investigator |
TODA Fumio Okayama University of Science, Department of Chemistry Professor, 理学部, 教授 (50036232)
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| Co-Investigator(Kenkyū-buntansha) |
MIYAMOTO Hisakazu Ehime Univ., Applied Chemistry, Assistant Prof., 工学部, 助手 (30229893)
TANAKA Koich Ehime Univ., Applied Chemistry, Associate Prof., 工学部, 助教授 (10116949)
TOYOTA Shinji Okayama Univ. of Science, Chemistry, Associate Prof., 理学部, 助教授 (80207646)
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| Project Period (FY) |
1997 – 1999
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| Keywords | Dynamic Behaviors of Molecules in Crystal / Chemical Reactions in Crystal / Reaction from Single-Crystal-to-Single-Crystal / Enantioselective Reactions / Inclusion Complex Crystal / 包接錯体結晶 |
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| Research Abstract |
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.
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