| Project/Area Number |
07555581
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 試験 |
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| Research Field |
有機工業化学
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| Research Institution | The University of Tokyo |
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Principal Investigator |
SAIGO Kazuhiko The University of Tokyo, Graduate School of Engineering, Professor, 大学院・工学系研究科, 教授 (80016154)
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| Co-Investigator(Kenkyū-buntansha) |
SAKAI Kenichi Yamakawa Chemical Industry Co., Ltd., Isohara Plant, Senior Research Chemist, 磯原工場・技術研究室, 主任研究員
HASHIMOTO Yukihiko The University of Tokyo, Graduate School of Engineering, Associate Professor, 大学院・工学系研究科, 助教授 (50201710)
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| Project Period (FY) |
1995 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1996: ¥2,000,000 (Direct Cost: ¥2,000,000)
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| Keywords | Optical Resolution / Diastereomeric Method / Mandelic Acid / 1-Phenylethylamine / Enantiomer |
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| Research Abstract |
In order to understand the mechanism of chiral discrimination upon crystallization of diastereomeric salt and to develop novel resolving reagents, the resolution of 1-arylalkylamines by mandelic acid was studied. As a result, it was found that the position of a substituent on the aromatic group of the amines was correlated with the resolution efficiency to a considerable extent. A substituent, which elongated the molecular length of the amine, diminished the resolution efficiency. The crystal structures of less-soluble diastereomeric salts revealed that a characteristic hydrogen-bond layr, consisting of hydrogen-bond columns and having planar boundary surfaces, was commonly formed ; these crystals were considered to be stable from the viewpoint of both hydrogen-bonding and van der Waals interactions. Such a stable layr would be necessary for efficient resolution, and in order to realize such a stable hydrogen-bond layr, the molecular length of a racemate should be similar to or a little shorter than that of the resolving reagent. In contrast, in the cases of the corresponding more-soluble salts and diastereomeric salts, which could not be separated by crystallization, such a stable crystal structure was not realized in all cases. On the basis of these results, (S)-p-methylmandelic acid and (R)-p-methoxymandelic acid were selected as new resolving reagents for 1-arylalkylamines ; these resolving reagents were found to have a higher resolving ability for 1-arylalkylamines than mandelic acid.
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