| Project/Area Number |
16K13990
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Synthetic chemistry
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| Research Institution | Gunma University |
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Principal Investigator |
Amii Hideki 群馬大学, 大学院理工学府, 教授 (00284084)
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| Project Period (FY) |
2016-04-01 – 2019-03-31
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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
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| Keywords | フッ素 / 水素結合 / ジフルオロメチル基 / カルボニル基 / 分子触媒 / 立体選択的反応 |
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| Outline of Final Research Achievements |
The present research deals with the effects of the hydrogen bonds derived from difluoromethyl group on selective organic reactions. The difluoromethyl group has been proposed to act as a hydrogen bond donor to a carbonyl oxygen atom. For the effective introduction of a difluoromethyl group into organic molecules, we discovered selective synthesis of o-(difluoromethyl)benzoates by halogen-lithium exchange of (o-bromophenyl)difluoroacetates followed by quenching under basic conditions. Employing EtOH as a quenching agent for the reactions of (o-bromophenyl)difluoroacetates with n-butyllithium in THF at -78 ℃ afforded the corresponding o-(difluoromethyl)benzoates. Furthermore, the intramolecular hydrogen bonding between the difluoromethyl group and the ester moieties in o-(difluoromethyl)benzoates was observed by 1H NMR and IR spectra. Now, we continues the preparation of new organocatalysts possessing difluoromethyl group.
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| Academic Significance and Societal Importance of the Research Achievements |
本研究の学術的意義は、合成反応としての新規性、すなわち、ジフルオロメチル化合物の新しい合成法を開発できた点である。ジフルオロメチル基（HCF2）を有する化合物は、トリフルオロメチル基（CF3）を有する化合物と比べると、一般的に合成が困難であるために、様々な分野でその応用例が極めて乏しい。本研究では、ベンゼン環にジフルオロメチル基とカルボン酸部位が導入できた。さらに、水素結合ドナーとしての可能性の探索を行なった。現時点では社会的に有用な化合物創製には至っていないが、本研究で得られた基礎化学的知見は、将来の医薬品などの有用化合物の選択的合成に繋がると期待している。
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