| Project/Area Number |
06403022
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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 | 一般 |
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| Research Field |
有機工業化学
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| Research Institution | KYUSHU UNIVERSITY (1995-1996)
Nagaoka University of Technology (1994) |
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Principal Investigator |
AOYAMA Yasuhiro Kyushu University, Institute for Fundamental Research of Organic Chemistry Professor, 有機化学基礎研究センター, 教授 (00038093)
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| Co-Investigator(Kenkyū-buntansha) |
HAYASHIDA Osamu Kyushu University, Institute for Fundamental Research of Organic Chemistry Assoc, 有機化学基礎研究センター, 助教授 (20231532)
小林 健二 筑波大学, 化学系, 講師 (40225503)
戸井 啓夫 群馬工業高等専門学校, 教授 (90126475)
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| Project Period (FY) |
1994 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥29,500,000 (Direct Cost: ¥29,500,000)
Fiscal Year 1996: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1995: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1994: ¥22,700,000 (Direct Cost: ¥22,700,000)
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| Keywords | microporous crystals / network / stack / organic zeolites / solid catalysts / excimer fluorescence / Diels-Alder reactions / cavity / ゼオライト / 結晶工学 / 芳香環カラム / 水素結合 / 分子シート / 分子結晶 / 金属配位 / 構造規制 / クリスタルエンジニアリング |
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| Research Abstract |
An anthracene bisresorcinol derivative 1 has been shown to form molecular sheets composed of hydrogen-bonded polyresorcinol chains together with large cavities roofed and floored by the anthracene rings. The cavities selectively incorporate a variety of guest molecules.
(1) Diels-Alder Reaction As Catalyzed by Microporous Crystal 1
As confirmed before, crystal 1 incorporates two molecules of ethyl acetate and benzene in each cavity. When the guest molecules are changed respectively into acrolein (dienophile) and 1.3-cyclohexadiene, a facile and catalytic Diels-Alder reaction takes place in a highly stereoselective (endo-selective) manner, where the roles of 1 as a microporous catalyst are (a) to assemble two reactants in the cavity, (2) to activate the dienophile via acid-catalysis through host-guest hydrogen-bonding, (3) to exert steric constraint in a 3D cavity, and (4) to exchange reactants and products in the cavity.
(2) Functional Self-Assembly of 1D Chains
Anthracene monoresorcinol compound 2 forms similar but 1D hydrogen-bonded network. The chains are held together via intercalation of the orthogonal anthracene substituents ; in the cavities are included guest molecules in a 1 : 1 host-guest stoichiometry. The cavities are much less thick as compared with those in the 2D network of host 1 and show a novel thickness selectivity in the guest-binding, where a remarkable preference for linear alkyl groups to brached ones is observed. Closely packed anthracene-guest alternate columns can be constructed in this way.
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