| Project/Area Number |
03453030
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | KYUSHU UNIVERSITY |
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Principal Investigator |
INAZU Takahiko Kyushu University Faculty of Science Department of Chemistry Professor, 理学部, 教授 (60037207)
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| Co-Investigator(Kenkyū-buntansha) |
TAKEMURA Hiroyuki Kyushu University College of General Education Research Associate, 教養部, 助手 (60183456)
SUENAGA Masahiko Kyushu University Faculty of Science Department of Chemistry Research Associate, 理学部, 助手 (70216274)
SHINMYOZU Teruo Kyushu University Institute for Molecular Science Associate Professor, 助教授 (90037292)
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| Project Period (FY) |
1991 – 1992
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| Project Status |
Completed (Fiscal Year 1992)
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| Budget Amount *help |
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1992: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1991: ¥6,100,000 (Direct Cost: ¥6,100,000)
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| Keywords | Transannular pi-pi Interaction / annulenophane / anti-aromatic compound / cyclophane / annulene / aromatic compound / semi-empirical molecular orbital calculation / MOPAC / 渡環πーπ相互作用 / シアナミド / 1,6ーメタノ[10]アヌレン |
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| Research Abstract |
It is our interest to study how two pi-systems mutually interact when they overlap each other in a close proximity. According to the frontier molecular orbital calculations, Greenberg et al. predicted a destabilizing pi-pi interaction in a (4n+2)pi-(4n+2)pi system, a stabilizing interaction in a (4n+2)pi-(4n)pi system, and greater stabilization in a (4n)pi-(4n)pi system than in the (4n+2)pi-(4n)pi system. To verify this interesting prediction experimentally, we considered that [3.3]annulenophanes must be the most suitable models since [3.3]cyclophane permits exact evaluation of pi-pi interaction without interference of the strain effect.
As model compounds for the study of (4n+2)(4n+2)interaction (n*2), we synthesized [3.3]cyclophanes containing Vogel's 1,6-methano[10]annulene, which are the first example of [m.n]cyclophanes containing two annulene rings. The synthesis of double-layered annulenophanes containing trans-15,16-dimethyl-dihydropyrene units (14pi) and Paudler's 8b,8c-diazacyclopent[fg]acenaphthylene (12pi) is in progress. The structures and transannular pi-pi interactions of annuleno-phanes were studies based on the spectral properties and theoretical calculations by the MNDO-PM3 method.
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