| Project/Area Number |
61470020
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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 | University of Tsukuba |
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Principal Investigator |
SAKURAGI Hirochika Department of Chemistry, University of Tsukuba, 化学系, 助教授 (10011602)
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| Project Period (FY) |
1986 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥6,500,000 (Direct Cost: ¥6,500,000)
Fiscal Year 1988: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1987: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1986: ¥4,800,000 (Direct Cost: ¥4,800,000)
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| Keywords | Bichromophoric compounds / Exciplex / Intramolecular cycloaddition / Temperature dependence / Solvent dependence / Electron transfer / 磁場効果 / 環化付加 / 異性化 / 分子内励起錯体 / 付加環化 / 温度効果 / 溶媒効果 |
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| Research Abstract |
In order to clarify factors determining the reactivity of excited states of bichromophoric compounds, the following problems were studied:
1) Structure-reactivity relationships of exciplexes involved in intramolecular cycloadditions of phenanthrene derivatives: photoreactions of unsaturated phenahrenecarboxylate esters, bichromophoric compounds in which a phenanthrene and a styrene derivative are linked by an ester and a polymethylene group, were studied by using organic and physical techniques. The reaction course was dependent on the length of methylene chain and linking mode; some gave both of an oxetane, a carbonyl adduct, and a cyclobutane with the same structure as that of an intermolecular cycloadduct between a phenanthrene and a styrene, whereas others produced only the former. Exciplex quenching, temperature and solvent effects on exciplex cmission and product distribution were investigated to reveal behavior of plural exciplex intermediates. Preparation and photoreactions were also attempted for bichromophoric compounds with a long methylene chain. Intermolecular reactions of phenanthrene lactones with styrenesand intramolecular reactions of a cyano group with a styrene moiety were also investigated.
2) Isomerization of oxime ethers through exciplexes: behavior of exciplexes between dicyanonathracene and 2-acetylnaphthalene oxime ethers was studied. It was clarified that the isomerization proceeds through the triplet state of the oxime ethers generated from the exciplexes.
3) Isomerization of olefins through exciplex or electron transfer: mechanisms for isomerization of aromatic olefins due to interaction between olefin singlets and electron acceptors and due to sensitization with electron accepting sensitizers were studied on the basis of transient spectroscopy and amgnetic field effects.
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