1996 Fiscal Year Final Research Report Summary
Generation of Stable Biradical Intermediates in Intramolecular Photo-Cycloaddition of Aromatic Compounds
| Project/Area Number |
07640710
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | CHIBA University |
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Principal Investigator |
YAMADA Kazutoshi Chiba University, Department of Materials Science, Professor, 工学部, 教授 (60009230)
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| Co-Investigator(Kenkyū-buntansha) |
KISHIKAWA Keiki Chiba University, Department of Materials Science, Assistant Professor, 工学部, 助手 (40241939)
KOHMOTO Shigeo Chiba University, Department of Materials Science, Associate Professor, 工学部, 助教授 (90195686)
YAMAMOTO Makoto Chiba University, Department of Materials Science, Professor, 工学部, 教授 (50039294)
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| Project Period (FY) |
1995 – 1996
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| Keywords | Photo [2+2] cycloaddition / Photo [4+2] cycloaddion / Photo [4+4] cycloaddition / Biradical intermediate / Oxygen trapping / peri-Selectivity / Solid-state photochemistry / 不斉誘起 |
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| Research Abstract |
In order to establish the highly stereo and peri-selective in an aromatic photo-cycloaddition and to elucidate the involvement
of biradical intermediates, photochemical reactin of N-naphthamides and N-cimmamides were examined.,
(1) Inter- and Intra- molecular selection of photo-cycloaddition ; In the photo-cycloadditin of N-cimmanoylnaphthamides, the intramolecular cycloaddion occurred in solution and the intermolecular cycloadition was achieved in the solid state reaction depending on the substituents.
(2) The control of the peri-selectivity ; This was achieved in the photo-cycloaddition of N-1- (1-naphthyl) ethyl-cimmamides and N-1- (1-naphthyl) ethylacryl amides. In the former, the intramoleclar [4+2] cycloaddition was achieved and the [2+2] cycloaddition was achieved in the latter.
(3) Novel [2+2] photo-cycloaddition of a benzene ring with an enone double bond ; This rare example of the [2+2] photo-cycloaddition was observed in N-benzoylcimmamides.
(4) Generation of a biradical intermediate and its trapping with molecular oxygen ; The 1,8 biradical intermediate was generated in the intramolecular photo-cycloaddition of N-naphthoylnaphtamides. The generated biradical intermediate was efficiently trapped with molecular oxygen. The life time of the intermedaite was determined by laser flash photolysis.
(5) Asymmetric photo [4+4] cycloaddition ; The first example of an absolute asymmetric synthesis in aromatic photo-cycloaddion was achieved in the solid-state photochemistry of N-anthronylnaphthamieds.
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Research Products
(12 results)
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[Publications] S.Kohmoto, T.Kobayashi, J.Minami, X.Ying, K.Yamaguchi, T.Karatsu, A.Kitamura, K.Kishikawa, M.Yamamoto, and K.Yamada: "Trapping of 1,8-Biradical Intermedaites by Molecular Oxygen in Photocycloaddition of Naphthoylnaphthamides ; An Evidence of Stepwise Aromatic Cyclic addition." (Manuscript in preparation).
Description
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