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GENERATION OF BIRADICALOIDS AND BIRADICALS BY PHOTOINDUCED ELECTRON TRANSFER

Research Project

Project/Area Number 07640701
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

TAKAHASHI Yasutake  TOHOKU UNIVERSITY,GRADUATE SCHOOL OF SCIENCE,ASSISTANT PROFESSOR, 大学院理学研究科, 助手 (70197185)

Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1996: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1995: ¥1,200,000 (Direct Cost: ¥1,200,000)
KeywordsPhotoinduced Electron Transfer / Biradicals / omicron-Xylylene / Electrocyclic Reaction / Benzocyclobutanes / オルトキノジメタン / ビラジカロイド
Research Abstract

Photoinduced electron transfer reaction of methoxy-substituted benzocyclobutanes results in their electrocycloreversion to generate omicron-xylylenes, which can be trapped with dienophiles such as tetracyanoethylene to produce cycloadducts. It is found that stereochemistry for the ring opening is non-stereospecific. Accordingly, photoinduced electron transfer presents a new and remarkable method for facile disrotatory ring opening of ring fused benzocyclobutanes. These derivatives do not undergo thermal ring opening because its symmetry allowed conrotaory process is sterically constrained.
Photoinduced electron transfer reactions of 1,2-bis (1-phenylvinyl) benzene and 1,2-bis (1-phenylvinyl) furan have been investigated. These compounds undergo electron-transfer induced electrocyclization to generate an omicron-xylylene derivative and dimethylenefuran derivative When photolyzed with an electron-accepting sensitizer such as 9,10-dicyanoanthracene (DCA).Biradicaloid and biradical can be observed spectroscopically and trapped by dienophiles. It is clear that photoinduced electron transfer from 1,2-bis (1-phenylvinyl) benzene or 1,2-bis (1-phenylvinyl) furan to the singlet excited DCA is an important initial step. Substrate cation radicals in photogenerated ion radical pairs, [Substrate^<・+>, DCA^<・->] may undergo electrocyclization and omicron-xylylene and dimethylenefuran derivative can be produced by back ET possibly within the resulting ion pairs. The [4+2] cycloaddition of the resulting omicron-xylylene and dimethylenefuran derivative with added dienophiles leads to adducts.

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (40 results)

All Other

All Publications (40 results)

  • [Publications] C.Sato: "New Aspects on Fluorescence Quenching by Molecular Oxygen.2." J.Phys.Chem.99. 16925-16931 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Generation of o-Xylylene:Electrocyclization of 1,2-Bis(1-phenylvinyl)benzene Promoted by Photoinduced Electron Transfer" J.Chem.Soc.,Chem.Commun.1749-1750 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Electron-Transfer Photochemistry of 2,3-Diphenyl-1,3-butadiene" Res.Chem.Intermed.21. 765-775 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Photoinduced Skeletal Rearrangement of 1,1-Diphenylspiropentanes" Tetrahedron Lett.36. 5207-5210 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Photoinduced Electron-Transfer Reactions of 2,7-Diarylocta-1,7-dienes and 2,8-Diarylnona-1,8-dienes" Tetrahedron Lett.36. 1889-1892 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Stepwise but Potentially Stereoselective Intramolecular[2+2]Cycloaddition via 1,4-Cation Radical Intermediates" J.Chem.Soc.,Chem.Commun.521-522 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Photoinduced Skeletal Rearrangement of 1,1-Diarylspiropentanes" J.Chem.Soc.,Perkin Trans.1. 319-325 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Phenylcyclopropane Cation Radical Revisited:Generation,Direct Observation,and Determination of the Rates of Nucleophilic Capture" Tetrahedron Lett.37. 1841-1844 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Ikeda: "Phenyl Substitution Effects on Rate Acceleration of Cation Radical Deazetation of 2,3-Diazabicyclo[2.2.2]oct-2-enes" Tetrahedron Lett.37. 4377-4380 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Electrocycloreversion of Benzocyclobutenols Promoted by Photoinduced Electron Transfer" Tetrahedron Lett.37. 5547-5550 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Wakamatsu: "Isomerization of cis,trans-and trans,trans-1,4-Diphenyl-1,3-butadienes by Photoinduced Electron Transfer" J.Chem.Soc,Perkin Trans.2. 2105-2109 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Sato: "Fluorescence Quenching of Aromatic Molecules by SCN-in Acetonitrile:Effect of Molecular Size on Electron Transfer Fluorescence Quenching" Chem.Phys.Lett.276. 210-216 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi: "Charge-Transfer Excitation of the Arylcyclopropane Electron Donor-Acceptor Complexes" J.Chem.Soc.,Perkin2. 303-308 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Sato, K,Kikuchi, K.Okamura, Y.Takahashi, and T.Miyashi: "New Aspects on Fluorescence Quenching by Molecular Oxygen.2." J.Phys.Chem. 99. 16925-16931 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, Y.Ohya, H.Ikeda, and T.Miyashi: "Generation of omicron-Xylylene : Electrocyclization of 1,2-Bis (1-phenylvinyl) benzene Promoted by Photoinduced Electron Transfer" J.Chem.Soc., Chem.Commun.1749-1750 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, R.Iida, and T.Miyashi: "Electron-Transfer Photochemistry of 2,3-Diphenyl-1,3-butadiene" Res.Chem.Intermed.21. 765-775 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, H.Ohaku, S.Morishima, and T.Suzuki. and T.Miyashi: "Photoinduced Skeletal Rearrangement of 1,1-Diphenylspiropentanes" Tetrahedron Lett.36. 5207-5210 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, M.Ando, and T.Miyashi: "Photoinduced Electron-Transfer Reactions of 2,7-Diarylocta-1,7-dienes and 2,8-Diarylnona-1,8-dienes" Tetrahedron Lett.36. 1889-1892 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, M.Ando, and T.Miyashi: "Stepwise but Potentially Stereoselective Intramolecular [2+2] Cycloaddition via 1,4-Cation Radical Intermediates" J.Chem.Soc., Chem.Commun.521-522 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, H.Ohaku, S.Morishima, T.Suzuki, H.Ikeda, and T.Miyashi: "Photoinduced Skeletal Rearrangement of 1,1-Diarylspiropentanes" J.Chem.Soc., Perkin Trans.1. 319-325 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, N.Nishioka, F.Endoh, H.Ikeda, and T.Miyashi: "Phenylcyclopropane Cation Radical Revisited : Generation, Direct Observation, and Determination of the Rates of Nucleophilic Capture" Tetrahedron Lett.37. 1841-1844 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Ikeda, T.Minegishi, Y.Takahashi, and T.Miyashi: "Phenyl Substitution Effects on Rate Acceleration of Cation Radical Deazetation of 2,3-Diazabicyclo [2.2.2] oct-2-enes" Tetrahedron Lett.37. 4377-4380 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, K.Miyamoto, K.Sakai, H.Ikeda, T.Miyashi, Y.Ito, and K.Tabohashi: "Electrocycloreversion of Benzocyclobutenols Promoted by Photoinduced Electron Transfer" Tetrahedron Lett.37. 5547-5550 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Wakamatsu, Y.Takahashi, K.Kikuchi, and T.Miyashi: "Isomerization of cis, trans- and trans, trans-1,4-Diphenyl-1,3-butadienes by Photoinduced Electron Transfer" J.Chem.Soc, Perkin Trans.2. 2105-2109 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] C.Sato, K.Kikuchi, H.Ishikawa, M.Iwahashi, H.Ikeda, Y.Takahashi, and T.Miyashi: "Fluorescence Quenching of Aromatic Molecules by SCN- in Acetonitrile : Effect of Molecular Size on Electron Transfer Fluorescence Quenchig" Chem.Phys.Lett.276. 210-216 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Takahashi, H.Ohaku, N.Nishioka, T.Miyashi, D.A.Gormin, and E.F.Hilinski: "Charge-Transfer Excitation of the Arylcyclopropane Electron Donor-Acceptor Complexes" J.Chem.Soc., Perkin. 2. 303-308 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Yasutake Takahashi: "Charge-Transfer Excitation of the Arylcyclopropane Electron Donor-Acceptor Complexes" J. Chem. Soc., Perkin 2. (印刷中).

    • Related Report
      1996 Annual Research Report
  • [Publications] K. Wakamatsu: "Isomerization of cis, trans- and trans, trans-1, 4-Diphenyl-1, 3-butadienes by Photoinduced Electron Transfer" J. Chem. Soc, Perkin 2. 2105 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yasutake Takahashi: "Electrocycloreversion of Benzocyclobutenols Promoted by Photoinduced Electron Transfer" Tetrahedron Lett,. 37. 5547-5550 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H. Ikeda: "Phenyl Substitution Effects on Rate Acceleration of Cation Radical Deazetation of 2, 3-Diazabicyclo [2. 2. 2] oct-2-enes" Tetrahedron Lett,. 37. 4377-4380 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yasutake Takahashi: "Phenylcyclopropane Cation Radical Revisited : Generation, Direct Observation and Determination of teh Rates of Nucleophilic Capture" Tetrahedron Lett,. 37. 1841-1844 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yasutake Takahashi: "Photoinduced Skeletal Rearrangement of 1, 1-Diphenylspiropentanes" J. Chem. Soc., Perkin Trans. I. 319-325 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Yasutake Takahashi: "Stcpwisc but potcntially stcrosclcctivc intramolccular [2+2]cycloaddition via 1,4-cation radical intermediates" J. Chem. Soc., Chem. Commun.521-522 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yasutake Takahashi: "Photinduced electron-transfer reactions of 2,7-diarylocta-1,7-dienes 2,8-diarylnona-1,8-dienes" Tetrahedron Lett.36. 1889-1892 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yasutake Takahashi: "Photinduced skeletal rearrangement of 1,1-diphenylspiropentanes" 36. 5207-5210 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yasutake Takahashi: "Electron-transfer photochemistry of 2,3-diphenyl-1,3-butadiene" Res. Chem. Intermed.21. 765-775 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yasutake Takahashi: "Generation of an o-xylylene: electroclization of 1,2-bis (1-phenylvinyl) benzene promoted by photoinduced electron transfer" J. Chem. Soc., Chem. Commun.1749-1750 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] C. Sato: "New aspects on fluorescence quenching by molecular oxygen. 2." J. Phys. Chem.99. 16925-16931 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Yasutake Takahashi: "Photoinduced skeletal rearrangement of 1,1-diarylspiropentanes" J. Chem. Soc., Perkin Trans 1. (印刷中).

    • Related Report
      1995 Annual Research Report
  • [Publications] Yasutake Takahashi: "Phenylcyclopropane cation radical revisited: generation, direct observation, and determination of the rates of nucleophilic capture" Tetrahedron Lett.(印刷中).

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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