• Search Research Projects
  • Search Researchers
  1. Back to previous page

PROPERTIES OF REACTIVE INTERMEDIATES GENERATED BY PHOTOCHEMICAL METHOD

Research Project

Project/Area Number10044091
Research Category

Grant-in-Aid for Scientific Research (B).

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

Principal Investigator

MIZUNO Kazuhiko  OSAKA PREFECTURE UNIVERSITY, COLLEGE OF ENGINEERING, PROFESSOR, 工学部, 教授 (10109879)

Co-Investigator(Kenkyū-buntansha) MAEDA Hajime  OSAKA PREFECTURE UNIVERSITY, COLLEGE OF ENGINEERING, RESEARCH ASSOCIATE, 工学部, 助手 (40295720)
SUGIMOTO Akira  OSAKA PREFECTURE UNIVERSITY, COLLEGE OF ENGINEERING, ASSOCIATE PROFESSOR, 工学部, 助教授 (00081323)
CALDWELL Richard a.  THE UNIVERSITY OF TEXAS AT DALLAS, DEPARTMENT OF CHEMISTRY, PROFESSOR
コールドウェル リチャー  米国テキサス大学, ダラス校, 教授
Project Period (FY) 1998 – 1999
Project Status Completed(Fiscal Year 1999)
Budget Amount *help
¥3,000,000 (Direct Cost : ¥3,000,000)
Fiscal Year 1999 : ¥1,400,000 (Direct Cost : ¥1,400,000)
Fiscal Year 1998 : ¥1,600,000 (Direct Cost : ¥1,600,000)
Keywords1,n-Biradical / Exciplex / Cyclopropane / Photoisomerization / Photocycloaddition / Aromatic Hydrocarbon / Substituent Effect / Laser Flash Photolysis / ビニリデンシクロプロパン / 光転位反応 / 光定常状態 / 光異性化
Research Abstract

Photochemical properties and direct observations of reactive species in cis-trans photoisomerizations, photorearrangements, and photocycloadditions via 1,n-biradicals and exciplexes were examined and the following results were obtained.
1) Photoirradiation of 1,2-diphenylcyclopropane derivatives bearing one or two p-acetylphenyl group(s) caused cis-trans isomerization to give 45 : 55 photostationary state, accompanying with the formation of ring-opening products, 1,3-diphenylpropene derivatives. Nano-second order laser flash photolysis indicated that the photoisomerization proceeds via triplet 1,3-biradicals whose lifetimes are ca. 15 ns, and that the substituent effect at para position are negligible except for heavy atom effect by bromide group.
2) Photoirradiation of cis- and trans-1-diphenylvinylidene-2,3-dimethylcyclopropane in direct or in the presense of triplet sensitizer caused cis-trans isomerization. Cis/trans ratios in photostationary states were 50 : 50 in direct irradiation, 30 : 70 in the presense of triplet sensitizer, respectively.
3) Aromatic hydrocarbons such as pyrene and phenanthrene reacts with electron-deficient alkenes such as methyl cinnamate and cinnamonitrile under photoirradiation conditions, to give (2π+ 2π) photocycloadducts at 4,5-position of pyrene and 9,10-position of phenanthrene in high yields. Prolonged irradiation of a solution containing pyrene and electron-deficient alkene give 1 : 2 adduct efficiently. Intramolecular photocycloaddition of aromatic hydrocarbons connecting alkene moiety at appropriate position gave (2π+ 2π) photocycloadducts more selectively.

Report

(3results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report

Research Products

(24results)

All Other

All Publications

  • [Publications] N. Ichinose: "Photochemical C-C Bond Cleavage of 1,2-Diarylcyclopropanes Bearing an Acetylphenyl Group. Generation and Ovservation of Triplet 1,3-Biradicals"J. Org. Chem.. 63. 3176-3184 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Tamai: "Generation of Polyphenylene (PP) Radical and Cosensitization of PP in the 9,10-Dicyano-anthracene-Sensitized Photochemical Chain Reactionsof 1,2-Bis(4-methoxyphenyl) cyclopropane"J. Org, Chem.. 63. 3204-3212 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Yoshimi: "A Novel Photorearrangement of Aryl Naphthylmethyl Ethers. Formation of Cyclohexa-2,4-dienone Derivatives"Tetrahedron Lett.. 39. 4683-4586 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Mizuno: "A Novel Intramolecular Photocuyclization of 2-(4,5-Dimethyl-2-oxa-4-hexenyl)1-methoxycarbonylnaphthalene via 1,9-Hydrogen Abstraction"Chem. Commun. 1175-1177 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Sugimoto: "Thermally Unstable 5-(9-Anthrylmethyl)-10-methyl-5,10-dihydrophenazine"J. Chem. Res.(S). 72-73 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Sugimoto: "Successive Electron Transfer Reaction of the Lithium Salt of 5-Methyl-5,10-dihydrophenazine Anion with 4-Nitrophenethl Bromide via 4-Nitrostyrene"J. Heterocycl. Chem.. 36. 849-856 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 水野 一彦: "季刊化学総説 No.36, 「光化学の基礎と先端研究」"学会出版センター. 275 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Mizuno: "Advances in Electron Transfer Chemistry VI"JAI Press. 165 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N.Ichinose: "Photochemical C-C Bond Cleavage of 1,2-Diarylcyclopropanes Bearing an Acetylphenyl Group. Generation and Observation of Triplet 1,3-Biradicals."J.Org.Chem.. 63. 3176-3184 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Tamai: "Generation of Polyphenylene (PP) Radical Cations and Cosensitization of PP in the 9,10-Dicyano-anthracene-Sensitized Photochemical Chain Reactionsof 1,2-Bis(4-methoxyphenyl)cyclopropane."J.Org.Chem.. 63. 3204-3212 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.Yoshimi: "A Novel Photorearrangement of Aryl Naphthylmethyl Ethers. Formation of Cyclohexa-2,4-dienone Derivatives."Terahedron Lett.. 39. 4683-4686 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K.Mizuno: "A Novel Intramolecular Photocuyclization of 2-(4,5-Dimethyl-2-oxa-4-hexenyl)-1-methoxycarbonylnaphthalene via 1,9-Hydrogen Abstraction."Chem.Commun.. 1998. 1175-1177

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A.Sugimoto: "Thermally Unstable 5(9-Anthrylmethyl)-10-methyl-5,10-dihydroiphenazine."J.Chem.Res. (S). 1999. 72-73

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A.Sugimoto: "Successive Electron Transfer Reaction of the Lithium Salt of 5-Methyl-5,10-dihydrophenazine Anion with 4-Nitrophenethyl Bromide via 4-Nitrostyrene."J.Heterocycl.Chem.. 36. 849-856 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] A. Sugimoto: "Thermally Unstable 5-(9-Anthrylmethyl)-10-methyl-5,10-dihydrophenazine"J. Chem. Res. (S). 72-73 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A. Sugimoto: "Successive Electron Transfer Reaction of the Lithium Salt of 5-Methyl-5,10-dihydrophenazine Anion with 4-Nitrophenethyl Bromide via 4-Nitrostyrene"J. Heterocycl. Chem.. 36. 849-856 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] A. Sugimoto: "Hydrobromic Acid - Dimethyl Sulfoxide Reagent for Dealkylation of 5,10- Dialkyl-5,10-dihydrophenazines: Synthesis of 10-Alkyl-2(10H)-phenazinones"J. Heterocycl. Chem.. 36. 1057-1064 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K. Mizuno: "Advances in Electron Transfer Chemistry VI"JAI Press. 165 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Ichinose: "Photochemical C-C Bond Cleavage of 1,2-Diarylcyclopropanes Bearing an Acetylphenyl Group. Generation and Observation of Triplet 1,3-Biradicals." J.Org.Chem.63. 3176-3184 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Tamai: "Generation of Polyphenylene (PP) Radical Cations and Cosensitization of PP in the 9,10-Dicyanoanthracene-Sensitized Photochemical Chain Reactions…" J.Org.Chem.63. 3204-3212 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Yoshimi: "A Novel Photorearrangement of Aryl Naphthylmethyl Ethers. Formation of Cyclohexa-2,4-dienone Derivatives." Tetrahedron Lett.39. 4683-4686 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Mizuno: "A Novel Intramolecular Photocylization pf 2-(4,5-Dimethyl-2-oxa-4-hexenyl)-1-methoxycabonylnaphthalene via 1,9-Hydrogen Abstraction." Chem.Commun.1175-1177 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 水野一彦: "季刊化学総説 No.36,「光化学の基礎と先端研究」" 学会出版センター, 275 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Mizuno: "Novel Trends in Electroorganic Synthesis" Springer-Verlag Tokyo, 461 (1998)

    • Related Report
      1998 Annual Research Report

URL :

Published : 1998-04-01   Modified : 2016-04-21  

Information FAQ News Terms of Use

Powered by NII kakenhi