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Spectroscopic Detection and Reaction Analysis of Short-lived Species Generated in Solution Using an Electron-Transfer Stopped-Flow Method

Research Project

Project/Area Number 13640602
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 分離・精製・検出法
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

OYAMA Munetaka  Kyoto Univ., International Innovation Center, Associate Professor, 国際融合創造センター, 助教授 (90221861)

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 2003: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2001: ¥1,800,000 (Direct Cost: ¥1,800,000)
KeywordsStopped Flow / Electron-Transfer / Cation Radical / Aromatic Amines / Dimerization Reaction / Reaction Analysis / Precursor Effect / Electro-oxidation / ストップトフロー法
Research Abstract

Using an electron transfer stopped-flow method, spectroscopic detection and reaction analysis were carried out for various aromatic amine cation radicals. In the reaction of 4-bromo-N, N-dimethylaniline cation radical, the dimerization reaction mechanism accompanying the release of bromo-subsutituent was clarified. In the case of triphenylamine cation radical, a stabilized state was clarified to be formed with the presence of precursor molecules. In the reaction of N, N-dimethyl-toluidine cation radical, while the cation radicals was stable without the precursors, the cation radical decreased in the presence of precursors due to the acid-base reaction. The reaction of N, N-dimethyl-anisidine cation radical is the same, but the dimerization rate was ca. 1/100 due to the stabilization effect of methoxy group. The reactions of N-methylanisidine and anisidine cation radicals were also examined as well as the meta-and ortho-derivatives.
Furthermore, the reactions of carbazole derivative cation radicals could be analyzed using the proposed method. Finally, the study moved toward the detection and analysis of monomer cation radicals to form the electro-conducting polymer materials. In particular, for the thiophene derivatives, it was found that terthiophene canon radical can be detected to follow the decrease. In the cases of ethylenedioxithiophene derivative cation radicals, the study is now in underway.

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] Munetaka Oyama: "Spectroelectrochemical approach for analysing the reaction kinetic of N,N-dimethyl-p-anisidine cation radical with the neutral molecule in acetonitrile"Indian Journal of Chemistry A. 42. 733-738 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Jun Matsui: "Kinetics and mechanisms of the reactions of 9-substituted anthracene cation radicals with water or methanol in acetonitrile"Journal of Electroanalytical Chemistry. 558. 49-57 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama: "Substituent effect on the reactions of diphenylamine derivative cation radicals in acetonitrile"Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry. 129-132 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama: "Spectroscopic investigation of oxidation products of ortho- or meta- substituted aniline derivatives in acetonitrile using an electron-transfer stopped-flow method"Electrochimica Acta. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama: "Spectroscopic observation of the dimerisation reactions of 9-phenylcarbazole cation radical in acetonitrile"Bulletin of the Chemical Society of Japan. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama, Jun Matsui: "Kinetics analysis of the reactions of 1-substituted pyrene cation radicals with water in acetonitrile"Journal of Electroanalytical Chemistry. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masashi Goto, Koji Otsuka, Xi Chen, Ying Tao, Munetaka Oyama: "Kinetic analysis of the reactions of p-anisidine and N-methyl-p-anisidine cation radicals in acetonitrile using an electron-transfer stopped-flow method"Journal of Physical Chemistry A. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama, Jun Matsui: "Spectroscopic Observation of the Dimerization reactions of the 9-Phenylcarbazole Cation Radical in Acetonitrile"Bulletin of the Chemical Society of Japan. 77. 953-957 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Jun Matsui, Hyun Parka Koji Otsuka, Munetaka Oyama: "Kinetics and mechanisms of the reactions of 9-substituted anthracene cation radicals with water or methanol in acetonitrile"Journal of Electroanalytical Chemistry. 558. 49-57 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama, Masashi Goto: "Spectroelectrochemical approach for analysing the reaction kinetic of N, N-dimethyl-p-anisidine cation radical with the neutral molecule in acetonitrile"Indian Journal of Chemistry A. 42. 733-738 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama, Miyako Kambayashi: "Reaction of the triphenylamine cation radical with pyridine in acetonitrile. Electrochemical responses vs. decay reactions in homogeneous solution"Electrochemistry Communications. 4. 759-763 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masashi Goto, Hyun Park, Koji Otsuka, Munetaka Oyama: "Kinetics of the Decay Reactions of the N, N-Dimethyl-p-Toluidine Cation Radical in Acetonitrile. Acid-Base Interaction to Promote the CH_2-CH_2 Bonding"J.Physical Chemistry A.. 106. 8103-8108 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hyun Park, Munetaka Oyama: "Remarkable 3-Methyl Substituent Effect on the Cyclization Reaction of Diphenylamine Derivative Cation Radicals in Acetonitrile"Journal of the Chemical Society, Perkin Trans.. 2. 1335-1339 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama, Jun Matsui, Hyun Park: "Spectroscopic detection of short-lived anthracene derivative cation radicals using an electron transfer stopped-flow method with the tris(2, 4-dibromophenyl)amine cation radical"Chemical Communications. 604-605 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Munetaka Oyama: "Spectroelectrochemical approach for analysing the reaction kinetic of N,N-dimethyl-p-anisidine cation radical with the neutral molecule in acetonitrile"Indian Journal of Chemistry A. 42. 733-738 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Jun Matsui: "Kinetics and mechanisms of the reactions of 9-substituted anthracene cation radicals with water or methanol in acetonitrile"Journal of Electroanalytical Chemistry. 558. 49-57 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Munetaka Oyama: "Substituent effect on the reactions of diphenylamine derivative cation radicals in acetonitrile"Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry. 129-132 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Munetaka Oyama: "Spectroscopic investigation of oxidation products of ortho- or meta- substituted aniline derivatives in acetonitrile using an electron-transfer stopped-flow method"Electrochimica Acta. 49. 3801-3806 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Munetaka Oyama: "Spectroscopic observation of the dimerisation reactions of 9-phenylcarbazole cation radical in acetonitrile"Bulletin of the Chemical Society of Japan. 77. 953-957 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Hyun Park: "Remarkable 3-Methyl Substituent Effect on the Cyclization Reaction of Diphenylamine Derivative Cation Radicals in Acetonitrile"Journal of the Chemical Society, Perkin Trans. 2. 1335-1339 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Masashi Goto: "Kinetics of the Decay Reactions of the N, N-Dimethyl-p-Toluidine Cation Radical in Acetonitrile. Acid-Base Interaction to Promote the CH_2-CH_2 Bonding"Journal of Physical Chemistiy A. 106. 8103-8108 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Munetaka Oyama: "Reaction of the triphenylamine cation radical with pyridine in acetonitnle. Electrochemical responses vs. decay reactions in homogeneous solution"Electrochemistry Communications. 4. 759-763 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Hyun Park: "Electrochemical and Electron Transfer Behaviors of ο-Chloranil with the Presence of Mg^<2+> in Acetonitrile"Electroanalysis. 14. 1269-1274 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Neil V. Rees: "The Electro-oxidation of N, N-Dimethyl-p-toluidine in Acetonitrile : a Microdisk Voltammetry Study"Journal of Electroanalytical Chemistiy. 531. 33-42 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Munetaka Oyama: "Spectroelectrochemical approach for analysing the reaction kinetic of N, N-dimethyl-p-anisidine cation radical with the neutral molecule in acetonitrile"Indian Journal of Chemistry A. (印刷中). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Munetaka Oyama: "Electron Transfer Stopped-Flow Method. Its Validity for Spectrochemical Analysis of Electrogenerated Cation Radicals"Journal of the Electrochemical Society. 149. E12-E17 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Munetaka Oyama: "An Intermediate State of the Triphenylamine Cation Radical Revealed Using an Electron Transfer Stopped-Flow Method"Electrochemical and Solid State Letters. 5. E1-E3 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Munetaka Oyama: "Apparent acid-base reaction between the N, N-dimethyl-p-toluidine cation radical and the neutral molecule in acetonitrile"Electrochemistry Communications. 4. 110-114 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Hyun Park: "Electrochemical and Electron Transfer Behaviors of o-Chloranil with the Presence of Mg^<2+> in Acetonitrile"Electroanalysis. (印刷中).

    • Related Report
      2001 Annual Research Report
  • [Publications] Munetaka Oyama: "Competitive electrochemical deposition of barium salts of chloranil analogous anion radicals. Correlation with reactivity in homogeneous solution"Journal of the Electroanalytical Chemistry. (印刷中).

    • Related Report
      2001 Annual Research Report
  • [Publications] Munetaka Oyama: "Spectroscopic Detection of Short-Lived Anthracene Derivative Cation Radicals Using an Electron Transfer Stopped-Flow Method with the Tris(2,4-dibromophenyl)amine Cation Radical"Chemical Communications. (印刷中).

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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