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1995 Fiscal Year Final Research Report Summary

Design of Reactivity of Organic Cation Radicals Generated by Photoinduced Electron Transfer

Research Project

Project/Area Number 06640708
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionGunma College of Technology

Principal Investigator

AKABA Ryoichi  Gunma College of Technology, 物質工学科, 助教授 (70184091)

Project Period (FY) 1994 – 1995
KeywordsCation Radical / Photoinduced Electron Transfer / 2, 4, 6-Triphenylpyrylium Salt / Oxygenation / C-C Bond Cleavage / Deprotonation / Olefin Cation Radical / Laser Flash Photolysis
Research Abstract

The present study deals with the design of reactivity of organic cation radicals generated by photosensitized electron transfer in solution. The sensitizers employed are 2, 4, 6-triphenylpyrylium salt (TPP), 2, 4, 6-triphenylthiapyrylium salt (STPP), and 9, 10-dicyanoanthracene (DCA) 1. Firstly, cation radicals of diarylethanals were generated by TPP, STPP and/or DCA, and the products were compared. Laser flash photolysis has also been carried out to elucidate the reactive intermediates involved. The results suggest that the reacivity of diarylethanal having 4, 4-dimethoxy groups in the presence of oxygen is quite different between DCA and TPP sensitized reactions.
2. Secondary, tetrakis (4-methylphenyl) ethanone was investigated with DCA and TPP as sensitizers, and it was found that the C-C bond cleavage occurred in both reactions with different mechanisms for the product formation of same kinds.
3. Thirdly, Deprotonation of 9, 10-dihydroanthracene was studied in the presence of oxygen with DCA and TPP sensitization. We have found that TPP sensitized oxygenation gave anthracene whereas DCA sensitization gave anthrone as a primary, major product. The results were interpreted in terms of the acidity of superoxide radical anion (O_2^-.) involved in DCA sensitized oxygenation, which is absent in the TPP sensitized oxygenation. 4. Lastly, TPP and DCA sensitized oxygenation were carried out for stilbene (ST), triphenylethylene (TPE), and tetraphenylethylene (TEPE), and comparison of products revealed that TEPE does not react with molecular oxygen while ST and TPE react. All olefins studied were found to react with O_2^-. The observed difference of reactivity of olefin cation radicals were discussed in terms of stability of intermediate peroxy radical cations and dioxetane cation radicals.

  • Research Products

    (2 results)

All Other

All Publications (2 results)

  • [Publications] R. Akaba et al. ,: "Deprotonation of Organic Radical Cations. Chemical Evidence for Proton Transfer between 9, 10-Dihydroanthracene Radical Cations and Superoxide Radical Anions" Journal of Physical Organic Chemistry. (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Ryoichi, Akaba Mitsuru, Iwasaki Tsuyoshi, Matsumura Masaki, Kamata Hiroki, Itoh: "Deprotonation of Organic Radical Cations. Chemical Evidence for Proton Transfer between 9, 10-Dihydroanthracene Radical Cations and Superoxide Radical Anions" Journal of Physical Organic Chemistry. (in press). (1996)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1997-03-04  

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