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1993 Fiscal Year Final Research Report Summary

Study on the preparation and properties of polycyclic compounds bearing extremely bent benzene rings.

Research Project

Project/Area Number 04453018
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionHokkaido University

Principal Investigator

TSUJI Takashi  Hokkaido University Associate Professor, 理学部, 助教授 (20029482)

Co-Investigator(Kenkyū-buntansha) NISHIDA Shinya  Hokkaido University Professor, 理学部, 教授 (40029400)
Project Period (FY) 1992 – 1993
KeywordsCyclophane / Strained compound / Photochemical Reaction / Dewar Benzene
Research Abstract

1.Preparation of |1.1|paracyclophane and theoretical study on its structure and energetics. The preparation of |1.1|paracyclophane (2) via photochemical isomerization of bis (Dewar benzene) compound (1) was accomplished for the first time on the substituted derivative (R=CO_2Me) last year. To explore the chemistry of extremely strained cyclophanes further, unsubstituted 1a was prepared and 2a was successfully generated from 1a via its photochemical isomerization. According to theoretical calculations the interatomic distance between the opposing bridgehead carbons is exceptionally short at 2.3-2.4A and, thus, strong transannular interactions between the two aromatic rings in 2 is suggested. The calculations also suggest that removal of two electrons from 2a leads to electronically stabilized dication 2a^<2+> in which electronic charge is extensively delocalized and the interatomic distance mentioned above further diminishes to 2.05A,an unusually short interatomic distance for non-bonded carbon atoms. Investigation on the kinetic stabilization of 2 and the generation of 2^<2+> is now underway.
Study on photochemical reactivities of Dewar benzenes 1.4-bridged with functionalized four-carbon-chain. Interested in a possibility that bridged Dewar benzene-|4|paracyclophane system may function as a photochemically driven molccular switching device. Dewar benzene derivatives bearing electron-withdrawing groups on the side chain were prepared and their photochemical behaviors were studied. Compounds 3b and 4a underwent photochemically reversible transformation into 5b and 6a, respectively, which exhibited characteristic UV/V is absorption spectra extending to 500nm. The photochemical reactivities of 3a and 4b were strikingly different from those of 3b and 4a, and their isomerization into the |4|paracyclophane structures could not be detected.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Takashi Tsuji: "〔1.1〕Paracyclophane.Generation and Spectroscopic Characterization of the Bis (methoxycarbonyl)Derivative" Journal of the American Chemical Society. 115. 5284-5285 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masakazu Ohkita: "Single Step Synthesis of 2-Norbornanone Ethylene Acetals from 2-Cyclopenten-1-one Ethylene Acetals" Journal of Organic Chemistry. 58. 5200-5208 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masakazu Ohkita: "Single Step Synthesis of Norbornan-2-one Dithioacetals from Cyclopent-2-en-1-one Dithioacetals and Dienophiles" J.Chem.Soc.,Chemical Communications. 1676-1677 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takashi Tsuji: "Ring-Opening Cycloaddition of 4-Thiadispiro〔2.1.2.2.〕-non-8-ene with Tetracyanoquinodimethane via Zwitterion" Journal of Organic Chemistry. 58. 1601-1603 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takashi Tsuji: "Photochemical Generation of Bicyclo〔4.2.2〕decapentaene from 〔4.2.2〕Propellatetraene" Journal of the American Chemical Society.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masakazu Ohkita: "Generation,Spectroscopic Characterization,and Reactions of 3,4-Benzotropone" Journal of the American Chemical Society.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takashi Tsuji: "[1.1]Paracyclophane. Generation and Spectroscopic Characterization of the Bis (methoxycarbonyl) Derivative" Journal of the American Chemical Society. 115. 5284-5285 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masakazu Ohkita: "Single Step Synthesis of 2-Norbornanone Ethylene Acetals from 2-Cyclopenten-1-one Ethylene Acetals" Journal of Organic Chemistry.58. 5200-5208 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masakazu Ohkita: "Single Step Synthesis of Norbornan-2-one Dithioacetals from Cyclopent-2-en-1-one Dithioacetals and Dienophiles" J.chem.Soc., Chemical Communications. 1676-1677 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takashi Tsuji: "Ring-opening Cycloaddition of 4-Thiadispiro [2.1.2.2]-non-8-ene with Tetracyanoquinodimethane via Zwitterion" Journal of Organic Chemistry. 58. 1601-1603 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takashi Tsuji: "Photochemical Generation of Bicyclo [4.2.2] decapentaene from [4.2.2] Propellatetraene" Journal of the American Chemical Society.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masakazu Ohkita: "Generation, Spectroscopic Characterization, and Reactions of 3,4-Benzotropone" Journal of the American Chemical Society.

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

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Published: 1996-04-15  

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