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The Chemistry of Novel[7]Annulene Compounds

Research Project

Project/Area Number 04640489
Research Category

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

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

Principal Investigator

MACHIGUCHI Takahisa  Saitama University, College of Liberal Arts and Science, Professor, 教養部, 教授 (00008864)

Co-Investigator(Kenkyū-buntansha) YAMABE Shinichi  Nara University of Education, Educaitional Technology Center, Professor, 教育学部, 教授 (00109117)
HASEGAWA Toshio  Saitama University, College of Liberal Arts and Science, Technical Official Mini, 教養部, 教務職員 (00237976)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1993: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1992: ¥1,200,000 (Direct Cost: ¥1,200,000)
Keywords[7]Annulene / [7]Annulenethione / Fulvene / Cycloaddition / Cage Molecule / [7]Annulenimine / S-Oxide / Sulfine / アヌレンチオン / アヌレンイミン / 環状付加反応
Research Abstract

We have found the following results,
1.The absorption bands of tropothione are assigned by a new method "magnetic circular-dichroism".
2.[7]Annulenthione, which is valence isoelectronic with tropone, reacts concertedly with fulvene to give 1 : 1[8 + 2]cycloadducts. The product configuration is sharply different from that of the initially formed[6 + 4]cycloadduct between tropone and fulvene. The reaction mechanism are studies kinetically and by molecular orbital calculations. The obtained endo form of the[8 + 2]product is found to arise from the secondary orbital interaction in the course of the intrinsic reaction coordinate.
3.Thermally stable[7]annulenthiones have been synthesized by direct thiocarbonylation of the corresponding tropones in polar solvents. The products are characterized by IR, UV-visible, and ^1H, ^<13>C, ^<14>N NMR spectroscopies.
4.The reaction of 8, 8-dicyanoheptafulvene and cyclopentadienide anion affords under mild condition two unusual tetracyclic cage molecules. The structures are elucidated using various modern NMR spectroscopic techniques and deuterium-labeling experiments. The easy formation of the considerably strained molecules is ascribed to a nucleophilic addition, followed by protonation and an intramolecular Diels-Alder reaction with normal electron demand. MNDO-MO calculations suggest a possible mechanism.
5.[7]Annulenthione S-oxide have been synthesized as stable dark red needles (mp 68゚C)in high yield. The structure and chemical behaviors of the sulfur are investigated both by X-ray analysis and ^<13>C, ^<17>O, ^<33>S NMR spectroscopies and this compound is found to be the first exmaple of a sulfine charge reversion(umpoulung).
2-Amino[7]annulenimine is conveniently synthesized in high yield and is isolated in pure form.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (26 results)

All Other

All Publications (26 results)

  • [Publications] Takahisa Machiguchi: "Novel Formation of Highly-Strained Molecules" Proc.Isna. 7. 87 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Toshio Hasegawa: "Solid-state Structure of Monothiotropolone" Proc.Isna. 7. 88 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Takahisa Machiguchi: "A Simple Synthesis of Pure 2-Aminotroponimine,the Nitrogen Analogue of Tropolone" Chem.Lett.1821-1822 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Mieko Higashi: "Magnetic Circular Dichroism and Electronic Spectra of Trpothione" Helv.Chim.Acta. 75. 1880-1884 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Shinichi Yamabe: "Frontier Orbitals along Intrinsic Reaction Coordinates of Sulfur-containg [4+2] cycloadditions" J.Org.Chem.1122-1127 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Takahisa Machiguchi: "Novel Cage Molecules from the Reaction of 8,8-Dicyanoheptafulvene with Cyclopentadienide Anion:Structure and Mechanism" J.Am.Chem.Soc.115. 1669-1676 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Takahisa Machiguchi: "Tropothione Undergoes Cycloadditions a Way Different from Tropone:A Comparative Study of Their Reactivities on Cycloaddition to Fulvene" J.Am.Chem.Soc.115. 11536-11541 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Takahisa Machiguchi: "General Synthesis,Spectroscopic Properties,and Dipole Moments of 2-Substituted Tropothiones" Bull.Chem.Soc.Jpn.66. 3699-3706 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Takahisa Machiguchi: "Tropothione S-Oxide:The First Example of Sulfine Charge Reversion(Umpolung)" J.Am.Chem.Soc.116. 407-408 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Machiguchi: "Novel Formation of Highly-Strained Molecules" Proc.Isna. 7. 87 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Hasegawa: "Solid-state Structure of Monothiotropolone" Proc.Isna. 7. 88 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Machiguchi: "A Simple Synthesis of Pure 2-Aminotroponimine, the Nitrogen Analogue of Tropolone" Chem.Lett.1821-1822 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Higashi: "Magnetic Circular Dichroism and Electronic Spectra of Tropothione" Helv.Chim.Acta. 75. 1880-1884 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] S.Yamabe: "Frontier Orbitals along Intrinsic Reaction Coordinates of Sulfur-containg [4 + 2] and [8 + 2]Cycloadditions" J.Org.Chem.58. 1122-1127 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Machiguchi: "Novel Cage Molecules from the Reaction of 8, 8-Dicyanoheptafulvene with Cyclopentadienide Anion : Structure and Mechanism" J.Am.Chem.Soc.115. 1669-1676 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Machiguchi: "Tropothione Undergoes Cycloadditions in a Way Different from Tropone : A Comparative Study of Their Reactivities on Cycloaddition to Fulvene" J.Am.Chem.Soc.115. 11536-11541 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Machiguchi: "General Synthesis, Spectroscopic Properties, and Dipole Moments of 2-Substituted Tropothiones" Bull.Chem.Soc.Jpn.66. 3699-3706 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Machiguchi: "Tropothione S-Oxide : The First Example of a Sulfine Charge Reversion(Umpolung)" J.Am.Chem.Soc.116. 407-408 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Takahisa Machiguchi: "Novel Cage Molecules from the Reaction of 8,8-Dicyanoheptafulvene with Cyclopentadienide Anion: Structure and Mechanism" Journal of the American Chemical Society. 115. 1669-1676 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takahisa Machiguchi: "Tropothione Undergoes Cycloaddition in a Way Different from Tropone:A Comparative Study of Their Reactivities on Cycloaddition to Fulvene" Journal of the American Chemical Society. 115. 11536-11541 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takahisa Machiguchi: "General Synthesis,Spectroscopic Properties,and Dipole Moments of 2-Substituted Tropothiones" Bulletin of the Chemical Society of Japan. 66. 3699-3706 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takahisa Machiguchi: "Tropothione S-Oxide: The First Example of a Sulfine Charge Reversion(Umpolung)" Journal of the American Chemical Society. 116. 407-408 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takahisa Machiguchi: "A Simple Synthesis of Pure 2-Aminotroponimine,the Nitrogen Analogue of Tropolone" Chemistry Letters. 1821-1822 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Miwako Higashi: "Magnetic Circular Dichroism and Electronic Spectra of Tropolone" Helvetica Chimica Acta. 75. 1880-1884 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Shinichi Yamabe: "Frontier Orbitals along Intrinsic Reaction Coordinates of Sulfur-containing [4+2] and [8+2] Cycloadditions" The Journal of Organic Chemistry. 58. 1122-1127 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Takahisa Machiguchi: "Novel Cage Molecules from the Reaction of 8,8-Dicyanoheptafulvene with Cyclopentadienide Anion:Structure and Mechanism" Journal of the American Chemical Society. 115. (1993)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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