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2001 Fiscal Year Final Research Report Summary

Addition Reaction of Unique Aromatic Ring Systems and Their Ring Transformation and Tribological Application

Research Project

Project/Area Number 12650839
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionToyota Technological Institute

Principal Investigator

OHNO Masatomi  Toyota Technological Institute, Department of Engineering, Professor, 工学部, 教授 (50072682)

Co-Investigator(Kenkyū-buntansha) HONDA Humihiro  Toyota Technological Institute, Department of Engineering, Professor, 工学部, 教授 (20005953)
Project Period (FY) 2000 – 2001
Keywordsfullerene / squaric acid / cycloaddition reaction / radical addition / nucleophilic addition / azacyclopentadienone / anti-aromaticity / nitrogen-heterocycle
Research Abstract

Unique Aromatic Ring Systems have potentiality to show physical, chemical and biological characteristics, and therefore they are attractive to obtain various derivatives according to reasonable molecular design. In this study, we focus on [60]fullerene and squaric acid as the spherical π-electron delocalized unique ring system and the planar non-benzenoid strained ring system.
(1) As for [60]fullerene, various cycloaddition reactions were tried and successful results were obtained. In 1,3-dipolar cycloaddition, the reaction with thiocarbonyl ylide which gave a C_<60> derivative fused with S-containing five membered heterocycle was utilized for introduction of functional groups near the surface by S_N1 substitution, and a series of studies revealed that C_<60> core didi not affect the S_N1 reactivity substancially. Formal [3+2]cycloaddition with isocyanides was found to occur without catalyst, yet the use of Cu_2O was more effective to give dihydroproline- fused C_<60> [4+2]cycloaddition … More was carried out with cyclooctatetraene, and the cycloadduct was shown to have C_<60>-based characteristics. The same type of cycloaddition with 3,4-fused pyrrolosulfolene unusually afforded a cycloadduct originating from direct trap of 3,4-dimethylenepyrrole intermediate, and this may reflect high radicophilicity of [60]fullerene. Apart from these cycloaddition, radical and nucleophilic additions aided with inorganic reagents were attempted. The reaction of cyclopropanone silyl acetal was effected by the use of FeCl_3 rathan TiCl_4, also indicating high radicophilicity as above. Under irreversible conditions, inorganic nucleophiles were found to react with C_<60>; the required conditions are to realize trapping of a fullerenyl anion intermediate with a certain reagent.
(2) As for squaric acid, ring transformation was investigated and novel rearrangement induced by the nitrene inter-mediate which was generated at α-position of the cylobutenone ring was developed. In this case, the product was polysubstituted 2-azacyclopentdienone,and its stable structure, despite of intrinsic anti-aromatic nature, was attributed to double resonace. Further synthetic application was performed by cyclization with various mono- and bi- nucleophilic reagent, promising for the formation of nitrogen-heterocycles. Less

  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] A.Yashiro: "β-Hydroxy Nitrile and B-Hydroxy Oxime Derivatives of [60]Fullerene by Nucleophilic Ring Cleavage of Fulleroisoxazoline amd-Isoxazolidine in the Presence of Methanol"Synlett. 361-362 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Ishida: "Synthesis of Dicarboxylic acid Derivatives of [60]Fullerene Using Diels-Alder Reaction with Bis(methylene)butanedioates"Tetrahedron Letters. 41. 2153-2156 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Tsunenishi: "Heterocyclization of [60]Fullerene with Isocyanides"Synlett. 1318-1320 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Ishida: "Diels-Alder Reaction of [60]Fullerene with Cyclooctatetraene and Electrophilic Addition to the Cycloadduct"Tetrahedron Letters. 41. 9839-9842 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Ishida: "Cycloaddition Reaction of [60]Fullerene with 3,4-Fused Pyrrolo-3-sulfolene"Synlett. 296-299 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Ishida: Tetrahedron. 57. 1737-1747 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A. Yashiro, Y. Nishida, K. Kobayashi, and M. Ohno: "β-HYDROXY NITRILE AND β-HYDROXY OXIME DERIVATIVES OF [60]FULEERENE BY NUCLEOPHILIC RING CLEAVAGE OF FULLERO-ISOXAZOLINE AND -ISOXAZOLIDINE IN THE PRESENCE OF METHANOL"Synlett.. 361-362 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Ishida, H. Asaji, T. Hida, K. Itoh, and M. Ohno: "SYNTHESIS OF DICARBOXYLIC ACID DERIVATIVES [60]FULLERENE USING DIELS-ALDER REACTION WITH BIS(METHYLENEBUTANEDIOATES"Tetrahedron Lett.. 41. 2153-2156 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Tsunenishi, H. Ishida, K. Itoh, and M. Ohno: "HETEROCYCLIZATION OF [60]FULLERENE WITH ISOCYANIDES"Synlett.. 1318-1320 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Ishida K. Komori, K. Itoh, and M. Ohno: "DIELS-ALDER REACTION OF [60]FULLERENE WITH CYCLOOCTATETRAENE AND ELECTROPHILIC ADDITION TO THE CYCLOADDUCT"Tetrahedron Lett.. 41. 9839-9842 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Ishida, K. Itoh, S. Ito, N. Ono, and M. Ohno: "CYCLOADDITION REACTION OF [60]FULLERENE WITH 3,4-FUSED PYRROLO-3-SULFOLENES"Synlett.. 296-298 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Ishida, K. Itoh, and M. Ohno: "1,3-DIPOLAR CYCLOADDITION REACTION OF [60]FULLERENE WITH THIOCARBONYL YLIDE AND SYNTHETIC APPLICATION OF THE CYCLOADDUCT"Tetrahedron. 57. 1737-1747 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Ishida, H. Asaji, K. Itoh, and M. Ohno: "CYCLOADDITION REACTION OF C_60 WITH 2-DIAZO-1,3-DITHIANE AND OXIDATION OF THE CYCLOADDUCT TO SUFOXIDE DERIVATIVES"Heterocyclic Commun.. 7. 223-226 (2001)

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      「研究成果報告書概要(欧文)」より

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Published: 2003-09-17  

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