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SYNTHETIC AND STRUCTURAL STUDIES OF ULTRASTABLE CARBOCATIONS

Research Project

Project/Area Number 13640528
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionUniversity of Toyama

Principal Investigator

ODA Mitsunori  TOYAMA UNIVERSITY, FACULTY of ENGINEERING, DEPARTMENT OF APPLIED CHEMISTRY, ASSOCIATE PROFESSOR, 工学部, 助教授 (50251880)

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2003: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2002: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2001: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsCARBOCATIONS / AZULENES / TROPYLIUM IONS / CONJUGATION / THERODYNAMIC STABILITY / フェナレニウムイオン / トロピリウムイオン / スピカ化合物
Research Abstract

Synthesis of hydrocarbon carbocations having 1H-azulenium ion as its partial structure and and evaluation of their thermodynamic stability were studied. It is found that double annulation of spiro[4,5]diene on the tropylium ion increases its stability with pK_R+ value of up to 13.2. This can be suggested to be resulted from hybrid of inductive effect and π-π and σo-π conjugations. The stability of cations was found to be affected by their structure, particularly partial structure around the cationic center of the molecules ; steric crowdness reduces the stability because of uneffective solvation. A novel compound spiroalkylated at the, 1 position of 1H-azulenium ion by an adamanthyl group was synthesized and its solid-state strucure was confirmed by X-ray crystallographic analysis, which indicates that the azulenium ion part is deviated from a plane relatively greater than other cations. This cation showed moderate stability probably because its unplanarity offsets the inductive effect, with increased number of the carbon atoms in the substituent at the 1 position. The aryl-substituted cations at the 1 position were also synthesized and were less stable than the alkyl-substituted ions. It was also found that thees aryl-substituted cations show a charge-transfer band in their UV spectra which can be attributed to excitation from the aryl substituent to the azulenium ion part despite to their orthogonal relationship.

Report

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

    (25 results)

All Other

All Publications (25 results)

  • [Publications] M.Oda et al.: "Dicyclopenta[a, d]cyclooctene : A[14]Annulene Containing Two Zero-Atom Cross-Links"Angewandte Chemie International Edition. 40. 2660-2662 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda et al.: "Dispiro[cyclohexane-1,1'-(1,7'-dihydrocyclopenta[f]azulenium-7',1"-cyclo-hexane] perchlorate, a new highly stable hydrocarbon cation"Tetrahedron Letters. 43. 3485-3488 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] R.Miyatake et al.: "Synthesis and conformations of 3,5-disubstituted 4,9-methanothia[11]-annulenes"Tetrahedron. 58. 3647-3654 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda et al.: "Unamiguious detection of 2,4,6-cycloheotatrienol by NMR spectroscopy and trapping with phenyltriazolinedione"Tetrahedron. 59. 795-800 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda et al.: "Synthesis, stability, and molecular structures of novel hydrocarbon cations consisting of atropylium cation and two spiro[4,5]deca-2,4-dienes"Tetrahedron. 59. 2831-2841 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda et al.: "Thermal rearrangement of phenyl-substituted ketene ethylene acetals"Heterocycles. 60. 1673-1680 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Sakamoto, T.Kajioka, T.Uchiyama, R.Miyatake, S.Kuroda: "Dicyclopenta[a,d]cyclooctene ; A [14]annulene containing two zero-atom cross-links"Angew.Chem.Int.Ed.. 40(14). 2660-2662 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Sakamoto, T.Kajioka, T.Uchiyama, R.Miyatake, S.Kuroda: "Dicyclopenta[a,d]cyclooctene ; A [14]annulene containing two zero-atom cross-links"Angew.Chem.. 113(14). 2734-2736 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda, H.Kainuma, R.Miyatake, S.Kuroda: "Dispiro[cyclohexane-1,1'-(1',7'-dihydrocyclopenta[f]azulenium-7', 1''-cyclohexane] per-chlorate, a new highly stable hydrocarbon cation"Tetrahedron Lett.. 43(19). 3485-3488 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] R.Miyatake, S.Kuroda, T.Kajioka, A.Taketani, M.Oda: "Synthesis and conformations of 3,10-disubstituted 4,9-methanothia[11]annulenes"Tetrahedron. 58(19). 3647-3654 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda, K.Okawa, H.Tsuri, S.Kuroda: "Unambiguious detection of 2,4,6-cycloheptatrien-1-ol by NMR spectroscopy and trapping with phenyltriazolinedione"Tetrahedron. 59(6). 795-800 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda, H.Kainuma, T.Uchiyama, R.Miyatake, S.Kuroda: "Synthesis, stability and molecular structure of novel hydrocarbon cations consisting of a tropylium cation and two spiro[4,5]deca-2,4-dienes"Tetrahedron. 59(16). 2831-3841 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda, K.Morimoto, N.C.Thanh, R.Ohta, S.Kuroda: "Thermal rearrangement of phenyl-substituted ketene ethylene acetals"Heterocycles. 60(7). 1673-1680 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Oda et al.: "Synthesis, stability, molecular structures and some reactions of spiro[1H-azulenium-1,1'-cycloalkane]ions"Recent Research Developments in Organic Chemistry. 6. 543-563 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Oda et al.: "Synthesis, stability, and molecular structures of novel hydrocarbon cations consisting of atropylium cation and two spiro[4,5]deca-2,4-dienes"Tetrahedron. 59. 2831-2841 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Oda et al.: "Thermal rearrangement of phenyl-substituted ketene ethylene acetals"Heterocycles. 60. 1673-1680 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Kuroda et al.: "Endoperoxidation of 9,10-bis(1-hydroxyalkyl)anthracene and successive formation of 9,10-anthraquinone under Grignard reaction conditions"Heterocycles. 62. 153-159 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Kajioka et al.: "Reaction of 1-(ethoxycarbonyl)cyclohepta-1,3,5-triene with acetic anhydride ; A facile synthesis of 1-acetoxyl-2-acetylazulenes"Synthetic Communications. 32. 635-644 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Oda et al.: "Dispiro[cyclohexane-1,1'-(1,7'-dihydrocyclopenta[f]azulenium-7',1"-cyclo-hexane] perchlorate, a new highly stable hydrocarbon cation"Tetrahedron Letters. 43. 3485-3488 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Miyatake et al.: "Synthesis and conformations of 3,5-disubstituted 4,9-methanothia[11]annulenes"Tetrahedron. 58. 3647-3654 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Oda et al.: "Unamiguious detection of 2,4,6-cycloheptatrienol by NMR spectroscopy and trapping with phenyltriazolinedione"Tetrahedron. 59. 795-800 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Mouri et al.: "Synthesis, molecular structure and chemical reactivity of azuleno[1,2-a]ace-naphtylene"Tetrahedron. 59. 801-811 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Oda et al.: "Dicyclopenta[a, d]cyclooctene : A [14]Annulene Containing Two Zero-Atom Cross-Links"Angewandte Chemie International Edition. 40. 2660-2662 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Kuroda et al.: "Generation and [4+2]Cycloaddition of 1,6-Methano[10]annulene-3,9-quino-dimethane"Tetrahedron Letters. 42. 6345-6348 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Oda et al.: "Spiro[1H-azulenium-1.1'-cyclopropane] Ions ; Their Synthesis, Characterization and Some reactions"Recent Research Development in Organic & Bioorganic Chemistry. 4. 133-149 (2001)

    • Related Report
      2001 Annual Research Report

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

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