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SYNTHETIC STUDY OF NOVEL UNSATURATED HYDROCARBONS CONDENSED HIGHLY WITH FIVE-MEMBERED RINGS

Research Project

Project/Area Number 09640631
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionTOYAMA UNIVERSITY, DEPARTMENT OF ENGINEERING

Principal Investigator

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

Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1999: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsUNSATURATED HYDROCARBON / POLYCYCLIC COMPOUND / P-ELECTRON CONJUGATED COMPOUND / MULTISTEP REDOX COMPOUND / ELECTROCYCLIZATION / pi電子共役系化合物
Research Abstract

Synthetic efforts towards a series of compounds, which have cylopentene rings enclosing a cyclooctene ring as the core, such as di-, tri-, and tetracyclopentacyclooctanes and their ionic species, were reported.
A synthetic route to dicyclopenta[a,d]cyclooctene (1) was established. This hydrocarbon 1 shows an aromatic character in its NMR spectra and, judging from coupling constants of vicinal protons, 1 is estimated to have a symmetrical completely planar structure without bond alternation. Electrochemical properties of 1 clearly shows its oxidizable and reducable nature. It should be noted that a thermoheater and a gas chromatography apparatus obtained by this grant were very useful in our synthetic efforts to 1. Synthesis of dicyclopenta[a,c]cyclooctene (2) was attempted by two routes. One of them is a sequence which involves dimerization of 6-dimethylaminofulvene at the 1 position, substitution of one of dimethylamino groups with a vinyl group of the dimer, 14π-electrocyclization, an … More d subsequent deamination. Although the nickel-catalized dimerization of 2-chloro-6-dimethylaminofulvene was succeeded, substitution of the dimethylmino group with a vinyl one met with little success. On the other hand, an approach by cycloaddition between thialene S,S-dioxide (cyclopenta[b]thiapyrane S,S-dioxide)and 6-dimethylaminofulvene to 2 was also planned. Though a novel synthetic route to thialene was explored by addition-elimination reaction of sulfur and 6-(2-di-methylaminovinyl)fulvene, its yield was not good enough to use in a next reaction.
A novel, divergent synthetic approach to tri- and tetracyclopentacyclooctanes was also studied. The method employed pentafulvalenyl dianion as an active reaction species and, however, in spite of tremendous efforts its condensation with various dicarbonyl compounds was not succeeded. Further synthetic study in vinylogous dicyclohepta[a,e]cyclooctene (3) starting from 3,4-bis(bromomethyl)cycloheptatriene was discloed. Cycloaddition of 6,7-dimethylenecyclohepta-1,4-diene with 3,6,9-trihydrocyclohepta[d] 1,2-dithiin provided 3,6,8,11,14,16-hexahydrodicyclo[c,h][1,6]dithiecin (4), which is a prospective intermediate for synthesizing 3, and whose structure was confirmed by X-ray crystallographic analysis.
Difference of absorption spectra between dicyclopenta[a,c]- and [a, e]cyclooctenes was discussed based on results of semiempirical and ab initio calculations. Less

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] M. Oda et al.: "Rearrangements of Tricyclo[5.3.1.0^<1,7>]undecatrienide Anion : Circumambulation and Clevage of the Cyclopropane Ring"Bulletin of the Chemical Society of Japan. 71. 1959-1965 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "Dihydro-l(2H)-azulenones ; Their syntheses, cycloheptatriene-norcaradiene equilibria and cycloaddition reactions"Recent. Res. Devel. in Pure & Applied Chem.. 2. 145-155 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "Synthesis and Reactions of 1,1-Trimethylene-1 H-azulenium Ion"Tetrahedron Letters. 39. 6195-6198 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Kajioka et al.: "An Efficient Synthetic Pathway from Cyclohepta-1,3,5-triene to 2,3-Disubstituted 1,2,3,8-Tetrahydroazulen-1-one"Synthesis. 184-187 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "Thermolytic Fragmentation Reactions of Tricyclo[5.3.1.0^<1,7>]undeca-2,4-dien-10-one Tosylhydrazone under Basic Conditions"Synthesis. 184-187 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "A Divergent Method for Preparing 1-Aryl- and 1,3-Diarylazulenes from Ethyl 3-(Cyclohepta-1,3,5-trienyl-l-yl)-3-oxopropionate"Synthesis. 859-863 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "Synthesis and Stability of 1,1-Tetramethylene- and 1,1-Pentamethylene-1H-azulenium Ions"Tetrahedron Letters. 40. 3595-3596 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "1,1-Ethylene-1H-azulenium Ion and Its Alkyl Substituted Derivatives : Synthesis, Characterization, and Some Reactions Thereof"Tetrahedron. 55. 6081-6096 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "Formation, Characterization, Some Reactions of Spiro[cyclobutane-1,1'-1H-azulenium] Ion"Tetrahedron. 55. 12479-12492 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda et al.: "A Synthetic Method for Preparing 3,3-Dialkyl-1,2,3,8-tetrahydroazulen-1-one"Synth. Commun.. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda, Y. Masaki, Y. Okazaki, T. Kajioka, Y. Marita, R. Miyatake, and S. Kuroda: "Rearrangements of tricyclo[5.3.1.01, 7]undecatrienide anion : Circumambulation and cleavage of the cyclopropane ring"Bull. Soc. Chem. Jpn.. 71. 1959-1965 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda, A. Sakamoto, R. Miyatake, and S. Kuroda: "Synthesis and properties of 1, 1-trimethylene-1H-azulenium ion"Tetrahedron Lett.. 39. 6195-6198 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda and S. Kuroda: "Dihydro-1(2H)-azulenones : Their syntheses, cycloheptatriene-norcaradiene equilibria and cycloadditions"Recent Research Developments in Pure & Applied Chemistry Vol. 2 ; Transworld Research Network, Trivandrum. 2. 145-15 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Kajioka, M. Oda, S. Yamada, R. Miyatake, and S. Kuroda: "An efficient synthetic pathway from cyclohepta-1,3,5-triene to 2,3-disubstituted 1,2,3,8-tetra-hydroazen-1-ones"Synthesis. 184-187 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] "Synthesis and stability of 1,1-tetramethylene-and 1,1-pentamethylene-1H-azulenium ions"Tetrahedron Lett.. 40. 3595-3596 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda, T. Kajioka, T. Uchiyama, K. Nagara, T. Okujima, S. Ito, N. Morita, T. Sato, R. Miyatake, and S. Kuroda: "1,1-Ethylene-1H-azulenium ion and its alkyl substituted derivatives : Synthesis, characterization, and some reactions thereof"Tetrahedron. 55. 6081-6096 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda, Y. Masaki, S. Hayashi, R. Miyatake, and S. Kuroda: "Thermolytic fragmentation reactions of tricyclo[5.3.1.01,7]undeca-2,4-dien-10-one tosylhydrazone under basic conditions"Synthesis. 859-863 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda, T. Kajioka, K. Haramoto, R. Miyatake, and S. Kuroda: "A divergent method for preparing 1-aryl- and 1,3-diarylazulenes from ethyl 3-(cyclohepta-1,3,5-trien-1-yl)-3-oxopropionate"Synthesis. 1349-1353 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda, A. Sakamoto, R. Miyatake, and S. Kuroda: "Formation, chracterization, and some reactions of spiro[cyclobutane-1,1'-1'H-azulenium]ion"Tetrahedron. 55. 12479-12492 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Oda, T. Kajioka, K. Ikeshima, R. Miyatake, and S. Kuroda: "A synthetic method for preparing 3,3-dialkyl-1,2,3,8-tetrahydroazulen-1-one"Synth. Commun.. (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Oda et al.: "Thermolytic Fragmentation Reactions of Tricyclo[5.3.1.0^<1,7>]undeca-2,4-dien-10-one Tosylhydrazone under Basic Conditions"Synthesis. 859-863 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Oda et al.: "A Divergent Method for Preparing 1-Aryl- and 1,3-Diarylazulenes from Ethy1 3-(Cyclohepta-1,3,5-trienyl-1-yl)-3-oxopropionate"Synthesis. 1349-1353 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Oda et al.: "Synthesis and Stability of 1,1-Tetramethylene- and 1,1-Pentamethylene-1H-azulenium Ions"Tetrahedron Letters. 40. 3595-3596 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Oda et al.: "1,1-Ethylene-1H-azulenium Ion and Its Alkyl Substituted Derivatives: Synthesis, Characterization, and Some Reactions Thereof"Tetrahedron. 55. 6081-6096 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Oda et al.: "Formation, Characterization, Some Reactions of Spiro[cyclobutane-1,1'-1H-azulenium] Ion"Tetrahedron. 55. 12479-12492 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Oda et al.: "A Synthetic Method for Preparing 3,3-Dialkyl-1,2,3,8-tetrahydroazulen-1-one"Synth. Commun.. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Oda et al.,: "Rearrangements of Tricyclo[5.3.1.0^<1,7>]undecatrienide Anion: Circumambulation and Cleavage of the Cyclopropane Ring" Bulletin of the Chemical Society of Japan. 71. 1959-1965 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Oda et al.,: "Dihydro-1(2H)-azulenones; Their syntheses,cycloheptatriene-norcaradiene equilibria and cycloaddition reactions" Recent.Res.Devel.in Pure & Applied Chem.,. 2. 145-155 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Oda et al.,: "Synthesis and Reactions of 1,1-Trimethylene-1H-azulenium Ion" Tetrahedron Letters. 39. 6195-6198 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Oda et al.,: "An Efficient Synthetic Pathway from Cyclohepta-1,3,5-triene to 2,3-Disubstituted 1,2,3,8-Tetrahydroazulen-1-one" Synthesis. 184-187 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Oda et al.,: "Thermolytic Fragmentation Reactions of Tricyclo[5.3.1.0^<1.7>]undeca-2,4-dien-10-one Tosylhydrazone under Basic Conditions" Synthesis. in press. (1999)

    • Related Report
      1998 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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