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Synthesis of Biologically Active Perfluoroalkyl N-Heterocycles Using Organosilicon Reagents

Research Project

Project/Area Number 01550681
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionScience University of Tokyo

Principal Investigator

KONAKAHARA Takeo  Science University of Tokyo, Faculty of Science and Technology, Department of Industrial and Engineering Chemistry, Associate Professor, 理工学部, 助教授 (80084333)

Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 1990: ¥300,000 (Direct Cost: ¥300,000)
Keywordspyridines / quinolizines / 1, 6-naphthyridines / heterocycles / cyclization / organosilicon reagent / fluoro-compounds / N-silyl-1-aza-allyl anion / 有機ケイ素化合物 / N-シリル-1-アザ-アリルアニオン / キノリジノン / イソオキサゾ-ル / ペルフルオロアルケン
Research Abstract

Five 2-aryl-3-(3-methyl-5-isoxazolyl)-N-silyl-1-aza-allyl anions (1) (Ar = C_6H_5, pーCH_3C_6H_4, p-CH_3OC_6H_4, p-CIC_6H_4, p-N(CH_3) _2C_6H_4), generated from 3-methyl-5-(trimethylsilylmethyl) isoxazole and the corresponding aryl cyanides, reacted with perfluoro (2-methyl-2-pentene) (2) in the presence of Hunig's base in tetrahydrofuran at low temperature to give the corresponding 6-aryl-2-fluoro-5-(3-methyl-5-isoxazolyl)-4-pentafluoroethyl-3-trifluoromethylpyridines (3) in high yields (97, 74, 52, 80, 93%, respectively) under the optimized reaction conditions. Further-more, the isoxazole ring of the pyridine (3) was quantitatively hydrogenated to afford the corresponding bata-amion enone (4), which was intramolecularly cyclized to give 5-ary1-7-fluoro-2-methyl-8-trifluoromethyl-1, 4-dihydro-1, 6-naphthyridine (5) in good yields (Ar = C_6H_5, p-CIC_6H_5, yield = 63, 67%, respectively) in the presence of sodium hydroxide at room temperature. The mechanisms for these two reaction were also discussed on the basis of the reactivity of (3) against sodium hydroxide or alkylamines.
alpha-(Trimethylsilylmethyl)-N-heterocycles, such as pyridine, quinoline, and isoquinoline, reacted with (2) in the presence of fluoride anion to afford Rf-substituted quinolizin-4-ones (or the corresponding benzo derivatives) in poor to good yields through intermolecular addition-cyclization reaction.

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] 小中原 猛雄: "Nーシリルー1ーアザアリルアニオンを経るペルフルオロアルキル置換4ーフルオロピリジン誘導体のoneーpot合成" 日本化学会誌. 466-471 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T.Konakahara: "Novel synthesis of perfluoroalkylquinolizinー4ーone derivatives" Synthesis.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T.Konakahara: "Synthesis of perfluoroalky1ー1,6ーnaphthyridines" J.Chem.Soc.Perkin Trans 1.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T.Konakahara: "Oneーpot Synthesis of 2ーAminoーor 2ーHydroxypyridine Derivatives via NーSilylー1ーazaーallyl anion" Synthesis.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Takeo Konakahara: "One-pot Synthesis of Perfluoroalkylated 4-fluoropyridines via N-Silyl-1-aza-allyl Anion" J. Chem. Soc. Jpn.466-471 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T. Konakahara: "Novel Synthesis of Perfluoroalkyl-quinolizin-4-one derivatives" Synthesis.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T. Konakahara: "Synthesis of Perfluoroalkyl-1, 6-naph-thridines" J. Chem. Soc. Perkin Trans 1.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T. Konakahara: "One-pot Synthesis of 2-Amino- or 2-Hydroxy-pyridine derivatives via N-Silyl-1-aza-allyl anion" Synthesis.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] 小中原 猛雄: "Nーシリルー1ーアザアリルアニオンを経るペルフルオロアルキル置換4ーフルオロピリジン誘導体のoneーpot合成" 日本化学会誌. 466-471 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Konakahara: "Novel Synthesis of perfluoroalkylquinolizinー4ーone derivatives" Synthesis.

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Konakahara: "Synthesis of perfluoroalkylー1,6ーnaphthyridines" J.Chem.Soc.Perkin Trans。1.

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Konakahara: "Oneーpot Synthesis of 2ーAminoーor 2ーHydroxypyridine Derivatives via NーSilylー1ーazaーallyl anion" Synthesis.

    • Related Report
      1990 Annual Research Report
  • [Publications] 小中原猛雄: "N-シリル-1-アザ-アリルアニオンを経るペルフルオロアルキル置換4-フルオロピリジン誘導体のone-pot合成" 日本化学会誌. (5月号). (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Konakahara: "One-pot Synthesis of Pyrroles via N-Silyl-1-aza-allyl anions and the Reaction Mechanism" Synthesis,manuscript in preparation.

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Konakahara: "One-pot Synthesis of 3-Pentafluoroethyl-2-trifluoromethylquinolizin-1-one from 2-(Trimethylsilylmethyl)pyridine" Synthesis,manuscript in preparation.

    • Related Report
      1989 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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