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Synthesis and Function of Macrocyclic Polyethers bearing Catalytic Group

Research Project

Project/Area Number 63550637
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionGunma University

Principal Investigator

YANO Yumihiko  Gunma University, Faculty of Engineering Professor, 工学部, 教授 (30008510)

Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1989: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1988: ¥1,100,000 (Direct Cost: ¥1,100,000)
KeywordsCrown thiazolium ion / Crown thiol / Alkali metal ion / Electrostatic interaction / Multi-recognition / クラウンチオール / クラウンイミダゾール
Research Abstract

Since crown ethers are known to hold metal cations tightly intramolecular anion capping, the catalytic activity of the functionalized crown ethers having catalytic groups would be enhanced by a metal cation if the metal cation bound in the crown cavity could attract an anionic substrate by electrostatic interaction into the vicinity of the catalytic site. To test this possibility, we synthesized the following functionalized crown ethers, and the following are examined; (a)relationship of alkali metal ions and rate acceleration, (b)relationship between the crown cavity and the catalytic group, and (c)possibility of two points-recognition by employing bis-crown ethers. For the thiazolium salts, the effect of Alkali metal ions on the oxidative decarboxylation of alpha-keto acids, oxidation of carboxybenz- aldehydes, and cleavage of the Ellman reagent was examined kinetically in EtOH containing DBU as a base. For the crown thiols, thiolysis of p- nitrophenylhydrogen terephthalate was examined in EtOH (DBU). The results showed that the electrostatic field of the metal cation bound in the crown cavity is able to attract the anionic substrate to bring about rate- acceleration. It was also found that the distance between the crown cavity and the catalytic site is one of the important factors, and the biscrown thiazolium ion exhibits larger rate-enhancement for bis- anionic substrate. The present systems involve the nucleophilic attack of the catalytic groups to the reaction sites of the substrates. Other systems such as electron- transfer must be examined to generalize this concept.

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group.Rate Enhancement of Oxidative Decarboxylation of α-Keto Acids and Oxidation of Carboxybenzaldehyde in the presence of Alkali Metal Cation in EtOH" J.Chem.Soc.,Perkin Trans.2.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group.Rate Enhancement of Cleavage of Ellman′s Reagent in the Presence of Alkali Metal Cations in EtOH" Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group.Rate Enhancement of Thiolysis of p-Nitrophenyl hydrogenterephthalate by Crown Thiols in the Presence of Alkali Metal Ion EtOH" J.Chem.Soc.,Perkin Trans.2.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Specific Rate Enhancement of Oxidation of Benzaldehyde bearing Two Carboxylic Moieties by Bis-Crown Thiazolium Ions in the Presence of Alkali Metal Ion in MeCN" J.Chem.Soc.,Chem.Commun.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group. Rate Enhancement of Oxidative Decarboxylation of alpha-Keto Acid and Oxidation of Carboxybenzaldehyde in the Presence of Alkali Metal Cation in EtOH" J. Chem. Soc., Perkin Trans. 2.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group. Rate Enhancement of Cleavage of Ellman's Reagent in the Presence of Alkali Metal Cation in EtOH" Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group. Rate Enhancement of Thiolysis of p-Nitrophenyl hydrogenterephthalate by Crown Thiols in the Presence of Alkali Metal Ion EtOH" J. Chem. Soc., Perkin Trans. 2.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Specific Rate Enhancement of Oxidation of Benzaldehyde bearing Two Carboxylic Moieties by Bis-Crown Thiazolium Ions in the Presence of Alkali Metal Ion in MeCN" J. Chem. Soc., Chem. Commun.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group.Rate Enhancement of Oxidative Decarboxylation of α-keto Acids andOxidation of Carboxybenzaldehyde in the Presence of Alkali Metal Cation in EtoH" J.Chem.Soc.,Perkin Trans.2.

    • Related Report
      1989 Annual Research Report
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group.Rate Enhancement of Cleavege of Ellman's Reagent in the Paresence of Alkali Metal Cations in EtOH" Bull.Chem.Soc.Jpn.

    • Related Report
      1989 Annual Research Report
  • [Publications] Yumihiko Yano: "Crown Ethers bearing Catalytic Group.Rate enhancement of Thiolysis of p-Nitrophenyl hydrogenterephthalate by Crown Thiols in the Presence of Alkali Metal Ion in EtOH" J.Chem.Soc.,Perkin Trans.2.

    • Related Report
      1989 Annual Research Report
  • [Publications] Yumihiko Yano: "Specific Rate Enhancement of Oxidation of Benzaldehyde bearing Two Carboxylic Moieties by Bis-Crown Thiazolium Ions in the Presence of Alkali Metal Ion in MeCN" J.Chem.Soc.,Chem,Commun.

    • Related Report
      1989 Annual Research Report
  • [Publications] Yumihiko Yano: J.Chem.Soc.,Perkin Trans.2,.

    • Related Report
      1988 Annual Research Report
  • [Publications] Yumihiko Yano: Bull.Chem.Soc.Jpn.,.

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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