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DEVELOPMENT OF MODIFIED CYCLODEXTRINS FOR SELECTIVE ORGANIC SYNTHESIS

Research Project

Project/Area Number 04453085
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionUniversity of Tokyo

Principal Investigator

KOMIYAMA Makoto  DEPARTMENT OF INDUSTRIAL CHEMISTRY, FACULTY OF ENGINEERING, THE UNIVERSITY OF TOKYO PROFESSOR, 工学部, 教授 (50133096)

Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥6,100,000 (Direct Cost: ¥6,100,000)
Fiscal Year 1993: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1992: ¥3,500,000 (Direct Cost: ¥3,500,000)
KeywordsCyclodextrin / Phenol / Formaldehyde / Modified cyclodextrin / Selective synthesis / 分子複合体 / パラ選択性
Research Abstract

Development of new method for the selective synthesis of valuable chemicals in industry is quite important from the viewpoints of ecology, resource, energy, and so on. Previously we reported that cyclodextrins, cyclic oligomers of glucose, are highly effective for the selective organic synthesis. Various fine chemicals were synthesized in almost 100 % selectivities and in high yields. However, the reactions catalyzed by cyclodextrins are rather limited, since the hydroxyl residues are only the catalytic ones available. Still better catalysts should be obtained if appropriate functional residues are introduced to cyclodextrins by chemical modification.
Here we succeeded in the selective synthesis of 4-(hydroxymethyl)phenol from phenol and formaldehyde and of 4-(hydroxyethyl)phenol from phenol and acetaldehyde, by use of various modified cyclodextrins. The structures of the molecular complexes, formed in these reaction mixtures, are determined by NMR spectroscopy. The hydroxyl residue introduced by the chemical modification to the primary hydroxyl side of the cavity form hydrogen bond with the formaldehyde, resulting in the activation of the formaldehyde for the reaction. In addition, the formaldehyde is fixed in the vicinity of the papa-carbon of the phenol by the hydrogen bonding, and thus the electrophilic attack by the formaldehyde selectively proceeds at the para-carbon. Potentialities of the modified cyclodextrins as practical catalysts are strongly indicated.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 諸角達也: "修飾シクロデキストリンを触媒とする4-(ヒドロキシメチル)フェノールの選択的合成"" 旭硝子財団研究報告. 61. 137-142 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Sinya Sawata: "Potassium fluoride for the promotion of β-cyclodextrin-induced regioselective P-0(3')cleavage" Journal of Physical Organic Chemistry. 5. 502-506 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Makoto Komiyama: "Selective synthesis using cyclodextrin as catalyst 7.Preparation of 3-(hydroxymethyl)indole"" Supramolecular Chemistry. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Makoto Komiyama: "Lanthanide metal-induced selective synthesis of 3-(hydroxymethyl)indole" Supramolecular Chemistry. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] T.Morozumi and M.Komiyama: "Modified cyclodextrins for selective synthesis of 4-hydroxymethyl)phenol and 4-(hydroxyethyl)phenol" Asahi Garasu Shorei Kai Hokoku. 61. 137-142 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] S.Sawata and M.Komiyama: "Potassium fluoride for the promotion of cyclodextrin-induced regioselective P-O(3') cleavage" J.Physical Organic Chemistry. 5. 502-506 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Komiyama, K.Higuchi, and H.Noguchi: "Selective synthesis using cyclodextrins as catalysts 7.Preparation of 3-(hydroxymethyl)indole from indole and formaldehyde" Supramolecular Chem.(to be submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] M.Komiyama, T.Morozumi, Higuchi and H.Noguchi: "Lanthanide metalinduced selective synthesis of 3-(hydroxymethyl)indole" Supramolecular Chem.(to be submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Makoto Komiyama: "Selective synthesis using cyclodextrin as catalyst 7.Preparation of 3-(hydroxymethyl)indole" Supramolecular Chemistry. (発表予定).

    • Related Report
      1993 Annual Research Report
  • [Publications] Makoto Komiyama: "Lanthanide-induced selective synthesis of 3-(hydroxymethyl)indole" Supramolecular Chemistry. (発表予定).

    • Related Report
      1993 Annual Research Report
  • [Publications] M.Komiyama,S.Sawata,andY.Takeshige: "Cooperation of cyclodextrin and alkali-metal halide for regio-selective cleavage of ribonucloeside 2´,3´-cyclic phosphates" J.Am.Chem.Soc.114. 1070-1074 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] S.Sawata and M.Komiyama: "Potassium fluoride for the promotion of β-cyclodextrin-induced regioselective P-O(3´)cleavage of adenosine 2´,3´-cyclic phophate" J.Phys.Org.Chem.5. 502-506 (1992)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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