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Atmospheric Pressure Carbonylation of Allylic Compounds

Research Project

Project/Area Number 01550674
Research Category

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

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

Principal Investigator

KIJI Jitsuo  Tottori Univ., Mat Sci., Prof., 工学部, 教授 (60026002)

Co-Investigator(Kenkyū-buntansha) OKANO Tamon  Tottori Univ., Mat. Sci., Ass. Prof., 工学部, 助教授 (20112104)
KONISHI Hisatoshi  Tottori Univ., Matsci., Prof., 工学部, 教授 (40112106)
Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1990: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1989: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsPalladium Catalyst / Allylic Compounds / Atmospheric Pressure Carbonylation / alpha, beta-Unsatureated Fatty Acid / 常圧カルボニル化 / β,γ-不飽和脂肪酸
Research Abstract

The palladium-catalyzed carbonylation of allylic compounds offers a synthetic method of alpha, beta-unsaturated acid. However, the carbonylation has found less application, because it requires a high carbon monoxide pressure. Several years ago we have found that the atmospheric pressure carbonylation proceeds smoothly at room temperature in the presence of strong bases such as or It was necessary to add sodium alkoxide slowly and dropwise to the allylic halides, to avoid an excess of the bases.
In the present study we aimed at simplifying the reaction procedure and the catalyst system and optimizing the reaction using cinnamyl chloride as the substrate. As the catalyst of the biphasic reaction of aq. NaOH/organic solvent pDCl_2p[ph_2p(m-C_6H_4SO_3Na)]_2 gave the best results in terms of yield and rate of CO uptake. We considered a possibility that the facile carbonylation involved the CO insertion into a pd-O bond, rather than a pd-C bond. It seemed likely that this process occurs in the aqueous phase.
In the carbonylation of the homogeneous CH_3ONa/CH_3OH system, Na_2PdCl_<4'> without any phosphorus ligand, gave methyl esters in high yields. On the other hand, palladium complexes with phosphorus ligand gave methyl ethers as the major product. The presence of the phosphorus ligand affects the carbonylations significantly.
More work is needed to define the pathway of this carbonylation.

Report

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

    (6 results)

All Other

All Publications (6 results)

  • [Publications] J.Kiji,T.Okano,H. Konishi, W. Nishiumi: "PalladiumーCatalyzed, Atmospheric Pressure Ethoxycarbonylation of Allylic Halides under the lnfluence of Sodium Ethoxide" Chemistry Letters. 1873-1876 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J. Kiji, T. Okano: "Trends in Organic Chemistry" Council of Scientific Research Integration, India, 9

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] JITSUO KIJI, TAMON OKANO, HISATOSHI KONISHI, WATARU NISHIUMI: "Palladium-Catalyzed, Atmospheric Pressure Ethoxycarbonylation of Allylic Halides Under the Influence of Sodium Ethoxide. A Facile Synthesis of alpha, beta-Unsaturated Esters" Chemistry Letters. 1873-1876 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] JITSUO KIJI, TAMON OKANO: "Transition Metal-Catalyzed Organic Reacitons in Aqueous Media" Trends in Organic Chemistry, Council of Scientific Research Integration, India.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] J.Kiju,T.Okano: "Trends in Organic Chemistry" Council of Scientific Research Integration,India, 9

    • Related Report
      1990 Annual Research Report
  • [Publications] Jitsuo Kiji,Tamon Okano,Hisatoshi Konishi,and Wataru Nishiumi: "Palladium-Catalyzed,Atmospheric Pressure Ethoxy-carbonylation of Allylic Halides under the Influence of Sodium Ethoxide" Chemistry Letters. 1873-1876 (1989)

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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