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Exploitation of New Synthetic Reactions via Thermal Activation of Alkane C-H Bonds by Transition Metals

Research Project

Project/Area Number 02453093
Research Category

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

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

Principal Investigator

FUJIWARA Yuzo  Hiroshima University, Fac. of Eng., Professor, 工学部, 教授 (10029481)

Co-Investigator(Kenkyū-buntansha) TAKAKI Ken  Hiroshima University, Fac. of Eng., Research Associate, 工学部, 助手 (80116615)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥5,800,000 (Direct Cost: ¥5,800,000)
Fiscal Year 1991: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1990: ¥5,000,000 (Direct Cost: ¥5,000,000)
KeywordsAlkane C-H Bond Activation / Palladium Catalysts / Cyclohexanecarboxylic Acid / Activation of Methane / Acetic Acid from Methane / Electrophilic Substitution / Copper Sulfate / Carbon Monoxide / 一酸化炭素 / アルカンCーH結合活性化 / 脂肪酸 / 銅塩 / モンサント酢酸プロセス / シクロアルカンのカルボキシル化 / transー1,4ージメチルシクロヘキサン / アルカンのカルボキシル化 / Pd^<II>のアルカンへの親電子反応 / メチル置換シクロヘキサン / 酢酸パラジウム / アダマンタンのカルボニル化
Research Abstract

By studies on this project, the following novel useful synthetic reactions have been found and developed using alkanes as a starting material.
1. Fatty Acid Synthesis from Alkanes and CO
We found that the Pd (OAc)_2/K_2S_2O_8/CF_3COOH system catalyzes the carboxylation of alkanes with CO via thermal C-H bond activation. For example, cyclohexane reacts with CO (20 atm) to give cyclohexanecarboxylic acid in ca. 20000% yield (based on Pd). The reactions of cycloalkanes such as methyl-, t-butyl-, 1, 3-dimethyl-, trans-1, 4-dimethylcyclohexanes and adamantane with CO proceed regio- and stereo-selectively to give corresponding carboxylic acids. The reactivity of C-H bonds of cyclohexanes decreases in the order : tert->sec->primcarbon, and the stereochemistry of the substituents on the main products are all equatorial. By isotopic experiment, k_H/k_D=3 was obtained in the reaction of cyclohexane with CO. These results support that the reaction proceeds via electrophilic attack of Pd (II) to the C-H bond.
2. Acetic Acid Synthesis from Methane with CO
Utilizing the above alkane activation reaction, acetic acid has been prepared in high yield from methane and CO. The catalysts are Pd (OAc)_2, Pd (O-COEt)_i or CuSO_4 and pressure of methane and CO is 20-40 atm, and reaction temperature is about 80゚C.
Through this research project, alkanes such as methane have been found to act as good starting materials for organic synthesis.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Yuzo Fujiwara: "Look what Pd Catalyzes" Chemtech. 636-640 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Koichi Satoh: "Pd-Catalyzed Regio-and Stereo-selective Carboxylation of Cycloalkanes with CO" Chem.Lett.1433-1436 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kazuyuki Nakata: "Palladium Catalyzed Carboxylation of Cyclohexane with Carbon Monoxide" Cehm.Lett.1437-1438 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 高木 謙: "アルカンのCーH結合活性化(総説)" 化学. 46. 80-81 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Ken Takaki: "Palladium(II)-Catalyzed Carboxylation of Alkanes with CO via C-H Bond Activation" J.Am.Chem.Soc.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Yuzo Fujiwara: "Look What Pd Catalyzes" Chemtech. 636-640 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Koichi Satoh: "Pd-Catalyzed Regio- and Stereo-selective Carboxylation of cycloalkanes with CO" Chem. Lett.1433-1436 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kazuyuki Nakata: "Palladium Catalyzed Carboxylation of Cyclohexane with Carbon Monoxide" Chem. Lett.1437-1438 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Ken Takaki: "Alkane C-H Bond Activation" Kagaku (Chemistry). 46. 80-81 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Ken Takaki: "Palladium (II) -Catalyzed Carboxylation of Alkanes with CO via C-H Bond Activation" J. Am. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Koichi Satoh: "PdーCatalyzed Regioーand Stereoーselective Carboxylation of Cycloalkanes with CO" Chem.Lett.1433-1436 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Kazuyuki Nakata: "Palladium Catalyzed Carboxylation of Cyclohexane with Carbon Monoxide" Chem.Lett.1437-1438 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 高木 謙: "アルカンのCーH結合活性化(総説)" 化学. 46. 80-81 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Ken Takaki: "Palladium(II)ーCatalyzed Carboxylation of Alkanes with CO via CーH Bond Activation" J.Am.Chem.Soc.

    • Related Report
      1991 Annual Research Report
  • [Publications] Tetsuro Jintoku: "PalladiumーCatalyzed Synthesis of Aromatic Acids from Carbon Monoxide and Aromatic Compounds via the Aromatic CarbonーHydrogen Bond Activation" J.Organomet.Chem.385. 297-306 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Tetsuro Jintoku: "PalladiumーCatalyzed Direct Oxidation of Benzene with Molecular Oxygen to Phenol" Bull.Chem.Soc.Jpn.63. 438-441 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Tetsuro Jintoku: "Palladium Catalyzed Transformation of Benzene to Phenol with Molecular Oxygen" Chem.Lett.1687-1688 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yuzo Fujiwara: "Look What Pd Catalyzes" Chemtech. 636-640 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 高木 謙: "アルカンのCーH結合活性化" 化学. 46. 80-81 (1991)

    • Related Report
      1990 Annual Research Report

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

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