Exploitation of New Synthetic Reactions via Thermal Activation of Alkane C-H Bonds by Transition Metals
| Project/Area Number |
02453093
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Hiroshima University |
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Principal Investigator |
FUJIWARA Yuzo Hiroshima University, Fac. of Eng., Professor, 工学部, 教授 (10029481)
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| Co-Investigator(Kenkyū-buntansha) |
TAKAKI Ken Hiroshima University, Fac. of Eng., Research Associate, 工学部, 助手 (80116615)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| 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)
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| Keywords | Alkane 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 |
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| 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.
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Report
(3 results)
Research Products
(19 results)
