| Project/Area Number |
10450337
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
有機工業化学
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| Research Institution | Kansai University |
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Principal Investigator |
ISHII Yasutaka Kansai University, Faculty of Engineering, Professor, 工学部, 教授 (50067675)
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| Co-Investigator(Kenkyū-buntansha) |
SAKAGUCHI Satoshi Kansai University, Faculty of Engineering, Assistant, 工学部, 助手 (50278602)
NAKABAYASHI Yasuo Kansai University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (70172385)
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| Project Period (FY) |
1998 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1999: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1998: ¥2,800,000 (Direct Cost: ¥2,800,000)
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| Keywords | Palladium / Heteropolyacid / Wacker-type oxidation / Halogen-free / Cyclopentene / Alkene / Dioxygen / Acetalization / Wacker型酸化 / ヘテロポリ酸塩 / 酸素 / アルキン / 一酸化炭素 / 還化三量化 / カルボキシル化 / クロライドフリー |
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| Research Abstract |
The oxidation of terminal alkenes by the Wacker system consisting of PdClィイD22ィエD2/CuClィイD22ィエD2/OィイD22ィエD2 to form the corresponding ketones is a well-established method and a very important process in both synthetic and industrial chemistry. However, this catalytic system has disadvantages caused by the cholorine anion which leads to the formation of chlorinated by-products and corrodes the reactor, and it is not suitable for oxidation of higher olefins and cycloalkenes.
In this work, Wacker-type oxidation of cyclopentene to cyclopentanone under dioxygen atmosphere was developed by the use of Pd(OAc)ィイD22ィエD2 and molybdovanadophosphate supported on activated carbon, [Pd(OAc)ィイD22ィエD2-NPMoV/C], catalyst under chloride-free conditions. Thus, the reaction of cyclopentene under OィイD22ィエD2(1 atm) in aqueous acetonitrile acidified by CHィイD23ィエD2SOィイD23ィエD2H in the presence of [Pd(OAc)ィイD22ィエD2-NPMoV/C] produced cyclopentanone in 85% yield along with a small amount of cyclopentenone (1%). In addition, the acetalizaiton of terminal alkenes such as ethyl acrylate and acrylonitrile with alcohols under OィイD22ィエD2 was efficiently achieved by Pd(OAc)ィイD22ィエD2 supported on activated carbon combined with molybdovanadophosphate (NPMoV). For example, ethyl acrylate was subjected to acetalization with EtOH acidified by CHィイD23ィエD2SOィイD23ィエD2H under OィイD22ィエD2 (1 atm) in the presence of [Pd(OAc)ィイD22ィエD2/C] and NPMoV to form ethyl 3,3-diethoxypropionate in quantitative yield.
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