Breakthrough of an established theory on organic reaction mechanism
| Project/Area Number |
12440203
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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 |
物質変換
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| Research Institution | Saitama University |
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Principal Investigator |
MACHIGUCHI Takehisa Saitama University, Faculty of Science, Professor, 理学部, 教授 (00008864)
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| Co-Investigator(Kenkyū-buntansha) |
YAMADA Shinichi Nara University of Education, Educational Technology Center, Professor, 教育学部, 教授 (00109117)
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| Project Period (FY) |
2000 – 2002
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| Project Status |
Completed (Fiscal Year 2002)
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| Budget Amount *help |
¥13,300,000 (Direct Cost: ¥13,300,000)
Fiscal Year 2002: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2001: ¥4,800,000 (Direct Cost: ¥4,800,000)
Fiscal Year 2000: ¥5,300,000 (Direct Cost: ¥5,300,000)
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| Keywords | ketene / olefin / cycloaddition / α-methyleneoxetanee / NMR / UV-vis / zwitterion / 分子軌道理論 / C=O結合 / 低温モニター / クライオスタット |
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| Research Abstract |
Cycloaddition of a ketene to produce a cyclobutanone was found by Staudinger in early years of 20th century. A large number of experimental data have been reported regarding ketene-olefin cycloaddition. They showed the preference that ketenes reacts with olefins across the C=C bond rather than the C=C one. There have been many arguments on the mechanism of whether ketene-olefin reaction proceeds in the two-step pathway via zwitterion. We investigated the reaction of a ketene with an activated olefin. The initial product in the ketene-olefin reaction has been found to be an α-methyleneoxetane by low-temperature NMR spectroscopy. We studied the isomerization of α-methyleneoxetane to cyclodutanone (final product) by low-temperature Uv-vis spectroscopy. Ketenes reacts with an activated olefin across the ketene C=O bond to form initially a [2 + 2] cycloadduct. The α-methyleneoxetane is isomerized to the [2 + 2] product (cyclobutanone). We have thus made an innovation in an important organic reaction.
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Report
(4 results)
Research Products
(11 results)
