| 硅(磷)中心自由基与2-丁烯二酸二乙酯的加合反应机理 |
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| 引用本文： | 郭金梁,李勇.硅(磷)中心自由基与2-丁烯二酸二乙酯的加合反应机理[J].波谱学杂志,1994,11(4):383-390. |
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| 作者姓名： | 郭金梁 李勇 |
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| 作者单位： | 清华大学化学系, 北京 100084 |
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| 摘 要： | 用ESR方法研究了硅(磷)中心自由基与2-丁烯二酸二乙酯的加合反应机理.具有顺式构型的马来酸二乙酯(DEM)与硅(磷)中心自由基反应,生成自由基加合物。DEM的聚合反应受到抑制。具有反式构型的富马酸二乙酯(DEF)易发生聚合反应,DEF与硅(磷)中心自由基的加合反应受到抑制.DEF与DEM在反应性能上的差异,主要来自DEF有较大的空间位阻效应.
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| 关 键 词： | 硅中心自由基 磷中心自由基 马来酸二乙酯 富马酸二乙酯 自由基加合反应 ESR |
| 收稿时间： | 1993-07-07 |
STUDING ON MECHANISM OF ADDITION REACTIONS OF Si-OR P-CENTERED RADICALS TO DIETHYL 2-BUTENEDIOATE |
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| Guo Jinliang,Li Yong.STUDING ON MECHANISM OF ADDITION REACTIONS OF Si-OR P-CENTERED RADICALS TO DIETHYL 2-BUTENEDIOATE[J].Chinese Journal of Magnetic Resonance,1994,11(4):383-390. |
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| Authors: | Guo Jinliang Li Yong |
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| Institution: | Department of Chemistry, Qinghua University Beijing, 100084 |
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| Abstract: | The mechanism of the addition reactions Si-or P-centered radicals to diethyl 2-butenedioate has been studied by ESR method.Si-or P-centered radicals could be added to diethyl maleate which possesses cis-configuration.Hypertine splitting constants of the silyl radical adducts linked with different substituents were measured in our experiments. Radical polymerization of diethyl fumarate which possessetrans-configuration was initiated by radical Bu1O·and produeed telomer or polymer. The addition reactions of Si-or P-centered radicals to diethyl fumarate could not happen due to steric hindranee. |
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| Keywords: | Si-centered radical P-centered radical Diethyl maleate Diethyl fumarate Kadical addition reaction ESR |
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