| 2，5－二叔丁基对二甲氧基苯的去叔丁基反应的研究 |
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| 引用本文： | 龚跃法,赵成学,蒋锡夔.2，5－二叔丁基对二甲氧基苯的去叔丁基反应的研究[J].高等学校化学学报,1994(5). |
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| 作者姓名： | 龚跃法 赵成学 蒋锡夔 |
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| 作者单位： | 华中理工大学化学系，中国科学院上海有机化学研究所 |
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| 摘 要： | ２，５－二叔丁基对二甲氧基苯（１）在ＣＦ_３ＣＯ_２Ｈ，ｎ－Ｃ_３Ｆ_７ＣＯ_２Ｈ或ＡｌＣｌ_３－ＣＨ_２Ｃｌ_２体系中易发生去叔丁基化反应，而在强质子酸ＨＩ（ａｑ）．ＨＢＦ_４或ＣＣｌ_３ＣＯ_２Ｈ中不发生此反应。在前一类体系中，都可在反应过程中观察到较强的阳离子基１￣＋的ＥＰＲ信号，而在后一类体系中则无此信号。动力学测定表明，受物１与三氟乙酸的反应表现为三级动力学，其中１为二级，ＣＦ_３ＣＯ_２Ｈ为一级。这些结果揭示了去叔丁基化反应与离子自由基的形成有着内在的联系。
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| 关 键 词： | 去叔丁基化反应，单电子转移，全氟羧酸，取代苯阳离子自由基 |
A Mechanistic Study of the De-t-butylation Reaction of 2,5-Di-t-butyl-p-dimethoxybenzene in Acid Systems |
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| GONG Yue-Fa,ZHAO Cheng-Xue.A Mechanistic Study of the De-t-butylation Reaction of 2,5-Di-t-butyl-p-dimethoxybenzene in Acid Systems[J].Chemical Research In Chinese Universities,1994(5). |
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| Authors: | GONG Yue-Fa ZHAO Cheng-Xue |
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| Abstract: | We have observed that the debutylation reaction can readily occur when 2,5-di-tbutyl-p-dimethoxybenzene (1) was mixed with perfluorocarboxylic acids or with AlCl3CH2Cl2 system,but did not occur with aqueous HI or HBF4 or absolute trichloroacetic acid.EPR observation shows that radical intermediates were generated in the former systems,but not in the latter case.Kinetic study indicates that the reaction of substrate 1 with trifluoroacetic acid behaves third-order kinetics,second in 1 and first in the acid.All the results reveal that an intrinsic relation may exist between the debutylation and the formation of the radical intermediates. |
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| Keywords: | De-t-butylation Single electron transfer Perfluorocarboxylic acid Substituted benzene radical cation |
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