| 配位诱导的硝酸铜与水杨酸甲酯的高选择性自由基硝基化反应 |
| Coordination-Mediated Radical Nitration of Methyl Salicylate by Copper(Ⅱ) Nitrate with High Regioselectivity |
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| 摘要: 硝酸铜与水杨酸酯的硝基化反应得到了高收率的对位产物。电子吸收光谱、循环伏安、电喷雾质谱的研究表明该反应经历的是一个自由基硝基化机理。硝酸铜与水杨酸甲酯的配位促使硝酸根断裂氮氧键产生硝基自由基、氧自由基和配合物自由基。硝基自由基与水杨酸甲酯或配合物反应得到硝基水杨酸甲酯或硝基化配合物。硝基化配合物经过水解将铜离子转化成氧化铜沉淀而生成硝基水杨酸甲酯。 |
| 关键词: 水杨酸甲酯|硝酸铜|自由基硝基化|配位 |
| 基金项目: 国家自然科学基金（No.21161014）资助项目。 |
| Abstract: High yield and para-selective products were obtained by the nitration of methyl salicylate (MeS) and copper(Ⅱ) nitrate(CuN). The results of electron absorption spectra (EAS),Cyclic Voltammetry(CV) and electrospray ionization mass spectra (ESIMS) reveal that the reaction favors a radical nitration mechanism. It is the coordination of MeS with CuNthat promotes the splitting of N-O bonds of nitrate group in CuN, and results in the formation of nitro radicals, oxygen radicals and complex radicals. The nitro radicals can react with MeS or the complexes of MeS to form nitration products. The nitrated complexes immediately turn to methyl nitrosalicylate by Cu(Ⅱ) ions being hydrolyzed to copper(Ⅱ) oxides. |
| Keywords: methyl salicylate Cu(Ⅱ) nitrate radical nitration coordination |
| 投稿时间：2013-09-26 修订日期：2013-11-04 |
| 摘要点击次数: 2383 |
| 全文下载次数: 1917 |
| 刘艳珠*,黄伊宁,李霞,张玲,李永绣*.配位诱导的硝酸铜与水杨酸甲酯的高选择性自由基硝基化反应[J].无机化学学报,2014,30(1):121-126. |
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