| 第 39 卷第 6 期 |  | Vol. 39 No. 6 | | 2009 年 12 月 | Dec 2009 |
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所屬欄目：有機合成原料
硝酸銅硝化水楊酸甲酯的綠色硝化方法研究 |
| 李 霞，劉艷珠，張 玲，李永繡*
（南昌大學(xué) 理學(xué)院化學(xué)系，江西 南昌 330031） |
| 摘 要：以硝酸銅為硝化劑，在回流的乙酸乙酯溶液中硝化水楊酸甲酯來(lái)合成3-硝基水楊酸甲酯（O）和5-硝基水楊酸甲酯（P）。對比研究了在不同硝酸根和水楊酸甲酯配比條件下用硝酸銅和硝酸作硝化試劑時(shí)的硝化收率和區域選擇性。結果表明：以硝酸銅作硝化劑時(shí)的硝化收率可達80%，P／O比值最高為5.4，均比用相同濃度的硝酸作硝化劑時(shí)要高。而且，硝化過(guò)程中銅以氫氧化物固體沉淀的形式析出，便于與硝基化產(chǎn)物分離。用紅外光譜、元素分析和差熱-熱重分析確定了析出沉淀的組成為Cu（OH）1.46（NO3）0.47（MNS）0.07 1.15H2O。該沉淀經(jīng)硝酸溶解和濃縮結晶可以得到硝酸銅，其回收率為82.32%（以銅含量為基準）。 |
| 關(guān)鍵詞：硝化；硝酸銅；水楊酸甲酯；區域選擇性 |
| 中圖分類(lèi)號：0625.61 文獻標識碼：A 文章編號：1009-9212（2009）06- 0040-04 |
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| Green Nitration of Methyl Salicylate with Copper（II）Nitrate |
| LI Xia，LIU Yan-zhu，ZHANG Ling，LI Yong-xiu*
（Department of Chemistry，School of Science，Nanchang University，Nanchang 330031，China） |
| Abstract：A green nitration process using copper nitrate as the nitrating agent has been proposed. Methyl salicylate was mononitrated by copper（II） nitrate in refluxing ethyl acetate to synthesize methyl 3-nitrosalicylate（O） and methyl 5-nitrosalicylate（P）. The yield and regioselectivity were investigated at various ratios of nitrate to salicylate with copper nitrate comparing with nitrous acid. Results showed that the former afforded an yield over 80% and the regioselectivity （P／O ratio） up to 5.4，both were higher than that using nitrous acid as nitrating agent. Moreover，copper ions were isolated as hydroxides，which is beneficial to the separation of copper from nitrated products. The isolated solid was determined with IR，elemental analysis and DSC-TGA to be Cu（OH）1.46（NO3）0.47（MNS）0.071.15H2O. By treating this precipitate with nitrous acid followed by a recrystallization process，copper（II） nitrate was recovered in 82.32% yield. |
| Key words：nitration；copper（II）nitrate；methyl salicylate；regioselectivity |
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作者簡(jiǎn)介：李 霞（1986-），女，江西大余人，碩士研究生，主要從事金屬有機化學(xué)研究。
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聯(lián) 系 人：李永繡（1962-），教授。（E-mail：liuyanzhu2001@yahoo.com.cn）
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收稿日期：2009-10-16
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