摘要
以硝酸铜为硝化剂,在回流的乙酸乙酯溶液中硝化水杨酸甲酯来合成3-硝基水杨酸甲酯(O)和5-硝基水杨酸甲酯(P)。对比研究了在不同硝酸根和水杨酸甲酯配比条件下用硝酸铜和硝酸作硝化试剂时的硝化收率和区域选择性。结果表明:以硝酸铜作硝化剂时的硝化收率可达80%,P/O比值最高为5.4,均比用相同浓度的硝酸作硝化剂时要高。而且,硝化过程中铜以氢氧化物固体沉淀的形式析出,便于与硝基化产物分离。用红外光谱、元素分析和差热-热重分析确定了析出沉淀的组成为Cu(OH)1.46(NO3)0.47(MNS)0.071.15H2O。该沉淀经硝酸溶解和浓缩结晶可以得到硝酸铜,其回收率为82.32%(以铜含量为基准)。
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）L46（NO3）0.47 （MNS）0.oTI.15H20. By treating this precipitate with nitrous acid followed by a recrystallization process, copper （Ⅱ） nitrate was recovered in 82.32% yield.
出处
《精细化工中间体》
CAS
2009年第6期40-43,共4页
Fine Chemical Intermediates
关键词
硝化
硝酸铜
水杨酸甲酯
区域选择性
nitration
copper （Ⅱ） nitrate
methyl salicylate
regioselectivity
