用硝酸铁对水杨酸甲酯硝化合成了3-硝基水杨酸甲酯和5-硝基水杨酸甲酯.考察了反应时间、反应物配比、反应溶液酸碱性对产物收率和位置选择性的影响.得出较好的反应条件为:反应时间3 h,n(硝酸铁): n(水杨酸甲酯)=2: 3.少量硝酸有利于硝基化反应,且优先生成5-硝基水杨酸甲酯,而碱性不利于硝基化反应,且优先生成3-硝基水杨酸甲酯.用量化计算解释了硝化反应的位置选择性机理.
The nitration of methyl salicylate by iron(Ⅲ) nitrate was studied to obtain 3-nitrosalicylate and 5-nitrosalicylate. The effects of reaction time, molar ratio of iron(Ⅲ) nitrate to methyl salicylate, acidity and basicity on the yield and regioselectivity were reported. When the reaction time is 3 h and the molar ratio of iron(Ⅲ) nitrate to methyl salicylate is 2: 3, the yield is the highest. Furthermore, a small amount nitric acid is beneficial to the nitration and the formation of 5-nitrosalicylate, whereas a small amount base is not benefiical to the nitration but to the formation of 3-nitrosalicylate under a strong base condition. The regioselectivity was explained by the quatum chemical computations.
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