可选择性识别重金属离子的肟类化合物的合成  

Synthesis of Oxime Compound Capable of Selectively Recognizing Heavy Metal Ions

作　　者：蔡苗 林怡婷 黄莉 詹红菊[1] 王勇[1] CAI Miao;LIN Yiting;HUANG Li;ZHAN Hongju;WANG Yong(Jingmen Pharmaceutical Industry Technology Research Institute,College of Chemical Engineering and Pharmacy,Jingchu University of Technology,Jingmen 448000,China)

机构地区：[1]荆楚理工学院化工与药学院,荆门医药工业技术研究院,湖北荆门448000

出　　处：《合成化学》2024年第4期360-368,共9页Chinese Journal of Synthetic Chemistry

基　　金：湖北省自然科学基金计划项目(2022CFB532);湖北省高等学校优秀中青年科技创新团队计划项目(T2020023);大学生创新创业项目(202311336002);荆楚理工学院教育教学研究重点项目(JX2023-016)。

摘　　要：具有芳香结构的肟类化合物不仅表现出良好的荧光性能,且肟上的氮和氧可以与各种金属离子配位,因此这类化合物广泛用于重金属离子检测。以2-甲氧基-4-溴苯甲酸(1)为原料,在二氯亚砜的无水乙醇条件下制得2-甲氧基-4-溴苯甲酸乙酯(2)。将2与氰化亚铜在DMF(N,N-二甲基甲酰胺)溶剂中回流反应得到2-甲氧基-4-氰基苯甲酸乙酸(3)。将化合物3与盐酸羟胺在碳酸钠溶液中反应得到2-甲氧基-4-甲醛肟基苯甲酸乙酯(4)。化合物2~4的结构经^(1)H NMR、^(13)C NMR、元素分析和红外光谱表征,并对反应可能的机理进行了推测。电子吸收光谱和荧光光谱研究表明:化合物4对Cu(Ⅱ),Fe(Ⅲ)和Pb(Ⅱ)金属离子具有较强的选择性,而对其他金属离子几乎没有选择性。Oxime compounds with aromatic structure not only show good fluorescence properties,but also the nitrogen and oxygen on the oxime can coordinate with various metal ions,so these compounds are widely used in the detection of heavy metal ions.2-methoxy-4-bromobenzoic ester(2)were prepared by reaction of 2-methoxy-4-bromobenzoic acid(1)and thionyl chloride in ethanol.Refluxed compound 2 with cuprous cyanide in DMF(N,N-dimethylformamide)to obtain 2-methoxy-4-cyano benzoic ester(3).Compound 3 was reacted with hydroxylammonium chloride in sodium carbonate solution to prepare 2-methoxy-4-formoxime ethyl benzoate(4).Compounds 2~4 were characterized by ^(1)H NMR,^(13)C NMR,elemental analysis and IR,and the possible reaction mechanism was speculated.Electron absorption spectroscopy and fluorescence spectroscopy studies have shown that compound 4 has strong selectivity for Cu(Ⅱ),Fe(Ⅲ),and Pb(Ⅱ)metal ions,while it has almost no selectivity for other metal ions.

关 键 词：肟 重金属 荧光 电子吸收光谱 设计合成 

分 类 号：O621.3[理学—有机化学]