3-甲醛肟基苯甲酸乙酯的合成及其对部分重金属离子的荧光选择识别  

Synthesis of 3-(hydroxyimino-methyl)-benzoic Acid Ester and its Fluorescence Recognition of Selected Heavy Metal Ions

作　　者：董艳芹 刘欣宇 曾展鹏 彭佩[1] 王勇[1] DONG Yan-qin;LIU Xin-yu;ZENG Zhan-peng;PENG Pei;WANG Yong(Key Laboratory of Drug Synthesis and Optimization,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、药物合成与优化湖北省重点实验室,湖北荆门448000

出　　处：《化学试剂》2023年第2期121-127,共7页Chemical Reagents

基　　金：湖北省教育厅科学技术研究重点项目(D20214302);荆楚理工学院项目(ZD202101);大学生创新创业训练计划项目(S202211336030)。

摘　　要：基于肟类化合物对重金属离子具有很好的配位能力,是一类制备荧光探针的优良配体。将3-溴苯甲酸与二氯亚砜在乙醇中直接反应制得中间体3-溴苯甲酸乙酯(L2)。接着将中间体L2与氰化亚铜直接反应得到中间体3-氰基苯甲酸乙酯(L3),最后将中间体L3与盐酸羟胺在碳酸钠存在下制得标题化合物L4。对化合物L2~L4进行核磁共振氢谱、碳谱和红外光谱等结构表征。利用电子吸收光谱和荧光光谱研究了常见重金属离子(Cu(Ⅱ)、Fe(Ⅲ)、Pb(Ⅱ)、Co(Ⅱ)、Cr(Ⅲ)、Ni(Ⅱ)、Fe(Ⅱ)、Mn(Ⅱ)、Zn(Ⅱ)和Cd(Ⅱ))对目标化合物L4的选择性,研究表明目标化合物对Cu(Ⅱ)、Fe(Ⅲ)和Pb(Ⅱ)离子表现优良的选择作用。随着金属离子Cu(Ⅱ)、Fe(Ⅲ)和Pb(Ⅱ)的加入,目标化合物L4的荧光强度均逐渐减弱至基本完全猝灭,而对其他重金属离子没有选择识别作用或选择识别作用较弱。Oxime-based compounds have good coordination ability to heavy metal ions,and which are excellent ligands for the preparation of fluorescent probes.3-Bromobenzoic acid ethyl ester(L2)was obtained by reaction of 3-bromobenzoic acid(L1)with thionyl chloride in ethanol.4-Cyano-2-methyl-benzoic acid methyl ester(L3)was synthesized by reaction of L2 with cuprous cyanide.And finally reaction of ethyl 3-cyanobenzoate with hydroxylamine hydrochloride in the presence of sodium carbonate affords ethyl formaloximinobenzoate(L4).The structures of L2~L4 were characterized by 1HNMR,13 CNMR and IR.The electron absorption spectroscopy and fluorescence spectroscopy were used to investigate the interaction of selected heavy metal ions(Cu(Ⅱ),Fe(Ⅲ),Pb(Ⅱ),Co(Ⅱ),Cr(Ⅲ),Ni(Ⅱ),Fe(Ⅱ),Mn(Ⅱ),Zn(Ⅱ)and Cd(Ⅱ))with L4.The study showed that L4 possessed excellent selectivity for Cu(Ⅱ),Fe(Ⅲ)and Pb(Ⅱ)ions.With the addition of metal ions Cu(Ⅱ),Fe(Ⅲ)and Pb(Ⅱ),the fluorescence intensity of L4 gradually weakened,and even almost to be quenched completely,while it had no selective recognition effect or weak selective recognition effect on other heavy metal ions.

关 键 词：肟 重金属离子 荧光光谱 电子吸收光谱 设计合成 

分 类 号：O621.3[理学—有机化学]