新型二茂铁噻唑和咪唑衍生物的合成及其对Fe3＋的选择性识别
收稿日期: 2016-11-25
修回日期: 2017-02-09
网络出版日期: 2017-02-27
基金资助
北京市自然科学基金（No.2173060）和北京市教委科研计划（No.KM201710028007）资助项目.
Synthesis of Novel Ferrocenyl Thiazole and Imidazole Derivatives and Its Selective Recognition to Fe3＋
Received date: 2016-11-25
Revised date: 2017-02-09
Online published: 2017-02-27
Supported by
Project supported by the Beijing Natural Science Foundation (No. 2173060) and the General Plan of Beijing Municipal Education Commission (No. KM201710028007).
设计合成了5个新型二茂铁噻唑和咪唑衍生物，其特点是二茂铁共轭单元与杂环共轭单元之间用羰基亚甲基（COCH2）相连.以二茂铁为原料，经氯乙酰化反应生成氯乙酰基二茂铁（1a），1a分别与不同的杂环化合物（2-巯基苯并噻唑、2-巯基苯并咪唑、咪唑和苯并咪唑）反应生成相应的四种新化合物；二茂铁经乙酰化、溴代反应生成1，1'-二（溴乙酰基）二茂铁（1b），1b与2-巯基苯并噻唑反应生成1，1'-二茂铁二[（2-苯并噻唑-2-硫基）-1-乙酮]（2e）.五种新化合物的结构都经1H NMR，13C NMR，ESI-MS，HRMS和IR确认，并得到3个化合物的X射线单晶结构.利用紫外-可见光谱研究了5个新化合物对14种金属离子的识别性质，发现这5个化合物只对Fe3＋离子具有离子识别作用，其中2a具有最大的吸收光谱响应.
关键词： 二茂铁; 噻唑; 咪唑; 铁（III）离子识别; 互变异构
邬孝芳 , 武沛 , 李敬瑜 , 陆婧 , 王健春 . 新型二茂铁噻唑和咪唑衍生物的合成及其对Fe3＋的选择性识别[J]. 有机化学, 2017 , 37(6) : 1412 -1416 . DOI: 10.6023/cjoc201611037
Five novel ferrocenyl thiazole and imidazole derivatives were synthesized. The structure characterization of the five products showed that ferrocene conjugative unit and thiazole or imidazole conjugative unit were linked by carbonyl methylene skeleton (COCH2). Chloroacetylferrocene (1a) was prepared by chloroacetylation of ferrocene which reacted with different heterocyclic compounds (2-mercaptobenzothiazole, 2-mercaptobenzimidazole, imidazole and benzimidazole) to give four novel compounds, respectively. 1,1'-Bis(bromoacetyl)ferrocene (1b) was prepared by acetylation and subsequent bromination of ferrocene, which then reacted with 2-mercaptobenzothiazole to produce 2e. All the new compounds were confirmed by 1H NMR, 13C NMR, ESI-MS, HRMS and IR. Three single crystal structures were obtained. Recognition properties on 14 metal ions of the five new compounds were investigated by UV-vis spectrum. The results showed that the five new compounds possessed recognition properties only to iron(III), in which 2a had maximum spectra response.
Key words： ferrocene; thiazole; imidazole; iron(III) ion recognition; tautomerism
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