苯并香豆素硫脲类受体分子的设计、合成与阴离子识别研究  

Design, Synthesis and Anion Recognition of Benzocoumarin-Based Thiourea Receptors

作　　者：晏希泉 卓继斌[1] 王吉成[1] 谢莉莉[1,2] 袁耀锋[1,2] 

机构地区：[1]福州大学化学学院,福州350116 [2]中国科学院福建物质结构研究所结构化学国家重点实验室,福州350002

出　　处：《有机化学》2015年第10期2184-2190,共7页Chinese Journal of Organic Chemistry

基　　金：国家基础科学人才培养基金(No.J1103303);中国科学院福建物质结构研究所结构化学国家重点实验室(No.20120010)资助项目~~

摘　　要：以β-萘酚为原料,经过多步反应合成了5种不同电子效应的1-(5,6-苯并香豆素-3-甲酰基)-4-芳基氨基硫脲衍生物,并通过1H NMR,13C NMR,IR及元素分析等测试手段对受体分子进行表征.利用紫外-可见吸收光谱和荧光光谱考察了这类受体分子与F-,Ac O-,C1-,Br-,I-,HSO4-等阴离子的作用,发现受体分子对其它阴离子无响应;而对F-和Ac O-离子具有良好的选择性检,检测限分别为5.45与7.00μg/L,响应时间分别为5与10 min.实验结果表明该类受体分子与阴离子通过氢键形成配位物,从而导致光谱信号的变化.通过主客体间结合比和稳定常数的计算,证实了受体分子对F-和Ac O-选择性好,形成稳定化合物.Job’s曲线可知受体分子与阴离子形成1∶2的配合物,并利用核磁滴定与理论计算[B3LYP/6-31G(d,p)]进一步证实了受体分子与阴离子的氢键作用.Anions display a great significant role in the environment and life science. The design and synthesis of receptors with high selective recognition anion has attracted considerable attention. The selective identification fluoride anion of benzocoumarin-based thiourea receptors 4a-4e were obtained starting from β-naphthol by a multi-step reaction. Their structures were characterized by 1H NMR, 13 C NMR, IR and elemental analysis. The interactions between receptors 4a-4e and anions（F-, Ac O-, C1-, Br-, I-, HSO4-） were studied by optical（UV-Vis absorption and fluorescence） and 1H NMR spectroscopy.The results showed that the receptors with anion through hydrogen bonds formed stable 1∶2 complexes, which leaded to the change spectroscopy of receptor molecules. Determination of the combined ratio and the stability constants of complexes were borne out receptor molecules with high alternative recognition F- or Ac O- anions with limit of detect of 5.45 and 7.00 μg/L and the effect of reaction time of 5 min and 10 min respectively. However, there is no selectively responds to other anions. Using NMR titration and theoretical（B3LYP/6-31G（d, p）） methods further confirmed the hydrogen bond acceptor molecules and anions.

关 键 词：苯并香豆素 硫脲 阴离子识别 氢键 

分 类 号：O625.7[理学—有机化学]