CN105348141B - 一种苯甲酰肼衍生物的制备和应用 - Google Patents

一种苯甲酰肼衍生物的制备和应用 Download PDF

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CN105348141B
CN105348141B CN201510621130.1A CN201510621130A CN105348141B CN 105348141 B CN105348141 B CN 105348141B CN 201510621130 A CN201510621130 A CN 201510621130A CN 105348141 B CN105348141 B CN 105348141B
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hydrazine derivative
benzoyl hydrazine
ethyl alcohol
absolute ethyl
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于春伟
张军
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Hainan Medical College
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Abstract

本发明涉及荧光分子探针，具体的说是一种苯甲酰肼衍生物的制备和应用。苯甲酰肼衍生物P结构如式一；制备方法，将邻氨基苯甲酸乙酯与水合肼在无水乙醇中，加热回流4‑6h，冷却至室温后，析出固体过滤，无水乙醇洗涤，干燥后所得中间体化合物；中间体在无水乙醇中，70‑80℃下与邻羟基萘甲醛反应4‑6h，冷却后将析出固体抽滤，而后洗涤，干燥获得淡黄色固体纯品P；所述苯甲酰肼衍生物P可作为荧光探针实现对Mg2+的识别检测。本发明通过有效的合成手段得到的苯甲酰肼衍生物P，对Mg2+表现出较好的选择性，在优化实验条件基础上，可以实现对Mg2+的检测。

Description

一种苯甲酰肼衍生物的制备和应用
技术领域
本发明涉及荧光分子探针，具体的说是一种苯甲酰肼衍生物的制备和应用。
背景技术
在已报道的荧光分子探针中，大多具有以下缺点：合成分离复杂、测试过程中其它共存离子干扰大、检出限偏高、响应信号为猝灭型等(Y.T.Li and C.M.Yang,Chem.Commun.,2003,2884-2885.；L.Fabbrizzi,M.Licchelli,P.Pallavicini,A.Perotti,A.Taglietti and D.Sacchi,Chem.Eur.J.,1996,2,75-82.；M.N.Elizabeth,J.L.Stephen,J.Mater.Chem.,2005,15,2778-2783.)，这对金属离子的检测带来了很大的影响及不便。尤其是由于受到Ca2+的干扰，Mg2+探针的研究较少(张灯青.化学进展,2009,21，715-723.)。
苯甲酰肼类衍生物具有优良的光学性质、合成简单，在金属离子荧光探针中有着广泛的应用。基于苯甲酰肼衍生物的荧光探针已被应用到Hg2+、Pb2+、Fe3+、Cr3+以及Cu2+的检测中。但在对Mg2+检测方面的报道较少。
发明内容
本发明的目的是提供一种基于苯甲酰肼衍生物的制备和应用。
为实现上述目的，本发明所采用的技术方案为：
一种苯甲酰肼衍生物，苯甲酰肼衍生物P结构如式一，
一种苯甲酰肼衍生物的制备方法，将邻氨基苯甲酸乙酯与水合肼在无水乙醇中，加热回流4-6h，冷却至室温后，析出固体过滤，无水乙醇洗涤，干燥后所得中间体化合物；
中间体在无水乙醇中，70-80℃下与邻羟基萘甲醛反应4-6h，冷却后将析出固体抽滤，而后洗涤，干燥获得淡黄色固体纯品P；
其中，邻氨基苯甲酸乙酯与水合肼之间摩尔比为1:1-2；中间体与邻羟基萘甲醛之间摩尔比1︰1-1.3。
所述加热回流冷却后析出固体，经过滤再用无水乙醇洗涤，干燥后获得中间体化合物；
中间体与邻羟基萘甲醛反应，冷却后析出固体抽滤，而后依次用大量水和无水乙醇洗涤，干燥获得淡黄色固体纯品P。
一种苯甲酰肼衍生物P的应用，所述苯甲酰肼衍生物P用于荧光探针的制备。
所述苯甲酰肼衍生物P作为荧光探针实现对Mg2+的检测。
本发明所具有的优点：
本发明通过有效的合成手段得到苯甲酰肼衍生物P，合成步骤简单，成本低，易于提纯，产率高。该化合物对Mg2+具有好的选择性，在实际测试中检出限低。
附图说明
图1为本发明实施例提供的苯甲酰肼衍生物P的合成方法。
图2为本发明实施例提供的苯甲酰肼衍生物P的质谱图。
图3为本发明实施例提供的苯甲酰肼衍生物P的核磁谱图。
图4为为本发明实施例提供的苯甲酰肼衍生物P(50μM)与Mg2+的荧光滴定光谱曲线。其中，P(50μM)与Mg2+的荧光滴定光谱(乙醇-水溶液，v/v，9:1，20mM HEPES,pH 10.0)[Mg2+](0—50.0μM).插图为P(50μM)对Mg2+响应的曲线。
具体实施方式
实施例1
式1所示苯甲酰肼衍生物P化合物的合成(参见图1)：
将1mmol邻氨基苯甲酸乙酯与1.5mmol水合肼在无水乙醇中，加热回流4h，冷却至室温后，析出固体过滤，无水乙醇洗涤，干燥后所得中间体化合物直接用于下一步。中间体在无水乙醇中，80℃下与邻羟基萘甲醛以摩尔比1︰1反应4h，冷却后将析出固体抽滤，依次用大量水和无水乙醇洗涤，干燥，得淡黄色固体纯品P(参见图2和3)，产率85％。
从图2的分子离子峰和图3中H的化学位移可知苯甲酰肼衍生物P的生成。
苯甲酰肼衍生物P对Mg2+的光学识别
1)稀释液为：在乙醇/水(9/1，v/v)介质中，用20mM HEPES缓冲溶液控制体系pH为10.0。
2)实验方法：5mL比色管中，加入不同浓度的Mg2+标准溶液，而后加入50μL，含1mM上述实施例获得的作为探针分子的衍生物P的DMSO溶液，再用稀释液稀释至刻度，摇匀。测试时，激发/发射狭缝＝5/5nm，激发/发射波长为415/483nm。
3)光学性质测定：图4为Mg2+的荧光滴定谱图，含50μM上述实施例获得的作为探针分子的衍生物P的稀释液，荧光很弱，说明体系中P自身无荧光；加入Mg2+后，483nm处出现荧光峰，说明P与Mg2+络合后，产生强荧光，并且随着Mg2+浓度的增加，483nm处的荧光强度随之增强。在最佳实验条件下，P对Mg2+具有较高的选择性响应，得到P(50μM)对Mg2+响应的曲线，线性范围为0.9-4.0μM，检出限为0.3μM，如图4。

Claims (3)

1.一种苯甲酰肼衍生物P的应用，其特征在于：苯甲酰肼衍生物P作为荧光探针实现对Mg2+的检测中的应用，
所述苯甲酰肼衍生物P结构如式一，
2.按权利要求1所述的苯甲酰肼衍生物P的应用，其特征在于：所述苯甲酰肼衍生物P的制备为：将邻氨基苯甲酸乙酯与水合肼在无水乙醇中，加热回流4-6h，冷却至室温后，析出固体过滤，无水乙醇洗涤，干燥后所得中间体化合物；
中间体在无水乙醇中，70-80℃下与邻羟基萘甲醛反应4-6h，冷却后将析出固体抽滤，而后洗涤，干燥获得淡黄色固体纯品P；
其中，邻氨基苯甲酸乙酯与水合肼之间摩尔比为1:1-2；中间体与邻羟基萘甲醛之间摩尔比1︰1-1.3。
3.按权利要求2所述的苯甲酰肼衍生物P的应用，其特征在于：所述加热回流冷却后析出固体，经过滤再用无水乙醇洗涤，干燥后获得中间体化合物；
中间体与邻羟基萘甲醛反应，冷却后析出固体抽滤，而后依次用大量水和无水乙醇洗涤，干燥获得淡黄色固体纯品P。
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CN106966924B (zh) * 2017-04-17 2018-11-02 济南大学 一种基于席夫碱的锌离子荧光探针的制备与应用
CN107759489A (zh) * 2017-11-08 2018-03-06 海南医学院 一种苯甲酰肼衍生物p及其合成和应用
CN108997164A (zh) * 2018-08-11 2018-12-14 安康学院 2-甲基-3-苯基苯甲酰肼及其合成方法

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