CN104151288A - 一种噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成及应用 - Google Patents

一种噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成及应用 Download PDF

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CN104151288A
CN104151288A CN201410417847.XA CN201410417847A CN104151288A CN 104151288 A CN104151288 A CN 104151288A CN 201410417847 A CN201410417847 A CN 201410417847A CN 104151288 A CN104151288 A CN 104151288A
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thiophene
schiff
base
near amino
amino thiophenols
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刘峥
李巍
魏席
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Guilin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Abstract

本发明公开了一种噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成及应用。噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的分子式为C11H7NS2，分子量为217.32，熔点为163-165℃，晶体属于单斜晶系，空间群为P21/c，晶胞参数为a=9.8547(7)，b=12.6996(8)，c=16.3895(14)，α=90.00，β=101.268(8)，γ=90.00，V=2011.6(3)。（1）将0.224g噻吩-2-甲醛溶解于5mL无水乙醇中；（2）将0.248g邻氨基苯硫酚溶解于5mL无水乙醇中；（3）将步骤（2）所得溶液滴加到步骤（1）所得溶液中，55℃水浴条件下磁力搅拌反应4小时，过滤，滤液在室温下静置一周后有棕黄色晶体生成，过滤，晾干后得到噻吩-2-甲醛缩邻氨基苯硫酚席夫碱。噻吩-2-甲醛缩邻氨基苯硫酚席夫碱能作为荧光探针应用于荧光分析领域。

Description

一种噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成及应用
技术领域
本发明涉及一种噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成方法，所述的席夫碱晶体具有层状结构，其较强的荧光性质使其可作为荧光探针在分析领域得到应用。
背景技术
席夫碱是指含有亚胺或甲亚胺特性基团(-RC＝N-)的一类化合物，通常由醛或酮的羰基和伯胺缩合而成。席夫碱化合物在分析化学领域具有重要的用途，但以光度分析居多，随着对席夫碱及其配合物在分析化学领域的应用研究的日益深入，发现其可以作为良好的荧光试剂而应用于荧光分析领域。一般情况下，“刚性、平面、大共轭∏键”是荧光化合物的结构特征，本发明专利根据这一结构特征，设计合成了将噻吩环和苯硫酚环，通过亲核加成反应，以C＝N作为桥梁，相连接，合成了具有较大的共轭体系的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱，并获得了晶体结构。有针对性的合成结构新颖的具有强的荧光性质的席夫碱及其配合物是一项很有意义的研究工作，这可为进一步研究噻吩-2-甲醛缩邻氨基苯硫酚席夫碱结构及其与荧光性质的关系提供基础数据。
发明内容
本发明的目的就是要合成具有层状结构的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱，使其具有较强的荧光性质，而能作为荧光探针在分析领域得到应用。
本发明涉及的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱分子式为C11H7NS2，分子量为217.32，熔点为163-165℃，其晶体学数据见表1，键长和键角见表2。
表1 噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的晶体学数据
注：w＝1/[σ2(Fo2)+0.2P)2],P＝(Fo2+2Fc2)/3
表2 噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的键长和键角(°)
噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成方法具体步骤为：
(1)将0.224g噻吩-2-甲醛溶解于5mL无水乙醇中。
(2)将0.248g邻氨基苯硫酚溶解于5mL无水乙醇中。
(3)将步骤(2)所得溶液滴加到步骤(1)所得溶液中，滴加过程中有大量黄绿色沉淀生产，55℃水浴条件下磁力搅拌反应4小时，过滤，滤液在室温下静置一周后有棕黄色晶体生成，过滤，晾干后得到噻吩-2-甲醛缩邻氨基苯硫酚席夫碱(C11H7NS2)。
本发明制得的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱能作为荧光探针应用于荧光分析领域。
附图说明
图1为本发明实施例制得的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱席夫碱晶体结构图。
图2为本发明实施例制得的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱晶体三维堆积图。
图3为本发明实施例制得的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱DMF溶液荧光光谱图。
具体实施方式
实施例：
(1)将0.224g噻吩-2-甲醛溶解于5mL无水乙醇中。
(2)将0.248g邻氨基苯硫酚溶解于5mL无水乙醇中。
(3)将步骤(2)所得溶液滴加到步骤(1)所得溶液中，滴加过程中有大量黄绿色沉淀生产，55℃水浴条件下磁力搅拌反应4小时，过滤，滤液在室温下静置一周后有棕黄色晶体生成，过滤，晾干后得到噻吩-2-甲醛缩邻氨基苯硫酚席夫碱(C11H7NS2)。
噻吩-2-甲醛缩邻氨基苯硫酚席夫碱红外光谱分析：在1605.75cm-1位置出现了C＝N的伸缩振动吸收峰，在1564.83cm-1及1459.58cm-1出现苯环的骨架振动吸收峰，证明有苯基存在。紫外光谱图中在310nm处有吸收峰，根据分子结构判断，为共轭的C＝N发生的π-π*跃迁。
噻吩-2-甲醛缩邻氨基苯硫酚席夫碱晶体结构分析：选取尺寸为0.35×0.33×0.32mm的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱棕黄色单晶安装在玻璃纤维上，在Bruker Smart CCD型X-射线衍射分析仪面探衍射仪进行晶体结构测定，在293(2)K下，采用石墨化的Mo Kα射线以ω扫描方式在3.4≤θ≤24.9°范围内共收集9121个衍射点，其中4103个独立衍射点，2704个I>2σ(I)的可观测衍射点用于结构分析和结构修正。全部数据经Lp因子和经验吸收校正，晶体结构由直接法解出，对全部非氢原子及其各向异性热参数进行全矩阵最小二乘法修正，氢原子由理论值给出。所有计算使用SHELXS97、SHELXL97程序完成。
从噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的结晶学参数和结构精修参数(表1)可知，噻吩-2-甲醛缩邻氨基苯硫酚席夫碱属于单斜晶系，空间群为P21/c，晶胞参数为a＝7.0655(4)，b＝26.1707(18)，c＝9.1052(6)，α＝90.00，β＝97.687(6)，γ＝90.00，V＝1668.52(18)。由图1和图2看出，噻吩-2-甲醛缩邻氨基苯硫酚席夫碱晶体分子结构是线性的非对称分子，在该结构中，邻氨基苯硫酚上的巯基与C7相连，使得苯环与形成的五元环形成π—π共轭呈平面结构，并且与相连的噻吩环也在一个平面上，使得整个体系共轭。从三维堆积图可以看出，噻吩-2-甲醛缩邻氨基苯硫酚席夫碱以垂直与ab面的单分子单元为轴线，轴线两侧分别为相互重叠的单分子和单个分子，相互重叠的单分子间可能是静电引力，范德华力，分子间的弱作用力的共同作用，这样交叉排序，堆垛成三维结构。
制得的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱作为荧光探针应用于荧光分析领域。

Claims (3)

1.一种噻吩-2-甲醛缩邻氨基苯硫酚席夫碱，其特征在于噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的分子式为C11H7NS2，分子量为217.32，熔点为163-165℃，其晶体学数据见表1，键长和键角见表2；
表1：噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的晶体学数据
注：w＝1/[σ2(Fo2)+0.2P)2],P＝(Fo2+2Fc2)/3
表2：噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的键长和键角(°)
2.根据权利要求1所述的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成方法，其特征在于具体步骤为：
(1)将0.224g噻吩-2-甲醛溶解于5mL无水乙醇中；
(2)将0.248g邻氨基苯硫酚溶解于5mL无水乙醇中；
(3)将步骤(2)所得溶液滴加到步骤(1)所得溶液中，滴加过程中有大量黄绿色沉淀生产，55℃水浴条件下磁力搅拌反应4小时，过滤，滤液在室温下静置一周后有棕黄色晶体生成，过滤，晾干后得到噻吩-2-甲醛缩邻氨基苯硫酚席夫碱即C11H7NS2。
3.根据权利要求1或2所述的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的应用，其特征在于所述的噻吩-2-甲醛缩邻氨基苯硫酚席夫碱能作为荧光探针应用于荧光分析领域。
CN201410417847.XA 2014-08-23 2014-08-23 一种噻吩-2-甲醛缩邻氨基苯硫酚席夫碱的合成及应用 Pending CN104151288A (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107602413A (zh) * 2017-09-13 2018-01-19 哈尔滨理工大学 Binol‑diform缩邻氨基苯酚类席夫碱及其合成方法与应用
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Application publication date: 20141119