CN104193684B - 4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱及应用 - Google Patents

4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱及应用 Download PDF

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CN104193684B
CN104193684B CN201410417953.8A CN201410417953A CN104193684B CN 104193684 B CN104193684 B CN 104193684B CN 201410417953 A CN201410417953 A CN 201410417953A CN 104193684 B CN104193684 B CN 104193684B
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刘峥
李巍
魏席
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Guilin University of Technology
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Abstract

本发明公开了一种4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱及应用。4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的分子式为C18H17N3O3，分子量为323.35，熔点为299℃-301℃。（1）称取0.61g 2,5-二羟基苯甲醛溶于10 mL无水甲醇中，完全溶解后转移至三口烧瓶中，在35℃水浴条件下磁力搅拌；（2）称取1.0162g4-氨基安替比林溶于10 mL无水甲醇中，超声溶解；（3）将步骤（2）所得溶液缓慢滴加到步骤（1）所得溶液中；在60℃磁力搅拌条件下回流4小时，冷却、过滤、滤液在室温下静置一周后有黄褐色晶体生成，过滤，晾干后得到4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱。4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱能作为荧光探针在荧光分析领域得到应用。

Description

4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱及应用
技术领域
本发明涉及4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的合成，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
席夫碱是指含有活泼羰基和氨基的两类物质通过缩合反应形成的含C＝N基的一类有机化合物。在国内，关于席夫碱的合成工作起步较晚，但发展较快。近年来，已有大量文献对有关席夫碱及其配合物进行报道。随着席夫碱及其金属配合物研究的不断深入，人们发现其具有良好的荧光特性,可以用作荧光分子探针和荧光分子开关，应用于分析化学和生物化学领域。一般情况下，“刚性、平面、大共轭∏键”是荧光化合物的结构特征，有针对性的合成具有荧光特征结构的席夫碱化合物是一项很有意义的研究工作。4-氨基安替比林席夫碱具有以下几个明显的特点：(1)4-氨基安替比林分子结构中的芳香环可增大分子共轭体系且席夫碱的C＝N又有流动性的电子桥，能增强荧光发射，另外大的共轭体系在使低维分子形成更高维的超分子网络结构起到重要的作用，所以4-氨基安替比林席夫碱可以成为性能优良的荧光试剂；(2)从弱相互作用和分子几何学的角度来看，芳香环的存在也为网络内和网络间的π…π堆积的形成提供了更便利的条件，这也有利于超分子网络结构的形成，从而影响荧光的性质，因此4-氨基安替比林席夫碱合成，为此类化合物在荧光分析领域中的应用开发提供了可能。4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱是一种新的4-氨基安替比林席夫碱，其晶体结构未见报道，本发明提出了一种具有层状结构的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的合成方法，为进一步研究4-氨基安替比林缩2,5-二羟基苯甲醛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4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱，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4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱分子式为C18H17N3O3，分子量为323.35，熔点为299℃-301℃，其晶体学数据见表1，键长和键角见表2。
表14-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的晶体学数据
注：w＝1/[σ2(Fo2)+(0.060P)2+5.787P],P＝(Fo2+2Fc2)/3
表24-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的键长和键角(°)
4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的合成方法的具体步骤为：
(1)称取0.61g2,5-二羟基苯甲醛溶于10mL无水甲醇中，完全溶解后转移至三口烧瓶中，在35℃水浴条件下磁力搅拌。
(2)称取1.0162g4-氨基安替比林溶于10mL无水甲醇中，超声溶解。
(3)将步骤(2)所得溶液缓慢滴加到步骤(1)所得溶液中；在60℃磁力搅拌条件下回流4小时，冷却、过滤、滤液在室温下静置一周后有黄褐色晶体生成，过滤，晾干后得到4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱(C18H17N3O3)。
4-氨基安替比林缩2,5-二羟基苯甲醛能作为荧光探针在荧光分析领域得到应用。
附图说明
图1为本发明实施例制得的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱晶体结构图。
图2为本发明实施例制得的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱晶体三维堆积图。
图3为本发明实施例制得的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱DMF溶液荧光光谱图。
具体实施方式
实施例：
4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的合成方法的具体步骤为：
(1)称取0.61g2,5-二羟基苯甲醛溶于10mL无水甲醇中，完全溶解后转移至三口烧瓶中，在35℃水浴条件下磁力搅拌。
(2)称取1.0162g4-氨基安替比林溶于10mL无水甲醇中，超声溶解。
(3)将步骤(2)所得溶液缓慢滴加到步骤(1)所得溶液中；在60℃磁力搅拌条件下回流4小时，冷却、过滤、滤液在室温下静置一周后有黄褐色晶体生成，过滤，晾干后得到4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱(C18H17N3O3)。
制得的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱晶体结构分析：选取尺寸为0.35×0.33×0.32mm的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱黄褐色单晶安装在玻璃纤维上，在BrukerSmartCCD型X-射线衍射分析仪面探衍射仪进行晶体结构测定，在298(2)K下，采用石墨化的MoKα射线以ω扫描方式在3.9≤θ≤28.7°范围内共收集8046个衍射点，其中3184个独立衍射点，2597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4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的结晶学参数和结构精修参数(表1)可知，4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱属于单斜晶系，空间群为P21/n，晶胞参数为a＝7.5411(3)，b＝7.4350(4)，c＝27.9267(11)，α＝90.00，β＝97.687(6)，γ＝90.00，V＝1557.62(12)。由图1和图2看出，4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱晶体分子结构是线性的非对称分子，在该结构中，羟基和苯环及相邻的碳原子形成π-π共轭呈平面结构，亚氨基和吡唑啉酮不在平面结构。从三维堆积图可以看出，席夫碱以两分子单元重叠的苯环为轴线，4-氨基安替比林上的苯环相互平行，轴线两侧的堆积方向是相反的，交叉排列形成一个波浪型图案，层与层之间可能是静电引力，范德华力，分子间的弱作用力的共同作用下，交叉排列，堆垛成三维结构。
4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱红外光谱分析：C＝N的伸缩振动吸收峰为1652.34cm-1，在3398.58cm-1位置应为酚羟基O-H键的伸缩振动吸收峰，苯环的骨架振动吸收峰位于1590.59cm-1、1492.79cm-1及1459.90cm-1处，证明有苯基存在，1400.27cm-1和1384.84cm-1为CH3的弯曲振动峰，1590.59cm-1处的吸收峰可归属为酮C＝O的伸缩振动峰。从紫外光谱图中可知4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱在出现3个明显的吸收峰，264nm处出现的吸收峰，根据分子结构判断，可将其归属为共轭的C＝N发生的π～π*跃迁，337nm处的吸收峰可归属为二个酚O-H的n～π*跃迁，而在375nm处的尖锐吸收峰为吡唑环羰基的n～π*跃迁。
4-氨基安替比林缩2,5-二羟基苯甲醛作为荧光探针在荧光分析领域得到应用。

Claims (2)

1.一种具有层状结构的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱，其特征在于具有层状结构的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱熔点为299℃-301℃，其晶体学数据见表1，键长和键角见表2；
表1：4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的晶体学数据
其中：w＝1/[σ2(Fo2)+(0.060P)2+5.787P],P＝(Fo2+2Fc2)/3
表2：4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的键长和键角°
2.根据权利要求1所述具有层状结构的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱的合成方法为：
(1)称取0.61g2,5-二羟基苯甲醛溶于10mL无水甲醇中，完全溶解后转移至三口烧瓶中，在35℃水浴条件下磁力搅拌；
(2)称取1.0162g4-氨基安替比林溶于10mL无水甲醇中，超声溶解；
(3)将步骤(2)所得溶液缓慢滴加到步骤(1)所得溶液中；在60℃磁力搅拌条件下回流4小时，冷却、过滤、滤液在室温下静置一周后有黄褐色晶体生成，过滤，晾干后得到具有层状结构的4-氨基安替比林缩2,5-二羟基苯甲醛席夫碱晶体。
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