CN116284064A - 一种锌金属配合物 - Google Patents

一种锌金属配合物 Download PDF

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CN116284064A
CN116284064A CN202310313991.8A CN202310313991A CN116284064A CN 116284064 A CN116284064 A CN 116284064A CN 202310313991 A CN202310313991 A CN 202310313991A CN 116284064 A CN116284064 A CN 116284064A
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罗梅
张丽
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Hefei University of Technology
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Abstract

一种由以下化学式(Ⅰ)所示的锌配合物的合成方法，是称取0.167g2,3‑吡啶二甲酸放入100ml圆底烧瓶中，加入20ml去离子水搅拌使其溶解；将0.220g二水合醋酸锌加入到上述溶液中，在90℃下加热回流48h；反应结束后趁热将反应溶液过滤到50ml烧杯中，在烧杯上覆盖一层保鲜膜并用细针扎孔，使其在室温下自然挥发，三天后有白色晶体析出。该锌配合物(I)的用途，是在色酮‑3‑甲醛与5‑甲基靛红的鲁卡特反应中，显示了一定的催化活性，其转化率达74％。
Figure DDA0004149545300000011

Description

一种锌金属配合物
一、技术领域
本发明涉及一种锌配合物的制备及合成方法，具体地说是一种2,3-吡啶二甲酸锌金属配合物的制备及合成方法。
二、背景技术
[1]Yaghi O M，Li G M，Li H L.Selective binding and removal of guests ina microporous metal-organic framework[J].Nature，1995，37：703-706.
[2]Fang R Q，Zhang X M.Diversity of Coordination Architecture of Metal4,5-Dicarboxyimidazole[J].Inorganic Chemistry，2006，45：4801-4810.
[3]Sarra S，Melek H，Jin X M，et al.Synthesis，structure and theoreticalsimulation of a zinc(II)coordination complex with 2,3-pyridinedicarboxylate[J].Journal ofMolecular Structure，2020，1199：127015-127025.
三、发明内容
本发明旨在为药物化学合成领域特别是制备药物化合物提供一种合成方法，所要解决的技术问题是遴选合适的配体2,3-吡啶二甲酸和二水合醋酸锌合成锌金属配合物。
(一)本发明所称的化合物是以下化学式(I)所示的锌配合物：
Figure BDA0004149545280000011
其化学名称：双2，3-吡啶二甲酸锌金属配合物，简称化合物(I)。
该锌配合物的合成方法，包括合成、分离和纯化，所述的合成是称取0.167g2,3-吡啶二甲酸放入100ml圆底烧瓶中，加入20ml去离子水搅拌使其溶解；将0.220g二水合醋酸锌加入到上述溶液中，加热回流48h；反应结束后趁热将反应溶液过滤到50ml烧杯中，在烧杯上覆盖一层保鲜膜并用细针扎孔，使其在室温下自然挥发，三天后有白色晶体析出。
其合成路线如下：
Figure BDA0004149545280000021
该反应的反应机理可推测如下：
采用简易，高效的有机合成方法，一步合成络合物，经X-衍射，NMR，IR及元素分析确定其结构。
该配合物在色酮-3-甲醛的鲁卡特反应中，显示了一定的催化活性，其转化率达74％。
四、附图说明
图1是目标化合物I的晶体结构图。
五、具体实施方式
1.锌配合物I的制备
称取0.167g 2,3-吡啶二甲酸放入100mL圆底烧瓶中，加入20mL去离子水搅拌使其溶解；将0.220g二水合醋酸锌加入到上述溶液中，加热回流48h；反应结束后趁热将反应溶液过滤到50ml烧杯中，在烧杯上覆盖一层保鲜膜并用细针扎孔，使其在室温下自然挥发，三天后有白色晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物，产率为70％，熔点为320-322℃；晶体的元素分析应带一分子结晶水：C7H11NO8Zn。其理论值：N.，4.63％；C，27.79％；H，3.665％；测试值：N，4.98％；C，28.07％；H，3.465％；ESI：理论值C7H11NO8Zn·DMSO·CH3OH；其理论值：393.6540；测试值：393.9497；红外光谱数据(KBr，cm-1)：3380；3280；2530；2250；2000；1960；1910；1630；1590；1560；1460；1410；1380；1280；1240；1160；1110；1060；885；831；713；676；619；549；
化合物的晶体数据：
经验式 C7H9NO7Zn
分子量 284.52
温度 100.00K
波长
Figure BDA0004149545280000031
晶系，空间群 三斜晶系，Pea21
晶胞参数
Figure BDA0004149545280000032
alpha＝90°.
Figure BDA0004149545280000033
beta＝90°.
Figure BDA0004149545280000034
gamma＝90°.
体积
Figure BDA0004149545280000035
电荷密度 4，2.040g/m^3
吸收校正参数 2.616mm^-1
单胞内的电子数目 576
晶体大小 0.10x 0.06x 0.04mm
Theta角的范围 4.748to 58.890°
HKL的指标收集范围 -17<＝h<＝20，-8<＝k<8，-10<＝I<＝10
收集/独立衍射数据 6371/1828[R(int)＝0.050]
theta＝30.5的数据完整度 99.2％
吸收校正的方法 多层扫描
精修使用的方法 F^2的矩阵最小二乘法
数据数目/使用限制的数目/参数数目 1828/2/151
精修使用的方法 1.090
衍射点的一致性因子 R1＝0.0346，wR2＝0.0824
可观察衍射的吻合因子 R1＝0.0429，wR2＝0.0870
差值傅里叶图上的最大峰顶和峰谷
Figure BDA0004149545280000036
2.晶体典型的键长数据：
Figure BDA0004149545280000041
Figure BDA0004149545280000051
Figure BDA0004149545280000061
Symmetry transformations used to generate equivalent atoms：
#1-x+1/2，y，z+1/2 #2-x+1/2，y，z-1/2
2、锌配位化合物的鲁卡特反应
Figure BDA0004149545280000062
称取0.043g(0.15mmol)配合物，置于25ml烧杯中，再依次加入2ml无水甲醇、0.0885g 5-甲基靛红和0.2696g甲酸铵，在85℃下反应48小时，进行1HNMR检测。
Figure BDA0004149545280000063
(二)本化合物I在抗肿瘤肝癌活性中的用途
本发明依据目标设计合成在肝癌细胞SMMC-7721的化合物(I)试验中均显示出一定的抑制活性(ED50<10.0μ g/mL)。因此，预期本发明的化合物可用于治疗多种癌症，例如肝癌。本发明化合物的部分抗癌活性测试结果见表1：
表1.(I)的抗癌活性数据(IC50值)
Figure BDA0004149545280000064
IC 50是抑制半数癌细胞生长的有效浓度，表示抗癌活性。单位是μM；NA：无抑制活性。本试验所用的上述人体癌细胞从美国ATCC购买。

Claims (4)

1.一种由以下化学式(Ⅰ)所示的锌配合物：
Figure FDA0004149545270000011
2.由权利要求1所述的锌配合物(I)晶体，其晶胞参数如下：在273k温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线，
Figure FDA0004149545270000012
以ω-θ扫描方式收集衍射数据，其特征在于晶体属单斜晶系,P21/c；其晶胞参数：/>
Figure FDA0004149545270000013
alpha＝90；
Figure FDA0004149545270000014
beta＝110.927(9)°；/>
Figure FDA0004149545270000015
gamma＝85.352(2)°。
3.由权利要求1所述的锌配合物(I)的合成方法，包括合成、分离和纯化，所述的合成是称取0.167g 2,3-吡啶二甲酸放入100ml圆底烧瓶中，加入20ml去离子水搅拌使其溶解；将0.220g二水合醋酸锌加入到上述溶液中，在90℃下加热回流48h；反应结束后趁热将反应溶液过滤到50ml烧杯中，在烧杯上覆盖一层保鲜膜并用细针扎孔，使其在室温下自然挥发，三天后有白色晶体析出。
4.由权利要求1所述的锌配合物(I)的用途，其特征在于：该配合物在色酮-3-甲醛与5-甲基靛红的鲁卡特反应中，显示了一定的催化活性，其转化率达74％。
CN202310313991.8A 2023-03-28 2023-03-28 一种锌金属配合物 Pending CN116284064A (zh)

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