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论文中文题名:

 C24H22N4O6、C19H16N2O3及C19H16N2O3过渡金属配合物的合成及性能研究    

姓名:

 李兰兰    

学号:

 201105158    

保密级别:

 公开    

学科代码:

 081704    

学科名称:

 应用化学    

学生类型:

 硕士    

学位年度:

 2014    

院系:

 化学与化工学院    

专业:

 应用化学    

第一导师姓名:

 刘向荣    

第二导师姓名:

 赵顺省    

论文外文题名:

 Synthesis, property study of C24H22N4O6, C19H16N2O3 and C19H16N2O3 transition metal complexes    

论文中文关键词:

 配合物 ; 酰腙 ; 晶体结构 ; 热稳定性 ; 生物活性    

论文外文关键词:

 Complex ; Hydrazone ; Crystal structure ; Thermal stability ; Biological activity    

论文中文摘要:
酰腙类化合物是一种有机合成中间体,由于含有结构独特的-CONHN=CH-基团,配位方式多样,因此作为合成配合物的一类新型配体,被广泛应用于生物化学、材料化学、医药以及光电材料等领域。 本文合成了2种新型酰腙化合物3-羟基-4-甲氧基苯甲醛-1,4-苯二甲双酰腙C24H22N4O6和2-羟基-1-萘甲醛2-甲氧基苯甲酰腙C19H16N2O3及C19H16N2O3与4种过渡金属(Cu、Ni、Co、Zn)的配合物。主要工作如下: 1.以对苯二甲酸二甲酯、水合肼为原料合成了对苯二甲双酰肼,该酰肼进一步与3-羟基-4-甲氧基苯甲醛在二甲基亚砜中反应,得到3-羟基-4-甲氧基苯甲醛-1,4-苯二甲双酰腙C24H22N4O6及其单晶,通过X单晶射线衍射测定了酰腙化合物的结构,表明该晶体属单斜晶系,空间群为P2(1)/c,Z=4,晶胞参数a=22.127(6)Å,b=16.839(4)Å,c=8.501(2)Å,α=γ=90º,β=96.636(4)º。 2.以2-甲氧基苯甲酸甲酯、水合肼为原料合成了2-甲氧基苯甲酰肼,在无水乙醇中该酰肼与2-羟基-1-萘甲醛反应得到2-羟基-1-萘甲醛2-甲氧基苯甲酰腙C19H16N2O3及其单晶,通过X单晶射线衍射测定了酰腙化合物的结构,表明该晶体属单斜晶系,空间群为P2(1)/c,Z=4,晶胞参数为a=4.8540(10)Å,b=22.104(5)Å,c=15.471(3)Å,α=γ=90º,β=94.056(4)º。 3.合成了2-羟基-1-萘甲醛苯甲酰腙C19H16N2O3及其4种过渡金属(Cu、Ni、Co、Zn)配合物,并且在甲醇溶液中培养出了Cu配合物的单晶,X射线单晶衍射结果表明Cu配合物晶体属单斜晶系,化学式为[Cu(C19H15N2O3)(CH3OH)]NO3•CH3OH,通过元素分析、红外光谱分析对上述4种配合物进行了表征,结果表明其化学式与Cu配合物类似。 4.通过热重技术,在5.00,10.00,15.00 ℃•min-1的升温速率下对C24H22N4O6和C19H16N2O3及C19H16N2O3与4种过渡金属(Cu、Ni、Co、Zn)配合物的热分解过程进行了分析,采用Kissinger和Ozawa公式计算了热分解过程中的表观活化能;C24H22N4O6的热分解过程分为两个阶段,吸收峰的最高温度为357.3 ℃;C19H16N2O3的热分解呈现一个过程,吸收峰的最高温度为321.7 ℃;C19H16N2O3的4种过渡金属配合物热分解过程均为两个阶段,主要吸收峰的最高温度均在300 ℃左右;结果表明2种酰腙及其配合物都具有较好的热稳定性。 5.利用C80微量热仪,初步探讨了C19H16N2O3的Cu配合物与CT-DNA的相互作用。Cu配合物在1.000-5.000 mg与CT-DNA相互作用的时间范围为0.50-40.00 min,焓变值的变化范围为0.50-14.00 kJ/mol,其中2.000 mg时焓变值最大,表明不同质量的Cu配合物均与CT-DNA发生了一定作用,2.000 mg时作用效果最佳。
论文外文摘要:
Acylhydrazone, a new kind of organic ligand, it has been used as a new type of ligand which could synthesize the complexes due to contain the unique -CONHN =CH- group and plentiful coordination mode, therefore, it has been widely applied in the fields, such as biochemistry, material chemistry, medicine and luminescent material. In this paper, two new types of acylhydrazone are synthesized, which are 3-hydroxy-4-methoxy benzene formaldehyde-1,4-benzene metformin acylhydrazone C24H22N4O6 and 2-hydroxy-1-naphthalene formaldehyde-2-methoxy benzoyl acylhydrazone C19H16N2O3, respectively. Meantime, Cu, Ni, Co and Zn complexes of C19H16N2O3 are obtained. Main researches in this paper are as follows: 1. The 3-hydroxy-4-methoxy benzene formaldehyde-1,4-benzene metformin acylhydrazone was synthesized by the reaction of dimethyl terephthalate and 80% hydrazine hydrate with 3-hydroxy-4-methoxy benzene formaldehyd in DMSO. The crystal structure, crystal structure for the acylhydrazone compound was determined by the single crystal X-ray diffraction analysis. The crystal belongs to monoclinic, P2(1)/c space group with Z=4, a=4.8540(10)Å,b=22.104(5)Å,c=15.471(3)Å,α=γ=90º,β=94.056(4)º。 2. Adjacent methoxy benzoyl hydrazine was prepared under the condition of water bath using 2-methoxy-benzoic acid methyl ester and 80% hydrazine hydrate as raw materials, 2-hydroxy-1-naphthalene formaldehyde-2-methoxy benzoyl acylhydrazone was synthesized and its crystal structure was obtained. Crystal structure for the hydrazone compound was determined by the single crystal X-ray diffraction analysis. The result shows that the compound crystallizes in the monoclinic space group P2(1)/c with a=4.8540(10)Å,b=22.104(5)Å,c=15.471(3)Å,α=γ=90º,β=94.056(4)º。 3. 2-hydroxy-1-naphthalene formaldehyde-2-methoxy benzoyl acylhydrazone C19H16N2O3 and its Cu, Ni, Co and Zn complexes were synthesized. The crystal structure of Cu complexe was obtained in methanol as solvent. The result of X-ray single crystal diffraction indicates that Cu complexe belongs to monoclinic, chemical formula is [Cu(C19H15N2O3)(CH3OH)]NO3•CH3OH, the above four complexes were characterized by elemental analysis and FT-IR, the result demonstrates that their chemical formulas are similar to Cu complex. 4. The thermal decomposition process of C19H16N2O3 and its Cu, Ni, Co and Zn complexes were studied at the heating rates of 5.00,10.00,15.00 ℃•min-1 by thermogravimetry method and the apparent activation energy values of the decomposition reaction for ligand were calculated by Kissinger and Ozawa methods. The thermal decomposition process of C24H22N4O6 were divided into two stages, the maximum temperature of exothermic peak were 321.7 ℃, while C19H16N2O3 presented one stage in the whole thermal decomposition process, Cu, Ni, Co and Zn complexes of C19H16N2O3 were divided into two stages, the temperatures of main exothermic peaks for three compounds were almost more than 300 ℃, which indicate all of the compounds have the good stabilities. 5. The interaction of Cu complexes of C19H16N2O3 with CT-DNA were investigated by C80 microcalorimetry. The time of interaction of Cu complexes and CT-DNA while the weight of the Cu complex changed from 1.000 to 5.000 mg were within 0.50-40.00 min, and the interaction enthalpy changes ranged from 0.50 to 14.00 kJ/mol, indicating that Cu complexes in different concentration were interacted with CT-DNA, what is more, the interaction of 2 mg Cu complex with CT-DNA was the strongest.
中图分类号:

 O641.4    

开放日期:

 2014-06-19    

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