【作者】 徐丽英；

【导师】 李宁；

【作者基本信息】 哈尔滨工业大学 ， 化学工程与技术， 2013， 博士

【摘要】 酰基吡唑啉酮配合物由于在功能材料、金属离子萃取、生物活性等领域应用广泛，其新型配体及配合物的合成、性能及配体与中心离子间的作用成为配位化学研究的热点。以1-苯基-3-甲基-吡唑啉酮-5（PMP）为母体，4位杂环基团取代形成的酰基吡唑啉酮已有许多报道。但4位脂肪链烃取代的此类化合物报道相比较少，因此，本论文以含氮五元杂环PMP为前驱体，选取碳数为7和10脂肪链烃为取代基，设计合成出4-庚酰基、癸酰基吡唑啉酮及其衍生物，并同过渡金属盐配位形成配合物，对产物进行结构表征及性能测试。采用非水溶剂法合成1-苯基-3-甲基-4-庚酰基吡唑啉-5-酮（HL）、HL缩苯胺（HL1）、HL缩对甲基苯胺吡唑啉酮（HL2）、1-苯基-3-甲基-4-癸酰基吡唑啉酮-5（HQ）、HQ缩对甲基苯胺（HQ1）、1-苯基-3-甲基-4-苯甲酰基吡唑啉-5-酮缩噻吩（HQ2）和1-苯基-3-甲基-4-苯甲酰基吡唑啉酮-5缩邻氯苯胺（HQ3）7种新型的酰基吡唑啉酮及其衍生物，采取非水溶剂法与锌、镍、铜、锰、钡等金属二价盐反应制备出19种配合物，利用元素分析、紫外光谱、红外光谱、差热分析和X射线衍射等分析测试方法表征产物的组成和结构。制得的产物经干燥后为粉末状物质，在空气中稳定。通过挥发溶剂法对产物进行单晶培养，获得其中11种产物的单晶。通过单晶X射线衍射仪测试并解析出产物的晶胞参数及空间点群信息。表明配体中主要配位原子有：-RC=N-的N原子、羰基的O原子，水分子常参与配位，如Co（L）₂·（H₂O）₂、Zn（L）2·（H₂O）。 N,N-二甲基甲酰胺（DMF）作为培养单晶溶剂也参与配位，如Ni（Q）2（DMF）2。晶体多为单斜、三斜晶系。采用琼脂平板扩散法测定了部分配体及配合物的抑菌性能，通过抑菌圈直径的大小评定产物的抑菌效果，得出抑菌能力顺序，大肠杆菌：ZnL2>CuL2>NiL2>ZnL22> CoL22；枯草杆菌：MnL12>NiL12>BaL2>ZnL2>ZnL22>BaL12>CoL12>CuL2；金黄色葡萄球菌;CuL₂>NiL₂>CuL₂²>ZnL₂>BaL₂>MnL₂，筛选出具有广谱抗菌活性或对某菌种具有选择性抑制作用的配合物。抑菌实验表明，配合物的抑菌活性一般强于其配体本身，且抑菌活性与抑菌剂浓度呈正相关。采用电化学分析方法测试了产物的电化学性能，筛选出庚酰基吡唑啉酮与金属Sn（II）的络合吸附波峰形尖锐且随离子浓度的改变变化灵敏，可用于电化学方法分析检测溶液中的Sn（II）。确立了分析测试体系的最佳pH为4.0；探究出电极过程峰电流与浓度的线性关系及线性范围为Ip=0.2615c＋0.2635，（0.002～0.005mg/L）r=0.9986，Ip=0.1763c＋0.2345，（0.005～0.007mg/L） r=0.9995；确定电极过程为吸附过程控制；通过实验结果计算得出配合物稳定常数为4.05×10⁷。更多还原

【Abstract】 Studies of sythesis, properties and the effect between ligands and ions of newacylpyrazolones ligands and their complexes are becoming hot spots in the developmentof the coordination chemistry,due to the fact that are widely used in functional materials,solvent extractions of metal ions and antibacterial reagents. Literature reviews showmany heterocyclic derivatives about1-phenyl-3-methyl-pyrazolone-5(PMP) compoundbut few about long chain fatty hydrocarbon replacing4-acylpyrazolone. Therefore, inthis paper,4-heptylpyrazolone and4-caprylpyrazolone were designed and synthesisedwith the precursor of PMP. Complexes were prepared by reacting pyrazolone and theirderivatives with transition metal salts. All the compounds were studied by performancetesting and structure characterization.Seven acylpyrazolones and their deriveateives,1-phenyl-3-methyl-4-heptylpyrazo-lone (HL)，(Z)-4-(aniline)1-phenyl-3-methyl-4-heptylpyrazolone (HL1),(Z)-4-(ptoluidi-ne)1-phenyl-3-methyl-4-heptylpyrazolone(HL2),1-phenyl-3-methyl-4-caprylpyrazolone(HQ),(Z)-4-(p-toluidine)1-phenyl-3-methyl-4-caprylpyrazolone（HQ1）,(Z)-4-(thiof-uran)(phenyl)methylene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-on（HQ2）and (Z)-4-((2-chlorophenylamino)(phenyl)methylene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one(HQ3) have been sythesised. Nineteen transition complexes were sythesised by thereaction of metal salts with seven acylpyrazolones and their deriveateives in nonaqu-eous solvents. The compositions and structures have been characterized by element ana-lysis, infrared absorption spectrometry, ultraviolet absorption spectrometry, thermal ana-lysis and X-ray single crystal diffraction(XRD).In moderate conditions, all of the ligands and complexes are stable. Eleven single c-rystals of products have been accessed through the method of volatile solvent. The unitcell parameter and information of space point group were ascertained by single crystalXRD.The results of XRD data showed that the oxygen atom of carbony and nitrogenatom of derivatives coordinated to the metal ions in the complexes.Water moleculeswere coordinated to the complexes, such as Co(L)2·(H2O)2, Zn(L)2·(H2O). N,N-dimeth-yl formamide(DMF) as solvent cultivation of single crystal was also involved in coordi- nation, such as Ni(Q)2(DMF)2. Most of single crystals of products are monoclinic andtriclinic crystal system.The complex and ligand were individually tested against pathogenic bacteria suchas escherichia coli, bacillus subtilis and staphylococcus epidermidis. Antibacterialactivities of the ligand and metal complex were detected by using the disc diffusionmethod.The screened strains for some selective inhibition and have broad spectrumactivity of the complexes.Bacteriostatic order is follows: e. coli: ZnL2> CuL2> NiL2>ZnL22> CoL22; Bacillus subtilis: MnL12> NiL12> BaL2> ZnL2> ZnL22> BaL12>CoL12> CuL2; Staphylococcus aureus: CuL2> NiL2> CuL22> ZnL2> BaL2>MnL2.The results also show that bacteriostatic activities of compounds were positivelycorrelated with their concentration and the activities of the complexes is generallyhigher than the corresponding ligands.Electrochemical analysis method was used in this paper to test the electrochemicalproperties of the products. SnL2complexing adsorption wave was sensitive withconcentration change of Sn(II), which is expected to a useful electrochemical method forthe quantitative determination of tin. Electrochemical behavior of HL-Sn (II) system wastested as complexing adsorption wave. The best pH of system is4.0; The peak currenthas a linear relation with concentration of Sn (II) in electrode process and the linearequation is: Ip=0.2615+0.2635c,(0.002~0.005mol/mL) r=0.9986; Ip=0.1763+0.2345c (0.005~0.007mol/mL) r=0.9995; the stability constant of complexes is4.05x10~7.更多还原