双水杨醛席夫碱桥连环钯配合物的合成及反应性

发布时间：2018-03-24 10:45

本文选题：双水杨醛席夫碱　切入点：环钯配合物　出处：《辽宁大学》2017年硕士论文

【摘要】：目前顺铂类药物在临床化疗中发挥了重要的作用。然而,该类药物对身体有较高的毒副作用,主要是肾毒性以及恶心呕吐。因此在癌症治疗领域迫切需要寻找铂类药物的替代品。已有研究表明与Pt配合物具有相似结构和热力学相似性的C,N-环金属化钯配合物具有一定的抗癌活性。席夫碱是一类重要的含氮化合物,其亚胺基团中的N上含有孤对电子,可以与大部分金属离子形成稳定的配合物。已有研究表明,席夫碱配合物广泛应用于药物、催化、检测等领域。其中水杨醛类席夫碱以独特的抗菌效果得到人们的青睐。而对称双席夫碱占有重要的地位,源于结构的特殊且具有多个配位点。可以与很多过渡金属配位形成配合物,配体中N、O为主要配位原子与中心金属配位。鉴于环金属化钯配合物和水杨醛席夫碱在药物领域的潜在应用价值,我们设计合成了一系列双水杨醛席夫碱桥连环钯配合物。生成的钯配合物通过IR、1H NMR、X-ray单晶衍射判断其分子结构。席望为进一步研究该系列配合物的抗癌活性提供一些新思路。具体工作内容如下:首先我们合成了本课题组前期工作中已报道的化合物[Pd{(4-R)C_6H_3CH=NC_6H_3-2,6-i-Pr_2}(μ-Cl)]_2(R=H,1;R=OMe,2)并通过与双水杨醛衍生的席夫碱反应合成了新的环金属化钯配合物[Pd_2(4-R)(C,N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2)_2{N,O-k~2-1,4-(N=CH-2-O-C_6H_4)_2-C_6H_4}](R=H,3;R=OMe,4)[Pd_2(4-R)(C,N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2)_2{N,O-k~2-1,4-(C_6H_4N=CH-2-O-C_6H_4)_2-CH_2}](R=H,5;R=OMe,6)[Pd(4-R)(C,N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2){N,O-k~2-1,4-(C_6H_4N=CH-2-O-C_6H_4)_2-C_6H_4]_2(R=H,7;R=OMe,8)[Pd(4-R)(C,N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2){N,O-k~2-1,4-(C_7H_6N=CH-2-O-C_6H_4)_2-C_6H_4}]_2(R=H,9;R=OMe,10)。对以上化合物采用了IR,1HNMR等分析手段进行表征,其中化合物4和8的分子结构通过X-射线单晶衍射进行了测定,确定了化合物的结构。研究已合成的化合物3-10的反应性,分别与1,4-二苯基膦丁烷和三苯基膦反应,对所合成的配合物做了红外光谱表征,为研究此类配合物各种性质提供了有利条件。
[Abstract]:At present, cisplatin drugs play an important role in clinical chemotherapy. However, this kind of drugs have high toxicity to the body, mainly is the kidney toxicity and nausea and vomiting. Therefore in the field of cancer therapy is an urgent need to find a platinum substitute. Studies have shown that Pt complexes have similar structure and thermodynamics the similarity of C, N- cyclometalated palladium complexes have anti-tumor activity. Schiff base is a kind of important nitrogen-containing compounds, the imine group in N containing lone pair electrons can form stable complexes with most metal ions. Studies have shown that the Schiff base complexes are widely used in medicine, catalysis, detection and other fields. The Salicylaldehyde Schiff base with a unique antibacterial effect is favored by people. While the symmetric double schiff base occupies an important position, due to the special structure and has many coordination sites and can be. Many transition metal coordination complexes formed in the ligand N, O as the main ligand and metal coordination center. In view of cyclometalated palladium complexes and salicylaldehyde Schiff base in the field of medicine potential application value, we designed and synthesized a series of double salicylaldehyde Schiff base palladium bridged coordination at the palladium complexes generated by IR, 1H, NMR, X-ray diffraction to determine its molecular structure. I hope to provide some new ideas for the further research of this series of complexes with anticancer activity. The specific work is as follows: firstly we synthesized have been reported in our previous work in the compound [Pd{(4-R) C_6H_3CH=NC_6H_3-2,6-i-Pr_2} (U -Cl)]_2 (R=H, 1; R=OMe, 2) and by Schiff base reaction and synthesis of salicylaldehyde derivatives of double ring metal new palladium complexes [Pd_2 (4-R) (C, N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2) _2{N, O-k~2-1,4- (N= CH-2-O-C_6H_4 _2-C_6H_4}] (R=H), 3; R=OMe, 4) [Pd_2 (4-R) (C, N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2) _2{N, O-k~2-1,4- (C_6H_4N=CH-2-O-C_6H_4) _2-CH_2}] (R=H, 5; R=OMe, 6) [Pd (4-R) (C, N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2) {N, O-k~2-1,4- (C_6H_4N=CH-2-O-C_6H_4) _2-C_6H_4]_2 (R=H, 7; R=OMe, 8) [Pd (4-R (C, N-k~2-C_6H_3CH=NC_6H_3-2,6-i-Pr_2) {N), O-k~2-1,4- (C_7H_6N=CH-2-O-C_6H_4) _2-C_6H_4}]_2 (R=H, 9; R=OMe, 10). Of the above compounds by IR, 1HNMR and other analytical methods of characterization, molecular structure of the compounds 4 and 8 by X- ray diffraction were measured, the structures of these compounds were determined. The research has reaction of compound 3-10 the 1,4- respectively with two phenyl phosphine butane and three phenyl phosphine reaction of the complexes were characterized byInfrared Spectroscopy Research of various properties of these complexes have provided favorable conditions.

【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;TQ460.1

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