雙水楊醛席夫堿橋連環(huán)鈀配合物的合成及反應(yīng)性
發(fā)布時(shí)間:2018-03-24 10:45
本文選題:雙水楊醛席夫堿 切入點(diǎn):環(huán)鈀配合物 出處:《遼寧大學(xué)》2017年碩士論文
【摘要】:目前順鉑類藥物在臨床化療中發(fā)揮了重要的作用。然而,該類藥物對(duì)身體有較高的毒副作用,主要是腎毒性以及惡心嘔吐。因此在癌癥治療領(lǐng)域迫切需要尋找鉑類藥物的替代品。已有研究表明與Pt配合物具有相似結(jié)構(gòu)和熱力學(xué)相似性的C,N-環(huán)金屬化鈀配合物具有一定的抗癌活性。席夫堿是一類重要的含氮化合物,其亞胺基團(tuán)中的N上含有孤對(duì)電子,可以與大部分金屬離子形成穩(wěn)定的配合物。已有研究表明,席夫堿配合物廣泛應(yīng)用于藥物、催化、檢測(cè)等領(lǐng)域。其中水楊醛類席夫堿以獨(dú)特的抗菌效果得到人們的青睞。而對(duì)稱雙席夫堿占有重要的地位,源于結(jié)構(gòu)的特殊且具有多個(gè)配位點(diǎn)?梢耘c很多過(guò)渡金屬配位形成配合物,配體中N、O為主要配位原子與中心金屬配位。鑒于環(huán)金屬化鈀配合物和水楊醛席夫堿在藥物領(lǐng)域的潛在應(yīng)用價(jià)值,我們?cè)O(shè)計(jì)合成了一系列雙水楊醛席夫堿橋連環(huán)鈀配合物。生成的鈀配合物通過(guò)IR、1H NMR、X-ray單晶衍射判斷其分子結(jié)構(gòu)。席望為進(jìn)一步研究該系列配合物的抗癌活性提供一些新思路。具體工作內(nèi)容如下:首先我們合成了本課題組前期工作中已報(bào)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)并通過(guò)與雙水楊醛衍生的席夫堿反應(yīng)合成了新的環(huán)金屬化鈀配合物[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)。對(duì)以上化合物采用了IR,1HNMR等分析手段進(jìn)行表征,其中化合物4和8的分子結(jié)構(gòu)通過(guò)X-射線單晶衍射進(jìn)行了測(cè)定,確定了化合物的結(jié)構(gòu)。研究已合成的化合物3-10的反應(yīng)性,分別與1,4-二苯基膦丁烷和三苯基膦反應(yīng),對(duì)所合成的配合物做了紅外光譜表征,為研究此類配合物各種性質(zhì)提供了有利條件。
[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.
【學(xué)位授予單位】:遼寧大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2017
【分類號(hào)】:O641.4;TQ460.1
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