芳香亚硒酸类茂锆及有机锡化合物的合成、结构及性质研究

发布时间：2018-07-03 02:57

本文选题：茂锆化合物 + 有机锡化合物　；参考：《聊城大学》2017年硕士论文

【摘要】：在硒化合物中,特别是有机硒化合物,已经展现出了非常有前景的化疗特性。这就使有机硒化合物成为预防及治疗肿瘤细胞的研究热点。此外,茂锆类及有机锡化合物具有各种各样的美学结构且在催化、生物活性等方面具有广泛的潜在应用,从而激起了人们对它们的浓厚兴趣。因此,设计并合成新型茂锆及有机锡化合物对金属有机化学的研究具有重要意义。基于有机硒、茂锆及有机锡化合物都具有生物活性的特性,我们选择了多种芳香亚硒酸作为配体并将其与二氯二茂锆或烃基氯化锡反应,得到了一系列新型的芳香亚硒酸类茂锆及有机锡化合物。本论文的主要工作包括以下几个方面:1、合成了多种芳香亚硒酸(噻吩亚硒酸、苯亚硒酸、4-氟苯亚硒酸、3,4-二氟苯亚硒酸酸、3,5-二氟苯亚硒酸、3-三氟甲基苯亚硒酸),研究了它们与二氯二茂锆反应,得到了6个芳香亚硒酸类茂锆化合物。结果表明:(1)当4-氟苯亚硒酸与二氯二茂锆反应时,得到了中心对称的八锆核的32元金属大环和二锆核的共晶产物。其中,大环化合物是通过C-Zr键断裂失去茂环的同时和亚硒酸反应得到的,每个亚硒酸分子都是以桥联的形式参与双齿配位的且在大环化合物部分中,中心锆原子均为六配位的变形八面体构型。(2)另一种二锆核的化合物仅仅是二氯二茂锆的水解产物,中锆原子均是呈现四配位的四面体结构。2、噻吩亚硒酸、苯亚硒酸、3,4-二氟苯亚硒酸、3,5-二氟苯亚硒酸及3-三氟甲基苯亚硒酸与二氯二茂锆进行反应时,得到了三锆核的单体结构的产物。合成了多种芳香亚硒酸配体(噻吩亚硒酸、萘亚硒酸、苯亚硒酸、3-氟苯亚硒酸,3,5-二氟苯亚硒酸、3-三氟甲基苯亚硒酸),研究了它们与二、三烃基氯化锡的反应,得到了13个新型芳香亚硒酸类有机锡化合物。结果表明:(1)当配体与三甲基氯化锡以摩尔比1:1反应时,均得到了一维链状的聚合物结构。(2)芳香亚硒酸配体与二苯基二氯化锡以摩尔比2:1反应得到4个四锡核的笼形结构。(3)当芳香亚硒酸配体与二叔丁基二氯化锡以摩尔比2:1反应时,得到了7个二锡核的四元环结构和1个一维链状结构。3、在研究了芳香亚硒酸茂锆及有机锡化合物结构的基础上,对部分茂锆化合物及有机锡化合物进行了体外抗癌活性进行了初步研究。我们得到了部分化合物对MDA-MB-231(乳腺癌细胞),Hela(人宫颈癌细胞)等癌细胞的半抑制浓度,并对实验数据做了比较分析。
[Abstract]:Selenium compounds, especially organic selenium compounds, have shown promising chemotherapeutic properties. This makes organic selenium compounds become the focus of prevention and treatment of tumor cells. In addition, zirconocene and organotin compounds have a variety of aesthetic structures and have a wide range of potential applications in catalysis, biological activities and so on, thus arousing great interest in them. Therefore, the design and synthesis of new zirconocene and organotin compounds are of great significance in the study of organometallic chemistry. Based on the biological activity of organoselenium, zirconocene and organotin compounds, a variety of aromatic selenous acids were selected as ligands and reacted with zirconium dichloride or alkyl tin chloride. A series of novel aromatic selenite zirconocene and organotin compounds were obtained. The main work of this thesis includes the following aspects: 1, synthesis of a variety of aromatic selenous acid (thiophene selenite), Benzene selenite 4 fluorobenzenes selenite 3 5 difluorobenzene selenite 3 fluoromethyl phenylselenite) have been studied for their reaction with zirconium dichloride. Six aromatic selenite zirconocene compounds have been obtained. The results show that: (1) when 4-fluorobenzene-selenite reacts with zirconium dichloride, the products of the center symmetric large metal ring of the octa-zirconium nucleus and the eutectic product of the dizirconium nucleus are obtained. Among them, macrocyclic compounds are obtained by the C-Zr bond breaking and the reaction with selenite. Each selenite molecule participates in the bicententate coordination in the form of bridge and in the macrocyclic compound part. The central zirconium atoms are all hexagonal deformed octahedrons. (2) another kind of dizirconium nucleus compound is only the hydrolysis product of zirconium dichloride. The zirconium atoms in the center are tetrahedron structure of tetrahedral coordination, thiophene selenite, and thiophene selenite. The products of monomeric structure of zirconium trifluorobenzene were obtained by the reaction of trifluorobenzoic acid and 3-trifluoromethylphenylselenoic acid with zirconium dichloride. A variety of aromatic selenite ligands (thiophene selenite, naphthalene selenoic acid, benzene selenite 3-fluorobenzene-selenite) have been synthesized and their reactions with di-, trialkyltin chloride have been studied. Thirteen new aromatic selenite organotin compounds were obtained. The results show that: (1) when the ligand reacts with trimethyltin chloride at 1:1, (2) aromatic selenite ligands reacted with diphenyltin dichloride at 2:1 to obtain the cage structure of four tetratin nuclei. (3) when aromatic selenite ligands reacted with tertiary Ding Ji tin dichloride at 2:1, Seven quaternary ring structures of ditin nuclei and one one-dimensional chain structure .3were obtained. The structures of aromatic zirconocene selenite and organotin compounds were studied. The anticancer activities of some zirconocene compounds and organotin compounds were studied in vitro. The semi-inhibitory concentrations of some compounds on MDA-MB-231 (breast cancer cell) Hela (human cervical cancer cell) and other cancer cells were obtained, and the experimental data were compared and analyzed.
【学位授予单位】：聊城大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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