节点文献
杂环及双核有机锡配合物的合成及其阴离子识别特性研究
Investigation on Synthesis and Anion Response Characteristics of Heterocyclic and Binuclear Organotin Complexes
【作者】 李桂芝;
【导师】 李志强;
【作者基本信息】 湖南大学 , 无机化学, 2005, 硕士
【摘要】 有机锡化合物已广泛应用于杀虫剂、船舶涂料、PVC塑料热稳定剂以及有机反应的均相催化剂等。自从发现有机锡配合物具有较强的抗癌活性以来,人们对其合成及生物活性的研究倍加重视,近年来也逐渐出现了有机锡化合物用作阴离子识别载体物质的报道,这是金属有机化学和化学传感器等多学科之间新发展起来的交叉研究领域,具有很大的发展前景。本文以三苄基氯化锡、三苯基氯化锡和二苄基二氯化锡为原料,分别和邻羟基苯甲醛、2,4-二羟基苯甲醛、2-羟基-3-甲氧基苯甲醛、邻羟基苯乙酮、2,4-二羟基苯乙酮以及乙酰乙酰基二茂铁反应合成了十六种新型杂环有机锡(Ⅳ)配合物,并研究了其中一些物质的阴离子识别性能,主要包括以下四部分的工作: (1)通过三苄基氯化锡和邻羟基苯甲醛、2,4-二羟基苯甲醛、2-羟基-3-甲氧基苯甲醛、邻羟基苯乙酮、2,4-二羟基苯乙酮等双齿配体的反应,合成了五种新型五配位杂环苄基锡(Ⅳ)化合物,其结构经元素分析、红外光谱、核磁共振氢谱和质谱等测试方法得到确认。探讨了其阴离子响应行为,并通过对比研究分析了载体结构对电极响应性能的影响。 (2)通过三苯基氯化锡和邻羟基苯甲醛、2,4-二羟基苯甲醛、2-羟基-3-甲氧基苯甲醛、邻羟基苯乙酮、2,4-二羟基苯乙酮等双齿配体的反应,合成了五种新型五配位杂环苯基锡(Ⅳ)化合物,其结构经元素分析、红外光谱、核磁共振氢谱和质谱等测试方法得到确认。 (3)通过二苄基二氯化锡与双齿配体按1:2物质的量之比反应,合成出了二(邻羟基苯甲醛)合二苄基锡(Ⅳ)、二(2,4-二羟基苯甲醛)合二苄基锡(Ⅳ)、二(2-羟基-3-甲氧基苯甲醛)合二苄基锡(Ⅳ)、二(邻羟基苯乙酮)合二苄基锡(Ⅳ)、二(2,4-二羟基苯乙酮)合二苄基锡(Ⅳ)五个六配位杂环苄基锡(Ⅳ)化合物。其结构经元素分析、红外光谱、核磁共振氢谱以及质谱得到确证。 (4)以二茂铁为起始原料与乙酸酐反应合成出乙酰基二茂铁,再与乙酸乙酯反应得到乙酰乙酰基二茂铁。将其与三苄基氯化锡反应合成出乙酰乙酰基二茂铁合三苄基锡(Ⅳ),一种新型五配位双核有机锡配合物。其结构经元素分析、红外光谱、核磁共振氢谱以及质谱得到确证。探讨了基于此配合物为载体的阴离子响应行为,并考察了不同增塑剂的电极对水杨酸根离子响应性能的影响,以及缓冲体系和溶液pH值对该电极响应性能的影响。将基于乙酰乙酰基二茂铁合三苄基锡为载体的电极应用于药物分析,取得满意结果。
【Abstract】 Organotin compounds are widely used as biocides, coatings for ship, heat stabilizer for PVC plastic and homogeneous catalyst in organic reaction. Since organotin complexes were found be of strong antitumour activities, there has been growing interest in the synthesis and biological activity of novel organotin complexes. In recent years, there are more and more reports that organotin complexes were used as neutral carries for anions recognition. It has been a new domain with widely developing prospect among metal organic chemistry, chemical sensor and even more other subjects. In this paper, tribenzyltin chloride, triphenzyltin chloride, dibenzyltin dichloride reacted with 2-hydroxybenzaldehyde, 2,4-dihydroxybenzaldhyde, 2-hydroxy-3-methoxybenzaldehyde, 2-hydroxyacetophenone, 2,4-hydroxylacetophenone, acetoacetyl ferrocene respectively to give sixteen novel heterocyclic organotin complexes, their anion recognition characteristics were also studied. The four main parts in this paper were as follows:(1) Tribenzyltin chloride reacted with 2-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2-hydroxyacetophenone and 2,4-dihydroxyacetophenone respectively to give five novel pentacoordinated heterocyclic organotin compounds. Their structures were confirmed by IR, ~1H NMR, mass spectra and elemental analysis. Their anion response characteristics have been investigated. Effect of the structures of the carriers on the response characteristics towards anions has been discussed based on the experimental results.(2) Five novel pentacoordinated triphenzyltin compounds were first synthesized by the reaction of triphenzyltin chloride with 2-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2-hydroxyacetophenone and 2,4-dihydroxyacetophenone respectively. Their structures were also characterized by IR, ~1H NMR, mass spectra and elemental analysis. They all were found to be pentacoordinated compounds.(3) Di(2-hydroxybenzaldehyde) dibenzyltin, di(2,4-dihydroxybenzaldehyde) dibenzyltin, di(2-hydroxy-3-methoxybenzaldehyde) dibenzyltin, di(2-hydroxyacetophenone) dibenzyltin and di(2,4-dihydroxyacetophenone) dibenzyltin have been synthesized in our laboratory. Their structures were confirmed by IR, ~1H NMR, mass spectra and elemental analysis. These complexes were found to be six-coordinated.(4) Acetyl ferrocene was synthesized by the reaction of ferrocene with acetic anhydride in the presence of phosphoric acid, it reacted with ethyl acetate to give acetoacetyl ferrocene. A novel organotin compound, acetoacetyl ferrocene tribenzyltin was synthesized by the reaction of acetoacetyl ferrocene with tribenzyltin chloride. Its
【Key words】 Heterocyclic organotin(Ⅳ) complex; Synthesis; Characterization; Salicylate; Anion recognition;
- 【网络出版投稿人】 湖南大学 【网络出版年期】2005年 07期
- 【分类号】O641.4;O627.41
- 【被引频次】1
- 【下载频次】229