【作者】 杨红伟；

【导师】 王吉德； 岳凡；

【作者基本信息】 新疆大学 ， 物理化学， 2004， 硕士

【摘要】 Schiff 碱及其金属配合物，长期成为研究热点，主要源自它们所含 C=N 基团的功能性、与中心离子的作用以及电子效应等因素.最近的几十年中,对 Schiff 碱及其配合物的制备和物理、化学特性作了广泛的报道.它们可用作螯合剂、稳定剂、催化剂和生物活性剂. 而苯并咪唑类衍生物能够抑制细菌和酵母菌生成，许多烷基苯并咪唑，具有抗维生素 B12的活性，其中一些具有抗病毒性质，含苯并咪唑的配体的配位化学是在配位化学领域中的一个十分活跃的课题，含苯并咪唑的过渡金属配合物常用作为 SOD 活性中心的模拟物. 近年来，此类杂环化合物的合成及其生物活性研究日益成为杂环化学研究的热点.人工合成的氧载体在分离和储存氧以及在工业生产中的催化剂等方面都具有十分重要的应用价值. 在本课题组的研究中，固相合成 Schiff 碱与苯并咪唑类钴配合物具有氧合性能，并且氧合性能有一定差异，本文培养并测试了其配体的晶体结构，并利用晶体数据来阐释了其差异的原因.全文共分五部分：一、评述了人工氧载体合成意义及 Schiff 碱类与苯并咪唑类化合物的合成背景及 应用前景.二、分别用 3-甲氧基-4-羟基苯甲醛、对甲氧基苯甲醛与乙二胺反应合成了未见 报道的 N，N’-（4-甲氧基苯亚甲基）乙二胺、N，N’-（3-甲氧基-4-羟 基苯亚甲基）乙二胺，培养了其晶体，并用元素分析、IR、晶体结构分析进 行表征.三、用对甲氧基苯甲醛、对羟基苯甲醛、3-甲氧基-4-羟基苯甲醛、间硝基苯甲 醛等芳香醛与邻苯二胺直接合成了 1-(对甲氧苄基)-2-（对甲氧基苯基）- 苯并咪唑、1-(对羟基苄基)-2-（对羟基苯基）-苯并咪唑、1-(3-甲氧基-4- 羟基苄基)-2-（3-甲氧基-4-羟基苯基）-苯并咪唑、1-(间硝基苄基)-2-（间 I<WP=3>硝基苯基）-苯并咪唑，方法简单，产率较高(60%以上)，用 DEPT13C NMR确定对羟基苯甲醛与邻苯二胺的反应产物非双 Schiff 碱型化合物，而是苯并咪唑类衍生物，并用元素分析和 IR 进行了表征，并分别培养了晶体，报道了晶体结构.四、用对甲氧基苯甲醛分别与乙二胺和邻苯二胺反应，得到不同类型产物，前者产物为 Schiff 碱化合物，而后者可得到苯并咪唑类化合物，因此本文在前期实验的基础上，合成了相应的两个单核 Zn（II）的配合物，培养并报道了其晶体结构，并用元素分析、差热-热重、IR、电化学分析方法进行了表征.五、用固相法合成了 Schiff 碱类钴配合物与苯并咪唑类钴配合物，对其吸氧性能进行了对比，并研究了其吸氧性能差异的原因.更多还原

【Abstract】 Owing to the function of C=N, Schiff bases and their metallic complexes havebeen widely investigated for one a century. In recent years, the synthesis, physical andchemical properties about them were reported extensively. These metallic complexesare known to be biologically important and serve as catalysts in various chemical andphotochemical reactions. On the other side, there is considerable interest in the use ofbenzimidazole complexes to model the active site of a variety of metalloenzymes suchas carbonic anhydrase and carboxypeptidase. Because of their parasitic and antiviralactivities, benzimidazole and some substituted benzimidazole compounds have beenwidely investigated in commercial medical fields. The study on oxygen carrier is of significance in military and civil applications,especially in the fields of dioxygen separation, metal anti-corrosion and keeping fruitsfresh. In our lab, cobalt complexes of Schiff bases and of benzimidazoles synthesizedby solid-state reaction can absorb oxygen. But there are some differences in theirabilities to binding oxygen. In order to interpret the machanics to absorb oxygen fromcrystal structure, crystals of ligands were obtained and tested. The content of thiswork contains five parts. 1. Recent development of oxygenated complexes was reviewed. Synthesis and prospect for Schiff bases and benzimidazole derivatives were discussed. 2. N,N’-bis(4-methoxybenzyl)ethylenediamine and N,N’-bis(3-methoxy-4 -hydroxylbenzyl)ethylenediamine were synthesized by p-methoxy- benzaldehyde or vanillin and ethylenediamine, and these compounds were characterized by elemental analysis, IR and x-ray diffraction. 3. 1-(p-methoxylbenzyl)-2-(p-methoxylphenyl)-benzimidazole, 1-(3-metho xyl-4-hydroxylbenzyl)-2-(3-methoxylbenzyl-4-hydroxyphenyl)- benzi- midazole, 1-(p-hydroxylbenzyl)-2-(p-hydroxylbenzylphenyl) –benzi- midazole and 1-(m-nitrobenzyl)-2-(m-nitrophenyl)-benzimidazole were synthesized directly by p-methoxybenzaldehyde, vanillin, p-hydroxyl- benzaldehyde or m-nitrobenzaldehyde and o-phenylenediamine, and these III<WP=5>compounds were characterized by elemental analysis, IR and x-ray diffraction.4. The reactions of p-methoxybenzaldehyde with o-phenylenediamine and ethylenediamine yield two diffrent types of compounds N,N’-bis(3-methoxybenzyl)ethylenediamine and 1-(4-methoxybenzyl)-2- (4-methoxylphenyl)–benzimidazole. Zinc (II) complexes of these ligands were synthesized and characterized by x-ray diffraction, DTA-TG and cyclic voltammetry.5. Cobalt complexes of Schiff bases and cobalt complexes of benzimidazole were synthesized by solid-state reaction. Their oxygenation mechanics were proposed.更多还原