2-取代苯并咪唑二茂铁磺酰胺的合成、表征及量子化学计算

【作者】 张俊珍；

【导师】 杨秉勤；

【作者基本信息】 西北大学 ， 有机化学， 2007， 硕士

【摘要】 苯并含氮杂环化合物由于其高选择性和生物活性，在药物的研究和开发中发挥着重要作用。苯并咪唑及其衍生物具有良好的生物活性，广泛用于医药、农药、兽药、抗真菌剂等。苯并咪唑衍生物与过渡金属形成的配合物可作为生物分子的模拟酶。自从1952年确定二茂铁晶体结构以来，二茂铁及其衍生物在各个领域的作用愈来愈受到人们的重视。近年来，含有二茂铁基单元的新化合物层出不穷，激起人们的广泛兴趣。由于它们的独特结构，表现出许多特殊的性质，其应用已经涉及催化、助燃剂、非线性光学、电极的修饰、抗老剂、医学等多个领域。本文以二茂铁磺酰氯和苯并咪唑衍生物为原料，三氯甲烷或吡啶为溶剂，在NaOH和四正丁基溴化胺作用下合成了11种未见文献报道的二茂铁磺酰基苯并咪唑衍生物，用IR、1H NMR、Elemental analysis及MALDI-TOF MS对合成的化合物进行了表征，用德国Bruker Smart APEXⅡCCD X—射线衍射仪测定了化合物a₂、j₂的晶体结构，利用Gaussian03程序对晶体结构模型进行了量子化学计算，并用量子化学密度泛函B3LYP／6-31G方法对该化合物进行了几何全优化，同时对其成键情况、稳定性、原子净电荷分布以及前沿轨道布居进行了讨论。通过生成速率法对6种二茂铁磺酰基苯并咪唑衍生物进行了生物活性测试。测定了上述化合物对马铃薯干腐病菌（Pythium solani）、番茄早疫病菌（Alternaria lycopersici）、小麦赤霉病菌（Gibberella saubinetii）的抑菌活性。以市售苯并咪唑类杀菌剂50％多菌灵可湿性粉剂为对照，测试结果表明该系列化合物有较好的抑菌活性，部分化合物的抑菌活性高于对照药剂。更多还原

【Abstract】 Because of their high selectivity and bioactivity, nitrogen-containing benzoheterocyclic compounds play an important role in the research and exploitation of drugs. Benzimidazole and its derivatives possess a variety of biological characteristics, widely used as Pharmaceuticals, Pesticide, Veterinary, Fungicide, et al. Transition metal complexes of benzimidazoles also can be used as simulacrum of biology moleculars.Since the crystal structure of ferrocene was elucidated in 1952, the application of ferrocene and the derivatives have been attached the importance in many domains. In the last few years the new compounds containing ferrocene unit have emerged in endlessly, and have received much attention. Because of their unique structures, the ferrocene and its derivatives behaved many special properties, and they have been used in many areas, such as catalyst, helping combustion reagent, non-linear optics, modification of electrode, anti-ageing reagent, medicine, et al.Eleven new ferrocenesulfonyl benzimidazole derivatives were prepared by the reaction of ferrocenesulfonylchloride with benzimidazole derivatives in the presence n-tetrabutylammonia bromine, sodium hydroxide and trichloromethane or pyridine. The structures were confirmed by IR, ¹H NMR, Elemental analysis and MS. The crystal structures of a₂ and j₂ were determined by X-ray single crystal diffraction of Germanic Bruker Smart APEX II CCD. According to the crystal structure, the quantum chemistry calculation was performed by Gaussian 03 program, and full geometry optimizations of the title compound were carried out with DFT method at B3LYP/631G level. Its structure, stability, net charge distribution and frontier molecular orbital components were discussed.Six Compounds were tested in vitro against three fungicides: Pythium solani, Alternaria lycopersici, Gibberella saubinetii. Niveum in comparison with 50% carbendazim wet powder. All compounds show their fungicidal activities, some showed better activities than the contrast.更多还原