【作者】 张婷婷；

【导师】 梁洪泽；

【作者基本信息】 宁波大学 ， 无机化学， 2010， 硕士

【摘要】 咪唑衍生物配合物具有优良的生理活性、独特的光学性质和磁性,在医学、农药、功能材料、表面活性剂、分析化学试剂、有机合成等方面具有广阔的应用前景。本论文主要研究了咪唑类离子液体的合成及应用、咪唑类衍生物的配体及配合物的合成这两个领域,查阅大量文献后,主要作了以下几个方面的工作:（I）研究了硼酸、频哪醇、环己醇在离子液体1-甲基咪唑硫酸氢盐[Hmim]HSO₄、1-丁基-3-甲基咪唑硫酸氢盐[C4mim]HSO₄、1-丁基-3-甲基咪唑六氟磷酸盐[Bmim]PF6、1-丁基-3-甲基咪唑四氟硼酸盐[Bmim]BF4、1-甲基-3-丙磺酸基咪唑硫酸氢[（CH₂）3SO3Hmim]HSO₄、1-甲基咪唑四氟硼酸盐[Hmim]BF4中的酯化反应。考察了不同离子液体、反应温度、反应时间和离子液体与反应物物质的量比等对反应的影响。结果表明,当硼酸﹕频哪醇﹕环己醇﹕[Hmim]HSO₄=1:1:1:1,反应温度为80℃和反应时间为2 h时,硼酸酯的产率为95.6%,催化剂循环使用4次,催化活性没有明显下降。（II）研究了硼酸与直链醇（甲醇、乙醇、正丙醇、正丁醇、正戊醇）在[Hmim]HSO₄中的酯化反应,直链醇的长短对反应转化率有影响,硼酸三甲酯及硼酸三乙酯与[Hmim]HSO₄离子液互溶,反应体系为均相,随着链的增长,反应后,反应体系变成两相,且离子液体的催化活性随着链的增长有所增加。（III）以2,2′-联咪唑为原料,合成了三种新型的N-取代联咪唑衍生物,N,N’-二乙酸-2,2’联咪唑、N,N’-二丁酸-2,2’联咪唑、N,N’-二戊酸-2,2’联咪唑,并对其进行了表征。（IV）以N,N’-二乙酸-2,2’联咪唑为配体,与过渡金属钴、镍、锰配位,形成双核和聚合配合物,并对其结构进行X-射线单晶衍射仪、红外、元素分析以及对锰配合物进行磁性表征。更多还原

【Abstract】 Imidazole derivatives which possess good physiological activities, unique optical and magnetical properties have broad applications as drugs, pesticides, functional materials, surfactants, reagents in chemical analysis and organic synthesis. In this thesis, we mainly studied two areas: the synthesis and application of imidazolium ionic liquids; the synthesis of imidazole derivatives ligands and complexes. Based on the detailed investigation of related literature, our work was carried out as followed:（1） Esterification of boric acid, pinacol, and cycloexanol has been studied in ionic liquids, including 1-methylimidazolium hydrogen sulfate [Hmim]HSO₄, 1-butyl-3-methylimidazolium hydrogen sulfate [C4mim]HSO₄, 1-butyl-3-methylimidazolium hexafluorophosphate （[Bmim]PF6）, 1-butyl-3-methylimidazolium tetrafluoroborate （[Bmim]BF₄）, 1-methyl-3-（3-sulfopropyl）- imidazolium hydrogen sulfate [（CH2）3SO3Hmim]HSO₄, 1-methylimidazolium tetrafluoroborate [Hmim]BF4. The influences of the types of ionic liquids, reaction temperature, reaction time and mole ratio of reactants to IL on yields of boric acid esters have been investigated. The results showed that under the optimized conditions [n （boric acid）﹕ n （pinacol）﹕ n （cyclohexanol）﹕ n （[Hmim]HSO₄）=1﹕1﹕1﹕1, 80℃and 2 h], the yield of 2-cyclohexyloxy- 4,4,5,5–tetramethyl -[1,3,2] dioxaborolan could reach up to 95.6%. The ionic liquid can be used repeatedly for four times without remarkable loss of catalytic activity.（2） Esterification of boric acid, aliphatic alcohols with different length （methanol, ethanol, propanol, butanol, 1-pentanol） has been studied in [Hmim]HSO₄. The length of alkyl chains alcohols could affect the conversion rate greatly, the ionic liquid [Hmim]HSO₄ was entirely miscible with trimethyl borate and triethyl borate, the system was homogenous. With increasing the length of alkyl chains, the reaction systems were biphasic gradually at the end of reaction. It could be seen that the catalytic activity was slightly increased with the increasing the length of alkyl chains.（3） Three novel N,N’-sbustituted 2,2′-biimidazole derivatives, 2,2’-（2,2’-biimidazole-1,1’-diyl） diethanoic acid, 2,2’-（2,2’-biimidazole-1,1’-diyl） dibutyric acid, 2,2’-（2,2’-biimidazole-1,1’-diyl） dipentanoic acid have been prepared based on 2,2′-biimidazole, and the products were characterized by IR.（4） 2,2’-（2,2’-Biimidazole-1,1’-diyl）diethanoic acid was employed to synthesize binuclear metal complexes [Co2L2（H2O）4]·6H2O, [Ni2L2（H2O）4]·6H2O and polymeric complexes {[Mn₄L₄（H₂O）₄]·6H₂O}n, which were characterized by X-ray single-crystal diffraction, IR and elemental analysis. The magnetic property of Mn complex was investigated by solid state magnetic susceptibility （χm） measurements.更多还原