【作者】 张俊；

【导师】 周忠强；

【作者基本信息】 中南民族大学 ， 有机化学， 2015， 硕士

【摘要】 与传统的分步合成方法相比,多组分反应缩短了反应历程,在一锅反应中生成数个甚至更多个新的化学键而不需要分离中间产物,降低了对起始反应物的要求,需要更少的反应时间和分离操作,减少了人力和能源的消耗,从而能更高效地构建多功能化的化合物分子库。多组分反应因其本身所具有的高收敛性、高灵活性、高能量和资源利用性、高原子经济性及易操作性等优势,成为当代有机合成的研究热点。含有杂环结构单元的化合物在自然界广泛存在,具有重要的生理学和药理学作用。它们大多具有杀菌、除草、杀虫、抗病毒、抗消炎等生物活性,已有许多杂环的化合物被开发成医药、农药、燃料等的新品种及其它重要的化工产品。因此,开展杂环化合物及其衍生物的合成研究是有机化学领域的重要课题,具有重要的意义。本文对多组分反应合成2-氨基-3-氰基-4-芳基-色烯、八氢化氮杂蒽二酮、4,4’-芳亚甲基双（1-苯基-3-甲基-5-吡唑啉酮）进行了研究。此外,还合成了两种金属卟啉。用（NH₄）₂HPO₄、EDDA分别作为催化剂,在H2O-EtOH（V/V=1:1）作溶剂回流条件下合成了12种2-氨基-3-氰基-4-芳基-4H-苯并色烯类化合物。反应时间从20 min至6.5h不等,产率64-94%。将催化剂与其它被报道的催化剂进行了比较。与其它催化剂相比,（NH₄）₂HPO₄和EDDA具有反应时间短、产率高、后处理简单、催化剂制备简单、可循环利用等优点,是催化合成色烯类化合物的理想催化剂。提出了（NH₄）₂HPO₄及EDDA分别催化该反应的可能机理。用[BPy][H2PO₄]作为催化剂,在无溶剂130℃条件下合成了3,3,6,6-四甲基-9-苯基-八氢化氮杂蒽二酮类化合物。在50 min内,目标产率为69-94%。[BPy][H2PO₄]回收循环利用五次,催化活性无明显降低。提出了3,3,6,6-四甲基-9-芳基-八氢化氮杂蒽二酮合成的可能机理。用邻苯二甲酰亚胺钾盐催化醛、苯肼和乙酰乙酸乙酯在H2O-EtOH（V/V=1:2）作溶剂回流条件下反应合成了4,4’-芳亚甲基双（1-苯基-3-甲基-5-吡唑啉酮）类化合物。反应在3-8 h内,产率为70-88%。邻苯二甲酰亚胺钾盐循环使用五次,催化活性无明显降低。提出了可能的反应机理。设计合成了含有季铵盐基团的新型卟啉,进一步与Mn（CH3COO）₂和FeCl2反应制备出两种金属卟啉,并对其进行了表征。更多还原

【Abstract】 Compared with the traditional synthetic methods, multicomponent reaction shortens the reaction steps, generates several or more new chemical bonds in one pot without separating intermediates, reduces the demand for initial reactants, requires less reaction time and separation operation, reduces the manpower and energy consumption. Because of its high convergence and flexibility, multicomponent reaction has become the focus in the modern organic synthesis.Compounds containing heterocyclic structure unit exist widely in nature, have important physiological and pharmacological effects.One-pot synthesis of 2-amino-3-cyano-4H-chromenes, 4,4’-（arylmethylene） bis（1H-pyrazol-5-ols） and 1,8-dioxo-decahydroacridines catalyzed by catalysts were researched. In addition, two porphyrins have been synthetized. The main research content is as follows:We have synthesized 2-amino-3-cyano-4H-chromenes by three-component condensation of aldehyde, 1-naphthol, malononitrile under reflux conditions using（NH₄）₂HPO₄ and EDDA as catalyst respectively with good to excellent yield between 64% and 94% in 20 min to 6.5 h. The recovered catalyst can be reused at least five additional times in subsequent reactions without considerable decrease in catalytic activity. Two possible mechanisms for the reaction catalyzed by（NH₄）₂HPO₄ and EDDA are proposed.We have synthesized 1,8-dioxo-decahydroacridines by three-component condensation of aldehyde, ammonium acetate and 5,5-dimethyl-1,3-cyclohexanedione under solvent-free condition at 130℃ using [BPy][H2PO₄] as catalyst with good to excellent yield between 70% and 94% in 15 min to 40 min. A possible mechanism for the reaction is proposed.We have synthesized 4,4’-（arylmethylene） bis（1H-pyrazol-5-ols） by three-component condensation of aldehyde, ethyl acetoacetate and phenylhydrazine under reflux condition at using potassium phthalimide as catalyst with good to excellent yield between 70% and 94% in 3 h to 8 h.The catalyst can be reused at least four additional times in subsequent reactions without considerable decrease in catalytic activity.We have also designed and prepared a new porphyrin which contains quaternary ammonium groups, make porphyrin react with metal salts, and gotten the metal porphyrins.更多还原