【作者】 贾俊；

【导师】 陶京朝；

【作者基本信息】 郑州大学 ， 有机化学， 2003， 硕士

【摘要】 一、本论文共合成了四个系列共27种未见文献报道的聚合物固载的亚胺配体及其相应的亚胺环钯化合物。通过元素分析、红外光谱确定了它们的结构和组成。 化合物A₁-A₉ 化合物B₁-B₈ 化合物C₁-C₆ 化合物D₁-D₄ 二、聚合物固载的亚胺环钯化合物对Heck反应的催化性能研究 1．考察了上述制备的四个系列聚合物固载亚胺环钯化合物对卤代苯与丙烯酸酯偶联反应的催化活性，实验结果表明，所有固载环金属催化剂均可有效催化Heck反应，且转化数达到10⁴-10⁵，转化效率最高可达21000。以化合物A₁-A₉为催化剂，考察了在不同溶剂（DMF、CH₃CN）中催化碘代苯与丙烯酸丁酯的偶联，发现偶联反应均可在较短时间内完成。中文摘要 2.以化合物A:一扬为催化剂，考察了聚合物固载的环铭化合物用于催化碘代苯与苯乙烯的偶联反应。实验结果表明，所用催化剂对该类Heck反应具有同均相类似物相近的催化活性，且反式产物与1，1一二苯基乙烯产物之比约为10/1。仔，·一裂戮黯千导心·黔:一 l2 3.以化合物AS为代表，研究了聚合物固载的环把化合物对芳基嗅化物和氯化物与丙烯酸丁酷的偶联反应的催化活性，发现聚合物固载的环把化合物可用于催化多种带有活化基团的芳基澳化物和芳基氯化物，但活性均低于相应的芳基碘化物。R蕊〕^X‘eHZ一CHC02C4HgCat.100℃R粉 +COZC;H。R二H，P一NOZ，m一NOZ，P一N02，BrX=Cl，Br 4.考察了聚合物固载的亚胺环把化合物在催化碘代苯和丙烯酸丁酷的偶联反应中的稳定性和反复使用的可能性，发现随着催化剂使用次数增多，完成反应的时间增长，转化效率普遍降低，但在经历反复加热催化和冷却过程中催化剂仍具有很好的稳定性和选择性。 5.用气相色谱方法跟踪了催化偶联反应的进程。根据反应结果，结合聚合物固载亚胺环把化合物的特点，提出了聚合物固载催化剂催化Heek反应的可能机理。BaseHXB一少{Pd备可H·[Pd]一XR一IPd]X、人R、:Pd卜x少分ProPosed meehanism for Heck reaction catalyzedby Polymer一suPPorted eycloPalladated imine comPounds更多还原

【Abstract】 1. In this thesis, four series, Twenty-seven polymer-supported cyclopalladated inline compounds have been prepared and characterized by IR and E.A.compounds A1-A9 compounds B1-B8compounds C1-C9 compounds2. The catalytic properties of the four series polymer-supported cyclopalladated compounds in the Heck reaction have been studied as follows:a. The results obtained indicated that all of the catalysts studied could catalyze the coupling reaction of iodobenzene with acrylates. The TON and TOP were as high as 104-105 and 21000, respectively. Compounds A1-A9 were used as catalysts to catalyze the coupling reaction of iodobenzene with butyl acrylate in different solvent, such as DMF or CH3CN, in which the coupling reactions could be completed at 100癈 in short time.b. The catalysts A1-A9 were also used to catalyze the coupling reaction of iodobenzene with styrene. About 10/1 of trans-stilbene/l,l-diphenylethylene were obtained .The activity of the catalysts catalyzing this Heck reaction was almost the same as the homocatalyst analogues reported in the literature.c. The coupling reactions of aryl bromides and aryl chlorides with butyl acrylate catalyzed by catalyst A8 were also studied. It was found that the catalyst was also efficient to catalyzed the Heck reaction in the case of aryl bromides and aryl chlorides. But their activities were much lower than the corresponding aryl iodides.d. The catalyst A8 used to catalyze the coupling of indobenzene with butyl acrylate could be reused at least five times.e. The coordination of coupling reaction was followed by GC. According to the results and the properties of the polymer-supported cyclopalladated compounds, the mechanism based ori Pd(0) /Pd( II) circle was proposed.Proposed mechanism for Heck reaction catalyzed by polymer-supported cyclopalladated imine compounds更多还原