【作者】 卢茂玲；

【导师】 杨元法；

【作者基本信息】 浙江师范大学 ， 物理化学， 2007， 硕士

【摘要】 钯催化芳基卤化物与烯烃的Heck反应已成为有机合成中碳-碳键构造的强有力手段之一。文献调研发现，多数反应以芳基碘化物与活性烯烃作为偶联反应底物，并且开展了各种有效的钯催化剂体系的研究。相对芳基碘化物而言，芳基溴化物、芳基氯化物不但价格低廉，而且有原料易得的优势。近年来，研究者们致力于寻找合适的催化剂体系，使芳基溴化物、芳基氯化物的Heck反应能得到应用；但是在已报导的文献中，有的偶联反应产率不理想，有的反应条件比较苛刻（温度高、惰性氛围等），并且很少有催化剂能够对芳基溴化物、芳基氯化物表现出良好的催化活性的同时，也具有良好的循环使用性能。我们研究工作的目的是研制有效催化芳基溴化物甚至芳基氯化物，并且具有良好的重复使用性能的催化剂。本文选择胺基化改性树脂氯球作为载体。考察了系列胺试剂改性树脂负载钯催化剂对芳基溴化物、氯化物的催化活性，并对这类催化剂催化芳基溴化物的循环使用性能进行了考察。并对Heck反应的可能机理进行了初步探讨。首先以氨基碳酸胍改性氯球为载体，与氯化钯溶液反应并还原制备氨基胍树脂负载钯（O）催化剂。对催化剂进行了FT-IR、XRD、BET、TG-DTA表征。研究了该催化剂对各种取代卤代苯与丙烯酸、苯乙烯的Heck芳基化反应催化性能。实验结果表明，该催化剂对活性（吸电子基）溴代苯和碘苯具有很好的催化活性，特别对含活性吸电子基的溴代苯4-溴苯甲醛和4-溴硝基苯显示出特别好的活性，能在140℃时在20 min内完成Heck芳基化反应；催化剂具有突出的重复使用性能，在90℃下催化碘苯与丙烯酸的反应循环22次时仍能保持良好的催化活性；140℃下催化丙烯酸、苯乙烯与对溴苯甲醛的反应循环23、18次时催化活性没有明显下降，并且产率在90％以上。初步的机理研究表明：催化反应的主要活性物种可能是可溶性的钯；可溶性钯是通过卤代芳烃与钯的氧化加成生成的；可溶性钯在反应过程中能重新沉积回催化剂表面。其次，考察了系列胺试剂—碳酸胍、三氮唑改性树脂负载钯催化剂的催化性能。通过考察温度、溶剂、不同溶液中负载PdCl₂等因素对碳酸胍改性氯球负载钯催化剂的催化活性、重复性能的影响，得到最佳反应条件。探索了催化活性以及循环使用性能与活性钯物种的滤去、再沉积现象的关系。更多还原

【Abstract】 Palladium-catalyzed Heck reactions of aryl halides with alkeneshave become one of the most powerful tools in orgnic synthesis for theconstruction of carbon-carbon bond. Studying the correspondingliteratures, found that aryl iodides and activated alkenes are typicallyemployed as the coupling reactants of a great number of reactions, and avariety of the efficient palladium catalyst systems have been developed.Aryl bromides and aryl chlorides are cheaper and more easily availablethan aryl iodides. Resently, researchers make great efforts to establish theefficient catalyst systems for making Heck reactions of aryl bromides andaryl chlorides extensively, but among the reported literatures, the yeildsof coupling reactions are not satisfied, or conditions of reacitons arerigorous（higher temperature, inert atmosphere, and so on）, the catalystsystems reported which show high catalytic activity and excellentreusability in Heck reactions of aryl bromides are still few. The aim of ourresearch work is to develop a series of efficient catalysts for the Heckreaction of aryl bromides and aryl chlorides, and the catalysts havesuperexcellent reusability.In the thesis, we chose aminated resin as support. In Heck reactionsof aryl bromides and aryl chlorides, catalytic activity of series ofaminating-reagent-modified-resin supported palladium has beenresearched, and the reusability in the Heck coupling of aryl bromids catalyzed by aminated resin supported palladium has been investigated.And the possible mechanism of Heck reaction has been discussed.Firstly, amino-guanidine-resin supported Pd（0） was prepared by thereaction of amino- guanidine modified chloromethyl polystyrene resinwith PdCl₂, followed by reduction. The catalyst was characterized byFT-IR, XRD, BET, TG-DTA. The catalytic performance for the Heckreactions of various substituted aryl halides with acrylic acid or styrenewas researched. Experiments indicated that the catalyst hadsuperexcellent activity and outstanding recycling: Aryl bromides withelectron-withdrawing were converted completely within very short time（140℃,20 min）; at 90℃in the reaction of iodo-benzene with acrylic acid,the catalyst could kept high activity at 22th run, at 140℃in the reaction ofacrylic acid and styrene with 4-Bromobenzaldehyde,amino-guanidine-resin supported Pd（0） was able to re-use at least 23 and18 times without significant loss of activity, and the yield exceeded 90％.The mechanism of Heck reaction indicated that the active species wassoluble active Pd species, and the dissolving of palladium in the reactionmixture was due to the oxidative action ofhalides with palladium on thesurface of catalyst, the dissolved active palladium species redepositedonto the surface of catalyst during reaction.Secondly, the catalytic activity of series of amine reagants-guanidineand triazole modified resin supported palladium is investigated. The influence of tempareture, solvents, and catalyst prepared in differentsolvents of PdCl₂ on catalysis and reusability of GDR.Pd（O） catalyst wasstudied, too. By studying it, the better reaction condition was achieved.The relationship between catalitic activity, reusability and active Pdspecies, redeposition was researched.更多还原