【作者】 王涌；

【导师】 丁成荣； 张国富；

【作者基本信息】 浙江工业大学 ， 农药学， 2012， 硕士

【摘要】 本论文针对当前多相催化剂制备和使用中存在的问题，发展了一种高效制备结构新颖的多相催化剂的方法，并采用醇的氧化、芳香卤代物与芳基硼酸的Suzuki偶联等反应对催化剂的催化性能进行了评价。首先，采用Click化学作为一种均相催化多相化的有效策略制备了环钯类催化剂，并通过FT-IR、UV-Vis、ICP-MS、EA等方法对催化剂进行了表征和定量。系统地评价了该催化剂在醇的有氧氧化、Suzuki偶联反应中的催化性能。在优化条件下，催化剂能将芳香伯醇、仲醇高效、高选择性地氧化成相应的羰基化合物，产物分离收率最高可达99%；催化剂回收循环使用4次，活性未见明显下降。同时，该催化剂可实现芳香卤化物与苯硼酸的高效偶联，目标产物联芳香化合物分离收率高达99%，催化剂TON最高达9900。其次，以双功能Click三唑作为构建多相催化剂的新方法-Click反应生成的1,2,3-三唑既作为均相催化多相化的链接基团又作为催化配位基团的齿—制备了一种结构新颖的多相催化剂。通过XRD、氮气物理吸附-脱附、TEM和UV-Vis、~1H NMR、COSY等方法对催化剂的形貌结构和化学配位结构进行了表征和探讨，并通过醇的氧化反应对此催化剂的催化性能进行了考察。在优化条件下，催化剂能将芳香伯醇、仲醇高效、高选择性地氧化成相应的羰基化合物，产物分离收率最高可达98%，反应选择性>99%。该催化剂循环使用8次催化活性未见下降趋势。更多还原

【Abstract】 Aimed to overcome problems exsited in the field of heterogeneouscatalysis, a highly efficient and novel protocol has been developed for theconstruction of immobilized catalysts in this paper, whose catalyticactivity and recyclability have also been evaluated in organic catalysis.Via the [3+2] azide-alkyne “Click” reaction, an oxime palladacyclehas been supported onto silica gel. The structure and composition of thesolid catalyst were further characterized by FT-IR, UV-Vis, ICP-MS, EA.The obtained palladium catalyst has shown promising activity for aerobicoxidation of benzyl alcohols, with the isolated yield up to99%.Meanwhile, the solid catalyst could be easily separated from the reactionmixture and its catalytic activity did not deteriorate even after it wasrecycled four times. Moreover, the application of the catalyst could besucessfully expand to the Suzuki coupling reactions, given the desiredproducts in moderate to excellent yields, and the turn over number of thecatalyst in the reaction was up to9900. Via a dual functional click-triazole, a new mesoporous SBA-15supported catalyst PdLn@SBA-15have been prepared, of which theclick-triazole acts as a stable linker as well as a good chelator toparticipate in the catalytic reactions. The architecture and coordinationstate of the novel catalyst have been sufficiently characterized with XRD,TEM, nitrogen sorption measurements and UV-Vis,~1H NMR, COSYrespectively. The catalyst was further applied for the aerobic oxidation ofalcohols with promising yields and selectivities, which could be reusedfor8cycles with a consistent catalytic activity, giving the products inexcellent yields.更多还原