【作者】 王庆伟；

【导师】 任玉杰； 刘培念；

【作者基本信息】 华东理工大学 ， 有机化学， 2010， 硕士

【摘要】 本论文以1mol%用量的HClO4为催化剂,实现了β-二羰基化合物与仲醇或烯烃的直接加成反应。该反应可以很方便的在空气中和未经处理的溶剂中进行,对绝大部分底物都得到了85%以上的产率。另外,本论文将HClO4吸附在硅胶上,制备了硅胶负载的HClO4(HClO4-SiO2),与液体HClO4催化的β-二羰基化合物与仲醇或烯烃的加成反应相比,HClO4-SiO2催化的非均相加成反应对一些底物获得了更好的产率。HClO4-SiO2可以通过过滤的方法,方便的回收,并且在催化反应中可以循环利用四次。本论文还通过动力学实验,证明了HClO4催化的β-二羰基化合物与仲醇或烯烃的加成反应是SN1的反应机理。本论文第一次利用易得、廉价的硅胶负载的三氟甲磺酸(TfOH-SiO2)为催化剂,催化了磺酰胺类化合物对不饱和烯烃的加成反应。在5mol%的催化剂用量下,该反应可以很方便的在空气中和未经处理的溶剂中进行,催化剂可以循环使用6次,而催化剂的反应活性和产物的收率都不会降低,每次循环反应的收率都在95%以上。多种磺酰胺类化合物与烯烃的加成反应,在该非均相催化体系中都获得了80%以上的产率。更多还原

【Abstract】 In this thesis, the direct additions ofβ-diketones to secondary alcohols or alkenes have been achieved using perchloric acid (HClO4) as the catalyst in low catalytic loading (lmol%). The HClO4-catalyzed reactions could be conveniently conducted in air with undried solvents and majority of the substrate gave more than 85%yields. Moreover, when HClO4 was absorbed onto silica gel, the silica gel-supported HClO4-catalyzed heterogeneous additions also proceeded smoothly to give similar or even better results in comparison with the homogenous ones. The supported catalyst could be readily recovered by filtering method and reused for 4 runs. Furthermore, the mechanism for the HClO4 catalyzed-addition of theβ-diketone to alcohol was investigated thoroughly through experiments and the SN1 mechanism was established ambiguously.Highly efficient hydroamination reactions of sulfonamides, benzamide with inactivate olefins catalyzed by readily available and inexpensive silia gel-supported TfOH was achieved for the first time. The silica gel-supported TfOH catalyzed addition reactions could be conveniently conducted in air with unpredried solvent in catalytic loading (5mol%). The supproted catalyst could be readily recovered and reused for 6 runs with maitained reactivity and yields, and each yield of the reaction in run is more than 95%. These processes gave more than 80%yields for the addition reaction of various sulfonamides with alkenes.更多还原