硅胶负载离子液体液膜手性二胺催化剂的合成及在Henry反应中的应用.docxVIP

Henry反应是一种用途很广的碳-碳键生成反应，其反应产物β-硝基醇可以经过氧化、还原、消除等反应生成多种有用的中间体分子。Henry反应的催化一直是科学研究的热点，能够催化该反应的催化剂也多种多样，但是迄今为止关于该反应催化剂回收的报道不多，由于催化剂的合成繁琐，且成本不菲，导致其应用受到了限制，因此，如果能找到一种将催化剂回收利用的方法，就能够缓解这个问题。本文设计合成了两种可以进行循环利用的催化剂，考察了其对Henry反应的催化效果，与此同时，研究了这两种催化剂的循环利用性能。1.树状分子核心负载和链接负载胺的合成及其在Henry反应中的研究 以第0代到第4代树状分子为载体合成了几种树状分子核心负载胺催化剂以及树状分子链接负载胺催化剂，所有催化剂均通过核磁和质谱进行表征确认，将催化剂应用在2-硝基苯甲醛与硝基甲烷的模型反应中，研究溶剂，温度，时间等因素对反应的影响，通过分析反应结果发现，随着代数的升高，核心负载催化剂的催化性能下降，而将胺链接出树状分子，催化效果得到恢复，研究了链接碳链的个数发现当碳链个数为六个时催化效果基本达到最佳，通过溶剂沉淀法对催化剂进行了回收，循环再利用10次催化效果基本保持。2.硅胶离子液体液膜负载手性催化剂的合成及其在Henry反应中的研究合成了负载手性二胺的N-甲基咪唑离子液体液膜硅胶催化剂，将催化剂应用在以邻硝基苯甲醛和硝基甲烷为底物的模型反应中，研究了液膜厚度，溶剂，金属配比等因素对反应的影响，重点考察了其催化效果及催化剂回收性能。关键词：树状分子；负载；咪唑离子液体；Henry反应；循环利用Henry reaction is one of very useful carbon-carbon bond formation reaction, the reaction product β-nitro alcohol can be subjected to a variety of useful intermediates molecule via oxidation, reduction, elimination reaction. Development of novel javascript:void(0);catalyst for Henry reaction is very hot topic in recent years, and many kind of catalysts can be synthesized and applied to this reaction. But so far the reports on the catalyst recycling are not very much. This is because that the synthesis of the catalyst is very tedious and costly, and then its application has been limited. So in order to alleviate these problems for catalyst application and recycling, two kinds of novel catalysts were designed and synthesized, and then its catalytic effects were investigated on the Henry reaction, Certainly, the recycling performance of these two catalysts was also studied.1. Synthesis and application of core-loaded or link-loaded amines on dendrimer in Henry reactionUsing the 0 to 4th generation dendrimers as carriers, several catalyst of core-loaded and link-loaded amine on dendrimer have been synthesized and characterized by 1H NMR, 13C NMR and MS, and then applied in Henry reaction using 2-nitrobenzaldehyde and nitromethane as substrates.The effects of different factors,such as solvent,temperature an