【作者】 李全莲；

【导师】 王云普；

【作者基本信息】 西北师范大学 ， 高分子化学与物理， 2005， 硕士

【摘要】 高分子手性催化剂具有分离简单、可循环使用等多相催化剂的优点,克服了昂贵的均相催化剂回收困难等缺点,符合绿色化工和可持续发展的需要。本论文的主要工作是对聚合物负载的手性催化剂在不对称催化反应中的应用进展做了综述,本文主要是通过两种方法合成和表征了11种新的聚合物负载的手性季铵盐相转移催化剂并研究了它们在不对称烷基化反应中的应用,主要有以下三章组成。 第一章:高分子支载的手性催化剂在不对称催化反应中的应用进展 综述了手性化合物的研究方法、近年来手性技术中出现的新概念,获得手性化合物的几种途径以及近年来聚合物负载的金鸡纳生物碱催化剂在不对称双羟基化反应、不对称Michael加成反应、不对称烷基化反应、潜手性酮的不对称还原反应以及烯烃的不对称环氧化反应中的应用,并展望了聚合物负载手性催化剂的未来研究方向及应用前景。 第二章:聚合物负载的手性季铵盐相转移催化剂的合成与表征 聚乙二醇及其衍生物具有与冠醚类似的相转移催化作用。首次将不同分子量的聚乙二醇负载到氯甲基化聚苯乙烯上,经过氯代、碘代之后与辛可宁反应,合成了一系列聚合物负载的手性季铵盐相转移催化剂,使传统季铵盐与冠醚类催化剂的官能团集于一身,具有优良的催化性能。通过树脂的增重,FT-IR、SEM、XPS,元素分析等测试表明这几种聚合物负载的手性季铵盐相转移催化剂已经成功的合成;首次将作为药用的苦参碱、刺乌头碱这两种天然手性产物负载到氯甲基化聚苯乙烯树脂上,合成了聚合物负载的手性季铵盐相转移催化剂,并用FT-IR、TG-DTA,元素分析等测试手段进行了表征。 第三章:聚合物负载手性季铵盐相转移催化剂在不对称烷基化反应中的应用研究 合成了烷基取代底物N-二苯基亚胺乙酸乙酯,并用UV、NMR进行了表征,同时对催化产物也通过元素分析及GC-MS联用仪进行了表征,并用旋光仪,带更多还原

【Abstract】 Polymer-Supported chiral catalysts have many merits which are easily removed at the end of the reaction and can possibly be re-used and overcome these problem such as the high cost and diffculty in reuseability of homogeneous catalysts. Adapt to the need of green chemical industry and sustainable development. In this paper, kinds of new chiral quaternary ammonium salts were synthesized and characterized and the application of chiral quaternary ammonium salts as phase-transfer catalysts in the alkylation of active methylene group was discussed. This thesis consists of three parts as follows.Part I:Reviewchiral compound’s study methods ,new concept of chiral technology in recent ye ar, kinds of means of attaining chiral compound ,the application and recent developm -ent of polymer-supported cinchona alkaloid catalysts in asymmetric dihydroxylation reaction, the Michael addition reaction, the alkylation of active methylene group, asymmetric reduction reaction of prochiral ketone and asymmertric synthesis of chiral epoxides by catalyzing alkenes were reviewed.As a new catalysts, their prospect and the problems they faced were also discussed in this part.Part II: Synthesis and characterizing of polymer-supported chiral quaternary ammonium salts phase-transfer catalysts.Polyethylene glycol and its derivatives can be used as phase-transfer catalysts just like crown ether, polyethylene glycol with different molecular weight have been supported on chlormethylated polystyrene, after the polymer of chlormethylated polystyrene-polyethylene glycol was chlorinated and iodided, Cinchonine react with it and gained a kind of polymer-supported chiral quaternary ammonium salts.These catalysts can posses merits of quaternary ammonium salts and crown ether in the same time, moreover, it can demonstrated good catalysis properties.il kind of triphase chiral catalysts were prepared in the first time by using three kinds of Cinchonine, Matrine and Lappaconitine as raw material, cross-linked polystyrene supported polyethylene glycol and chlormethylated polystyrene as supporter . Theirstructures were characterized by FT-IR SEM XPS TG-DTA and elemental analysis.Part III: The application of polymer-supported chiral quaternary ammonium salts phase-transfer catalysts in asymmetric alkylation reactionN-(diphenylmethylene) aceethyl esters was synthesized and its structure was confirmed by UV, NMR, at the same time the catalystic product was characterized by elemental analysis and GC-MS, The enantiomeric excess was determined by chiral HPLC (chiralcel OD-H column) .Asymmetric alkylation under different condiction using the polymer-supported chiral quaternary ammonium salts which we have synthesized as catalysts was studied, The possible catalystic mechanism of the reaction was also discussed .Influences of catalysts structure, ratio between catalysts and substrates, different temperatures, different alkylated reagents and the reusability of catalysts were studied. It is demonstrated that the recovered catalyst can be reused without appreciable loss of activity更多还原