摘要 自从1971年,Kagan[1]将天然酒石酸带入实验室,完成了手性双膦配体的制备工作。磷配体的的研究在逆境中蒸蒸日上。由于磷配体具有原料廉价易得,有较大钢性骨架,合成步骤简单等优点,磷配体被用于广泛研究。87270
为了制备催化性能更好的手性磷配体,我们选用氨基酸为原始底物设计合成了一系列手性的配体。
本文的原始底物为氨基酸。实验研究的设计与合成分为三个步骤。
1。以酒石酸环己二胺为底物合成环己二胺。用饱和的氢氧化钠溶液来溶解酒石酸环己二胺。经过搅拌,萃取,干燥等手段合成了环己二胺。
2。以各种氨基酸为底物合成以环己二胺为骨架的手性配体。先通过加入(Boc)2O来达到保护氨基的目的。接着与环己二胺反应,生成了以环己二胺为骨架的手性配体。
3。也是以各种氨基酸为底物,但是这次合成的是以肼为骨架的手性配体。首先,也是加(Boc)2O来达到保护氨基的目的。但是,接着就是与肼反应,最终,生成了以肼为骨架的手性配体。
通过上面三个步骤,我设计了十几组实验,并得到了七组实验数据,核磁共振表征和质谱表征。
在做实验的过程中,经过反复摸索,比对时间,比对温度,以及比对活化剂,完成了实验的优化,并最终确定了反应的最佳条件。
毕业论文关键字:氨基酸;磷配体 ;合成与设计
Abstract Since 1971, Kagan [1] by natural tartaric acid as a raw material to complete the preparation work Chiral phosphine ligands。 Phosphorus ligands thriving in adversity。 Because phosphorus ligand having a readily available and inexpensive raw materials, a larger steel skeleton, synthetic steps and simple, phosphorus ligands are used extensively studied。
In order to prepare better catalytic properties of chiral phosphorus ligand, we selected amino acid is synthesized from the original substrate relates to a series of ligands。
1。 tartaric cyclohexanediamine as substrate synthesis cyclohexanediamine。 With a saturated solution of sodium hydroxide dissolved tartaric cyclohexanediamine。 After stirring, extraction, drying and other means of synthesis cyclohexanediamine。
2。 synthesis of amino acids as a substrate to cyclohexanediamine compound skeleton is。 First by the addition of (Boc) 2O to achieve the purpose of protecting the amino group。 Followed by reaction with cyclohexanediamine。 To generate a skeleton cyclohexanediamine compound。
3。 Also in the various amino acid as a substrate, but this compound is a hydrazine skeleton synthesized yes。 First, and added (Boc)2O to achieve the purpose of protecting the amino group。 However, followed by reaction with hydrazine, ultimately, to generate a compound hydrazine skeletons。
Through the above three steps, I designed a dozen experiments, and with the eight sets of experimental data, diagrams and their NMR characterization。
In the experiment course, through trial and error, over time, than the temperature, and the ratio of activator to complete the optimization experiments, and ultimately determine the optimum reaction conditions。
Keywords:Amino acids ;phosphine ligand;synthesis and design
目录
摘要。Ⅰ
AbstractⅡ
目录。Ⅲ
第一章 绪论。1
1。1 不对称催化的概述。。1
1。1。1 不对称催化的概念。1
1。1。2 不对称催化的发展。1
1。1。3 不对称催化技术的应用。2
1。2 手性磷配体的概述。。4
1。3 磷配体的研究历程。。5
1。4 磷配体的合成。。6
1。4。1 以Noyori的BINAP配体为基础手性双膦配体。。。6 以氨基酸为手性源的配体的合成:http://www.youerw.com/huaxue/lunwen_130863.html