氢键负载型手性铑催化剂的制备及其催化性能的研究

发布时间：2018-04-05 23:25

本文选题：串联反应　切入点：氢键负载型催化剂　出处：《上海师范大学》2017年硕士论文

【摘要】：均相催化剂中的金属化合物排放到环境中,给环境带来了严重的危害,这样极大地限制催化剂的持续循环使用。因此,将均相催化剂负载到载体材料上实现催化剂的循环使用成为了绿色化学研究的另一个重要范畴。而一锅法催化多步串联反应是绿色化学研究的一个重要方面,由于其简化了操作步骤,提高了原子利用率,因而成为现代化学工作者的一个重要研究热点。本论文主要分为以下两个部分:(1)在第一部分中,首先我们合成了一种无机骨架的短直孔道硅纳米小球,然后,将二氯(五甲基环戊二烯基)合铑(III)二聚体,即(Cp*RhCl2)2制备成离子对型铑复合物(Cp*Rh)+(BF4)-,再配上(1S,2S)-TsDPEN手性配体得到离子对型均相催化剂(Cp*RhTsDPEN)+(BF4)-,然后通过氢键将离子对型手性铑均相催化剂负载到载体材料上制备成手性铑单功能非均相催化剂,最后通过固体核磁13C谱、29Si谱,TEM,SEM,XRD,BET,XPS,IR,TG,ICP等表征证明氢键负载型手性铑单功能催化剂已成功制备。我们将该催化剂应用到芳香酮的不对称氢转移反应中,实验结果表明,该催化剂具有较好的催化活性,我们可以看到转化率和对映选择性最高都达到了99%。最后,我们还对该催化剂进行了回收再利用,测试结果显示,该催化剂在套用了10次之后,依然保持了良好的催化活性和对映选择性。(2)在第二部分中,首先我们将有机碱三乙烯二胺(DABCO)接在氯丙基硅烷上得到一种有机盐,然后通过共聚法制备成带有DABCO碱性功能基团的介孔硅基纳米小球。接着,将离子对型金属铑均相催化剂(Cp*RhTsDPEN)+(BF4)-负载到该载体上,最后通过固体核磁13C谱、29Si谱,TEM,SEM,XRD,BET,XPS,IR,TG,ICP等表征证明氢键负载型手性铑-碱双功能催化剂已成功制备。我们将该催化剂应用到一锅法合成手性环氧乙烷的串联反应中,实验结果表明,该催化剂活性良好,转化率和ee值都高达99%。接下来,我们还将该催化剂运用到一锅法合成手性β-氨基醇的串联反应中,我选择异丙醇和水作为混合溶剂,选用甲酸钠作为氢源,同样达到了很好的催化效果,转换率和ee值均高达99%。通过对该反应追踪该反应进程,可以发现,苯胺和2-溴苯乙酮在有机碱DABCO的催化剂先进行取代反应,然后在Cp*Rh TsDPEN的催化下进行不对称还原反应。最后我们还对该催化剂进行了重复再利用。结果显示,该催化剂在套用了7次之后,仍然具有较高的催化活性。
[Abstract]:The release of metal compounds from homogeneous catalysts into the environment has brought serious harm to the environment, which greatly limits the continuous recycling of catalysts.Therefore, it has become another important research area in green chemistry that the homogeneous catalyst is loaded on the support material to realize the recycling of the catalyst.One-pot catalytic multi-step series reaction is an important aspect of green chemistry research, because it simplifies the operation steps and improves the atomic utilization ratio, it has become an important research hotspot of modern chemistry workers.In the first part, we synthesized a kind of short straight channel silicon nanospheres with inorganic skeleton, and then synthesized dichloro (pentamethylcyclopentadienyl) and rhodium II I dimer.Functional heterogeneous catalyst,Finally, the characterization of solid state nuclear magnetic resonance (13C) ~ (29) Si spectrometer (TM) SEMN XRDX (BET) XPS / TGGICP shows that the hydrogen-bond supported chiral rhodium mono-functional catalyst has been successfully prepared. The results show that the chiral rhodium mono-functional catalyst supported on hydrogen bond has been successfully prepared.We have applied the catalyst to asymmetric hydrogen transfer reaction of aromatic ketones. The experimental results show that the catalyst has good catalytic activity, and we can see that the highest conversion and enantioselectivity are up to 9950%.Finally, the catalyst was recycled and reused. The test results showed that the catalyst maintained good catalytic activity and enantioselectivity in the second part after being applied for 10 times.Firstly, an organic salt was prepared by grafting organic base triethylenediamine (DABCO) onto chloropropyl silane, and then mesoporous silicon-based nanoparticles with DABCO basic functional group were prepared by copolymerization.The catalyst was applied to the series reaction of one-pot synthesis of chiral ethylene oxide. The experimental results show that the catalyst has good activity and the conversion rate and ee value are as high as 99%.Next, we used the catalyst in a one-pot series reaction to synthesize chiral 尾 -amino alcohol. I chose isopropanol and water as the mixed solvent and sodium formate as the hydrogen source, which also achieved a very good catalytic effect.The conversion rate and ee value are as high as 99g.It was found that aniline and 2-bromoacetophenone were substituted in the catalyst of organic base DABCO first, then asymmetric reduction reaction was carried out under the catalysis of Cp*Rh TsDPEN.Finally, we reused the catalyst.The results showed that the catalyst still had high catalytic activity after being applied for 7 times.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36

【参考文献】