本文選題：串聯(lián)反應　切入點：氫鍵負載型催化劑　出處：《上海師范大學》2017年碩士論文

【摘要】：均相催化劑中的金屬化合物排放到環(huán)境中,給環(huán)境帶來了嚴重的危害,這樣極大地限制催化劑的持續(xù)循環(huán)使用。因此,將均相催化劑負載到載體材料上實現(xiàn)催化劑的循環(huán)使用成為了綠色化學研究的另一個重要范疇。而一鍋法催化多步串聯(lián)反應是綠色化學研究的一個重要方面,由于其簡化了操作步驟,提高了原子利用率,因而成為現(xiàn)代化學工作者的一個重要研究熱點。本論文主要分為以下兩個部分:(1)在第一部分中,首先我們合成了一種無機骨架的短直孔道硅納米小球,然后,將二氯(五甲基環(huán)戊二烯基)合銠(III)二聚體,即(Cp*RhCl2)2制備成離子對型銠復合物(Cp*Rh)+(BF4)-,再配上(1S,2S)-TsDPEN手性配體得到離子對型均相催化劑(Cp*RhTsDPEN)+(BF4)-,然后通過氫鍵將離子對型手性銠均相催化劑負載到載體材料上制備成手性銠單功能非均相催化劑,最后通過固體核磁13C譜、29Si譜,TEM,SEM,XRD,BET,XPS,IR,TG,ICP等表征證明氫鍵負載型手性銠單功能催化劑已成功制備。我們將該催化劑應用到芳香酮的不對稱氫轉(zhuǎn)移反應中,實驗結果表明,該催化劑具有較好的催化活性,我們可以看到轉(zhuǎn)化率和對映選擇性最高都達到了99%。最后,我們還對該催化劑進行了回收再利用,測試結果顯示,該催化劑在套用了10次之后,依然保持了良好的催化活性和對映選擇性。(2)在第二部分中,首先我們將有機堿三乙烯二胺(DABCO)接在氯丙基硅烷上得到一種有機鹽,然后通過共聚法制備成帶有DABCO堿性功能基團的介孔硅基納米小球。接著,將離子對型金屬銠均相催化劑(Cp*RhTsDPEN)+(BF4)-負載到該載體上,最后通過固體核磁13C譜、29Si譜,TEM,SEM,XRD,BET,XPS,IR,TG,ICP等表征證明氫鍵負載型手性銠-堿雙功能催化劑已成功制備。我們將該催化劑應用到一鍋法合成手性環(huán)氧乙烷的串聯(lián)反應中,實驗結果表明,該催化劑活性良好,轉(zhuǎn)化率和ee值都高達99%。接下來,我們還將該催化劑運用到一鍋法合成手性β-氨基醇的串聯(lián)反應中,我選擇異丙醇和水作為混合溶劑,選用甲酸鈉作為氫源,同樣達到了很好的催化效果,轉(zhuǎn)換率和ee值均高達99%。通過對該反應追蹤該反應進程,可以發(fā)現(xiàn),苯胺和2-溴苯乙酮在有機堿DABCO的催化劑先進行取代反應,然后在Cp*Rh TsDPEN的催化下進行不對稱還原反應。最后我們還對該催化劑進行了重復再利用。結果顯示,該催化劑在套用了7次之后,仍然具有較高的催化活性。
[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.
【學位授予單位】：上海師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36

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