水相中苄醇及芳烃侧链的氧化反应研究

发布时间：2018-06-24 20:27

本文选题：氧化反应 + 2N2O铜配合物　；参考：《石河子大学》2017年硕士论文

【摘要】：苄醇及芳烃侧链氧化为羰基化合物是有机合成中的重要反应,反应生成相应的醛、酮及酸等羰基化合物广泛应用于农药杀虫剂、有机工业和医药领域等。随着绿色化学的发展,寻找一种条件温和、高效、绿色的氧化体系对苄醇及芳烃侧链氧化成为人们追求的目标。本论文探究了系列催化体系以实现苄醇及芳烃侧链的绿色氧化。第一,我们选择水溶性好含有磺酸基基团的2N2O2铜配合物作为催化剂,用于苄醇选择性氧化中,在水相体系中苄醇氧化为相应的芳醛,最高产率可达94%。该氧化体系具有理想的底物适用性及官能团的兼容性,且催化剂也具有优良的循环性能。此外,该氧化体系无有机溶剂、表面活性剂、相转移催化剂参与,选择4-甲基苯甲醇可扩大量至克级规模。第二,我们发展了条件温和、高效、环境友好的非金属氧化体系,在NBS/KOAc条件下对仲醇实现选择性氧化。该体系在室温条件系下,水相中H2O/CH2Cl2(V:V=3:1,1.5 m L)可对仲醇选择性氧化,产率在46-98%之间。该氧化体系具有理想的底物普适性及官能团的兼容性。此外,该方法对二苯甲醇可以扩大量至克级规模。第三,我们发展了一种简单、高效的非金属氧化体系,最优条件为:过氧化叔丁醇作为氧化剂(6或10 equiv.,70%TBHP),温度为100oC反应24小时,苯乙醇的最高产率达94%。该氧化体系无有机溶剂参与,对一系列醇类衍生物都具有优良的反应效果,且对各种官能团都具有很好的兼容性。最后,我们发展了一种温和、高效的氧化体系,在水相中铜催化过氧化叔丁醇氧化无配体参与条件下,对二芳基甲烷及芳醇实现选择性氧化。在该条件下含有不同官能团的二苯甲烷氧化为芳基酮,产率在67-98%之间。此外,在该条件下含有不同官能团的仲醇类衍生物氧化为芳基酮,产率在48-98%之间。另外,该方法优点是:无有机溶剂、无表面活性剂、无相转移催化剂参与,具有理想的底物普适性及官能团兼容性。综上所述,我们探究了苄醇及芳烃侧链氧化的系列方法,具有反应高效、条件温和、底物兼容性好、环境友好、更经济型等优点,且扩大量也能达到克级规模。
[Abstract]:The oxidation of benzyl alcohol and aromatics to carbonyl compounds is an important reaction in organic synthesis. The corresponding carbonyl compounds such as aldehydes, ketones and acids are widely used in pesticide, organic industry and pharmaceutical fields. With the development of green chemistry, it has become a goal to find a kind of mild, efficient and green oxidation system for benzyl alcohol and aromatics side chain oxidation. In this paper, a series of catalytic systems were investigated to realize the green oxidation of benzyl alcohol and aromatics side chain. Firstly, we choose 2N _ 2O _ 2 copper complex with good water solubility and sulfonic group as catalyst for selective oxidation of benzyl alcohol. In aqueous system, benzyl alcohol is oxidized to corresponding aromatic aldehydes, and the highest yield can be up to 94%. The oxidation system has ideal substrate applicability and functional group compatibility, and the catalyst also has excellent cycling performance. In addition, the oxidation system has no organic solvent, surfactant, phase transfer catalyst, and the selection of 4-methyl benzyl alcohol can be expanded to g scale. Secondly, we developed a mild, efficient and environmentally friendly system for selective oxidation of secondary alcohols under NBS / KOAc conditions. Under the condition of room temperature, H _ 2O _ 2 / Ch _ 2Cl _ 2 (V: v _ (3: 1: 1) 1.5 mL) can selectively oxidize secondary alcohols in 46-98% yield. The oxidation system has ideal substrate universality and functional group compatibility. In addition, the method can be expanded to scale up to g-scale for diphenyl methanol. Thirdly, we developed a simple and efficient nonmetallic oxidation system. The optimum conditions are as follows: tert-butanol peroxide as oxidant (6 or 10 equiv. 70 TBHP) and reaction temperature of 100oC for 24 hours, the highest yield of phenylethanol can reach 94g. The oxidation system has excellent reaction effect on a series of alcohols derivatives without the participation of organic solvents, and has good compatibility with various functional groups. Finally, we developed a mild and efficient oxidation system for the selective oxidation of diaryl methane and aromatic alcohols under the conditions of copper catalyzed oxidation of tert butanol peroxide without ligand in aqueous phase. Under these conditions, diphenylmethane with different functional groups was oxidized to aryl ketone in 67-98% yield. In addition, the secondary alcohols containing different functional groups were oxidized to aryl ketones in 48-98% yield. In addition, the method has the advantages of no organic solvent, no surfactant, no phase transfer catalyst, ideal substrate universality and functional group compatibility. To sum up, we explored a series of oxidation methods of benzyl alcohol and aromatics side chain, which have the advantages of high reaction efficiency, mild conditions, good substrate compatibility, environmental friendliness, more economical type, etc.
【学位授予单位】：石河子大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.254.1

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