本文選題：氧化反應(yīng) + 2N2O銅配合物��； 參考：《石河子大學(xué)》2017年碩士論文

【摘要】：芐醇及芳烴側(cè)鏈氧化為羰基化合物是有機(jī)合成中的重要反應(yīng),反應(yīng)生成相應(yīng)的醛、酮及酸等羰基化合物廣泛應(yīng)用于農(nóng)藥殺蟲劑、有機(jī)工業(yè)和醫(yī)藥領(lǐng)域等。隨著綠色化學(xué)的發(fā)展,尋找一種條件溫和、高效、綠色的氧化體系對芐醇及芳烴側(cè)鏈氧化成為人們追求的目標(biāo)。本論文探究了系列催化體系以實(shí)現(xiàn)芐醇及芳烴側(cè)鏈的綠色氧化。第一,我們選擇水溶性好含有磺酸基基團(tuán)的2N2O2銅配合物作為催化劑,用于芐醇選擇性氧化中,在水相體系中芐醇氧化為相應(yīng)的芳醛,最高產(chǎn)率可達(dá)94%。該氧化體系具有理想的底物適用性及官能團(tuán)的兼容性,且催化劑也具有優(yōu)良的循環(huán)性能。此外,該氧化體系無有機(jī)溶劑、表面活性劑、相轉(zhuǎn)移催化劑參與,選擇4-甲基苯甲醇可擴(kuò)大量至克級規(guī)模。第二,我們發(fā)展了條件溫和、高效、環(huán)境友好的非金屬氧化體系,在NBS/KOAc條件下對仲醇實(shí)現(xiàn)選擇性氧化。該體系在室溫條件系下,水相中H2O/CH2Cl2(V:V=3:1,1.5 m L)可對仲醇選擇性氧化,產(chǎn)率在46-98%之間。該氧化體系具有理想的底物普適性及官能團(tuán)的兼容性。此外,該方法對二苯甲醇可以擴(kuò)大量至克級規(guī)模。第三,我們發(fā)展了一種簡單、高效的非金屬氧化體系,最優(yōu)條件為:過氧化叔丁醇作為氧化劑(6或10 equiv.,70%TBHP),溫度為100oC反應(yīng)24小時(shí),苯乙醇的最高產(chǎn)率達(dá)94%。該氧化體系無有機(jī)溶劑參與,對一系列醇類衍生物都具有優(yōu)良的反應(yīng)效果,且對各種官能團(tuán)都具有很好的兼容性。最后,我們發(fā)展了一種溫和、高效的氧化體系,在水相中銅催化過氧化叔丁醇氧化無配體參與條件下,對二芳基甲烷及芳醇實(shí)現(xiàn)選擇性氧化。在該條件下含有不同官能團(tuán)的二苯甲烷氧化為芳基酮,產(chǎn)率在67-98%之間。此外,在該條件下含有不同官能團(tuán)的仲醇類衍生物氧化為芳基酮,產(chǎn)率在48-98%之間。另外,該方法優(yōu)點(diǎn)是:無有機(jī)溶劑、無表面活性劑、無相轉(zhuǎn)移催化劑參與,具有理想的底物普適性及官能團(tuán)兼容性。綜上所述,我們探究了芐醇及芳烴側(cè)鏈氧化的系列方法,具有反應(yīng)高效、條件溫和、底物兼容性好、環(huán)境友好、更經(jīng)濟(jì)型等優(yōu)點(diǎn),且擴(kuò)大量也能達(dá)到克級規(guī)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.
【學(xué)位授予單位】：石河子大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O621.254.1

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 楊景蘭,李德江;苯甲酸的合成[J];天津化工;2003年03期

，

本文編號：2062809