本文選題：Wacker氧化 + 過氧化氫　； 參考：《南京理工大學》2017年碩士論文

【摘要】：Wacker氧化是一種由烯烴直接合成羰基化合物的重要方法,最早被應用于乙烯工業(yè)制備乙醛,傳統(tǒng)Wacker氧化方法使用鈀鹽催化劑和氯化亞酮氧化劑在空氣下反應。隨著環(huán)境經(jīng)濟的發(fā)展,傳統(tǒng)的Wacker氧化反應顯現(xiàn)出越來越多的局限性,如金屬銅離子污染、含氯副產(chǎn)物的生成、底物普適性差、烯烴異構(gòu)化和催化劑難以回收等缺陷。因此,研究探索和建立新方法以實現(xiàn)反應可持續(xù)性發(fā)展,具有重要實際意義。雙氧水作為一種綠色氧化劑已被應用于芳香族烯烴的Wacker氧化反應,但目前相關報道所用鈀催化劑較為復雜。因此,我們嘗試使用簡單無配體的二價鈀催化劑催化雙氧水實現(xiàn)芳香族烯烴的Wacker氧化。研究發(fā)現(xiàn),以醋酸鈀為催化劑,在酸性條件下,應用乙腈為反應介質(zhì),雙氧水溶液為氧化劑,芳香族烯烴能在溫和條件下,高選擇性和高產(chǎn)率地轉(zhuǎn)化為相應的甲基酮化合物,呈現(xiàn)出較好的底物普適性。研究發(fā)現(xiàn)不同芳烯烴的反應活性不同,空間效應與雙鍵上的電子云密度直接影響Wacker氧化反應過程。進一步研究發(fā)現(xiàn),以零價鈀為催化劑,雙氧水作為氧化劑,在最佳反應條件下,芳香族烯烴轉(zhuǎn)化為芳香族甲基酮的產(chǎn)率高達93%,所用催化劑重復使用五次后,仍能保持較好的催化活性。研究探討了新方法可能的催化反應機理,為發(fā)展Wacker氧化反應提供了一個新的選擇。
[Abstract]:Wacker oxidation is an important method for the direct synthesis of carbonyl compounds from olefin. It was first used in ethylene industry to produce acetaldehyde. Traditional Wacker oxidation method uses palladium salt catalyst and ketone chloride oxidant to react in air. With the development of environment and economy, the traditional Wacker oxidation reaction shows more and more limitations, such as metal copper ion pollution, the formation of chlorinated by-products, the poor substrate universality, isomerization of olefins and the difficulty of catalyst recovery and so on. Therefore, it is of great practical significance to explore and establish new methods to realize the sustainable development of response. As a green oxidant, hydrogen peroxide has been used in the Wacker oxidation of aromatic olefin. Therefore, we try to realize the Wacker oxidation of aromatic olefin using simple ligand-free palladium catalyst to catalyze hydrogen peroxide. It was found that under mild conditions, using palladium acetate as catalyst, acetonitrile as reaction medium and hydrogen peroxide solution as oxidant, aromatic olefins could be converted into corresponding methyl ketones with high selectivity and high yield. It presents better substrate universality. It was found that the reaction activity of different alkenes was different, and the space effect and the electron cloud density on the double bond directly affected the oxidation process of Wacker. It was further found that under the optimum reaction conditions, the conversion of aromatic olefin to aromatic methyl ketone was as high as 933%, and the catalyst was reused for five times, using zero valent palladium as catalyst and hydrogen peroxide as oxidant, and under the optimum reaction conditions, the yield of aromatic olefin to aromatic methyl ketone was as high as 933%. It can still maintain good catalytic activity. The possible catalytic reaction mechanism of the new method is discussed, which provides a new choice for the development of Wacker oxidation reaction.
【學位授予單位】：南京理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.25

【參考文獻】

相關期刊論文 前1條

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本文編號：2047188