三價銠催化喹啉-8-甲醛類衍生物酯化反應(yīng)方法學(xué)研究
發(fā)布時間：2019-04-18 08:43
【摘要】：喹啉骨架廣泛存在于眾多天然產(chǎn)物中,并且很多具有較好的生物活性。如果使用傳統(tǒng)的酯化方法來實現(xiàn)芳基甲醛類化合物中醛基的酯化反應(yīng),通常對反應(yīng)條件的要求較為苛刻,或難以通過一步反應(yīng)得到酯化產(chǎn)物。另外,關(guān)于喹啉-8-甲醛的一步成酯的反應(yīng)未曾被報道過。為探索溫和條件下喹啉-8-甲醛通過一步反應(yīng)成酯的方法,我們將注意力轉(zhuǎn)向了具有較高催化效率的三價銠金屬催化劑有關(guān)的研究。為此,首先探索了喹啉-8-甲醛中C-8位的醛基在不同反應(yīng)條件下生成酯的反應(yīng)。通過篩選最合適的反應(yīng)條件包括溫度,溶劑,催化劑及配體等,發(fā)現(xiàn)在以(Cp*RhCl_2)_2作為催化劑,AgSbF6作為配體,室溫下在四氫呋喃溶液中喹啉-8-甲醛能夠與甲醇反應(yīng)生成喹啉-8-甲酸甲酯。進一步,為了探究底物的適用范圍,在上述條件下將底物擴展。在實驗室已有六個醛基底物的基礎(chǔ)上制備了另外四個醛基底物c8,c9,c10,c11,并應(yīng)用這些喹啉-8-甲醛類化合物與不同的醇類發(fā)生反應(yīng)。如之前所預(yù)期的,在溫和的反應(yīng)條件下,得到了一系列的喹啉-8-甲酸酯類化合物,收率在40%-75%之間。同時,用芳甲醛(1,2,3,4,5a)代替喹啉-8-甲醛類底物進行底物拓展性實驗。遺憾的是,沒有得到預(yù)期的酯類產(chǎn)物,卻意外地發(fā)現(xiàn)該反應(yīng)體系下能以70%的收率使N-對甲苯磺�；�-4-甲基-2-氨基苯甲醛(5a)生成苯乙腈類化合物5b,由于時間原因,未對這類反應(yīng)做進一步研究,其機理也有待于探索。本論文發(fā)現(xiàn)將含有不同取代基的喹啉-8-甲醛類化合物與醇類化合物在三價銠配合物(Cp*RhCl_2)_2催化下發(fā)生酯化反應(yīng)的方法,具有一定的底物適用性,可用于各類喹啉-8-甲醛的酯化。同時,該反應(yīng)也有局限性,如三價銠試劑價格昂貴,底物只適用于喹啉-8-甲醛類化合物,反應(yīng)需要無水無氧等。另外,我們推測了可能的反應(yīng)機理。值得指出的是,本論文闡述的反應(yīng)方法具有一定的應(yīng)用價值,同時也豐富了三價銠催化C-H鍵活化反應(yīng)的類型。
[Abstract]:Quinoline framework is widely found in many natural products, and many of them have good biological activity. If the traditional esterification method is used to esterify the aldehyde groups in aryl formaldehyde compounds, the requirements of reaction conditions are usually more stringent, or it is difficult to obtain the esterification products by one-step reaction. In addition, the reaction of quinoline-8-formaldehyde to one-step ester has not been reported. In order to explore the one-step reaction of quinoline-8-formaldehyde to ester under mild conditions, we turned our attention to the study of rhodium metal catalysts with high catalytic efficiency. In this paper, firstly, the reaction of the aldehyde group at the C = 8 position in quinoline-8-formaldehyde to form esters under different reaction conditions was studied. By screening the most suitable reaction conditions, such as temperature, solvent, catalyst and ligand, it was found that (Cp*RhCl_2) _ 2 was used as catalyst and AgSbF6 was used as ligand. At room temperature, quinoline-8-formaldehyde can react with methanol to form methyl quinoline-8-formate in tetrahydrofuran solution. Further, in order to explore the scope of substrate application, the substrate is expanded under the above conditions. Four other aldehydes, c8, c9, c10, c11, were prepared on the basis of six aldehydes in the laboratory, and these quinoline-8-formaldehyde compounds were used to react with different alcohols. As previously expected, under mild reaction conditions, a series of quinoline-8-formate compounds were obtained in a yield of 40% ~ 75%. Meanwhile, aromatic formaldehyde (1, 2, 3, 4, 5 a) was used to replace quinoline-8-formaldehyde substrate for substrate extensibility test. Unfortunately, no expected ester products were obtained, but it was unexpectedly found that N-p-toluenesulfonyl-4-methyl-2-aminobenzaldehyde (5a) was produced by N-p-toluenesulfonyl-4-methyl-2-aminobenzaldehyde (5a) in 70% yield. Due to time reasons, no further study has been made on this kind of reaction, and its mechanism has yet to be explored. In this paper, it is found that the esterification of quinoline-8-formaldehyde and alcohols with different substituents under the catalysis of rhodium complex (Cp*RhCl_2) _ 2 has certain substrate applicability. It can be used for esterification of quinoline-8-formaldehyde. At the same time, the reaction has some limitations, such as the high price of the trivalent rhodium reagent, the substrate is only suitable for quinoline-8-formaldehyde, the reaction requires anhydrous and no oxygen and so on. In addition, we speculate the possible reaction mechanism. It is worth pointing out that the reaction method described in this paper has a certain application value, and it also enriches the type of activation reaction of rhodium catalyzed C _ (?) H bond.
【學(xué)位授予單位】：蘭州理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O621.251
本文編號：2459908
[Abstract]:Quinoline framework is widely found in many natural products, and many of them have good biological activity. If the traditional esterification method is used to esterify the aldehyde groups in aryl formaldehyde compounds, the requirements of reaction conditions are usually more stringent, or it is difficult to obtain the esterification products by one-step reaction. In addition, the reaction of quinoline-8-formaldehyde to one-step ester has not been reported. In order to explore the one-step reaction of quinoline-8-formaldehyde to ester under mild conditions, we turned our attention to the study of rhodium metal catalysts with high catalytic efficiency. In this paper, firstly, the reaction of the aldehyde group at the C = 8 position in quinoline-8-formaldehyde to form esters under different reaction conditions was studied. By screening the most suitable reaction conditions, such as temperature, solvent, catalyst and ligand, it was found that (Cp*RhCl_2) _ 2 was used as catalyst and AgSbF6 was used as ligand. At room temperature, quinoline-8-formaldehyde can react with methanol to form methyl quinoline-8-formate in tetrahydrofuran solution. Further, in order to explore the scope of substrate application, the substrate is expanded under the above conditions. Four other aldehydes, c8, c9, c10, c11, were prepared on the basis of six aldehydes in the laboratory, and these quinoline-8-formaldehyde compounds were used to react with different alcohols. As previously expected, under mild reaction conditions, a series of quinoline-8-formate compounds were obtained in a yield of 40% ~ 75%. Meanwhile, aromatic formaldehyde (1, 2, 3, 4, 5 a) was used to replace quinoline-8-formaldehyde substrate for substrate extensibility test. Unfortunately, no expected ester products were obtained, but it was unexpectedly found that N-p-toluenesulfonyl-4-methyl-2-aminobenzaldehyde (5a) was produced by N-p-toluenesulfonyl-4-methyl-2-aminobenzaldehyde (5a) in 70% yield. Due to time reasons, no further study has been made on this kind of reaction, and its mechanism has yet to be explored. In this paper, it is found that the esterification of quinoline-8-formaldehyde and alcohols with different substituents under the catalysis of rhodium complex (Cp*RhCl_2) _ 2 has certain substrate applicability. It can be used for esterification of quinoline-8-formaldehyde. At the same time, the reaction has some limitations, such as the high price of the trivalent rhodium reagent, the substrate is only suitable for quinoline-8-formaldehyde, the reaction requires anhydrous and no oxygen and so on. In addition, we speculate the possible reaction mechanism. It is worth pointing out that the reaction method described in this paper has a certain application value, and it also enriches the type of activation reaction of rhodium catalyzed C _ (?) H bond.
【學(xué)位授予單位】：蘭州理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O621.251
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 代偉;劉玉臣;童濤;李興偉;羅芳;;銠(Ⅲ)催化的醛的氧化胺化:一種有效的構(gòu)建N-吡啶酰胺及酰亞胺的合成方法[J];催化學(xué)報;2014年07期
，本文編號：2459908
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