三价铑催化喹啉-8-甲醛类衍生物酯化反应方法学研究
发布时间：2019-04-18 08:43
【摘要】：喹啉骨架广泛存在于众多天然产物中,并且很多具有较好的生物活性。如果使用传统的酯化方法来实现芳基甲醛类化合物中醛基的酯化反应,通常对反应条件的要求较为苛刻,或难以通过一步反应得到酯化产物。另外,关于喹啉-8-甲醛的一步成酯的反应未曾被报道过。为探索温和条件下喹啉-8-甲醛通过一步反应成酯的方法,我们将注意力转向了具有较高催化效率的三价铑金属催化剂有关的研究。为此,首先探索了喹啉-8-甲醛中C-8位的醛基在不同反应条件下生成酯的反应。通过筛选最合适的反应条件包括温度,溶剂,催化剂及配体等,发现在以(Cp*RhCl_2)_2作为催化剂,AgSbF6作为配体,室温下在四氢呋喃溶液中喹啉-8-甲醛能够与甲醇反应生成喹啉-8-甲酸甲酯。进一步,为了探究底物的适用范围,在上述条件下将底物扩展。在实验室已有六个醛基底物的基础上制备了另外四个醛基底物c8,c9,c10,c11,并应用这些喹啉-8-甲醛类化合物与不同的醇类发生反应。如之前所预期的,在温和的反应条件下,得到了一系列的喹啉-8-甲酸酯类化合物,收率在40%-75%之间。同时,用芳甲醛(1,2,3,4,5a)代替喹啉-8-甲醛类底物进行底物拓展性实验。遗憾的是,没有得到预期的酯类产物,却意外地发现该反应体系下能以70%的收率使N-对甲苯磺酰基-4-甲基-2-氨基苯甲醛(5a)生成苯乙腈类化合物5b,由于时间原因,未对这类反应做进一步研究,其机理也有待于探索。本论文发现将含有不同取代基的喹啉-8-甲醛类化合物与醇类化合物在三价铑配合物(Cp*RhCl_2)_2催化下发生酯化反应的方法,具有一定的底物适用性,可用于各类喹啉-8-甲醛的酯化。同时,该反应也有局限性,如三价铑试剂价格昂贵,底物只适用于喹啉-8-甲醛类化合物,反应需要无水无氧等。另外,我们推测了可能的反应机理。值得指出的是,本论文阐述的反应方法具有一定的应用价值,同时也丰富了三价铑催化C-H键活化反应的类型。
[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.
【学位授予单位】：兰州理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
本文编号：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.
【学位授予单位】：兰州理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
【参考文献】
相关期刊论文 前1条
1 代伟;刘玉臣;童涛;李兴伟;罗芳;;铑(Ⅲ)催化的醛的氧化胺化:一种有效的构建N-吡啶酰胺及酰亚胺的合成方法[J];催化学报;2014年07期
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