铜催化的由醛制备过酸叔丁酯及烯丙酯的一锅法合成研究
发布时间：2018-08-25 11:50
【摘要】：近年来,过酸酯以及烯丙基酯类化合物由于它们在化学领域的诸多应用而受到了人们广泛的关注。目前,虽然已有多种方法可以用来合成该类物质,但其中大部分存在诸如反应条件比较苛刻,底物适应性较差等缺点。随着绿色化学这一观念的逐渐深入人心,探究操作简单、条件温和且环境友好的碳碳、碳杂键构筑方法已经成为如今有机合成领域的研究热点。与此同时,C-H活化在有机合成化学领域受到了广泛关注。它具有原子经济性高、污染小等优点。正因为如此,通过醛的C-H活化来合成过酸酯以及由此衍生的烯丙基酯无疑具有重要的研究价值,为这类化合物的合成提供了一种新的合成方法。本文通过对配体、催化剂、温度、溶剂等条件的探索优化,发展了一种以醛为底物,高效的铜催化的合成过酸叔丁酯的方法,然后在此基础上与烯烃反应成功实现了烯丙基酯的一锅法串联合成反应。具体研究内容如下:(1)Cu(I)配合物催化的以醛为底物合成过酸叔丁酯的方法研究该方法以10 mol%Cu I为催化剂、10 mol%bpy为配体,醛为原料,无需溶剂,在近于室温条件下与TBHP(过氧叔丁醇)反应2~6 h,以良好的收率合成得到过酸酯化合物。实验证明:多齿氮配体的加入对该铜催化的反应起到了关键的调控作用。与以往文献中所报道的方法相比,该反应体系显著缩短了反应时间,无需溶剂,具有更好的官能团容忍性和底物适应性,并以较高收率得到目标产物。(2)Cu(I)配合物催化的一锅法合成烯丙基酯的方法研究在不需要添加额外催化剂的情况下,Cu I催化醛与TBHP反应2~6 h后,向体系中添加适量的环己烯,升温反应6~18 h便可成功地以醛为底物一锅法制备烯丙基酯。与以往文献报道不同的是,该反应体系使用了廉价易得的铜催化剂,无需溶剂,反应可以在较短时间内以良好的收率得到一系列烯丙基酯类化合物,该反应体系同时也具有很好的底物适应性。此外,据我们所知,这是首次报道的铜催化一锅法串联合成烯丙基酯类化合物。通过以上两种合成方法,成功地得到了十三种过酸叔丁酯及十一种烯丙基酯,并对它们进行了结构表征。
[Abstract]:In recent years, peracid esters and allyl esters have attracted wide attention due to their many applications in the chemical field. At present, although there are many methods to synthesize this kind of substances, most of them have disadvantages such as harsh reaction conditions, poor substrate adaptability and so on. With the development of green chemistry, the carbon and carbon bond construction methods, which are simple in operation, mild in conditions and friendly in environment, have become the research focus in the field of organic synthesis. At the same time, the activation of C-H has attracted extensive attention in the field of organic synthesis chemistry. It has the advantages of high atomic economy and low pollution. Because of this, the synthesis of peracid esters by C-H activation of aldehydes and the allyl esters derived from them are undoubtedly of great research value, which provides a new synthetic method for the synthesis of these compounds. In this paper, by optimizing the conditions of ligand, catalyst, temperature, solvent and so on, a method of synthesis of tert-butyl peracid catalyzed by copper with aldehydes as substrate was developed. On this basis, the one-pot series synthesis of allyl esters was successfully realized with olefin reaction. The main contents of the study are as follows: (1) the synthesis of tert-butyl peracid using aldehyde as substrate catalyzed by) Cu (I) complex was studied. The method used 10 mol%Cu I as catalyst, 10 mol%bpy as ligand, aldehyde as raw material, no solvent, Peracid ester compound was synthesized by reaction with TBHP (peroxy tert-butanol) at room temperature for 2 h for 6 h. Experimental results show that the addition of polydentate nitrogen ligands plays a key role in the copper-catalyzed reaction. Compared with the methods reported in previous literatures, the reaction system can significantly shorten the reaction time, do not need solvent, and has better functional group tolerance and substrate adaptability. The method of one-pot synthesis of allyl ester catalyzed by 2) Cu (I) complex was used to study the reaction of aldehydes with TBHP in the presence of CuI catalyst for 2h, and then the cyclohexene was added to the system for 6 h. Allyl esters were prepared by one pot method using aldehydes as substrate in 6 鈩，
本文编号：2202797
[Abstract]:In recent years, peracid esters and allyl esters have attracted wide attention due to their many applications in the chemical field. At present, although there are many methods to synthesize this kind of substances, most of them have disadvantages such as harsh reaction conditions, poor substrate adaptability and so on. With the development of green chemistry, the carbon and carbon bond construction methods, which are simple in operation, mild in conditions and friendly in environment, have become the research focus in the field of organic synthesis. At the same time, the activation of C-H has attracted extensive attention in the field of organic synthesis chemistry. It has the advantages of high atomic economy and low pollution. Because of this, the synthesis of peracid esters by C-H activation of aldehydes and the allyl esters derived from them are undoubtedly of great research value, which provides a new synthetic method for the synthesis of these compounds. In this paper, by optimizing the conditions of ligand, catalyst, temperature, solvent and so on, a method of synthesis of tert-butyl peracid catalyzed by copper with aldehydes as substrate was developed. On this basis, the one-pot series synthesis of allyl esters was successfully realized with olefin reaction. The main contents of the study are as follows: (1) the synthesis of tert-butyl peracid using aldehyde as substrate catalyzed by) Cu (I) complex was studied. The method used 10 mol%Cu I as catalyst, 10 mol%bpy as ligand, aldehyde as raw material, no solvent, Peracid ester compound was synthesized by reaction with TBHP (peroxy tert-butanol) at room temperature for 2 h for 6 h. Experimental results show that the addition of polydentate nitrogen ligands plays a key role in the copper-catalyzed reaction. Compared with the methods reported in previous literatures, the reaction system can significantly shorten the reaction time, do not need solvent, and has better functional group tolerance and substrate adaptability. The method of one-pot synthesis of allyl ester catalyzed by 2) Cu (I) complex was used to study the reaction of aldehydes with TBHP in the presence of CuI catalyst for 2h, and then the cyclohexene was added to the system for 6 h. Allyl esters were prepared by one pot method using aldehydes as substrate in 6 鈩，
本文编号：2202797
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