醇胺类和胍类催化剂在二氧化碳化学转化合成喹唑啉二酮和环状碳酸酯中的应用

发布时间：2017-12-27 09:19

本文关键词：醇胺类和胍类催化剂在二氧化碳化学转化合成喹唑啉二酮和环状碳酸酯中的应用　出处：《华东师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：二氧化碳(CO2)化学,是当前化学和环境科学领域的研究热点之一,利用CO2作原料合成化学品和材料非常符合可持续发展的需求,另一方面,具有化学稳定性的CO2的转化,是我们在催化研究中面临的一大挑战。科研工作者发展了多种多样的催化体系应用于二氧化碳的化学转化,其中有机碱和离子液体都是常用的高效催化剂。有机碱类催化剂可用于催化多种反应,适用面广;而离子液体对有机物具有良好的溶解能力,常同时作为可循环使用的反应溶剂和催化剂。论文开发了三种有机碱或离子液体类催化剂分别用于催化CO2化学转化合成喹唑啉二酮和环状碳酸酯系列衍生物,具体研究内容如下:1)以二乙醇胺作为有机碱类催化剂,催化CO2与邻氨基苯甲腈的反应。此催化体系以水为反应溶剂,在100℃、1MPa的CO2压力、12h的条件下实现了喹唑啉-2,4(1H,3H)-二酮的高产率合成。溶剂水在其中起到了关键性作用。该体系的高催化活性来源于羟基与胺基的协同催化作用。根据实验结果我们推测了反应机理,并通过密度泛函理论计算结合FT-IR、1HNMR等表征来验证机理的合理性。2).以四甲基胍为原料,通过两步法合成了五种胍醋酸盐离子液体,在其可修饰N原子上连接着不同长度的烷基。实验证明这些离子液体可以高效催化合成喹唑啉二酮类衍生物,取代基越长催化活性越高。以N-正丁基-四甲基胍醋酸盐为催化剂,反应条件为80 ℃、0.5 MPa的CO2压力、24 h时,可以得到90%的收率,该离子液体经反应循环5次而活性保持不变。3)以二乙醇胺为阳离子,通过与溴乙烷的离子化合成了一种新型的富含羟基的离子液体。该离子液体可以在120 ℃、1 MPa的CO2压力、3 h的条件下有效催化CO2与各类环氧化物合成环状碳酸酯的反应。该离子液体中丰富的羟基官能团活化了环氧化物,促进了溴离子对环氧化物的开环。
[Abstract]:Carbon dioxide (CO2) is one of the hotspot in chemistry, chemical and environmental science, using CO2 as raw material of synthetic chemicals and materials is consistent with the demand of sustainable development, on the other hand, has transformed the chemical stability of CO2, is a big challenge we face in catalysis. Researchers have developed various catalytic systems for the chemical conversion of carbon dioxide, in which organic base and ionic liquids are commonly used efficient catalysts. Organic base catalysts can be used to catalyze many reactions and have wide applications. Ionic liquids have good solubility for organic compounds, and are often used as reacting solvents and catalysts at the same time. This paper developed three kinds of organic alkali or ionic liquid catalysts were used to catalyze CO2 chemical conversion synthesis of quinazoline ketone and two cyclic carbonate derivatives, the specific contents are as follows: 1) with two ethanol as organic amine alkali catalyst, CO2 catalyst and o-amino benzonitrile reaction. The high yield of quinazoline -2,4 (1H, 3H) - two ketone was synthesized under the condition of 100 C, 1MPa CO2 pressure and 12h, with water as the reaction solvent. Solvent water plays a key role in it. The high catalytic activity of the system is derived from the synergistic catalysis of hydroxyl and amine groups. According to the experimental results, we speculate the reaction mechanism and verify the rationality of the mechanism by means of density functional theory and FT-IR, 1HNMR and other characterization. 2). Four methyl guanidine as raw materials, five kinds of guanidine acetate ionic liquid was synthesized by two steps, which can be modified in N atoms connected with different length of alkyl. The experimental results show that these ionic liquids can catalyze the synthesis of quinazoline two ketone derivatives. The longer the substituent, the higher the catalytic activity. In four N- butyl - methyl guanidine acetate as catalyst, the reaction conditions of 80 DEG C, 0.5 MPa CO2 pressure, 24 h, 90% of the yield, the ionic liquid is 5 cycles by a reaction activity remained unchanged. 3) with two ethanol amine cation ionic liquids, a new type of rich hydroxyl were synthesized through ionization with ethyl bromide. The ionic liquid can catalyze the reaction of CO2 with various kinds of epoxides to synthesize cyclic carbonates under the conditions of CO2 pressure of 120 and 1 MPa and 3 h. The rich hydroxyl group in the ionic liquid activates the epoxide, which promotes the ring opening of the bromine ion to the epoxide.
【学位授予单位】：华东师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36

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