铜参与Buntes盐与酚的酯化反应研究

发布时间：2018-10-10 16:18

【摘要】：羧酸酯是一类重要的化工原料,可作为香料、溶剂、增塑剂及有机合成中间体广泛使用;同时在高分子聚合物、药物、液晶材料等研究领域也具有重要的应用价值。因此,发展更温和、高效、经济、绿色的合成羧酸酯的方法依然是有机化学合成领域的一个有挑战性的课题。近年来,化学家们成功的发现一些含硫试剂的C-S键活化断裂脱硫作为烷基化试剂参与反应。常用的含硫试剂有如磺酰肼、磺酰胺、磺酰氯、亚磺酸盐、硫醚、硫醇(酚)、Buntes盐等。从经济角度考虑,首选廉价、易得的试剂。而Buntes盐作为酰基化试剂的应用还未见文献报道。本论文首先对Buntes盐和二硫醚作为硫源在催化偶联中的应用作了简单的综述,接着有对酯合成方法作了简单的综述,最后根据大量实验数据,得到一个新的、经济的酯合成新方法。该反应以溴化亚铜作为氧化剂,咪唑为配体,碳酸钠为碱,Buntes盐与苯酚衍生物为底物,在100 oC条件下直接生成一系列的苯甲酸苯酯衍生物。实验结果表明该反应对具有吸电子的Buntes和带有给电子的酚类衍生物具有很好的兼容性。所得的化合物均通过1H NMR,13C NMR鉴定确定结构。通过一定的文献参考以及一些控制实验研究推断出可能的反应机理。
[Abstract]:Carboxylate is an important kind of chemical raw materials, which can be widely used as spices, solvents, plasticizers and organic synthesis intermediates, and also has important application value in polymer, medicine, liquid crystal materials and other research fields. Therefore, the development of more moderate, efficient, economical and green methods for the synthesis of carboxylate is still a challenging topic in the field of organic chemistry synthesis. In recent years, chemists have successfully found that some sulfur-containing reagents are activated by C-S bonds and broken desulfurization as alkylation reagents to participate in the reaction. Commonly used sulfur-containing reagents such as sulfonyl hydrazine, sulfonamide, sulfonyl chloride, sulfonate, sulfide, mercaptan (phenolic), Buntes salt, etc. From an economic point of view, the first choice of cheap, easily available reagent. However, the application of Buntes salt as acylation reagent has not been reported. In this paper, the application of Buntes salt and disulfide as sulfur source in catalytic coupling was briefly reviewed, and then the synthesis method of ester was briefly reviewed. Finally, according to a large number of experimental data, a new method was obtained. A new economic method for synthesis of esters. In this reaction, a series of benzyl benzoate derivatives were synthesized directly under the condition of 100 oC with copper bromide as oxidant, imidazole as ligand, sodium carbonate as base, Buntes salt and phenol derivative as substrate. The experimental results show that the reaction has good compatibility with Buntes with electron absorption and phenolic derivatives with electron donating. The compounds were identified by 1H NMR,13C NMR. The possible reaction mechanism was inferred by some references and some control experiments.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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