丁酮的Baeyer-Villiger氧化合成乙酸乙酯的研究

Study on oxidantion of Butanone to Synthesis ethyl acetate through Baeyer-Villiger reaction

本试验以三氟乙酸酐和30%过氧化氢为原料制备过氧三氟乙酸,通过Baeyer-Villiger反应将丁酮氧化成乙酸乙酯。在温度为40℃,三氟乙酸酐用量为40 mmol,过氧化氢用量为25 mmol,反应时间为3 h以及不加缓冲剂的条件下氧化15 mmol丁酮时取得较好效果,丁酮转化率为96.02%,产物乙酸乙酯的得率为48.38%。对与以三氟乙酸和过氧化氢为原料制备的过氧三氟乙酸的氧化效果进行了比较,结果表明,以三氟乙酸酐和过氧化氢为原料制备的过氧三氟乙酸的氧化效果要优于以三氟乙酸和过氧化氢为原料制备的过氧三氟乙酸。最后,还对过氧三氟乙酸氧化脂肪酮的机理进行了推导。

In this paper trifluoroacetic anhydride and 30% hydrogen peroxide were used as raw materials to produce peroxy trifluoroacetic acid,which can oxidize butanone to synthesis ethyl acetate through Baeyer-Villiger reaction.The suitable conditions of oxidizing butanone were as follows： the temperature 40℃,the dosage of trifluoroacetic anhydride 40 mmol per 15 mmol butanone,the dosage of hydrogen peroxide 25 mmol per 15 mmol butanone and the reaction time 3 hour.In addition,buffers should not be added into the reaction system.The conversion rate of butanone was 96.02% and the yield of ethyl acetate was 48.38%.The results showed that the peroxy trifluoroacetic acid prepared using trifluoroacetic anhydride and 30% hydrogen peroxide showed higher oxidation capability than that prepared form trifluoroacetic acid and 30% hydrogen peroxide.Finally,the possible mechanism of the oxidation of aliphatic ketones by peroxy trifluoroacetic acid was discussed.