以乙酰丙酸为原料合成5-羟基乙酰丙酸的研究  

Synthesis of 5-hydroxylevulinic acid from levulinic acid

作　　者：张艳[1] 吴林波[1] 李枫[1] 卜志扬[1] 李伯耿[1] 

机构地区：[1]浙江大学化学工程与生物工程学系聚合反应工程国家重点实验室,浙江杭州310027

出　　处：《浙江大学学报（工学版）》2006年第11期1895-1899,1917,共6页Journal of Zhejiang University：Engineering Science

基　　金：国家杰出青年科学基金资助项目(20125617);国家自然科学基金资助项目(20304012);国家重大基础研究前期研究专项资助项目(2004CCA05500);高等学校博士学科点专项科研基金资助项目(20020335101)

摘　　要：对新型聚酯单体5-羟基乙酰丙酸(5-HLA)的合成工艺进行了改进和优化.以来源于生物质资源的乙酰丙酸(LA)为原料,通过改进的溴化和水解反应合成了5-HLA.优化溴化反应温度、液溴滴加速率、反应介质用量等溴化反应条件;同时利用3-溴乙酰丙酸甲酯等溴化物的分子内重排和歧化反应,对溴化反应生成的副产物回收再利用,将中间产物5-溴乙酰丙酸甲酯的产率从文献值30%提高到45%.5-溴乙酰丙酸甲酯经一步水解、乙醚连续萃取和重结晶得到5-HLA.改进后的工艺基于乙酰丙酸的产率为30%,与二步法相比,操作时间短,产率大大提高.The synthetic method of polyester monomer 5-hydroxylevulinic acid （5-HLA） was improved and simplified. Using levulinic acid （LA） derived from biomass as raw material, 5-HLA was synthesized via modified bromination and hydrolysis processes. In the bromization reaction of LA, thereaction conditions such as reaction temperature, drop time of Br2 and reaction medium were optimized. The side product was reused via rearrangement of methyl 3-bromolevulinate to methyl 5-bromolevulinate （5-MBL） and the yield of 5-MBL was thus improved to 45% from an earlier reported value of 30%. Then pure 5-HLA in 30% yield was obtained via a simplified one-step hydrolysis of 5-MBL followed by concentration of the hydrolysate, extraction of 5-HLA in a continuous manner with stirring, and recrystallization in chloroform. Compared with the two-step method, the processing time was shortened and the yield of 5-HLA was improved.

关 键 词：乙酰丙酸 溴化 5-溴乙酰丙酸甲酯 5-羟基乙酰丙酸 

分 类 号：O621.3[理学—有机化学]