5-羟基乙酰丙酸的内酯化与缩聚反应  

Lactonization and condensation polymerization of 5-hydroxylevulinic acid

作　　者：张艳[1] 吴林波[1] 李枫[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

出　　处：《化工学报》2006年第4期992-996,共5页CIESC Journal

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

摘　　要：以乙酰丙酸(LA)为原料,通过改进的溴化、水解反应,合成5羟基乙酰丙酸(5HLA).基于5HLA的羟基和羧基,将其作为单体,氯化亚锡为催化剂,经缩聚得到了一种新的脂肪族聚酯———聚5羟基乙酰丙酸(PHLA).另以BF3·OEt2为催化剂,进行5HLA的内酯化反应,得到了二聚体1,6,9,13四氧双螺[4.2.4.2]十四烷2,10二酮(又称阿尔泰内酯),它是中药九节菖蒲的化学成分之一.分别用气质联用、核磁、红外、元素分析和凝胶渗透色谱等方法对所得二聚体以及聚合物结构进行表征,讨论了有关的反应机理.5-Hydroxylevulinic acid （5-HLA） was synthesized via modified bromination and hydrolysis using levulinic acid （LA） as starting material. Based on the hydroxyl and the carboxyl groups of the 5- HLA, poly （5-hydroxylevulinic acid）, a novel aliphatic polyester, was synthesized by direct polycondensation using SnCl2 · 2H2O as catalyst. In addition, 1, 6, 9, 13-tetraoxadispiro [4.2. 4.2] tetradecane-2, 10-dione （or altaicadispirolactone）, a dimer of the 5-HLA, was synthesized by cyclolactonization catalyzed by BF3 · OEt2. Altaicadispirolactone is one of the chemical components of Anemone altaica C. A. May, a traditional Chinese medicinal material. Structures of the dimer and the polymer were characterized with GC-MS, ^1H NMR, FT-IR, element analysis and GPC, respectively. Two plausible mechanisms for the cyclolactonization reaction were presented.

关 键 词：5-羟基乙酰丙酸 乙酰丙酸 脂肪族聚酯 缩聚 阿尔泰内酯 

分 类 号：O621.3[理学—有机化学]