乙酰乙酸酯类化合物肟化顺反异构选择性  

Selectivity of Cis-trans Isomerization in Oximation of Acetoacetate

作　　者：苏可[1] 王秋芬[1] 郑庚修[1] 滕江波[1] 刘春宏[1] 

机构地区：[1]济南大学化学化工学院,山东济南250022

出　　处：《济南大学学报（自然科学版）》2010年第1期61-63,共3页Journal of University of Jinan(Science and Technology)

基　　金：山东省科技发展计划(2008GG10002021)

摘　　要：对乙酰乙酸甲酯（MAA）、乙酰乙酸乙酯（EAA）、乙酰乙酸叔丁酯（TBAA）进行肟化，研究肟化剂、溶剂效应及温度对产物顺反异构的影响。采用硫酸和亚硝酸钠为肟化剂，乙酸乙酯和水为溶剂，MAA、EAA在（15～20）℃反应最佳；采用甲基异丁基酮和水为溶剂，TBAA在（20～25）℃反应最佳。经高效液相色谱检测，MAA、EAA、TBAA的最佳顺反异构（Z＆E型）转化率分别为94．5％＆3．9％；95．1％＆3．4％；92．1％＆5．6％。Through oximating methyl, ethyl and tert-butyl acetoacetates respectively, the effects of oximation agent, solvent and temperature on the cis-trans isomerization of the products were studied. Using sulfuric acid and sodium nitrite as the oximation agent, ethyl acetate and water as the solvent, the optimum temperature range of the reaction for methyl and ethyl acetoacetates was obtained between（ 15 -20）℃. With the same oximation agent, using methyl isobutyl ketone and water as the solvent, the optimum temperature range of the reaction concerning tert-butyl acetoacetate was obtained between （20- 25 ） ℃. By high-performance liquid chromatography （ HPLC）, it was found that the percentage of cis and trans isomers of methyl acetoacetate is 94.5% ＆ 3.9% , 95.1% ＆ 3.4% for ethyl acetoacetate and 92.1% ＆ 5.6% for tert-butyl acetoacetate, respectively.

关 键 词：乙酰乙酸甲酯 乙酰乙酸乙酯 肟化 顺反异构 

分 类 号：TQ225.24[化学工程—有机化工]