香料化合物-3甲基-2-羟基-环戊-2-烯-1-酮的合成  

Synthesis of Perfumery Compound 3-methyl-2-hydroxy-cyclopent-2-en-1-one

作　　者：阎峰[1] 姜岚[1] 沈月秋[1] 周永昌[1] 

机构地区：[1]沈阳化工学院应用化学学院,辽宁沈阳110142

出　　处：《沈阳化工学院学报》2005年第1期1-4,共4页Journal of Shenyang Institute of Chemical Technolgy

摘　　要：　以丙酸乙酯和草酸二乙酯为主要原料,经Claisen酯缩合、Michael加成、Dieckmann酯缩合和水解脱羧4步反应,合成目标产物3 甲基 2 羟基 环戊 2 烯 1 酮,产品总收率达51 09%.Claisen酯缩合反应在n(丙酸乙酯)∶n(草酸二乙酯)=1∶1 2,反应时间为3h,温度为60℃的条件下,中间产物2 甲基 3 羰基 丁二酸二乙酯(Ⅰ)收率达81 58%;Michael加成、Dieckmann酯缩合反应的较适宜条件为n(Ⅰ)∶n(丙烯酸乙酯)=1∶1 8,反应时间7 5h,反应温度80℃.最后用[W(H3PO4)=50%]的磷酸溶液脱羧基反应10h后,得到最终产品,产率95 17%.经红外光谱和核磁共振波谱鉴定,证明结构正确.3-methyl-2-hydroxy-cyclopent-2-en-1-one was prepared from ethyl propionate and dietthyl oxalate through Claisen ester condensation, Michael addition, Dieckmann ester condensation and decarboxylation reactions in total 51.09 % yield. The intermediate 2-methyl-3-oxo-butanedioic acid diethyl ester (Ⅰ) was synthesized in 81.58 % yield by Claisen ester condensation at temperature 60 ℃, reaction time 3 h and n(ethyl propionate)∶n(diethyl oxolate)=1∶1.2. The optimum conditions of Michael addition and Dieckmann ester condesation reactions were temperature 80 ℃, reaction time 7.5 h and (n(Ⅰ):n(ethyl acrylate))=1∶1.8. The final product was obtained by decarboxylation with H_3PO_4([w(H_3PO_4)=50 %]) as catalyst. Its molecular structure was identified by IR and ~1H-NMR analysis.

关 键 词：3-甲基-2-羟基-环戊-2-烯-1-酮 丙酸乙酯 草酸二乙酯 丙烯酸乙酯 

分 类 号：O623.5[理学—有机化学]