由月桂烯合成香叶基丙酮的研究

Synthesis of Geranyl Acetone from Myrcene

以月桂烯为原料,与氯化氢反应生成香叶基氯及其同分异构体,产物与乙酰乙酸乙酯发生取代反应,经水解脱羧制得香叶基丙酮。月桂烯的加成反应是整个反应过程的关键步骤,对合成香叶基丙酮有决定性影响;重点探讨了催化剂种类及用量、反应温度及原料配比对月桂烯与氯化氢加成反应的影响。得到最适宜反应条件:以Cu Cl和四丁基溴化铵为催化剂,用量为月桂烯摩尔分数的1%,温度为10℃,n(月桂烯)∶n(氯化氢)=1∶1。该条件下,氯化物的产率可达92.86%,且香叶基氯和橙花基氯占氯化物总量的75.71%。氯化物经取代反应,水解脱羧后得到香叶基丙酮,产率为76.62%。

Geranyl acetone has been synthesized by ethyl acetoacetate via substitution reaction and ketonic cleavage with geranyl chloride and its isomers,which were obtained by myrcene with the electrophilic addition of hydrogen chloride. The addition reaction of myrcene have a decisive influence on the synthesis of geranyl acetone,is a critical step in the reaction process. We mainly studied the influence of the catalyst type,catalyst dosage,reaction temperature,the ratio of reaction material on the addition reaction. The optimal reaction conditions were: using Cu Cl and tetrabutylammonium bromide as catalysts with a mole fraction of 1% base on myrcene,the reaction temperature was 10 ℃ and the n( myrcene) ∶ n( hydrogen chloride) = 1∶ 1. Under the optimal reaction conditions,the yield of the chloride reached 92. 86%,and the percentage of geranyl chloride and nerlyl chloride were 75. 71%. Geranyl acetone was preprared by the substitution reaction of the chloride and subsequent hydrolysis decarboxylation reaction with a yield of76. 62%.