由环香叶酸乙酯合成β-突厥酮

Synthesis of β-Damascone from Ethyl Cyclogeranate

β-突厥酮为重要香原料,具有复合的果香型花香。开发了经格氏反应、分解反应和异构化3步合成β-突厥酮的新工艺。β-突厥酮适宜的合成工艺为:(1)格氏反应,物料比n(烯丙基氯):n(环香叶酸乙酯):n(镁)=2.2:1:2.4,产率85.6%;(2)分解反应,物料比n(叔丁基钾):n(2,6,6-三甲基-1-(4-羟基-庚-1,6-二烯-4-基)环己-1-烯)=1.1:1,产率62.5%;(3)异构反应,物料比w(2,6,6-三甲基-1-(丁-3-烯酰)环己-1-烯):w(对甲苯磺酸)=1:0.05,产率95.6%。结果表明,该路线的中间体和产品易提纯,β-突厥酮纯度大于98%,香气符合调香要求。中间体和目标产物经1 H NMR、GC-MS和IR等进行结构确证。

β-Damascone,as important aroma chemical,possesses a complex fruity floral odor.A new synthesis route including Grignard reaction,decomposition reaction and isomerization was developed.The parameters of as-presented procedure were as following：（1） Grignard reaction,material ratio n（allyl chloride）：n（ethyl cyclogeranate）：n（Mg）=2.2：1：2.4,the yield was 85.6%;（2） Decomposition reaction,material ratio n（t-BuOK）：n（2,6,6-trimethyl-1-（4-hydroxy-hepta-1,6-dien-4-yl）-cyclohex-1-ene）=1.1：1,the yield was 62.5%;（3）Isomerization,material ratio w（2,6,6-trimethyl-1-（but-3-enoyl）-cyclohex-1-ene）：w（PTSA）=1：0.05,the yield was 95.6%.Results showed that the intermediates and product could be easily refined,the purity of β-damascone was more than 98%,and the odor of the product was good for flavoring and perfumering.The structure of the intermediates and target product were confirmed through ^1 H NMR,MS and IR.