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通过烯烃异构化以及随后高锰酸钾促进的氧化烯烃基团裂解,将香精油烯丙基苯快速绿色地微波辅助转化为相应的醛。

Fast and green microwave-assisted conversion of essential oil allylbenzenes into the corresponding aldehydes via alkene isomerization and subsequent potassium permanganate promoted oxidative alkene group cleavage.

作者信息

Luu Thi X Thi, Lam Trinh To, Le Thach Ngoc, Duus Fritz

机构信息

Department of Science, Systems, and Models, Roskilde University, DK-4000, Roskilde, Denmark.

出版信息

Molecules. 2009 Sep 3;14(9):3411-24. doi: 10.3390/molecules14093411.

Abstract

Essential oil allylbenzenes from have been converted quickly and efficiently into the corresponding benzaldehydes in good yields by a two-step "green" reaction pathway based on a solventless alkene group isomerization by KF/Al(2)O(3) to form the corresponding 1-arylpropene and a subsequent solventless oxidation of the latter to the corresponding benzaldehyde by KMnO(4)/CuSO(4).5H(2)O. The assistance by microwave irradiation results in very short reaction times (<15 minutes). The green conversion of eugenol (4-allyl-2-methoxyphenol) into vanillin (4-hydroxy-3-methoxybenzaldehyde) has been carried out in a similar way, requiring however two additional microwave-assisted synthetic steps for acetylation of the hydroxy group prior to the oxidation reaction, and for the final deacetylation of vanillin acetate (4-acetoxy-3-methoxybenzaldehyde) by KF/Al(2)O(3) under solvent-free conditions, respectively.

摘要

通过基于KF/Al₂O₃的无溶剂烯烃基团异构化形成相应的1-芳基丙烯,以及随后通过KMnO₄/CuSO₄·5H₂O将后者无溶剂氧化为相应苯甲醛的两步“绿色”反应途径,来自[具体来源未提及]的香精油烯丙基苯已快速有效地转化为相应的苯甲醛,产率良好。微波辐射的辅助使得反应时间非常短(<15分钟)。丁香酚(4-烯丙基-2-甲氧基苯酚)向香草醛(4-羟基-3-甲氧基苯甲醛)的绿色转化也以类似方式进行,不过在氧化反应之前需要另外两个微波辅助的合成步骤,分别用于羟基的乙酰化,以及在无溶剂条件下通过KF/Al₂O₃对乙酸香草醛(4-乙酰氧基-3-甲氧基苯甲醛)进行最终的脱乙酰化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/63ac/6255098/e23ff39a8230/molecules-14-03411-g003.jpg

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