钯催化下1,3-二甲酰基薁类衍生物的合成

Palladium-Catalyzed Efficient Synthesis of 1,3-Diformylazulene Derivatives

在钯催化作用下,以一氧化碳和氢气为甲酰化试剂,以苯做反应溶剂,在6×106Pa、120℃下,反应底物、有机碱和催化剂的物质的量比为1∶2∶0.02,合成了1,3-二甲酰基薁,产品收率为77%。在此反应条件基础上,通过改变取代基,进行酰基化反应合成了1,3-二甲酰基-5-甲基薁,1,3-二甲酰基-6-叔丁基薁,1,3-二甲酰基-2,4,6-3甲基薁3种薁类衍生物,收率分别为68%、60%、65%。实验反应收率良好、操作简单、条件温和。4种新型化合物的产品结构通过红外光谱仪、核磁共振光谱仪以及元素分析仪进行了表征。

1,3-diformylazulene was synthesized by 1,3-dibromoazulenes,organic base and catalyst under 6×106 Pa at 120 ℃ with carbon monoxide-hydrogen for the formylation reagent,while palladium(Ⅱ) was as the catalyst,benzene as solvent.The yield was 77% under the condition the molar ratio of 1,3-dibromoazulenes,organic base and catalyst was 1∶2∶0.02.Based on the reaction,by changing the substituent,1,3-dimethylacyl-5-methyl azulene,1,3-dimethylacyl-6-tert-butyl-azulene,1,3-diformy-2,4,6-trimethyl-azulene were synthesized by acylation reactions,the yields were 68%,60%,65%.This method provides several advantages such as good yields,simple work-up procedures and mild conditions.All the products are confirmed by 1H-NMR,IR spectra and elemental analysis.