连续流微反应合成4-醛基-2,2-二氟苯并-1,3-间二氧杂环戊烯工艺研究  

Continuous synthesis processes of 2,2-difluorobenzo[d][1,3]dioxole-4-carbaldehyde by micro-reaction technology

作　　者：毛明珍[1] 王威[1] 王列平[1] 郑晓蕊[1] 黄晓瑛[1] MAO Ming-zhen;WANG Wei;WANG Lie-ping;ZHENG Xiao-rui;HUANG Xiao-ying(Xi’an Modern Chemistry Research Institute,State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi’an 710065,China)

机构地区：[1]西安近代化学研究所氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《应用化工》2022年第8期2315-2318,共4页Applied Chemical Industry

基　　金：陕西省科技厅重点研发计划项目(2021GY-125,2022GY-167)。

摘　　要：以二氟胡椒环、正丁基锂和N,N-二甲基甲酰胺(DMF)为原料,在微通道中进行连续锂-氢交换、甲酰化反应,合成目标产物4-醛基-2,2-二氟苯并-1,3-间二氧杂环戊烯。考察了反应温度、物料比、停留时间、质量浓度等因素对反应的影响。获得了优化工艺参数为:二氟胡椒环四氢呋喃溶液质量浓度45%,n(二氟胡椒环)∶n(正丁基锂)∶n(DMF)=1∶1.05∶1.05,反应温度-10℃,停留时间18 s,收率93.0%,产物含量99%以上。与传统釜式合成工艺相比,连续流微反应工艺实现了目标产物合成的安全稳定进行,提升了反应效率。The continuous flow micro-reaction technology was used to synthesis the 2,2-difluorobenzo[d][1,3]dioxole-4-carbaldehyde via continuous Li/H exchange,formylation reaction by using 2,2-difluoro-1,3-benzodioxole,n-butyllithium and DMF as raw materials.The influences of reaction temperature,residence time,the ratio of materials and concentration on the yield of target compound were investigated.The optimized process conditions are as follows:the mass concentration of 2,2-difluoro-1,3-benzodioxol/tetrahydrofuran solution is 45%,molar ratio of 2,2-difluoro-1,3-benzodioxole:n-butyllithium:DMF is 1∶1.05∶1.05,the reaction temperature of-10℃,the residence time of 18 s,the yield of process is 93.0%and the purity of product is 99%.The new process could make the target compound synthesis reaction stable and more safe,efficient.

关 键 词：连续流 微反应 合成 正丁基锂 甲酰化 

分 类 号：TQ56[化学工程—炸药化工] O69[理学—化学] O621.3