超声波促进3-(4-苯磺酰基-3-甲基-2-丁烯基)-4,5,6-三甲氧基-2-甲基苯基苄基醚的合成  

Synthesis of 3-(3-Methyl-4-benzenesulfonyl-2-butenyl)-4,5,6-trimethoxy-2-methylphenyl Benzyl Ether by Ultrasonic

作　　者：王威燕[1] 杨运泉[1] 童刚生[1] 周恩深[1] 刘文英[1] 匡志敏[1] 

机构地区：[1]湘潭大学化工学院,湖南湘潭411105

出　　处：《精细化工》2008年第12期1220-1224,共5页Fine Chemicals

基　　金：湖南省科技厅科技攻关项目(04FJ4116)~~

摘　　要：以3,4,5-三甲氧基甲苯(Ⅰ)为原料,经过Vilsmeier-Haack反应合成了6-甲基-2,3,4-三甲氧基苯甲醛(Ⅱ),收率94.1,Ⅱ经过Dakin反应得到2,3,4-三甲氧基-6-甲基苯酚(Ⅲ),收率96.2,用溴化苄对Ⅲ进行酚羟基保护得到2,3,4-三甲氧基-6-甲基苯基苄基醚(Ⅳ),收率95.0,Ⅳ在有机碱作用下发生溴代反应,得到6-甲基-5-溴-2,3,4-三甲氧基苯基苄基醚(Ⅴ),收率92.2,Ⅴ在超声波作用下制成格氏试剂(Ⅵ),再与4-溴-2-甲基-1-苯磺酰基-2-丁烯发生格氏偶联反应得到辅酶Q10的关键中间体3-(4-苯磺酰基-3-甲基-2-丁烯基)-4,5,6-三甲氧基-2-甲基苯基苄基醚(Ⅶ),收率72.0,五步反应总收率为57.1,产物经FTIR和1H NMR确定结构。3-（3-Methyl-4-benzenesulfonyl-2-butenyl）-4,5,6-trimethoxy-2-methylphenyl benzyl ether, a key intermediate of coenzyme Ql0 ,was synthesized from 3,4,5-trimethoxytoluene（Ⅰ） in overall yield of 57. 1%. 6-Methyl-2,3,4-tri-methoxybenzaldehyde （Ⅱ） was obtained from Ⅰ via Vilsmeier-Haack reaction in 94. 1% yield and converted to 6-methyl-2,3,4-trimethoxyphenol （Ⅲ） via Dakin reaction in 96. 2% yield. Phenolic hydroxyl protection of Ⅲ .with benzyl bromide produced 6-methyl-2,3,4- trimethoxyphenyl benzyl ether（Ⅳ） in 95.0% yield. Bromination of Ⅳ in the presence of organic base produced 5-bromo-2,3,4-trimethoxy-6-methylphenyl benzyl ether （Ⅴ） in 92. 2% yield. Under the condition of ultrasonic, Grignard reagent was prepared from V, and then coupled with 4-bromo-2- methyl-1-benzenesulfonyl-2-butene to give the target product in 72. 0% yield. Structure of the products were confirmed by FTIR and ^1HNMR

关 键 词：辅酶Q10 格氏反应 3-(4-苯磺酰基-3-甲基-2-丁烯基)-4 5 6-三甲氧基-2-甲基苯基苄基醚 超声波 医药 原料 

分 类 号：O621.256.7[理学—有机化学] TQ223.121[理学—化学]