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6-(4-苯磺酰基-3-甲基-2-丁烯)-基-2,3-二甲氧基-5-甲基氢醌
双苄醚的合成

陈 田,杨运泉,刘文英,王威燕,周国平   

  1. 湘潭大学化工学院
  • 出版日期:2008-05-05 发布日期:2008-05-05

Synthesis of 6-(4-phenylsulfonyl-3-methyl-2-butenyl)-2,3-dimethoxy- 5-methyl hydroquinone-O,O′-dibenzyl ether

CHEN Tian,YANG Yunquan,LIU Wenying,WANG Weiyan,ZHOU Guoping   

  1. School of Chemical Engineering,Xiangtan University
  • Online:2008-05-05 Published:2008-05-05

摘要: 以异戊二烯为原料,经与苯磺酰氯加成、水解乙酰化、皂化3步反应,制得末端羟基取代的异戊二烯短侧链——(E)-1-苯磺酰基-2-甲基-4-羟基-2-丁烯(简称产物A),并用乙酸乙酯-乙醚混合溶剂对产物A进行提纯精制。以还原型辅酶Q0(氢醌)为母环,杂多酸为催化剂,与产物A进行偶联反应,然后采用溴化苄对母环羟基进行保护,用乙醚-异丙醚的混合溶剂进行提纯精制,选择性结晶得到了侧链延长法合成辅酶Q10的关键中间体辅酶Q1前体,即6-(4-苯磺酰基-3-甲基-2-丁烯)-基-2,3-二甲氧基-5-甲基氢醌双苄醚(简称产物B)。探讨了各主要影响因素对合成反应过程及结果的影响,目标产物B收率达75%(以产物A为基准)。产物A与目标产物B经测熔点、1H NMR分析和FTIR分析鉴定,确证其为(E)-异构体。

Abstract: (E)-1-phenylsulfonyl-2-methyl-4-hydroxy-2-butene(product A)was synthesized through the three-step process(addition,acetolysis and saponification)by using isoprene as the starting material and purified by crystallization from ether-ethyl acetate mixtures. 6-(4-phenylsulfonyl-3-methyl-2- butenyl)-2,3-dimethoxy-5-methylhydroquinone-O,O′-dibenzyl ether(product B)was synthesized by coupling reaction between hydroquinone and product A by using heteropoly acid as catalyst and with the hydroxyl group on hydroquinone protected by bromobenzyl. The end product B was purified by crystallization from ether-diisopropyl ether mixtures. The influence factors of the synthesis process were also studied. The yield of end product B was 75%(based on product A). This process has distinct advantages,such as simple process,much milder reaction conditions,green chemical catalytic technology and so on. The structures of product A and end product B were identified by FTIR and 1H NMR.

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