文献类型：期刊文献

中文题名：4,4’-二(氯甲基)联苯在乙腈/水中的水解反应

英文题名：Hydrolysis of 4,4'-Bis(chloromethyl)biphenyl in the Mixture of Acetonitrile/H_2O

作者：来国桥[1];方奇[1];任晓莉[1];沈永嘉[1]

机构：[1]华东理工大学精细化工研究所

年份：2006

卷号：20

期号：6

起止页码：1013

中文期刊名：高校化学工程学报

外文期刊名：Journal of Chemical Engineering of Chinese Universities

收录：CSTPCD;;Scopus;北大核心:【北大核心2004】；CSCD:【CSCD2011_2012】；

基金：教育部博士点基金(20030251001)。

语种：中文

中文关键词：4,4’-二(氯甲基)联苯;亲核取代;水解反应;4,4'-二(羟甲基)联苯

外文关键词：4,4＇-bis（chloromethyl）biphenyl; nucleophilic substituted reaction; hydrolysis; 4,4＇-bis（hydroxymethyl）biphenyl

摘要：4,4’-二(氯甲基)联苯在蒸馏水中受热至回流,40h内未观察到有羟基取代苄基中氯原子的亲核取代反应发生。水中有乙腈存在,该反应就会发生,产物是4,4’-二(羟甲基)联苯。反应速度与乙腈/H2O的比例相关,当乙腈/H2O=20/1(容积比)时,完成该反应需要29h;而当乙腈/H2O=1/50时,完成该反应需要46h。若在乙腈/H2O介质中添加KOH,反应速度会加快,但同时会发生副反应以致生成一种淡黄色的树脂状物质。4,4’-二(氯甲基)联苯的纯度高,水解反应的产率及4,4’-二(羟甲基)联苯的纯度也高。当4,4’-二(氯甲基)联苯的纯度从98%降低到92%时,水解反应的产率从98.6%降低到94.4%,产物4,4’-二(羟甲基)联苯纯度从99.2%下降到98.6%。如4,4’-二(氯甲基)联苯的纯度进一步降低到85%,则反应产率急剧下降到80.9%,同时产物4,4’-二(羟甲基)联苯纯度下降到94.3%。
The nucleophilic substituted reaction between hydroxyl group in water and chlorine group in 4,4＇-bis（chloromethyl）biphenyl was not observed within 40 h under reflux. However, the hydrolysis reaction will take place when there is acetonitrile existing in the water and the reaction product will be 4,4＇-bis（hydroxymethyl）biphenyl. The experiments show that the reaction rate is proportional to the concentration of acetonitrile in water. When the volumetric ratio of acetonitrile to water is 20/1, the hydrolysis reaction will complete in 29 h, while when the ratio of acetonitrile to water is 1/50, the complete time of the reaction will extend to 46 h. The experiments also show that, if KOH is added into the aqueous solution of acetonitrile, the reaction will be accelerated, but side reactions will happen too and the by-product will be some pale yellow resin-like substance. It is found that the higher purity of 4,4＇-bis（chloromethyl）biphenyl is, the higher yield and higher purity of the main product, 4,4＇-bis（hydroxymethyl）biphenyl, will be. When the purity of 4,4＇-bis（chloromethyl）biphenyl used decreases from 98% to 92%, the purity of the main product will only decrease from 99.2% to 98.6%, although the yield of the reaction will decrease from 98.6% to 94.4%. When the purity of4,4＇-bis（chloromethyl）biphenyl used is 85%, the yield will reduce to 80.9%, and the purity of the main product is 94.3% only.