Brønsted酸性离子液体催化Fries重排合成对羟基苯乙酮的研究  

Synthesis of p-hydroxyacetophenone through Fries rearrangement catalyzed by Brønsted acidic ionic liquid

作　　者：李萍 崔颖娜[1] 张腾 曹洪玉[2] 张殊佳 郑学仿[2] 王爱玲[1] LI Ping;CUI Ying-na;ZHANG Teng;CAO Hong-yu;ZHANG Shu-jia;ZHENG Xue-fang;WANG Ai-ling(College of Environmental and Chemical Engineering,Dalian University,Dalian 116622,China;Liaoning Provincial Key Laboratory of Bioorganic Chemistry,Dalian University,Dalian 116622,China;College of Chemistry and Food Science,Yulin Normal University,Yulin 537000,China)

机构地区：[1]大连大学环境与化学工程学院,辽宁大连116622 [2]大连大学辽宁省生物有机化学重点实验室,辽宁大连116622 [3]玉林师范学院化学与食品科学学院,广西玉林537000

出　　处：《现代化工》2023年第4期149-153,160,共6页Modern Chemical Industry

基　　金：广西自然科学基金项目(2020GXNSFAA159126);大连大学科研平台项目重点项目(202101ZD01)。

摘　　要：采用一步法合成了[PPh_(3)][TfOH]_(2)、[TNOA][TfOH]_(2)、[TNOA][TfOH]和[PPh_(3)][TfOH]共4种离子液体。通过红外探针法对离子液体的酸性类型与酸性强弱进行了表征;同时对离子液体催化Fries重排选择性合成对羟基苯乙酮的收率进行了条件优化。结果表明,当选择[PPh_(3)][TfOH]_(2)作催化剂兼溶剂时,在反应温度为60℃、n(乙酸苯酯)∶n(离子液体)为1∶2、反应时间为6 h的条件下,选择性生成对羟基苯乙酮最高收率达到75%;催化剂可循环利用5次不失活。通过1HNMR监测反应前后催化剂结构变化,推导了其可能的反应机理。Four kinds of ionic liquids(ILs),including[PPh_(3)][TfOH]_(2),[TNOA][TfOH]_(2),[TNOA][TfOH]and[PPh_(3)][TfOH],are synthesized via one-step method.The type and intensity of acidity of the ILs are characterized through FT-IR probe method.The catalytic performance of these Brønsted ILs is evaluated in selective synthesis of p-hydroxyacetophenone through Fries rearrangement process.It is shown that the yield of p-hydroxyacetophenone reaches 75%,the highest when[PPh_(3)][TfOH]_(2)is used as catalyst and solvent,the reaction temperature is at 60℃,n(PA):n(IL)=1:2,and the reaction time is 6 h.[PPh_(3)][TfOH]_(2)will not lose its activity after it has been recycled for 5 times.The changes of catalyst structure before and after the reaction are monitored by means of 1H NMR and the possible reaction mechanism is deduced.

关 键 词：Brønsted酸性离子液体 Fries重排反应 对羟基苯乙酮 红外探针法 

分 类 号：O626[理学—有机化学] O643.36[理学—化学]