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液体配位配合物催化合成对羟基苯乙酮工艺研究

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液体配位配合物尿素/三氯化铝(Ur/AlCl3)同时作为催化剂与溶剂,催化乙酸苯酯(PA)弗瑞斯(Fries)重排以制备对羟基苯乙酮(p-HAP)。对比了一系列不同催化剂的反应活性,结果表明相同条件下Ur/AlCl3表现出较高的催化性能。与传统催化剂相比:Ur/AlCl3原材料廉价易得且自身物化性质稳定;反应过程无需添加其他组分参与反应,催化体系副反应程度低;反应条件温和、反应速度快。研究了不同摩尔配比、反应时间、反应温度、Ur/AlCl3循环使用次数等条件对实验结果的影响,验证了催化剂自身不同摩尔配比对其Lewis酸度及催化性能的影响。最适宜的反应条件为:Ur/AlCl3摩尔配比=0。6,反应时间:3 h,反应温度:65 ℃,n(Cat。):n(PA)=0。5:1,收率92。3%。产物结构经核磁共振氢谱、红外光谱、质谱确认。催化剂循环使用4次后仍表现出较好的催化活性。
Study on synthesis technology of p-hydroxy acetophenone catalyzed by liquid coordination complexes
Liquid coordination complex(Ur/AlCl3)performed as both catalyst and solvent,to catalyze the Fries rearrangement reac-tion of phenyl acetate(PA)to preparep-hydroxyacetophenone(p-HAP).A series of different catalysts were compared in terms of the reaction activity,and results showed that Ur/AlCl3 exhibited higher catalytic performance under the same conditions.Compared with traditional catalysts:Ur/AlCl3 raw materials were cheaper and easy to obtain;No other components needed to be added in the process to participate the reaction,which led to low degree of side reactions in the catalytic system;With milder reaction conditions and faster reaction rate.The influence of different molar ratio,reaction time,reaction temperature and Ur/AlCl3 recycling times on the experimental results were studied,and the effects of catalyst molar ratio on its Lewis acidity and catalytic performance were veri-fied.Optimum reaction conditions were:Ur/AlCl3 molar ratio=0.6,reaction time:3 h,reaction temperature:65 ℃,n(Cat.):n(PA)=0.5:1,and the yield was 92.3%.The product structure was confirmed by 1 H-NMR,IR and MS.The catalyst still showed good catalytic activity after being recycled for four times.

Fries rearrangementp-hydroxyacetophenoneliquid coordination complexur/AlCl3synthesis

沈京华、张念椿、刘健斌、张逸伟

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达高工业技术研究院(广州)有限公司,广东 广州 510535

西陇科学股份有限公司,广东 广州 510535

弗瑞斯重排 对羟基苯乙酮 液体配位配合物 尿素/三氯化铝 合成

2025

化学研究与应用
四川省化学化工学会 四川大学

化学研究与应用

北大核心
影响因子:0.555
ISSN:1004-1656
年,卷(期):2025.37(1)