Br?nsted酸性离子液体催化双酚芴的合成  

Br?nsted Acidic Ionic Liquid Catalyzed Synthesis of Bisphenolfluorene

作　　者：闫磊 于丽梅[1,2] 申茂昌 高占先[1,2] YAN Lei;YU Li-mei;SHEN Mao-chang;GAO Zhan-xian(School of Chemistry,Dalian University of Technology,Dalian 116024,Liaoning,China;State Key Lab of Fine Chemicals,Dalian University of Technology,Dalian 116024,Liaoning,China)

机构地区：[1]大连理工大学化学学院,辽宁大连116024 [2]大连理工大学精细化工国家重点实验室,辽宁大连116024

出　　处：《精细化工》2019年第7期1357-1363,共7页Fine Chemicals

摘　　要：以1-甲基咪唑、1,3-丙磺酸内酯、硫酸、磷酸、四氟硼酸、对甲苯磺酸为原料,合成4种BrФnsted酸性离子液体(ILs),通过FTIR、NMR和TG对其结构进行了表征,同时采用UV-vis测定了离子液体的酸度H0。将离子液体应用于双酚芴(BHPF)的合成反应中,离子液体的酸度H0≤1.94时有催化作用,H0≤1.69的ILs催化剂有应用价值。采用单变量优化法考察了反应参数对9-芴酮和苯酚缩合反应的影响,确定较优反应条件为:苯酚、9-芴酮和IL1的物质的量比为6∶1∶0.125,IL1和助催化剂巯基乙酸的物质的量比为5∶2,反应温度110℃,反应时间6 h。在上述条件下,考察了4种离子液体催化剂对双酚芴合成反应的催化效果,使用IL1、IL2、IL4催化反应时,9-芴酮转化率均为100%,双酚芴的选择性约为87%。此外,离子液体IL1连续使用5次催化效果无明显降低。Four BrФnsted acidic ionic liquids(ILs)were synthesized using 1-methylimidazole,1,3-propane sultone,sulfuric acid,phosphoric acid,tetrafluoroboric acid and p-toluene sulfonic acid as raw materials.Their structures were characterized by FTIR,NMR and TG and the acidity H0 was measured by UV-vis.These ionic liquids were applied to the synthesis of bisphenolfluorene.When the H0 was less than or equal to 1.94,the ionic liquid had catalytic effect,when that was less than or equal to 1.69,the ionic liquid had applicable value.A method for the determination of bisphenolfluorene by liquid chromatography was developed.The reaction products were separated and the structures of the three products were determined by NMR.The effect of reaction parameters on the condensation reaction of 9-fluorenone and phenol was investigated by univariate optimization.The optimal reaction conditions were obtained as follows∶n(phenol)∶n(9-fluorenone)∶n(IL1)=6∶1∶0.125,n(IL1)∶n(thioglycolic acid)=5∶2,reaction temperature 110℃and reaction time 6 h.The catalytic effects of the four catalysts in the synthesis of bisphenolfluorene were investigated under the above conditions.For IL1,IL2 and IL4 catalysts,the conversion of 9-fluorenone was 100%,and the selectivity of bisphenolfluorene was nearly 87%.In addition,the catalytic effect of ionic liquid IL1 was not significantly reduced after 5 consecutive uses.

关 键 词：离子液体 9-芴酮 双酚芴 缩合反应 助催化剂 催化技术 

分 类 号：O625.3[理学—有机化学]