苯并噻唑型功能化离子液体催化酮酚缩合反应的研究  

Study on benzothiazole-type ionic liquids for condensation reaction of ketone with phenol

作　　者：鲁鑫鑫 于丽梅[1,2] 闫磊 魏佳伦 高占先[1,2] LU Xin-xin;YU Li-mei;YAN Lei;WEI Jia-lun;GAO Zhan-xian(School of Chemistry,Dalian University of Technology,Dalian 116024,China;State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,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：《现代化工》2024年第3期194-199,205,共7页Modern Chemical Industry

摘　　要：以N-(3-磺酸基丙基)苯并噻唑、N-(3-磺酸基丙基)-2-巯基苯并噻唑为阳离子和硫酸氢根、对甲苯磺酸根为阴离子合成了4种功能化离子液体(ILs)。利用IR、1HNMR和MS对ILs进行结构表征;利用Hammett法和Ellman法对功能化离子液体的酸度和有效巯基含量等催化性能指标进行表征。同时,评价了该系列功能化离子液体在苯酚分别与环己酮、苯乙酮缩合反应中的催化效果,其中以阳离子结构中含有—SH、阴离子为对甲苯磺酸根的功能化离子液体对不同的酮底物均表现出良好的催化效果。考察反应温度对ILs催化酮酚缩合反应的影响,探究脂肪酮和芳酮的反应活性差异,结果表明,环己酮反应活性明显高于苯乙酮,且酚酮缩合反应是具有动力学和热力学控制特征的反应。基于实验结果分析了ILs催化酮酚缩合反应的可能机理。Four kinds of functional ionic liquids(ILs)are synthesized with 3-(benzothiazol-3-ium-3-yl)-propane-1-sulfonate and 3-(2-mercaptobenzothiazol-3-ium-3-yl)propane-1-sulfonate as cations,and bisulfate and p-toluenesulfate as anions.Their structure is characterized by means of IR,1HNMR and MS.Their catalytic properties such as acidity and effective thiol content are characterized through Hammett equation and Ellman method.Their catalytic effect on the condensation of phenol with cyclohexanone and acetophenone,respectively is evaluated.It is found that the prepared ILs containing sulfydryl in its cationic structure and taking p-toluenesulfonic group as anion always exhibits good catalytic effects on various ketone substrates.The influence of reaction temperature on the catalytic performance of ILs in catalyzing the condensation reaction of ketone with phenol is investigated,and the difference of reaction activity between fatty ketone and aromatic ketone with phenol is explored.The results indicate that the reaction activity of cyclohexanone is significantly higher than that of acetophenone,and the phenol-ketone condensation reaction is a reaction with kinetic and thermodynamic control characteristics.Based on experimental results,the possible mechanism of ILs in catalyzing the condensation reaction of ketone with phenol is given.

关 键 词：巯基官能团 功能化离子液体 双酚Z 双酚AP 环己酮 苯乙酮 

分 类 号：O621.251[理学—有机化学]