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.

鲁鑫鑫(1997-),女,硕士生,研究方向为绿色有机催化,18669331224@163.com;于丽梅(1971-),女,博士,副教授,研究方向为绿色有机催化,通讯联系人,ochem@dlut.edu.cn。