有机化学 ›› 2015, Vol. 35 ›› Issue (4): 890-897.DOI: 10.6023/cjoc201409040 上一篇    下一篇

研究简报

新型异核双阳离子型磺酸功能化离子液体的合成及其催化活性

崔文辉a,b, 张有明b, 贾如琰a, 王昱a, 魏太保,b   

  1. a 陇南师范高等专科学校生化系 成县 742500;
    b 西北师范大学化学化工学院 教育部生态环境相关材料重点实验室 甘肃省高分子材料重点实验室 兰州 730070
  • 收稿日期:2014-09-24 修回日期:2014-12-01 出版日期:2015-04-25 发布日期:2015-01-06
  • 通讯作者: 崔文辉 E-mail:cwh0939@126.com
  • 基金资助:

    甘肃省自然科学基金(No. 1107RJZK243)资助项目.

Synthesis and Catalytic Activity of Novel Heternuclear Dication Brønsted Acidic Ionic Liquids

Cui Wenhuia,b, Zhang Youmingb, Jia Ruyana, Wang Yua, Wei Taibao,b   

  1. a Department of Biology & Chemistry, Longnan Normal College, Chengxian 742500;
    b Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070
  • Received:2014-09-24 Revised:2014-12-01 Online:2015-04-25 Published:2015-01-06
  • Supported by:

    Project supported by the Natural Science Foundation of Gansu Province (No. 1107RJZK243).

合成了三种基于1-吗啉基-3-咪唑基丙烷异核双阳离子的新型二磺酸功能化Brøsted酸性离子液体: 1-[4-(4-磺酸丁基)吗啉基-3-[3-(4-磺酸丁基)咪唑基]丙烷二(三氟甲烷磺酸)盐{A, [(C4SO3H)m(C4SO3H)i]p(OTf)2}、1-[4-(4-磺酸丁基)吗啉基-3-[3-(4-磺酸丁基)咪唑基]丙烷二硫酸氢盐{B, [(C4SO3H)m(C4SO3H)i]p(HSO4)2}及1-[4-(4-磺酸丁基)吗啉基-3-[3-(4-磺酸丁基)咪唑基]丙烷二磷酸二氢盐{C, [(C4SO3H)m(C4SO3H)i]p(H2PO4)2}. 其结构经FT-IR、MS、NMR等确认. 选择吗啉、甲基咪唑单磺酸功能化离子液体作为对照组, 以苯甲醛与环己酮之间的交叉Aldol缩合反应考察了其催化活性. 用Hammett方法测定了其酸性, 实验结果表明, 所合成的三种双磺酸功能化离子液体的催化能力比单磺酸功能化离子液体的强, 其酸性次序与催化活性相一致. 其中, 阴离子为三氟甲烷磺酸根的离子液体对18种Aldol缩合反应底物有极好的适应性, 并且催化活性最强, 产率高达90%, 在重复使用10次后, 仍保持较高的反应活性.

关键词: 二磺酸功能化离子液体, 合成, 催化活性, Hammett方法, 交叉Aldol缩合反应, 重复使用

Three new Brøsted-acidic task-specfic ionic liquids (TSILS) that bear two butane sulfonic acid groups based on 1-(morpholinyl-4-yl)-3-(imidazolyl-1-yl)propane (mip) heternuclear dication: 1-[4-(4-sulfobutyl)morpholinium-4-yl]-3-[3-(4- sulfobutyl)-1H-imidazolium-1-yl]propane bis(trifluoromethane sulfonate) {A, [(C4SO3H)m(C4SO3H)i]p(OTf)2}, 1-[4-(sul- fobutyl)morpholinium-4-yl]-3-[3-(4-sulfobutyl)-1H-imidazolium-1-yl]propane bis(hydrogen sulfate) {B, [(C4SO3H)m(C4SO3- H)i]p(HSO4)2} and 1-[4-(4-sulfobutyl)morpholinium-4-yl]-3-[3-(4-sulfobutyl)-1H-imidazolium-1-yl]propane bis(bihydrogen phosphate) {C, [(C4SO3H)m(C4SO3H)i]p(H2PO4)2} were synthesized and characterized by NMR and FT-IR. The imidazolium-based and morpholinium-based single-SO3H functionalized acidic ionic liquids were used for comparison. Their catalytic activities were investigated in crossed-aldol condensation between cycloalkanone and various aromatic aldehydes. Hammett method has been used to determine the acidity order of these ionic liquids (ILs). The experiment results have shown that the catalytic activities of the three bi-SO3H-functionalized ILs were stronger than those of single SO3H functionalized ILs. Their acidity orders were consistent with their catalytic activities. Good adaptability to the reaction substrate and maximum product yield of 90% was observed when [(C4SO3H)m(C4SO3H)i]p(OTf)2 was used as catalyst and the catalyst can be reused at least ten times without obvious activity loss.

Key words: bi-SO3H-functionalized ionic liquids, synthesis, catalytic activity, crossed aldol reaction, Hammett method, reusability