新型苯并噻唑离子液体的合成及其催化蓖麻油酸酯化研究
收稿日期: 2015-11-12
修回日期: 2015-12-21
网络出版日期: 2016-01-15
基金资助
国家林业局948项目基金(No.2015-4-55)资助项目.
Synthesis of Novel Benzothiazolium Ionic Liquids and Research on Their Catalytic Esterification for Ricinoleic Acid
Received date: 2015-11-12
Revised date: 2015-12-21
Online published: 2016-01-15
Supported by
Project supported by the 948 Project Foundation of State Forestry Administration (No. 2015-4-55).
以价格低廉的苯并噻唑为原料,合成了4种新型功能化布朗斯特酸性离子液体:苯并噻唑硫酸氢盐([HBth]-HSO4)、苯并噻唑磷酸二氢盐([HBth]H2PO4)、苯并噻唑高氯酸盐([HBth]ClO4)、苯并噻唑硝酸盐([HBth]NO3),其结构经FT-IR、HRMS、NMR表征得到确认.考察了4种酸性离子液体在蓖麻油酸和乙二醇丁醚(EGBE)酯化反应中的催化活性,并与以浓硫酸为催化剂的催化体系相对照.结果表明:当n(蓖麻油酸):n(乙二醇丁醚)=1:1.15,离子液体催化剂用量为蓖麻油酸重量的2%,反应温度90℃,反应时间5h,酯化率可达98.8%,离子液体催化剂经真空干燥重复使用10次后,仍具有较高的催化活性.还考察了以苯并噻唑硫酸氢盐为催化剂催化合成系列蓖麻油酸二元醇醚酯和短链脂肪酸酯,也获得了较高的酯化率,且离子液体均能与酯产物自动分相.与传统硫酸催化酯化相比,此类离子液体催化酯化具有生产成本低、过程清洁、使用周期长等优点,完全可以替代传统浓硫酸催化蓖麻油酸酯化反应.
张海飞 , 刘冬梅 , 康婷婷 , 王也 , 张小祥 , 朱新宝 . 新型苯并噻唑离子液体的合成及其催化蓖麻油酸酯化研究[J]. 有机化学, 2016 , 36(5) : 1104 -1110 . DOI: 10.6023/cjoc201511019
Four new task-specfic benzothiazolium ionic liquids (ILs) [HBth]HSO4, [HBth]H2PO4, [HBth]ClO4, [HBth]NO3 were synthesized and characterized by NMR and FT-IR, which bear the proton acid groups based on low price benzothiazole as raw material. The catalytic activities of these acidic ionic liquids were investigated by the esterification of ricinoleic acid with ethanol ethylene glycol monobutyl ether (EGBE) and were compared with concentrated sulfuric acid. The results showed that under the optimized conditions: n(Ricinoleic acid):n(EGBE)=1:1.15, catalyst dosage 2% (wt) of ricinoleic acid, reaction temperature 90 ℃ and reaction time 5 h, esterification yield was up to 98.8%. The ionic liquids dried in vacuum till remained high activity after reused for 10 times. Finally, the yields of series of ricinoleic acid binary alcohol ether ester and short-chain fatty acids ester were also high with [HBth]HSO4 as catalyst, and the ionic liquids can form split-phases with ester product. Compared with the traditional sulfuric acid catalytic esterification, catalytic esterification of such ionic liquid has the advantages of low production cost, clean process, low corrosion rate, reusable, and has the potential of replacing the traditional sulfuric acid in catalytic esterification reaction of ricinoleic acid.
Key words： benzothiazolium; ionic liquids; ricinoleic acid; esterification; catalytic activity
[1] Zeng, Q.-F.; Dong, G.-N. Tribol. Lett. 2013, 52, 47.
[2] Tong, L.-G.; Rong, H.; Lin, S.-J. J. Beijing Inst. Petro-Chem. Technol. 2010, 18, 58 (in Chinese).
(佟拉嘎, 荣华, 林世静, 北京石油化工学院学报, 2010, 18, 58.)
[3] Doudin, K.; A-Malaika, S.; Dole, H. Polym. Degrad. Stab. 2011, 96, 438.
[4] Dias, J.-M.; Araujo, J.-M.; Costa, J.-F. Energy2013, 53, 58.
[5] Amador, P.; Martinez, E.; Sanchez-Daza, O. J. Chem. Thermodyn. 2012, 50, 15.
[6] Wu, J. Agric. Mach. 2011, 61, 61 (in Chinese).
(吴杰, 农业机械, 2011, 61, 61.)
[7] Zhao, D.-B.; Fei, Z.-F.; Geldbach, T.-J.; Scopelliti, R.; Laurenczy, G.; Dyson, P.-J. J. Am. Chem. Soc. 2005, 88, 665.
[8] Inui, K.; Kurabayashi, T.; Sato, S.; Ichikawa, N. J. Mol. Catal A: Chem. 2004, 216, 147.
[9] Amador, P.; Martinez E, Sanchez-Daza O. J. Chem. Thermodyn.2012, 50, 15.
[10] Li, Y.; Hu, S.-L.; Cheng, J.-H.; Lou, W.-Y. Chin. J. Catal. 2014, 35, 396.
[11] Zhao, D.-S.; Liu, M.-S.; Ge, J.-J.; Zhang, J.; Ren, P.-B. Chin. J. Org. Chem. 2012, 32, 2382 (in Chinese).
(赵地顺, 刘猛帅, 葛京京, 张娟, 任培兵, 有机化学, 2012, 32, 2382.)
[12] Hou, H. L.; Li, Z. F.; Ying, A. G. Chin. J. Org. Chem. 2014, 34, 1277 (in Chinese).
(侯海亮, 李志峰, 应安国, 许松林, 有机化学, 2014, 34, 1277.)
[13] Peter, W.; Wilhelm, K. Angew. Chem., Int. Ed. 2000, 39, 3772.
[14] Plechkova, N.-V.; Seddon, K.-R. Chem. Soc. Rev. 2008, 370, 123.
[15] Tokuda, H.; Tsuzuki, S.; Susan, M. A.-B. H.; Hayamizu, K.; Watanabe, M. J. Chin. Phys. Chem. B 2006, 110, 19593.
[16] Song, Y.-L.; Wang, X.-C.; Huang, C.-P.; Liang, F.-B.; Liu, Z.-C.; Chen, B.-H. Chin. J. Org. Chem. 2013, 33, 1715.
[17] Jankovic, M. R.; Sinadinovic-Fiser, S. V.; Govedarica, O.-M. Ind. Eng. Chem. Res.2014, 53, 9357.
[18] Elsheikh, Y.-A. Energy Convers. Manage.2011, 52, 804.
[19] Liu, S.-W.; Li, L.; Yu, S.-T. Chin. J. Catal. 2010, 31, 1433.
[20] Earle, M.-J.; Seddon, K.-R. Pure Appl. Chem. 2000, 72: 1391-1398.
[21] Marsh, K.-N; Boxall, J.-A.; Lichtenthaler, R. Fluid Phase Equilib.2004, 219: 93~98.
[22] Wu, K.; Li, C.-X. Chin. J. Org. Chem. 2011, 31, 119 (in Chinese).
(吴坤, 李存雄, 有机化学, 2011, 31, 119.)
[23] Li, J.-Y.; Peng, J.-J.; Qiu, H.-Y.; Jiang, J.-X.; Wu, J.-R.; Ni, Y.; Lai, G.-Q. Chin. J. Org. Chem. 2007, 27, 483 (in Chinese).
(厉嘉云, 彭家建, 邱化玉, 蒋剑雄, 邬继荣, 倪勇, 来国桥, 有机化学, 2007, 27, 483.)
[24] Wang, Y.-Y.; Wu, Y.-T.; Liu, K.; Dai, L.-Y. Chin. Chem. Lett. 2012, 23, 1031.
[25] Venkataraman, V-R; Ali, K.-S. Indian J. Heterocycl. Chem. 2001, 11, 93.
[26] Zhao, D. S.; Liu, M. S.; Xu, Z. C.; F, J. T.; Ren, P. B. Chem. Ind. Eng. Prog. 2011, 30, 2287 (in Chinese).
(赵地顺, 刘猛帅, 徐智策, 付江涛, 任培兵, 化工进展, 2011, 30, 2287.)
[27] Wasserscheid, P.; Keim, W. Angew. Chem., Int. Ed. 2000, 39, 3772.
[28] Huddleston, J. G.; Visser, A. E.; Reichert, W. M.; Willauer, H. D.; Broker, G. A.; Rogers, R. D. Green. Chem. 2001, 3, 156.
[29] Fredakle, C.-P.; Crosthwaite, J.-M.; Hert, D.-G. J. Chem. Eng. Data 2004, 49, 954.
[30] Yang, L.; Lu, J.; Bai, Y. J. Chin.. J. Org. Chem. 2003, 23, 659 (in Chinese).
(杨玲, 路军, 白银娟, 有机化学, 2003, 23, 659.)
[31] Anthony, J. L.; Maginn, E. J.; Brennecke, J.-F. J. Phys. Chem. B2001, 105, 10942.
[32] Ji, S. X.; Zhao, Y. J.; He, C. Petrochem. Technol. 2010, 39, 251 (in Chinese).
(纪世雄, 赵义军, 何春, 石油化工, 2010, 39, 251.)
[33] Wang, Q.; Ma, R. X. J. Langzhou Univ. Technol. 2005, 31, 57 (in Chinese).
(王俏, 马荣萱, 兰州理工大学学报, 2005, 31, 57.)
[34] Zeng, H. Y.; Ying, S. F.; Li, Y. Chin. J. Org. Chem. 2007, 27, 528 (in Chinese).
(曾鸿耀, 尹述凡, 李颖, 有机化学, 2007, 27, 528.)
[35] Peng, Q.; Zhang, Y. W.; Wang, X. M. Chin. J. Synth. Chem. 2012, 20, 28 (in Chinese).
(彭琦, 张义文, 王小敏, 王卓端, 姚舜, 宋航, 合成化学, 2012, 20, 28.)
[36] Huang, B.-H.; Li, Z.-J.; Shi, N.; Xu, X.-L.; Fang, Y.-X. Chin. J. Org. Chem. 2009, 29, 770 (in Chinese).
(黄宝华, 黎子进, 史娜, 徐效陵, 张焜, 方岩雄, 有机化学, 2009, 29, 770.)
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