Microwave-Assisted Alcoholysis of Cellulose to Methyl Levulinate Catalyzed by SnCl4/H2SO4

doi:10.6023/cjoc201511015

Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (6): 1438-1443.DOI: 10.6023/cjoc201511015 Previous Articles Next Articles

Notes

微波辅助SnCl₄/H₂SO₄二元体系催化纤维素醇解制备乙酰丙酸甲酯

黄耀兵, 杨涛, 刘安凤, 周新成, 潘晖

南京林业大学化学与工程学院南京 210037

收稿日期:2015-11-09 修回日期:2015-12-28 发布日期:2016-02-01
通讯作者: 黄耀兵, 潘晖 E-mail:hyb@njfu.edu.cn;hpan@njfu.edu.cn
基金资助:
国家自然科学基金(No.21502095)、江苏省自然科学基金(No.BK20150872)和江苏省生物质绿色燃料和化学品重点实验室开放基金(No.14003)资助项目.

Microwave-Assisted Alcoholysis of Cellulose to Methyl Levulinate Catalyzed by SnCl₄/H₂SO₄

Huang Yaobing, Yang Tao, Liu Anfeng, Zhou Xincheng, Pan Hui

College of Chemical and Engineering, Nanjing Forestry University, Nanjing 210037

Received:2015-11-09 Revised:2015-12-28 Published:2016-02-01
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21502095), the Natural Science Foundation of Jiangsu Province (No. BK20150872) and the Opening Fund from Jiangsu Key Laboratory of Biomass-based Green Fuels and Chemicals (No. 14003).

1. Microwave-Assisted Alcoholysis of Cellulose to Methyl Levulinate Catalyzed by SnCl₄/H₂SO₄.PDF(665KB)

Abstract

Microwave irradiation technology was used to assist the conversion of cellulose to methyl levulinate (ML) in methanol solution in the presence of mixed catalysts. The reactions were carried out in a microwave reactor and cellulose was rapidly converted into ML with a highest yield of 61.5% by the use of SnCl₄/H₂SO₄ as catalyst. The catalysts ratios, reaction time and reaction temperature were optimized and found to have great influences on both the ML product yield and the selectivity. Besides, an appropriate amount of water, which may participate the breakage of the glucosidic bond of cellulose, is highly desirable for the full conversion of cellulose. Several other biomass derived carbohydrates such as starch, sucrose and inulin were also tested in the optimized system and 48%~60% ML yields were achieved. Finally, the mixed catalysts can be recycled and reused for at least five times without much decrease in catalytic activity.

Key words: cellulose, methyl levulinate, microwave irradiation, alcoholysis

Cite this article

Huang Yaobing, Yang Tao, Liu Anfeng, Zhou Xincheng, Pan Hui. Microwave-Assisted Alcoholysis of Cellulose to Methyl Levulinate Catalyzed by SnCl₄/H₂SO₄[J]. Chin. J. Org. Chem., 2016, 36(6): 1438-1443.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Chen, X.; Han, Z. Q.; Kong, F. H.; Hu, X. T. Prog. Chem. 2007, 19, 1091 (in Chinese). (陈曦, 韩志群, 孔繁华, 胡徐腾, 化学进展, 2007, 19, 1091.)
[2] Hu, L.; Sun, Y.; Lin, L. Prog. Chem. 2012, 24, 483 (in Chinese). (胡磊, 孙勇, 林鹿, 化学进展, 2012, 24, 483.)
[3] Wu, S. C.; Wang, C. L.; Gao, Y. J.; Zhang, S. C.; Ma, D.; Zhao, Z. B. Chin. J. Catal. 2010, 31, 1157 (in Chinese). (吴树昌, 王春雷, 高勇军, 张少春, 马丁, 赵宋保, 催化学报, 2010, 31, 1157.)
[4] Peng, L. C.; Lin, L.; Li, H. Prog. Chem. 2012, 24, 801 (in Chinese). (彭林才, 林鹿, 李辉, 化学进展, 2012, 24, 801.)
[5] Runge, T.; Zhang, C. Ind. Eng. Chem. Res. 2012, 51, 3265.
[6] Yang, Z.; Fu, Y.; Guo, Q. X. Chin. J. Org. Chem. 2015, 35, 273 (in Chinese). (杨珍, 傅尧, 郭庆祥, 有机化学, 2015, 35, 273.)
[7] Zhang, T.; Chang, C. Chem. Ind. Eng. Prog. 2012, 31, 1224 (in Chinese). (张婷, 常春, 化工进展, 2012, 31, 1224.)
[8] Joshi, H.; Moser, B. R.; Toler, J.; Smith, W. F.; Walker, T. Biomass Bioenergy 2011, 35, 3262.
[9] Chia, M.; Dumesic, J. A. Chem. Commun. 2011, 47, 12233.
[10] Huang, Y.; Dai, J.; Deng, X.; Qu, Y.; Guo, Q.; Fu, Y. ChemsusChem 2011, 4, 1578.
[11] Alexandre, D.; Nadine, E.; Franck, R. ACS Sustainable Chem. Eng. 2014, 2, 1338.
[12] Climent, M. J.; Corma, A.; Iborra, S. Green Chem. 2014, 16, 516.
[13] Melero, J. A.; Morales, G.; Iglesias, J.; Paniagua, M.; Hernandez, B.; Penedo, S. Appl. Catal., A 2013, 466, 116.
[14] Huang, Y. B.; Yang, T.; Zhou, M. C.; Pan, H.; Fu, Y. Green Chem. 2016, 18, 1516.
[15] Liu, D.; Lin, L.; Zeng, S. S.; Peng, L. C. Chem. Ind. Forest Prod. 2013, 33, 66 (in Chinese). (刘娣, 林鹿, 曾姗姗, 彭林才, 林产化学与工业, 2013, 33, 66.)
[16] Yu, K. M. K.; Tsang, S. C. Catal. Lett. 2011, 141, 259.
[17] Tominaga, K.; Mori, A.; Fukushima, Y.; Shimada, S.; Sato, K. Green Chem. 2011, 13, 810.
[18] Ma, H.; Long, J. X.; Wang, F. R.; Wang; L. F.; Li, X. H. Acta Phys. Chim. Sin. 2015, 31, 973 (in Chinese). (马浩, 龙金星, 王芙蓉, 王乐夫, 李雪辉, 物理化学学报, 2015, 31, 973.)
[19] Sun, P. Q.; Zhao, S. Q.; Chang, Q.; Chen, J. W. J. Zhengzhou Univ. 2014, 35, 22 (in Chinese). (孙培勤, 赵世强, 常春, 陈俊武, 郑州大学学报, 2014, 35, 22.)
[20] Ding, D. Q.; Xi, J. X.; Wang, J. J.; Liu, X. H.; Lu, G. Z.; Wang, Y. Q. Green Chem. 2015, 17, 4037.
[21] Hishikawa, Y.; Yamaguchi, M.; Kubo, S.; Yamada, T. J. Wood Sci. 2013, 59, 179.
[22] Li, J.; Huang, Y. B.; Guo, Q. X.; Fu, Y. Acta Chim. Sinica 2014, 72, 1223 (in Chinese). (李江, 黄耀兵, 郭庆祥, 傅尧, 化学学报, 2014, 72, 1223.)
[23] Wu, X.; Fu, J.; Lu, X. Carbohydr. Res. 2012, 358, 37.
[24] Chang, C.; Jiang, X. X.; Zhang, T. Adv. Mater. Res. 2012, 512, 388.
[25] Peng, L.; Lin, L.; Li, H.; Yang, Q. Appl. Energ. 2011, 88, 4590.

微波辅助SnCl₄/H₂SO₄二元体系催化纤维素醇解制备乙酰丙酸甲酯

Microwave-Assisted Alcoholysis of Cellulose to Methyl Levulinate Catalyzed by SnCl₄/H₂SO₄

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Xin Chen, Chunxia Chen, Jinsong Peng. Research Progress of Cellulose and Its Derivatives Supported Copper Catalyst Catalyzed Organic Reactions [J]. Chinese Journal of Organic Chemistry, 2021, 41(4): 1319-1336.
[2]	Xie Tinghui, Jiang Xiaoying, Mi Zhisheng, Li Xue, Xu Xiaohe, Bai Renren, Shuai Qi, Xie Yuanyuan. Iron/O₂-Promoted C-H Bond Functionalization for the Exclusive Synthesis of 2-Quinoline Carboxaldehydes under Microwave Irradiation [J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3294-3298.
[3]	Zong Chaoyang, Gu Huiwen, Zhang Lijie, Jin Yudong, Sun Yaquan. Microwave-Accelerated Dimroth Rearrangement for the Synthesis of Pyrido [2, 3-d]pyrimidin-4-amine Derivatives [J]. Chin. J. Org. Chem., 2018, 38(5): 1165-1171.
[4]	Qu Renyu, Chen Nian, Liu Yuchao, Chen Qiong, Yang Guangfu. An Efficient Synthesis of Functionalized 6-Arylsubstituted Salicylates via Microwave Irradiation [J]. Chin. J. Org. Chem., 2017, 37(5): 1266-1272.
[5]	Zhang Bianxiang, Yang Lihua, Shi Ruixue, Kang Yongqiang. Synthesis of Heterocyclic Aromatic Sulfides under Microwave Irradiation [J]. Chin. J. Org. Chem., 2016, 36(2): 352-357.
[6]	Zhang Rui, Pan Jinhuan, Wu Qiongyou. Copper Mediated One-Pot Multi-Component Synthesis of 3-Substitued Isoquinolines [J]. Chin. J. Org. Chem., 2016, 36(12): 2906-2911.
[7]	Zhu Jihua, Zheng Xudong, Guo Guozhe, Zhang Yuquan, Wu Bowan. Microwave-Assisted Synthesis of Asymmetrical 1,5-Disubstituted Carbonohydrazide and Crystal Structure [J]. Chin. J. Org. Chem., 2015, 35(9): 1975-1980.
[8]	Feng Junna, Li Xiaohui, Shao Jie, Zhu Mo, Li Yan, Chen Hua, Li Xiaoliu. Microwave Assisted Synthesis and Anti-HIV-RT Activity of Diaryl Benzo[1,3]thiazin-4-ones [J]. Chin. J. Org. Chem., 2015, 35(6): 1370-1374.
[9]	Wang Juxian, Lin Wei, Liu Hongtao, Hu Minghua, Feng Xian, Ren Jinfeng, Huang Zhibin, Shi Daqing. An Efficient Synthesis of Coumarino[4,3-d]pyrazolo[3,4-b]-pyridine Derivatives Catalyzed by Silica Sulfuric Acid under Microwave Irradiation [J]. Chin. J. Org. Chem., 2015, 35(4): 927-933.
[10]	Li Yingjun, Shi Xiangling, Gao Lixin, Jin Kun, Sheng Li, Wu Jianghong, Peng Lina, Li Jia. Synthesis, Characterization and Biological Activities of 3,5,6-Trisubstituted-1,2,4-triazine Derivatives [J]. Chin. J. Org. Chem., 2015, 35(1): 191-199.
[11]	Zhao Yunhui, Ren Xinfang, Liu Hanwen, Tang Zilong. Study on Synthesis of ortho-Hydroxyl Aromatic N-tert-Butylsulfinyl Imines under Microwave Irradiation [J]. Chin. J. Org. Chem., 2014, 34(6): 1218-1221.
[12]	Chen Hua, Huang Changjun, Zhu Mo, Li Xiaoliu. Synthesis and Anti-HIV-RT Activity of Novel Thiazolindin-4-one Derivatives Possessing Hydrophilic Groups [J]. Chin. J. Org. Chem., 2014, 34(4): 756-760.
[13]	Yang Jiaqiang, Ma Jun, Che Wanli, Li Minggang, Li Gang, Song Baoan. Microwave-Assisted Synthesis and Antitumor Activity of Salicyl Acyloxy Phosphonate Derivatives [J]. Chin. J. Org. Chem., 2014, 34(12): 2566-2571.
[14]	Tong Guangjin, Fan Wei, Jiang Bo. Three-Component Synthesis of Oxazolo[3,4-b]quinoline Derivatives [J]. Chin. J. Org. Chem., 2013, 33(12): 2578-2582.
[15]	Sun Hongshun, Wang Jianqiang, Guo Cheng, Shen Linjiang. Synthesis of 5-Amino-2-oxo-7-aryl-2,3,4,7-tetrahydro-1,3-thiazolo[4,5-b]pyridine-6-carboxamide Derivatives under Microwave Irradiation [J]. Chin. J. Org. Chem., 2013, 33(10): 2220-2225.

微波辅助SnCl4/H2SO4二元体系催化纤维素醇解制备乙酰丙酸甲酯