Citation: Fu-Rong Tao, Chen Zhuang, Yue-Zhi Cui, Jing Xu. Dehydration of glucose into 5-hydroxymethylfurfural in SO₃H-functionalized ionic liquids[J]. Chinese Chemical Letters, ;2014, 25(05): 757-761. doi: 10.1016/j.cclet.2014.01.044 shu

Dehydration of glucose into 5-hydroxymethylfurfural in SO₃H-functionalized ionic liquids

1.
Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Ji'nan 250353, China

Corresponding author: Fu-Rong Tao,
Received Date: 11 November 2013
Available Online: 15 January 2014
Fund Project: We gratefully acknowledge the financial support of the National Natural Science Foundation of China (No. 21276149) (No. 21276149)the Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Province. (No. ZR2013BQ014)

The continuous dehydration of D-glucose into 5-hydroxymethylfurfural (HMF) was carried out under mild conditions, using SO₃H-functionalized acidic ionic liquids as catalysts and H₂O-4-methyl-2- pentanone (MIBK) biphasic system as solvent. High glucose conversion of 97.4% with HMF yield of 75.1% was obtained at 120 ℃ for 360 min, also, small amounts of levulinic acid (LA) and formic acid were generated. Generally, the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction. The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs. This paper provided a new strategy for HMF production from glucose.
- Glucose,
- Dehydration,
- HMF,
- Acidic ionic liquids
1. [1]
  [1] G. Yong, Y.G. Zhang, J.Y. Ying, Efficient catalytic system for the selective production of 5-hydroxymethylfurfural from glucose and fructose, Angew. Chem. Int. Ed. 47 (2008) 9345-9348.
2. [2]
  [2] F. Benvenuti, C. Carlini, P. Patrono, et al., Heterogeneous zirconium and titanium catalysts for the selective synthesis of 5-hydroxymethyl-2-furaldehyde from carbohydrates, Appl. Catal. A: Gen. 193 (2000) 147-153.
3. [3]
  [3] A.A. Rosatella, S.P. Simeonov, C.A.M. Afonso, et al., Supported ionic liquid silica nanoparticles (SILnPs) as an efficient and recyclable heterogeneous catalyst for the dehydration of fructose to 5-hydroxymethylfurfural, Green Chem. 13 (2011) 754-793.
4. [4]
  [4] F.M.A. Geilen, J. Klankermayer, W. Leitner, et al., Selective and flexible transformation of biomass-derived platform chemicals by a multifunctional catalytic system, Angew. Chem. Int. Ed. 49 (2010) 5510-5514.
5. [5]
  [5] K.I. Shimizu, R. Uozumi, A. Satsuma, Enhanced production of hydroxymethylfurfural from fructose with solid acid catalysts by simple water removal methods, Catal. Commun. 10 (2009) 1849-1853.
6. [6]
  [6] J.Y.G. Chan, Y.G. Zhang, Phosphotungstic acid encapsulated in metal-organic framework as catalysts for carbohydrate dehydration to 5-hydroxymethylfurfural, Chemsuschem 2 (2009) 731-734.
7. [7]
  [7] H.P. Yan, Y. Yang, D.M. Tong, et al., Catalytic conversion of glucose to 5-hydroxymethylfurfural over SO₄^-2/ZrO₂ and SO₄^-2/ZrO₂-Al₂O₃ solid acid catalysts, Catal. Commun. 10 (2009) 1558-1563.
8. [8]
  [8] Y.M. Zhang, V. Degirmenci, C. Li, E.J.M. Hensen, Phosphotungstic acid encapsulated in metal-organic framework as catalysts for carbohydrate dehydration to 5- hydroxymethylfurfural, Chemsuschem 4 (2011) 59-64.
9. [9]
  [9] Z.H. Zhang, Z.K. Zhao, Production of 5-hydroxymethylfurfural from glucose catalyzed by hydroxyapatite supported chromium chloride, Bioresour. Technol. 102 (2011) 3970-3972.
10. [10]
  [10] R.L. Huang, W. Qi, R.X. Su, et al., Integrating enzymatic and acid catalysis to convert glucose into 5-hydroxymethylfurfural, Chem. Commun. 46 (2010) 1115- 1117.
11. [11]
  [11] M. Bicker, J. Hirth, H. Vogel, Dehydration of fructose to 5-hydroxymethylfurfural in sub and supercritical acetone, Green Chem. 5 (2003) 280-284.
12. [12]
  [12] M. Watanable, Y. Aizawa, T. Iida, et al., Glucose reactions with acid and base catalysts in hot compressed water at 473 K, Carbohydr. Res. 340 (2005) 1925- 1930.
13. [13]
  [13] Y. Nakamura, S. Morikawa, The dehydration of D-fructose to 5-hydroxymethyl-2- furaldehyde, Bull. Chem. Soc. Jpn. 53 (1980) 3705-3706.
14. [14]
  [14] K.I. Seri, Y. Inoue, H. Ishida, Highly efficient catalytic activity of lanthanide(Ⅲ) ions for conversion of saccharides to 5-hydroxymethyl-2-furfural in organic solvents, Chem. Lett. 29 (2000) 22-23.
15. [15]
  [15] K. Seri, Y. Inoue, H. Ishida, Catalytic activity of lanthanide(Ⅲ) ions for the dehydration of hexose to 5-hydroxymethyl-2-furaldehyde in water, Bull. Chem. Soc. Jpn. 74 (2001) 1145-1150.
16. [16]
  [16] F.S. Asghari, H. Yoshida, Acid-catalyzed production of 5-hydroxymethyl furfural from d-fructose in subcritical water, Ind. Eng. Chem. Res. 45 (2006) 2163-2173.
17. [17]
  [17] R.P. Swatloski, S.K. Spear, Y. Aizawa, R.D. Rogers, A novel cellulose hydrogel prepared from its ionic liquid solution, J. Am. Chem. Soc. 124 (2002) 4974-4975.
18. [18]
  [18] X. Tong, Y. Ma, Y. Li, An efficient catalytic dehydration of fructose and sucrose to 5- hydroxymethylfurfural with protic ionic liquids, Cabohydr. Res. 345 (2010) 1698- 1701.
19. [19]
  [19] H. Zhao, J.E. Holladay, H. Brown, Z.C. Zhang, Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural, Science 316 (2007) 1597- 1599.
20. [20]
  [20] M. Lu, X.H. Guan, X.H. Xu, D.Z. Wei, Characteristic and mechanism of Cr(VI) adsorption by ammonium sulfamate-bacterial cellulose in aqueous solutions, Chin. Chem. Lett. 24 (2013) 253-256.
21. [21]
  [21] Y. Román-Leshkov, J.N. Chheda, J.A. Dumesic, Phase modifiers promote efficient production of hydroxymethylfurfural from fructose, Science 312 (2006) 1933- 1937.
22. [22]
  [22] F. Tao, H. Song, L. Chou, Efficient process for the conversion of xylose to furfural with acidic ionic liquid, Can. J. Chem. 89 (2011) 83-87.
23. [23]
  [23] K. Niknam, M. Damya, 1-Butyl-3-methylimidazolium hydrogen sulfate[bmim]HSO₄: an efficient reusable acidic ionic liquid for the synthesis of 1,8- dioxo-octahydroxanthenes, J. Chin. Chem. Soc. 56 (2009) 659-665.
24. [24]
  [24] A.C. Cole, J.L. Jensen, L. Ntai, et al., Novel Brønsted acidic ionic liquids and their use as dual solvent-catalysts, J. Am. Chem. Soc. 124 (2002) 5962-5963.
25. [25]
  [25] Q. Zhao, L. Wang, S. Zhao, et al., High selective production of 5-hydroymethylfurfural from fructose by a solid heteropolyacid catalyst, Fuel 90 (2011) 2289- 2293.
26. [26]
  [26] B.F.M. Kuster, 5-Hydroxymethylfurfural (HMF). A review focussing on its manufacture, Starch 42 (1990) 314-321.
27. [27]
  [27] X.H. Qi, M. Watanabe, R.L. Smith, et al., Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids, Green Chem. 11 (2009) 1327- 1331.
28. [28]
  [28] S.Q. Hu, Z.F. Zhang, Y.X. Zhou, et al., Conversion of fructose to 5-hydroxymethylfurfural using ionic liquids prepared from renewable materials, Green Chem. 10 (2008) 1280-1283.
29. [29]
  [29] X.H. Qi, M. Watanabe, T.M. Aida, et al., Efficient conversion of glucose into 5- hydroxymethylfurfural catalyzed by a common Lewis acid SnCl4 in an ionic liquid, Green Chem. 11 (2009) 1327-1331.
1. [1]
  Erzhuo Cheng , Yunyi Li , Wei Yuan , Wei Gong , Yanjun Cai , Yuan Gu , Yong Jiang , Yu Chen , Jingxi Zhang , Guangquan Mo , Bin Yang . Galvanostatic method assembled ZIFs nanostructure as novel nanozyme for the glucose oxidation and biosensing. Chinese Chemical Letters, 2024, 35(9): 109386-. doi: 10.1016/j.cclet.2023.109386
2. [2]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
3. [3]
  Zhi-Yuan Yue , Hua-Kai Li , Na Wang , Shan-Shan Liu , Le-Ping Miao , Heng-Yun Ye , Chao Shi . Dehydration-triggered structural phase transition-associated ferroelectricity in a hybrid perovskite-type crystal. Chinese Chemical Letters, 2024, 35(10): 109355-. doi: 10.1016/j.cclet.2023.109355
4. [4]
  Jiahui Li , Qiao Shi , Ying Xue , Mingde Zheng , Long Liu , Tuoyu Geng , Daoqing Gong , Minmeng Zhao . The effects of in ovo feeding of selenized glucose on liver selenium concentration and antioxidant capacity in neonatal broilers. Chinese Chemical Letters, 2024, 35(6): 109239-. doi: 10.1016/j.cclet.2023.109239
5. [5]
  Kezuo Di , Jie Wei , Lijun Ding , Zhiying Shao , Junling Sha , Xilong Zhou , Huadong Heng , Xujing Feng , Kun Wang . A wearable sensor device based on screen-printed chip with biofuel cell-driven electrochromic display for noninvasive monitoring of glucose concentration. Chinese Chemical Letters, 2025, 36(2): 109911-. doi: 10.1016/j.cclet.2024.109911
6. [6]
  Yixia Zhang , Caili Xue , Yunpeng Zhang , Qi Zhang , Kai Zhang , Yulin Liu , Zhaohui Shan , Wu Qiu , Gang Chen , Na Li , Hulin Zhang , Jiang Zhao , Da-Peng Yang . Cocktail effect of ionic patch driven by triboelectric nanogenerator for diabetic wound healing. Chinese Chemical Letters, 2024, 35(8): 109196-. doi: 10.1016/j.cclet.2023.109196
7. [7]
  Pei Cao , Yilan Wang , Lejian Yu , Miao Wang , Liming Zhao , Xu Hou . Dynamic asymmetric mechanical responsive carbon nanotube fiber for ionic logic gate. Chinese Chemical Letters, 2024, 35(6): 109421-. doi: 10.1016/j.cclet.2023.109421
8. [8]
  Qiangwei Wang , Huijiao Liu , Mengjie Wang , Haojie Zhang , Jianda Xie , Xuanwei Hu , Shiming Zhou , Weitai Wu . Observation of high ionic conductivity of polyelectrolyte microgels in salt-free solutions. Chinese Chemical Letters, 2024, 35(4): 108743-. doi: 10.1016/j.cclet.2023.108743
9. [9]
  Zimo Peng , Quan Zhang , Gaocan Qi , Hao Zhang , Qian Liu , Guangzhi Hu , Jun Luo , Xijun Liu . Nanostructured Pt@RuOx catalyst for boosting overall acidic seawater splitting. Chinese Journal of Structural Chemistry, 2024, 43(1): 100191-100191. doi: 10.1016/j.cjsc.2024.100191
10. [10]
  Hang Chen , Chengzhi Cui , Hebo Ye , Hanxun Zou , Lei You . Enhancing hydrolytic stability of dynamic imine bonds and polymers in acidic media with internal protecting groups. Chinese Chemical Letters, 2024, 35(5): 109145-. doi: 10.1016/j.cclet.2023.109145
11. [11]
  Yuanzhe Lu , Yuanqin Zhu , Linfeng Zhong , Dingshan Yu . Long-lifespan aqueous alkaline and acidic batteries enabled by redox conjugated covalent organic polymer anodes. Chinese Journal of Structural Chemistry, 2024, 43(3): 100249-100249. doi: 10.1016/j.cjsc.2024.100249
12. [12]
  Qiyan Wu , Ruixin Zhou , Zhangyi Yao , Tanyuan Wang , Qing Li . Effective approaches for enhancing the stability of ruthenium-based electrocatalysts towards acidic oxygen evolution reaction. Chinese Chemical Letters, 2024, 35(10): 109416-. doi: 10.1016/j.cclet.2023.109416
13. [13]
  Ling Tang , Yan Wan , Yangming Lin . Lowering the kinetic barrier via enhancing electrophilicity of surface oxygen to boost acidic oxygen evolution reaction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100345-100345. doi: 10.1016/j.cjsc.2024.100345
14. [14]
  Tong Zhang , Xiaojing Liang , Licheng Wang , Shuai Wang , Xiaoxiao Liu , Yong Guo . An ionic liquid assisted hydrogel functionalized silica stationary phase for mixed-mode liquid chromatography. Chinese Chemical Letters, 2025, 36(1): 109889-. doi: 10.1016/j.cclet.2024.109889
15. [15]
  Yanfei Liu , Yaqin Hu , Yifu Tan , Qiwen Chen , Zhenbao Liu . Tumor acidic microenvironment activatable DNA nanostructure for precise cancer cell targeting and inhibition. Chinese Chemical Letters, 2025, 36(1): 110289-. doi: 10.1016/j.cclet.2024.110289
16. [16]
  Jiajia Wang , XinXin Ge , Yajing Xiang , Xiaoliang Qi , Ying Li , Hangbin Xu , Erya Cai , Chaofan Zhang , Yulong Lan , Xiaojing Chen , Yizuo Shi , Zhangping Li , Jianliang Shen . An ionic liquid functionalized sericin hydrogel for drug-resistant bacteria-infected diabetic wound healing. Chinese Chemical Letters, 2025, 36(2): 109819-. doi: 10.1016/j.cclet.2024.109819
17. [17]
  Congyan Liu , Xueyao Zhou , Fei Ye , Bin Jiang , Bo Liu . Confined electric field in nano-sized channels of ionic porous framework towards unique adsorption selectivity. Chinese Chemical Letters, 2025, 36(2): 109969-. doi: 10.1016/j.cclet.2024.109969
18. [18]
  Ping Wang , Ting Wang , Ming Xu , Ze Gao , Hongyu Li , Bowen Li , Yuqi Wang , Chaoqun Qu , Ming Feng . Keplerate polyoxomolybdate nanoball mediated controllable preparation of metal-doped molybdenum disulfide for electrocatalytic hydrogen evolution in acidic and alkaline media. Chinese Chemical Letters, 2024, 35(7): 108930-. doi: 10.1016/j.cclet.2023.108930
19. [19]
  Luyu Zhang , Zirong Dong , Shuai Yu , Guangyue Li , Weiwen Kong , Wenjuan Liu , Haisheng He , Yi Lu , Wei Wu , Jianping Qi . Ionic liquid-based in situ dynamically self-assembled cationic lipid nanocomplexes (CLNs) for enhanced intranasal siRNA delivery. Chinese Chemical Letters, 2024, 35(7): 109101-. doi: 10.1016/j.cclet.2023.109101
20. [20]
  Zhenyu Hu , Zhenchun Yang , Shiqi Zeng , Kun Wang , Lina Li , Chun Hu , Yubao Zhao . Cationic surface polarization centers on ionic carbon nitride for efficient solar-driven H₂O₂ production and pollutant abatement. Chinese Chemical Letters, 2024, 35(10): 109526-. doi: 10.1016/j.cclet.2024.109526

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(681)
HTML views(17)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Dehydration of glucose into 5-hydroxymethylfurfural in SO3H-functionalized ionic liquids

Metrics

通讯作者: 陈斌, bchen63@163.com

Dehydration of glucose into 5-hydroxymethylfurfural in SO₃H-functionalized ionic liquids