Synthesis of renewable monomer 2, 5-bishydroxymethylfuran from highly concentrated 5-hydroxymethylfurfural in deep eutectic solvents

Ting Wang; Junnan Wei; Huai Liu; Yunchao Feng; Xing Tang; Xianhai Zeng; Yong Sun; Tingzhou Lei; Lu Lin

Journal of Industrial and Engineering Chemistry, Vol.81, 93-98, January, 2020

DOI10.1016/j.jiec.2019.08.057 Export Citation

Synthesis of renewable monomer 2, 5-bishydroxymethylfuran from highly concentrated 5-hydroxymethylfurfural in deep eutectic solvents

Ting Wang¹, Junnan Wei¹, Huai Liu¹, Yunchao Feng¹, Xing Tang^{1, 2, †}, Xianhai Zeng^{1, 2}, Yong Sun^{1, 2}, Tingzhou Lei³, and Lu Lin^{1, 2, †}

¹Xiamen Key Laboratory of Clean and High-valued Applications of Biomass, College of Energy, Xiamen University, Xiamen 361102, China
²Fujian Engineering and Research Center of Clean and High-valued Technologies for Biomass, Xiamen University, Xiamen 361102, China
³Henan Key Lab of Biomass Energy, Henan 450008, China

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2, 5-Bishydroxymethylfuran (BHMF) has been currently emerged as a promising biomass-derived monomer. It is highly desirable to proceed a chemical process at a high substrate concentration, by which a facile and cost-effective separation of products can be expected. Herein, we report for the first time on the hydrogenation of highly concentrated 5-hydroxymethylfurfural (HMF) in deep eutectic solvents (DESs), giving a near quantitative selectivity towards BHMF in ChCl-glycerol DES at 25 °C in 3 h using NaBH4 as the H-donor. DES is hailed as a new class of green solvent, in which HMF/BHMF could be stabilized by the strong hydrogen-bond interaction, and allowed the selective hydrogenation of HMF at high concentration up to 40 wt%. Notably, the resulting BHMF could be facilely separated by extraction with ethyl acetate, and then high purity of BHMF with a desirable isolated yield around 80% was obtained after removing of ethyl acetate. Additionally, the reaction efficiency of HMF hydrogenation in DESs was verified to be strongly associated with the viscosity of DESs and the pKa value of hydrogen-bonding donor.

Keywords:Biomass;5-Hydroxymethylfurfural;2;5-Bishydroxymethylfuran;Deep eutectic solvents;Hydrogen-bonding interaction

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[Referenced By]

[1] Corma A, Iborra S, Velty A, Chem. Rev., 107(6), 2411 (2007)

[2] Pang Z, Dong C, Pan X, Cellulose, 23, 323 (2016)

[3] Li C, Cai H, Zhang B, Li W, Pei G, Dai T, Wang A, Zhang T, Chin. J. Catal., 36, 1638 (2015)

[4] Agarwal B, Kailasam K, Sangwan RS, Elumalai S, Renew. Sust. Energ. Rev., 82, 2408 (2018)

[5] Perez GP, Mukherjee A, Dumont MJ, J. Ind. Eng. Chem., 70, 1 (2019)

[6] Li XLH, Yang T, ChemSusChem, 10, 1761 (2010)

[7] Hao W, Li W, Tang X, Zeng X, Sun Y, Liu S, Lin L, Green Chem., 18, 1080 (2016)

[8] Balakrishnan M, Sacia ER, Bell AT, Green Chem., 14, 1626 (2012)

[9] Wang F, Yuan Z, Liu B, Chen S, Zhang Z, J. Ind. Eng. Chem., 38, 181 (2016)

[10] Tang X, Wei J, Ding N, Sun Y, Zeng X, Hu L, Liu S, Lei T, Lin L, Renew. Sust. Energ. Rev., 77, 287 (2017)

[11] Hu L, Xu J, Zhou S, He A, Tang X, Lin L, Xu J, Zhao Y, ACS Catal., 8, 2959 (2018)

[12] Cao Q, Liang WY, Guan J, Wang L, Qu Q, Zhang XZ, Wang XC, Mu XD, Appl. Catal. A: Gen., 481, 49 (2014)

[13] Chatterjee M, Ishizaka T, Kawanami H, Green Chem., 16, 4734 (2014)

[14] Kang ES, Chae DW, Kim B, Kim YG, J. Ind. Eng. Chem., 18(1), 174 (2012)

[15] Kwon Y, Schouten KJP, van der Waal JC, de Jong E, Koper MTM, ACS Catal., 6, 6704 (2016)

[16] Zeng C, Seino H, Ren J, Hatanaka K, Yoshie N, Macromolecules, 46(5), 1794 (2013)

[17] Patil SKR, Lund CRF, Energy Fuels, 25(10), 4745 (2011)

[18] Ilgen F, Ott D, Kralisch D, Reil C, Palmberger A, Konig B, Green Chem., 11, 1948 (2009)

[19] Tang X, Zuo M, Li Z, Liu H, Xiong C, Zeng X, Sun Y, Hu L, Liu S, Lei T, Lin L, ChemSusChem, 10, 2696 (2017)

[20] Smith EL, Abbott AP, Ryder KS, Chem. Rev., 114(21), 11060 (2014)

[21] Zuo M, Le K, Li Z, Jiang Y, Zeng X, Tang X, Sun Y, Lin L, Ind. Crop. Prod., 99, 1 (2017)

[22] Le K, Zuo M, Song XQ, Zeng XH, Tang X, Sun Y, Lei TZ, Lin L, J. Chem. Technol. Biotechnol., 92(12), 2929 (2017)

[23] Zuo M, Le K, Feng Y, Xiong C, Li Z, Zeng X, Tang X, Sun Y, Lin L, Ind. Crop. Prod., 112, 18 (2018)

[24] Liu F, Audemar M, Vigier KDO, Cartigny D, Clacens JM, Gomes MFC, Padua AAH, De Campo F, Jerome F, Green Chem., 15, 3205 (2013)

[25] Li C, Li D, Zou S, Li Z, Yin J, Wang A, Cui Y, Yao Z, Zhao Q, Green Chem., 15, 2793 (2013)

[26] Aellig C, Jenny F, Scholz D, Wolf P, Giovinazzo I, Kollhoff F, Hermans I, Catal. Sci. Technol., 4, 2326 (2014)

[27] Cottier L, Descotes G, Soro Y, Synth. Commun., 33, 4285 (2003)

[28] Goswami S, Dey S, Jana S, Tetrahedron, 64, 6358 (2008)

[29] Francisco M, van den Bruinhorst A, Kroon MC, Angew. Chem.-Int. Edit., 52, 3074 (2013)

[30] Hu L, Sun Y, Lin L, Ind. Eng. Chem. Res., 51(3), 1099 (2012)

[31] Sho LAC, Takahashi, J. Org. Chem., 35, 1505 (1970)