Highly Selective Catalytic Hydrogenation and Etherification of 5-Hydroxymethyl-2-furaldehyde to 2,5-Bis(alkoxymethyl)furans for Potential Biodiesel ProductionThis Research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (C2001215-01-01) and performed as a cooperation project of ‘Basic project (referring to projects performed with the budget directly contributed by the Government to achieve the purposes of establishment of Government-funded research Institutes)’ and supported by the Korea Research Institute of Chemical Technology (KRICT)
Received: 08 May 2017
Accepted after revision: 22 June 2017
24 July 2017 (eFirst)
§ These authors contributed equally to this work
5-Hydroxymethyl-2-furaldehyde (HMF) was hydrogenated to 2,5-bis(hydroxymethyl)furan (BHMF) in various n-alcohol solvents with more than 99% yield using Ru(OH) x /ZrO2 catalyst. The BHMF in the same solvents was subsequently etherified to give 2,5-bis(alkoxymethyl)furans (BAMFs, four examples) as potential biodiesels with moderate to good yields using Amberlyst-15.
References and Notes
- 1a Stöcker M. Angew. Chem. Int. Ed. 2008; 47: 9200
- 1b Huber GW. Iborra S. Corma A. Chem. rev. 2006; 106: 4044
- 1c Corma A. Iborra S. Velty A. Chem. Rev. 2007; 107: 2411
- 1d Chheda JN. Huber GW. Dumesic JA. M. Angew. Chem. Int. Ed. 2007; 46: 7164
- 2a Saha B. Abu-Omar MM. Green Chem. 2014; 16: 24
- 2b Climent MJ. Corma A. Iborra S. Green Chem. 2014; 16: 516
- 2c Lewis JD. Van de Vyver S. Crisci AJ. Gunther WR. Michaelis VK. Griffin RG. Román-Leshkov Y. ChemSusChem 2014; 7: 2255
- 3 Sacia ER. Balakrishnan M. Bell AT. J. Catal. 2014; 313: 70
- 4 Liu A. Liu B. Wang Y. Ren R. Zhang Z. Fuel 2014; 117: 68
- 5 Balakrishnan M. Sacia ER. Bell AT. Green Chem. 2012; 14: 1626
- 6a Lew CM. Rajabbeigi N. Tsapatsis M. Ind. Eng. Chem. Res. 2012; 51: 5364
- 6b Murphy MJ. Taylor JD. McCormick RL. Compendium of Experimental Cetane Number Data. . National Renewable Energy Laboratory Golden; CO, USA; 2004
- 7 Luo J. Yu J. Gorte RJ. Mahmoud E. Vlachos DG. Smith MA. Catal. Sci. Technol. 2014; 4: 3074
- 8 Cao Q. Liang W. Guan J. Wang L. Qu Q. Zhang X. Wang X. Mu X. Appl. Catal., A 2014; 481: 49
- 9 Kim Y.-H. Hwang S.-K. Kim JW. Lee Y.-S. Ind. Eng. Chem. Res. 2014; 53: 12548
- 10 Han J. Kim Y.-H. Jang H.-S. Hwang S.-Y. Jegal J. Kim JW. Lee Y.-S. RSC Adv. 2016; 6: 93394
- 11 Lecomte J. Finiels A. Geneste P. Moreau C. Appl. Catal., A 1998; 168: 235
- 12 Alamillo R. Tucker M. Chia M. Pagán-Torres Y. Dumesic J. Green Chem. 2012; 14: 1413
- 13 Preparation of Ru(OH) x /ZrO2: Ru(OH) x /ZrO2 catalyst was fabricated by using our previously reported method (see ref. 9). Briefly, zirconia (4 g) was stirred for a few minutes in deionized water and then RuCl3·nH2O (263.3 mg, 1 mmol) was mixed, followed by addition of sodium hydroxide solution to increase the pH to 13. The catalyst was obtained by filtration and the gained residue was dried in air at 90 °C for 15 min.
- 14 Hydrogenation of HMF to BHMF catalyzed by Ru(OH) x /ZrO2: HMF (100 μL, 0.97 mmol) was hydrogenated in n-alcohol solvent (3 mL) by using Ru(OH) x /ZrO2 (0.3 mol% of Ru) catalyst under H2 gas (15–30 bar). The reaction proceeded in a pressure vessel with a Teflon liner (200 mL), equipped with a glass vial (10 mL). After the HMF hydrogenation, the Ru(OH) x /ZrO2 catalyst was filtered and the filtrate was dried under vacuum for 1H NMR analysis. The product BHMF was analyzed by 1H NMR (400 MHz, DMSO-d 6, TMS): δ = 6.2 (s, 2 H), 5.2 (t, 2 H), 4.4 (d, 4 H). GC/MS analysis was also performed to ensure that no by-product was formed. The filtered Ru(OH) x /ZrO2 catalyst was washed with acetone and aqueous sodium hydroxide (0.1 N), and dried before being reused.
- 15 Etherification of BHMF to BAMF catalyzed by Amberlyst-15: BHMF (32 mg, 0.25 mmol) was etherified in various alcohol solvents (1.5 mL) by using Amberyst-15. The reaction proceeded in a glass vial (10 mL) with a magnetic stirring bar. The final products were analyzed by GC/MS and 1H NMR and the yields were calculated based on GC analysis. The product BBMF was analyzed by 1H NMR (400 MHz, CDCl3, TMS): δ = 6.2 (s, 2 H), 4.4 (s, 4 H), 3.4 (t, 4 H), 1.5 (m, 4 H), 1.3 (m, 4 H), 0.9 (t, 6 H).
- 16 Two-step sequential reaction of HMF to BAMF in various n-alcohol solvents: HMF (100 μL, 0.97 mmol) was hydrogenated to BHMF in methanol, ethanol, 1-propanol, and 1-butanol solvents (3 mL) by using Ru(OH) x /ZrO2 (0.3 mol% of Ru) catalyst under H2 gas (15 bar). The reaction proceeded in a pressure vessel with a Teflon liner (200 mL), equipped with a glass vial (10 mL) at 120 °C for 6 h. After the reaction, solvents were added to ca. 3 mL, then the catalyst was filtered. Subsequently, Amberlyst-15 (94.10 mg, 10 mol%) was added and the solution was stirred for 10 h at 60 °C. The final products were analyzed by GC/MS and the product yields were calculated based on GC analysis.