Highly Selective Catalytic Hydrogenation and Etherification of 5-Hydroxymethyl-2-furaldehyde to 2,5-Bis(alkoxymethyl)furans for Potential Biodiesel Production

Jusung Han; Yo-Han Kim; Byeong Yeon Jung; Seung Hyun Hwang; Jonggon Jegal; Jung Won Kim; Yoon-Sik Lee

doi:10.1055/s-0036-1589076

Synlett, Table of Contents

Synlett 2017; 28(17): 2299-2302
DOI: 10.1055/s-0036-1589076

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Highly Selective Catalytic Hydrogenation and Etherification of 5-Hydroxymethyl-2-furaldehyde to 2,5-Bis(alkoxymethyl)furans for Potential Biodiesel Production

Jusung Han §

^aSchool of Chemical and Biological Engineering, Seoul National University, Gwanak-Gu, Seoul 151-744, Republic of Korea Email: yslee@snu.ac.kr

,

Yo-Han Kim §

^aSchool of Chemical and Biological Engineering, Seoul National University, Gwanak-Gu, Seoul 151-744, Republic of Korea Email: yslee@snu.ac.kr

,

Byeong Yeon Jung

^aSchool of Chemical and Biological Engineering, Seoul National University, Gwanak-Gu, Seoul 151-744, Republic of Korea Email: yslee@snu.ac.kr

,

Seung Hyun Hwang

^bKorea Research Institute of Chemical Technology, Ulsan 681-802, Republic of Korea

,

Jonggon Jegal

^bKorea Research Institute of Chemical Technology, Ulsan 681-802, Republic of Korea

,

Jung Won Kim*

^cDepartment of Chemical Engineering, Kangwon National University at Samcheok, Joonang-Ro, Samcheok, Kangwon 245-711, Republic of Korea

,

Yoon-Sik Lee*

^aSchool of Chemical and Biological Engineering, Seoul National University, Gwanak-Gu, Seoul 151-744, Republic of Korea Email: yslee@snu.ac.kr

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Abstract

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^§ These authors contributed equally to this work

Abstract

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.

Key words

hydrogenation - biomass - ruthenium - biofuels - etherification

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References

References and Notes

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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.

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