A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol.
The acid-catalysed dehydration of the four 2-ketohexoses (fructose, sorbose, tagatose and psicose) to furanics was studied in methanol (65 g L(-1) substrate concentration, 17 and 34 mm sulfuric acid, 100 °C) with Avantium high-throughput technology. Significant differences in the reactivities of the hexoses and yields of 5-hydroxymethylfurfural (HMF) and its methyl ether (MMF) were observed. Psicose and tagatose were the most reactive, and psicose also afforded the highest combined yield of MMF and HMF of approximately 55 % at 96 % sugar conversion. Hydroxyacetylfuran and its corresponding methyl ether were formed as byproducts, particularly for sorbose and tagatose, with a maximum combined yield of 8 % for sorbose. The formation of hydroxyacetylfuran was studied through (13) C NMR spectroscopy with labelled sorbose, which provided new insights into the reaction mechanism.
Avantium Chemicals, Zekeringstraat 29, 1014 BV, Amsterdam, The Netherlands. robert-jan.vanputten@avantium.com.
Robert-Jan
http://orcid.org/0000-0003-1021-577X
RJ
van Putten
Avantium Chemicals, Zekeringstraat 29, 1014 BV, Amsterdam, The Netherlands.
Jan C
http://orcid.org/0000-0002-9830-6109
JC
van der Waal
Avantium Chemicals, Zekeringstraat 29, 1014 BV, Amsterdam, The Netherlands.
Martin
M
Harmse
Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Henk H
HH
van de Bovenkamp
Avantium Chemicals, Zekeringstraat 29, 1014 BV, Amsterdam, The Netherlands.
Ed
E
de Jong
Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands. h.j.heeres@rug.nl.
Hero J
HJ
Heeres
D066241:Carbon-13 Magnetic Resonance Spectroscopy; D005663:Furans / Q000737:chemistry*; D006601:Hexoses / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry*
D005663:Furans; D006601:Hexoses; D000432:Methanol
biomass; carbohydrates; isotopic labelling; oxygen heterocycles; reaction mechanisms