A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol

Robert-Jan van Putten; Jan C. van der Waal; Martin Harmse; Henk H. van de Bovenkamp; Ed de Jong; Hero J. Heeres

doi:10.1002/cssc.201600252

A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol

Robert-Jan van Putten, Jan C. van der Waal, Martin Harmse, Henk H. van de Bovenkamp, Ed de Jong, Hero J. Heeres

Green Chemical Reaction Engineering

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Abstract

The acid-catalysed dehydration of the four 2-ketohexoses (fructose, sorbose, tagatose and psicose) to furanics was studied in methanol (65 gL(-1) substrate concentration, 17 and 34 mm sulfuric acid, 100 degrees 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 C-13 NMR spectroscopy with labelled sorbose, which provided new insights into the reaction mechanism.

Original language	English
Pages (from-to)	1827-1834
Number of pages	8
Journal	Chemsuschem
Volume	9
Issue number	14
DOIs	https://doi.org/10.1002/cssc.201600252
Publication status	Published - 21-Jul-2016

Keywords

biomass
carbohydrates
oxygen heterocycles
isotopic labelling
reaction mechanisms
D-FRUCTOSE
LEVULINIC ACID
D-PSICOSE
D-GLUCOSE
CONVERSION
MONOSACCHARIDES
DEHYDRATION
CELLULOSE
WATER

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A Comparative Study on the Reactivity of Various KetohexosesFinal publisher's version, 883 KBLicence: Taverne

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@article{be48ec04b93f44d4b098264c65a48481,

title = "A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol",

abstract = "The acid-catalysed dehydration of the four 2-ketohexoses (fructose, sorbose, tagatose and psicose) to furanics was studied in methanol (65 gL(-1) substrate concentration, 17 and 34 mm sulfuric acid, 100 degrees 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 C-13 NMR spectroscopy with labelled sorbose, which provided new insights into the reaction mechanism.",

keywords = "biomass, carbohydrates, oxygen heterocycles, isotopic labelling, reaction mechanisms, D-FRUCTOSE, LEVULINIC ACID, D-PSICOSE, D-GLUCOSE, CONVERSION, MONOSACCHARIDES, DEHYDRATION, CELLULOSE, WATER",

author = "{van Putten}, Robert-Jan and {van der Waal}, {Jan C.} and Martin Harmse and {van de Bovenkamp}, {Henk H.} and {de Jong}, Ed and Heeres, {Hero J.}",

year = "2016",

month = jul,

day = "21",

doi = "10.1002/cssc.201600252",

language = "English",

volume = "9",

pages = "1827--1834",

journal = "Chemsuschem",

issn = "1864-5631",

publisher = "WILEY-V C H VERLAG GMBH",

number = "14",

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TY - JOUR

T1 - A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol

AU - van Putten, Robert-Jan

AU - van der Waal, Jan C.

AU - Harmse, Martin

AU - van de Bovenkamp, Henk H.

AU - de Jong, Ed

AU - Heeres, Hero J.

PY - 2016/7/21

Y1 - 2016/7/21

N2 - The acid-catalysed dehydration of the four 2-ketohexoses (fructose, sorbose, tagatose and psicose) to furanics was studied in methanol (65 gL(-1) substrate concentration, 17 and 34 mm sulfuric acid, 100 degrees 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 C-13 NMR spectroscopy with labelled sorbose, which provided new insights into the reaction mechanism.

AB - The acid-catalysed dehydration of the four 2-ketohexoses (fructose, sorbose, tagatose and psicose) to furanics was studied in methanol (65 gL(-1) substrate concentration, 17 and 34 mm sulfuric acid, 100 degrees 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 C-13 NMR spectroscopy with labelled sorbose, which provided new insights into the reaction mechanism.

KW - biomass

KW - carbohydrates

KW - oxygen heterocycles

KW - isotopic labelling

KW - reaction mechanisms

KW - D-FRUCTOSE

KW - LEVULINIC ACID

KW - D-PSICOSE

KW - D-GLUCOSE

KW - CONVERSION

KW - MONOSACCHARIDES

KW - DEHYDRATION

KW - CELLULOSE

KW - WATER

U2 - 10.1002/cssc.201600252

DO - 10.1002/cssc.201600252

M3 - Article

SN - 1864-5631

VL - 9

SP - 1827

EP - 1834

JO - Chemsuschem

JF - Chemsuschem

IS - 14

ER -

A Comparative Study on the Reactivity of Various Ketohexoses to Furanics in Methanol

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Keywords

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