Metal-free dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a promoter.
The dehydration of glucose and other hexose carbohydrates to 5-(hydroxymethyl)furfural (HMF) was investigated in imidazolium-based ionic liquids with boric acid as a promoter. A yield of up to 42% from glucose and as much as 66% from sucrose was obtained. The yield of HMF decreased as the concentration of boric acid exceeded one equivalent, most likely as a consequence of stronger fructose-borate chelate complexes being formed. Computational modeling with DFT calculations confirmed that the formation of 1:1 glucose-borate complexes facilitated the conversion pathway from glucose to fructose. Deuterium-labeling studies elucidated that the isomerization proceeded via an ene-diol mechanism, which is different to that of the enzyme-catalyzed isomerization of glucose to fructose. The introduced non-metal system containing boric acid provides a new direction in the search for catalyst systems allowing efficient HMF formation from biorenewable sources.
Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark.
Tim
T
Ståhlberg
Sergio
S
Rodriguez-Rodriguez
Peter
P
Fristrup
Anders
A
Riisager
D001888:Boric Acids / Q000737:chemistry*; D002384:Catalysis; D005662:Furaldehyde / Q000031:analogs & derivatives* / Q000737:chemistry; D005947:Glucose / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D015394:Molecular Structure
D001888:Boric Acids; D052578:Ionic Liquids; C008046:5-hydroxymethylfurfural; D005662:Furaldehyde; D005947:Glucose; C032688:boric acid