Efficient and selective dehydration of fructose to 5-hydroxymethylfurfural catalyzed by Brønsted-acidic ionic liquids.
The dehydration of D-fructose and glucose has been studied with acidic ionic liquids as catalysts. A series of Brønsted-acidic ionic liquids has been synthesized and tested in the dehydration of D-fructose. The results showed that N-methyl-2-pyrrolidonium methyl sulfonate [NMP](+)[CH(3)SO(3)](-) and N-methyl-2-pyrrolidonium hydrogen sulfate [NMP](+)[HSO(4)](-) have high catalytic activity. Highly efficient and selective dehydration of D-fructose to 5-hydroxymethylfurfural (HMF) was achieved in dimethyl sulfoxide (DMSO) under mild conditions. For example, a 72.3 % yield of HMF with 87.2 % selectivity were obtained for 2 h at 90 degrees C in the presence of 7.5 mol % [NMP](+)[CH(3)SO(3)](-). The effects of the reaction temperature, time, and solvent were investigated in detail. The catalyst and solvent can be recycled for the dehydration of D-fructose. The Hammett method was used to determine the acidities of these ionic liquids, which indicated that the acidity and molecular structure have strong effects on the catalytic activity of ionic liquids. Based on the experimental results, a possible reaction mechanism for the dehydration of D-fructose is proposed.
Tong
Xinli
X
Tianjin Key Laboratory of Applied Catalysis Science and Technology and State Key Laboratory of Chemical Engineering, School of Chemical Engineering, Tianjin University, Tianjin, PR China.
Li
Yongdan
Y
D000143:Acids / Q000737:chemistry*; D018533:Biomass; D002384:Catalysis; D003247:Conservation of Natural Resources / Q000379:methods*; D003890:Desiccation; D005632:Fructose / Q000737:chemistry*; D005662:Furaldehyde / Q000031:analogs & derivatives* / Q000737:chemistry; D007093:Imidazoles / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013463:Sulfuric Acid Esters / Q000737:chemistry; D014867:Water / Q000737:chemistry*
D000143:Acids; D007093:Imidazoles; D052578:Ionic Liquids; D012997:Solvents; D013463:Sulfuric Acid Esters; C483970:imidazolium methylsulfonate; D014867:Water; D005632:Fructose; C008046:5-hydroxymethylfurfural; D005662:Furaldehyde