Synthesis of 5‐Bromomethylfurfural from Cellulose as a Potential Intermediate for Biofuel

Abstract

Cellulose can be converted into 5‐bromomethylfurfural (BMF), a brand new biofuel or biofuel intermediate, in 80 % yield by treatment with HBr and LiBr and continuous extraction with toluene. From other carbohydrates and straw, BMF was also obtained in high yields. The mechanism of BMF formation was investigated, and the results indicate that this furfural is formed during the depolymerization of cellulose and that glucose is not an intermediate.

Effective conversion of biomass into bromomethylfurfural, furfural, and depolymerized lignin in lithium bromide molten salt hydrate of a biphasic system

“…In addition, the enhanced acidity in molten salt hydrate, 41 compared with that in water at the same acid concentration, promotes the hydrolysis of the polysaccharides to monomeric saccharides and the following dehydration of the monomeric saccharides to furans. Furthermore, the free bromide anions in the solution are strong nucleophiles, which are able to catalyze the dehydration of saccharides to furans and likely the cleavage of b-O-4 ether bonds of lignin resulting in the depolymerization of lignin, 22,27,30,31 which will be further discussed later. Finally, the salting-out effect of the inorganic salt (LiBr) can enhance the partition coefficient of BMF and FF in the extraction solvent and thereby facilitate effective extraction of the furans from the aqueous phase to the organic phase.…”

“…30 Recently, halomethylfurfurals such as 5-bromomethylfurfural (BMF) and 5-chloromethylfurfural (CMF) have been investigated as platform chemicals for the production of solvents, polymers, and liquid hydrocarbon fuels. [31][32][33][34][35] Diverse approaches were explored, but these processes had some limitations such as high acid loading or concentration, unsatisfactory product yield, and insufficient utilization of hemicelluloses and lignin. 26,27,29,31,32 For effective conversion of biomass to the furans, selection of a proper reaction medium is crucial.…”

“…[31][32][33][34][35] Diverse approaches were explored, but these processes had some limitations such as high acid loading or concentration, unsatisfactory product yield, and insufficient utilization of hemicelluloses and lignin. 26,27,29,31,32 For effective conversion of biomass to the furans, selection of a proper reaction medium is crucial. In the previous studies, water with acid catalyst was the most common medium, but low yield and poor selectivity are the major issues due to the rehydration of HMF to levulinic acid and formic acid and/or the condensation of the furans to humins.…”

Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: organic synthesis based on biomass-derived products

“…Next, 5-HMF ( 1a ), 5-(chloromethyl)furfural ( 1b ) and 5-(bromomethyl)furfural ( 1c ), both of which are also promising biomass-derived products [58–59], were reacted with benzene under the action of various acids (Table 3). In all cases 5-(phenylmethyl)furfural ( 3a ) as Friedel–Crafts reaction product was obtained.…”

Efficient Conversion of Carbohydrates to 5-Hydroxymethylfurfural (HMF) Using ZrCl4 Catalyst in Nitromethane

“…5-Hydroxymethylfurfural (99%) was purchased from Aldrich Chemicals and was used establishing the calibration curve. 5-Chloromethylfurfural was synthesized based on the literature suggested by Kumari et al (2011).…”