Cascade Synthesis of 5‐(Acetoxymethyl)furfural from Carbohydrates over Sn‐Mont Catalyst

Abstract

The 5-(Acetoxymethyl)furfural (AcMF) is emerged as an important alternative for 5-(hydroxymethyl)furfural (HMF). It is also a starting material for those products which are typically prepared from HMF. The growing importance of AcMF encouraged us to prepare it directly from cheap and abundant carbohydrates. The production AcMF from glucose and glucose-like carbohydrates is an exigent assignment, owing to tough isomerisation of glucose to fructose. The Sn-Mont catalyst having a unique combination of Lewis as well as Brønsted acid sites was employed for direct glucose conversion into AcMF. Lewis acid sites of Sn-Mont facilitate the isomerisation of glucose to fructose. At the same time, dehydrativeesterification of fructose to AcMF is catalyzed by Brønsted acid sites of Sn-Mont. Different concentrations of Sn containing Sn-Mont catalysts were by prepared mixing montmorillonite clay with different molar concentration (e. g. 0.1 M-0.4 M) of aqueous solutions of SnCl 4 ⋅5H 2 O. AcMF was produced in as high as 43% yield directly from glucose over Sn-Mont(0.3 M) catalyst owing to its highest acid strength. The efficacy of Sn-Mont(0.3 M) catalyst was also probed for sucrose and fructose that resulted in 53% and 58% yield of AcMF, respectively. The critical properties of all the prepared Sn-Mont catalysts were investigated through XRD, BET surface area, ICP-OES, temperature-programmed desorption of NH 3 and pyridine-FTIR and XPS techniques.

Catalytic conversion of 5-hydroxymethylfurfural (5-HMF) over Pd-Ru/FAU zeolite catalysts

“…In the same way, all the evaluated catalysts, Pd-Ru and Pt-Ru supported on FAUY zeolites Y-5-4h, Y-5-8h and Y-6-8h; were found to be active in the esterification of 5-HMF. The conversion of HMF was ranging from 47.65 to 87.28%, and high selectivity to AcMF up to 71.29%, compared to values reported by Shinde et al [13], where a 43% yield of AcMF directly from glucose was achieved. A direct comparison between the different zeolites and bimetallic catalysts performance can be made, the highest conversion and selectivity with pure zeolite Y-5-8h were achieved (87.28% conversion and 71.29% selectivity) and with catalyst Pd-Ru/Y-5-8h (84.23% conversion and 60.42% selectivity).…”

“…AcMF presents an energetic density of 8.7 kWhL -1 , which is higher than ethanol (6.1 kWhL -1 ) and similar to gasoline (8.8 kWhL -1 ) [11]. Furthermore, AcMF presents several advantages compared to 5-HMF in terms of industrial production, it is relatively more stable, less reactive, its recovery is simpler and cheaper and it can be used as reagent for the production of other added-value chemicals [12,13]. Through the years several processes for 5-HMF transformation have been developed, where heterogeneous catalytic processes have been widely researched.…”

“…Recently, Perez-Bustos et al [19] studied FAU type zeolite using structure directing agents (SDAs) and alumina as catalyst supports for bimetallic Pd-Ru and Pt-Ru with low metal content of 0.5 %, to obtain 2,5-DMF and AcMF hydrogenation and esterification products respectively, reaching 5-HMF conversion of 89% and up to 61% of selectivity to AcMF, this means that combinations of noble metals Pd-Ru and Pt-Ru are highly active at low concentrations. Also, the production of AcMF from 5-HMF have been reported, Shinde et al [13] studied the a cascade reaction to produce AcMF from glucose, with 5-HMF as a reaction intermediary, using Sn-Mont (Sn supported on montmorillonite clay) catalysts, reaching maximum 5-HMF conversion of 99% and 43% of selectivity to AcMF.…”

Two-Step One-Pot Reductive Amination of Furanic Aldehydes Using CuAlOx Catalyst in a Flow Reactor

“…5-Acetoxymethylfurfural (AMF), which can be prepared from carbohydrates without isolating HMF, is less reactive, more stable and easily extracted from the aqueous reaction mixture. Therefore, AMF represents a good substitute for HMF [ 17 , 18 , 19 ]. Similar to HMF, AMF reacts with aniline in methanol to form imine with the yield of 98% ( Supplementary Materials, Figure S2 ).…”

3-Bromopyridine-Heterogenized Phosphotungstic Acid for Efficient Trimerization of Biomass-Derived 5-Hydroxymethylfurfural with 2-Methylfuran to C21 Fuel Precursor

“…Therefore, it is urgent to find a renewable and benign matter for energy production via a new type of synthetic approaches. The terrestrial biomass was regarded as an environmental and sustainable feedstock to produce various platform molecules which can be directly employed for the synthesis of biofuels or valueadded chemicals [8][9][10][11][12][13][14][15].…”