Ionic Liquids in Selective Oxidation: Catalysts and Solvents.

Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.

Niobium phosphotungstates: excellent solid acid catalysts for the dehydration of fructose to 5-hydroxymethylfurfural under mild conditions.

The efficient conversion of carbohydrates to 5-hydroxymethylfurfural (5-HMF) under mild conditions represents a very attractive and promising method of producing important building blocks. In this work, niobium phosphotungstates, with Nb/P molar ratios of 0.6, 1.0, 2.0 and 4.0 (NbPW-06, NbPW-1, NbPW-2, and NbPW-4, respectively) have been prepared by a facile, one-pot, alcohol-mediated thermal process and used for the direct conversion of fructose to 5-HMF. By adding a certain amount of Nb, the surface of the catalyst became enriched in P, and this enrichment was associated with the presence of surface P-OH groups that offered Brønsted acid sites that can activate superficial hydrogen species to facilitate 5-HMF generation. Pyridine-FTIR confirmed the presence of Brønsted and Lewis acid sites, which might play important roles in the dehydration of fructose to 5-HMF. Furthermore, polar aprotic solvents were well-suited for the conversion, and higher yields of 5-HMF were obtained in polar aprotic solvents than in nonpolar solvents. A 5-HMF yield of 96.7% with complete fructose consumption was obtained over NbPW-06 in DMSO at 80 °C after 90 min. In addition, NbPW-06 could be recycled several times without a significant decrease in the catalytic activity. A catalytic mechanism for this reaction was proposed. Moreover, this catalytic system can also be utilized for the dehydration of sucrose and inulin to 5-HMF in satisfactory yields. This study establishes an important platform for the further design of Nb-containing catalysts for the production of 5-HMF from carbohydrates under mild conditions.

One-pot conversion of disaccharide into 5-hydroxymethylfurfural catalyzed by imidazole ionic liquid.

Conversion of carbohydrate into 5-hydroxymethylfurfural (5- HMF), a versatile, key renewable platform compound is regarded as an important transformation in biomass-derived carbohydrate chemistry. A variety of ILs, not only acidic but also alkaline ILs, were synthesized and used as catalyst in the production of 5-HMF from disaccharide. Several factors including reaction temperature, IL dosage, solvent and reaction time,were found to influence the yield of 5-HMF from cellobiose. Of the ILs tested, hydroxy-functionalized ionic liquid (IL), 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate ([AEMIM]BF4) showed the highest catalytic activity and selectivity. 5-HMF yield of 68.71% from sucrose was obtained after 6 hrs at 160 °C. At the same condition with cellobiose as substrate, 5-HMF yield was 24.73%. In addition, 5-HMF also exhibited good stablity in this reaction system. Moreover, a kinetic analysis was carried out in both acidic and alkaline IL-catalyzed system, suggesting main side reaction in the conversion of fructose catalyzed by acidic and alkaline IL was polymerization of fructose and 5-HMF degradation, respectively.

Microwave-assisted conversion of microcrystalline cellulose to 5-hydroxymethylfurfural catalyzed by ionic liquids.

Ionic liquid (IL) has been widely investigated in 5-HMF production from biomass. However, most of studies employed IL as reaction solvent which requires a large amount of IL. In the present study, IL was utilized as catalyst in the conversion of microcrystalline cellulose (MCC) to 5-HMF under microwave irradiation (MI) in N,N-dimethylacetamide (DMAc) containing LiCl. 1,1,3,3-tetramethylguanidine (TMG)-based ILs, including 1,1,3,3-tetramethylguanidine tetrafluoroborate ([TMG][BF4]) and 1,1,3,3-tetramethylguanidine lactate ([TMG]L) which were commonly used in the absorption of SO2 and CO2 from flue gas, were synthesized and applied in the conversion of MCC to 5-HMF for the first time. Of the catalysts employed, [TMG]BF4 showed high catalytic activity in 5-HMF production from MCC. The condition including the ratio of IL to MCC, temperature and time for MCC conversion was optimized using Central Composite Design (CCD) and Response Surface Methodology (RSM). The highest 5-HMF yield of 28.63% was achieved with the optimal condition.

Efficient dehydration of glucose to 5-hydroxymethylfurfural catalyzed by the ionic liquid,1-hydroxyethyl-3-methylimidazolium tetrafluoroborate.

The dehydration of fructose or glucose to 5-hydroxymethylfurfural (5-HMF) using room temperature ionic liquids (ILs) as a solvent is a promising method for producing liquid fuels from renewable resources. The IL, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate ([C(2)OHMIM]BF(4)), was used a catalyst-rather than as a solvent-in the conversion of fructose or glucose to 5-HMF. With glucose, the yield of 5-HMF reached as high as 67.3% after 1h at 180°C in dimethylsulfoxide (DMSO) as solvent. The catalyst was separated from the reaction mixture by distilling solvent and reused six times without loss of activity. Furthermore, a kinetic analysis was carried out to illustrate the formation of 5-HMF, and the values of the activation energy and the pre-exponential factor for the reaction were 55.77 kJ mol(-1) and 1.6 × 10(4)min(-1) respectively.

Efficient dehydration of fructose to 5-hydroxymethylfurfural catalyzed by a recyclable sulfonated organic heteropolyacid salt.

The dehydration of fructose to 5-hydroxymethylfurfural (5-HMF) with room temperature ionic liquids (ILs) is a way of producing liquid fuels from renewable resources, but separation of products and IL is energy intensive. In this work, a heteropolyacid salt of an IL-forming cation functionalized with a propanesulfonate group, 1-(3-sulfonicacid)propyl-3-methyl imidazolium phosphotungstate ([MIMPS](3)PW(12)O(40)), was used as a catalyst-rather than as a solvent-in the conversion of fructose to 5-HMF. The maximum yield of 5-HMF was 99.1% at 120°C after 2h using sec-butanol as solvent, and the catalyst was separated from the reaction mixture by a simple process at the end of the reaction and reused six times without loss of activity.