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Production of hybrid diesel fuel precursors from carbohydrates and petrochemicals using formic acid as a reactive solvent.

ChemSusChem (2013-01-03)
Xiaoyuan Zhou, Thomas B Rauchfuss
ABSTRACT

We report the one-pot alkylation of mesitylene with carbohydrate-derived 5-(hydroxymethyl)furfural (HMF) as a step toward diesel-range liquids. Using FeCl(3) as a catalyst, HMF is shown to alkylate toluene, xylene, and mesitylene in high yields in CH(2)Cl(2) and MeNO(2) solvents. Efforts to extend this reaction to greener or safer solvents showed that most ether-based solvents are unsatisfactory. Acid catalysts (e.g, p-TsOH) also proved to be ineffective. Using formic acid as a reactive solvent, mesitylene could be alkylated to give mesitylmethylfurfural (MMF) starting from fructose with yields up to approximately 70 %. The reaction of fructose with formic acid in the absence of mesitylene gave rise to low yields of the formate ester of HMF, which indicates the stabilizing effect of replacing the hydroxyl substituent with mesityl. The arene also serves as a second phase into which the product is extracted. Even by using formic acid, the mesitylation of less expensive precursors such as glucose and cellulose proceeded only in modest yields (ca. 20 %). These simpler substrates were found to undergo mesitylation by using hydrogen chloride/formic acid via the intermediate chloromethylfurfural.

MATERIALS
Product Number
Brand
Product Description

Supelco
5-(Hydroxymethyl)furfural, analytical standard
Sigma-Aldrich
Iron(III) chloride, sublimed grade, ≥99.9% trace metals basis
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Cesium formate, 98%
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5-Hydroxymethyl-2-furaldehyde, 99%
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5-(Hydroxymethyl)furfural, ≥99%, FG
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Furfural, 99%
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Mesitylene, 98%
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Furfural, ACS reagent, 99%
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Ammonium formate, ≥99.995% trace metals basis
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Furfural, ≥98%, FCC, FG
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Furfural, natural, ≥98%, FCC, FG
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Iron(III) chloride, anhydrous, powder, ≥99.99% trace metals basis
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Calcium formate, BioUltra, ≥99.0% (T)
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Thallium(I) formate, 97%
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Ammonium formate, eluent additive for LC-MS, LiChropur, ≥99.0%
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Mesitylene, analytical standard
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Ammonium formate, BioUltra, ≥99.0% (calc. based on dry substance, NT)
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Calcium formate, Standard for quantitative NMR, TraceCERT®
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Basosiv M050, produced by BASF
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Iron(III) chloride hexahydrate, puriss. p.a., reag. Ph. Eur., ≥99%
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Iron(III) chloride hexahydrate, reagent grade, ≥98%, chunks
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Iron(III) chloride hexahydrate, ACS reagent, 97%
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Ammonium formate, reagent grade, 97%
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Iron(III) chloride hexahydrate, puriss. p.a., ACS reagent, crystallized, 98.0-102% (RT)
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Ammonium formate solution, 10 mM in H2O, suitable for HPLC
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TDA Reagent, suitable for microbiology
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1,3,5-Trimethylbenzene solution, certified reference material, 5000 μg/mL in methanol
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