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

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
ZUSAMMENFASSUNG

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.

MATERIALIEN
Produktnummer
Marke
Produktbeschreibung

Sigma-Aldrich
Ameisensäure, reagent grade, ≥95%
Sigma-Aldrich
Ameisensäure, ACS reagent, ≥96%
Sigma-Aldrich
Eisen(III)-chlorid Hexahydrat, ACS reagent, 97%
Sigma-Aldrich
Ammoniumformat, reagent grade, 97%
Sigma-Aldrich
Eisen(III)-chlorid Hexahydrat, reagent grade, ≥98%, chunks
Sigma-Aldrich
Ammoniumformat, ≥99.995% trace metals basis
Sigma-Aldrich
Eisen(III)-chlorid Hexahydrat, puriss. p.a., ACS reagent, crystallized, 98.0-102% (RT)
Sigma-Aldrich
Natriumformiat, ACS reagent, ≥99.0%
Sigma-Aldrich
Ameisensäure, ACS reagent, ≥88%
Sigma-Aldrich
5-(Hydroxymethyl)furfural, ≥99%, FG
Sigma-Aldrich
Ammoniumformiat -Lösung, BioUltra, 10 M in H2O
Sigma-Aldrich
5-Hydroxymethyl-2-furaldehyd, 99%
Sigma-Aldrich
Eisen(III)-chlorid, anhydrous, powder, ≥99.99% trace metals basis
Sigma-Aldrich
Eisen(III)-chlorid, sublimed grade, ≥99.9% trace metals basis
Sigma-Aldrich
Eisen(III)-chlorid -Lösung, purum, 45% FeCl3 basis
Sigma-Aldrich
Kaliumformiat, ReagentPlus®, 99%
Sigma-Aldrich
Natriumformiat, reagent grade, 97%
Sigma-Aldrich
2-Furaldehyd, ≥98%, FCC, FG
Sigma-Aldrich
Ameisensäure, ≥95%, FCC, FG
Supelco
Ammoniumformat, eluent additive for LC-MS, LiChropur, ≥99.0%
Sigma-Aldrich
Natriumformiat, BioUltra, ≥99.0% (NT)
Sigma-Aldrich
Cäsiumformiat, 98%
Sigma-Aldrich
2-Furaldehyd, natural, ≥98%, FCC, FG
Sigma-Aldrich
2-Furaldehyd, 99%
Sigma-Aldrich
Natriumformiat, 99.998% trace metals basis
Sigma-Aldrich
Eisen(III)-chlorid, 0.2 M in 2-methyltetrahydrofuran
Sigma-Aldrich
Mesitylen, 98%
Sigma-Aldrich
Natriumformiat-13C, 99 atom % 13C
Sigma-Aldrich
Calciumformat, BioUltra, ≥99.0% (T)
Sigma-Aldrich
Mesitylen, reagent grade, 97%