Phosphotungstic acid heterogenized by assembly with pyridines for efficient catalytic conversion of fructose to methyl levulinate

Solid acid-catalyzed sugar degradation has been considered to be an efficient approach to synthesize alkyl levulinates (which can be used as fuel additives and surfactants). However, those catalytic processes typically involve harsh reaction conditions and high cost for catalyst preparation. We prepared a series of phosphotungstic acid organic hybrids by a simple solvothermal method, and used them as heterogeneous catalysts for the selective degradation of fructose to methyl levulinate (ML) in methanol with high efficiency under mild reaction conditions. The catalysts were characterized systematically, and the effects of different substituents in pyridine, reaction temperature/time, catalyst dose, and fructose concentration studied. The 3-FPYPW hybrid prepared from 3-fluoropyridine and phosphotungstic acid exhibited superior catalytic activity for the synthesis of ML (82.5%) from fructose (97.8%). A possible reaction pathway was proposed. In addition, the catalyst could be separated from the reaction mixture readily, and reused without remarkable loss of reactivity.