Catalytic Synthesis of Hydroxymethyl-2-oxazolidinones from Glycerol or Glycerol Carbonate and Urea

Dibenedetto, Angela and Nocito, Francesco and Angelini, Antonella and Pápai, Imre and Aresta, Michele and Mancuso, Raffaella (2013) Catalytic Synthesis of Hydroxymethyl-2-oxazolidinones from Glycerol or Glycerol Carbonate and Urea. ChemSusChem, 6 (2). pp. 345-352. ISSN 1864-5631

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Abstract

Oxazolidinones have been synthesized by reacting glycerol carbonate or glycerol with urea in the presence of g-Zr phosphate as a catalyst. The conversion yield of the polyol or its carbonate depends on the temperature. Below 408 K the selectivity is 100% with a conversion of up to 25 %, whereas increasing the temperature means that conversion yield grows, but the selectivity decreases, which makes the separation process more difficult. Starting from glycerol carbonate, two isomers, 6 and 6’, are formed with a quasi 1:1 molar ratio because urea can attack the carbonate moiety on both sides of the carboxylic CO moiety. From glycerol the formation of the 6’ isomer is preferred: the ratio of 6’/6 is close to 7. The oxazolidinones formed act as templates because they interact through hydrogen bonding with glycerol. The intensity of the interaction depends on the 6 or 6’ isomer: DFT calculations showed that the energy was 22.6 kcalmol�1 for 6-oxazolidinone and 25.7 kcal/mol for 6’-oxazolidinone.

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