Catalytic synthesis of hydroxymethyl-2-oxazolidinones from glycerol or glycerol carbonate and urea

Angela Dibenedetto, Francesco Nocito, Antonella Angelini, I. Pápai, Michele Aresta, Raffaella Mancuso

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Oxazolidinones have been synthesized by reacting glycerol carbonate or glycerol with urea in the presence of γ-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 kcal mol-1 for 6-oxazolidinone and 25.7 kcal mol-1 for 6′-oxazolidinone.

Original languageEnglish
Pages (from-to)345-352
Number of pages8
JournalChemSusChem
Volume6
Issue number2
DOIs
Publication statusPublished - Feb 2013

Fingerprint

Oxazolidinones
Carbonates
Glycerol
Urea
urea
carbonate
Isomers
Polyols
Carbon Monoxide
Discrete Fourier transforms
temperature
catalyst
phosphate
hydrogen
Hydrogen bonds
Phosphates
Temperature
Catalysts
energy
isomer

Keywords

  • glycerol
  • homogeneous catalysis
  • hydrogen bonds
  • oxazolidinones
  • zirconium

ASJC Scopus subject areas

  • Energy(all)
  • Environmental Chemistry
  • Materials Science(all)
  • Chemical Engineering(all)

Cite this

Catalytic synthesis of hydroxymethyl-2-oxazolidinones from glycerol or glycerol carbonate and urea. / Dibenedetto, Angela; Nocito, Francesco; Angelini, Antonella; Pápai, I.; Aresta, Michele; Mancuso, Raffaella.

In: ChemSusChem, Vol. 6, No. 2, 02.2013, p. 345-352.

Research output: Contribution to journalArticle

Dibenedetto, Angela ; Nocito, Francesco ; Angelini, Antonella ; Pápai, I. ; Aresta, Michele ; Mancuso, Raffaella. / Catalytic synthesis of hydroxymethyl-2-oxazolidinones from glycerol or glycerol carbonate and urea. In: ChemSusChem. 2013 ; Vol. 6, No. 2. pp. 345-352.
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