Kinetics and thermodynamics of the decarboxylation of 1,2-glycerol carbonate to produce glycidol: computational insights
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The kinetics and thermodynamics of the decarboxylation of 1,2-glycerol carbonate to yield glycidol were studied using "chemically accurate" quantum chemical calculations. Both base- and acid-catalyzed reactions were examined, as were the potential reactions that yield the 3-hydroxyoxetane isomer. Under all conditions, glycidol was the preferred product. While the free energy barrier for the alkoxide form of 1,2-glycerol carbonate to form the epoxide ring is low, the rate-determining step of the overall reaction is the loss of carbon dioxide from the resultant carbonate anion (ca. 21.7 kcal mol -1 ). Protonation of 1,2-glycerol carbonate is expected to be difficult, but decarboxylation henceforth is exergonic, and the free energy barrier is lower (12.3 kcal mol -1 ). Calculations also indicate that oligomerization of 1,2-glycerol carbonate (G = 4.9 kcal mol -1 ), followed by degradation to glycidol, is unlikely on thermodynamic grounds. 2014 The Royal Society of Chemistry.
