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Issue 1, 2014
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Kinetics and thermodynamics of the decarboxylation of 1,2-glycerol carbonate to produce glycidol: computational insights

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Abstract

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 (ΔG = 4.9 kcal mol−1), followed by degradation to glycidol, is unlikely on thermodynamic grounds.

Graphical abstract: Kinetics and thermodynamics of the decarboxylation of 1,2-glycerol carbonate to produce glycidol: computational insights

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Publication details

The article was received on 12 Aug 2013, accepted on 05 Nov 2013 and first published on 05 Nov 2013


Article type: Paper
DOI: 10.1039/C3GC41643G
Green Chem., 2014,16, 247-252

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    Kinetics and thermodynamics of the decarboxylation of 1,2-glycerol carbonate to produce glycidol: computational insights

    D. J. Darensbourg and A. D. Yeung, Green Chem., 2014, 16, 247
    DOI: 10.1039/C3GC41643G

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