Reaction Kinetics, Mechanisms and Catalysis

, Volume 126, Issue 2, pp 903–919 | Cite as

Experimental and theoretical study on the kinetics and mechanism of the amine-catalyzed reaction of oxiranes with carboxylic acids

  • Yullia N. Bespalko
  • Elena N. ShvedEmail author


In this work, a systematic study on the kinetics and mechanism of ring-opening reaction of oxirane by carboxylic acid initiated by a tertiary amine is presented. Kinetic parameters of β-hydroxypropyl ester formation including reaction orders, rate constants, and activation energies were established at the temperature range 323–353 K. The experimental values of ΔH° and ΔS° are characteristic for the SN2-like processes. In the initial reaction system, the acid, oxirane and amine exist mainly as hydrogen-bonded complex acid-oxirane, free oxirane and free base. H-bonding was analyzed using IR-spectroscopy. The reaction pathways were examined by the density functional theory (DFT) method at the B3LYP/6-31+G** level. Optimized equilibrium configurations of transition states and corresponding activation parameters were established. In accordance to both experimental and theoretical approaches, it is reasonable to suggest that amine-catalyzed ring-opening reaction of oxirane by carboxylic acid is a series of parallel consecutive stages: (1) quaternization of tertiary amine by activated oxirane; (2) carboxylate anion participation in ring-opening of both nonactivated and activated oxirane. The kinetic model, which adequately describing all observations, is proposed.


Oxirane Ring-opening Kinetics DFT calculations Mechanism 



Funding was provided by Ministry of Education and Science of Ukraine (Grant No. 0116U002519).


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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.Educational and Scientific Institute of ChemistryVasyl’ Stus Donetsk National UniversityVinnytsiaUkraine

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