QUANTUM CHEMICAL STUDY OF THE STERIC EFFECT OF SUBSTITUENT ON THE REACTIVITY OF TERTIARY AMINES IN THE REACTION WITH 2-(CHLOROMETHYL)OXIRANE
DOI:
https://doi.org/10.15421/jchemtech.v31i3.283788Keywords:
epichlorohydrin, tertiary amines, ring opening, transition state, steric effect, quantum chemical modelingAbstract
The ring-opening reaction of 2-(chloromethyl)oxirane (epichlorohydrin) with tertiary amines was investigated using the ab initio method in the gas phase. A series of amines, MenEt3–nN, with varying steric factors was selected. Geometric parameters and the order of bond breaking and formation were established for localized transition states along the reaction pathway. Energy profiles for the quaternization reaction between amines and epoxide were obtained, and the activation parameters of the process were calculated. The influence of the hydrocarbon radical length in the amine molecule on the energy barrier and the reaction rate was determined. It was demonstrated that the rate of quaternization is determined by charge control. The dissociative nature of transition states was demonstrated via More O'Ferrall–Jenks plots. Correlation equations were derived to relate steric effects and nucleophilicity of amines to their reactivity with 2-(chloromethyl)oxirane.
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