A Computational Study of 2-oxirane Ring Opening by Bromide and Acetate Anions Considering Electrophilic Activation with Cations of Alkali Metals

Ring opening of 2-(chloromethyl)oxirane via the nucleophilic substitution with bromide and acetate anions was investigated using density functional theory (DFT) calculations. It was shown that the geometry of the transition states and the activation parameters of the reactions correspond to those of...

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Bibliographic Details
Published in:Croatica Chemica Acta 2019, Vol.92 (3), p.1-367
Main Authors: Yutilova, Kseniia, Bespal'ko, Yuliia, Shved, Elena
Format: Article
Language:English
Subjects:
2-(chloromethyl)oxirane
Acetates
Acids
Activation
alkali metal acetates
alkali metal bromides
Alkali metals
Analysis
Anions
Atoms & subatomic particles
Bromine compounds
Carbon
Cations
Computer simulation
Density
Density functional theory
DFT calculations
Energy (Physics)
Epichlorohydrin
Ethylene oxide
Geometry
mechanism
Metal ions
Nucleophiles
nucleophilic substitution
Organic chemistry
Potential energy
Quantum chemistry
Ring opening
Substitution reactions
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Summary:Ring opening of 2-(chloromethyl)oxirane via the nucleophilic substitution with bromide and acetate anions was investigated using density functional theory (DFT) calculations. It was shown that the geometry of the transition states and the activation parameters of the reactions correspond to those of [S.sub.N]2-like mechanism. The nature of localized transition states was analyzed using More O'Ferrall--Jencks plots. The quantum chemical simulations of the potential energy surface for the ring-opening reaction of oxirane by nucleophiles confirmed the theoretical assumptions about the favored path of interactions, which is a backside [alpha]-attack of nucleophile. The effect of alkali metal cation ([Li.sup.+], [Na.sup.+], [K.sup.+]) on that path was estimated. It was found that the electrophilic activation with alkali metal cation is more pronounced in the reaction of 2-(chloromethyl)oxirane with dissociated ions, than with ionic pairs. Keywords: 2-(chloromethyl)oxirane, alkali metal bromides, alkali metal acetates, nucleophilic substitution, mechanism, DFT calculations.
ISSN:0011-1643
1334-417X
DOI:10.5562/cca3505