Croatica Chemica Acta, Vol. 92 No. 3, 2019.
Izvorni znanstveni članak
https://doi.org/10.5562/cca3505
A Computational Study of 2-(chloromethyl)oxirane Ring Opening by Bromide and Acetate Anions Considering Electrophilic Activation with Cations of Alkali Metals
Kseniia Yutilova
; Educational and Scientific Institute of Chemistry, Vasyl’ Stus Donetsk National University, 21 600-richchia Str., Vinnytsia 21021, Ukraine
Yuliia Bespal’ko
; Department of Chemistry, University of Leuven, Celestijnenlaan 200 F box 2404, B-3001 Leuven (Heverlee) Belgium
Elena Shved
orcid.org/0000-0002-4868-550X
; Educational and Scientific Institute of Chemistry, Vasyl’ Stus Donetsk National University, 21 600-richchia Str., Vinnytsia 21021, Ukraine
Sažetak
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 SN2-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 α-attack of nucleophile. The effect of alkali metal cation (Li+, Na+, K+) 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.
This work is licensed under a Creative Commons Attribution 4.0 International License.
Ključne riječi
2-(chloromethyl)oxirane; alkali metal bromides; alkali metal acetates; nucleophilic substitution; mechanism; DFT calculations
Hrčak ID:
223842
URI
Datum izdavanja:
29.7.2019.
Posjeta: 1.496 *