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Experimental and computational studies of the mechanism of base‐catalyzed ring opening of 2‐(chloromethyl)oxirane by benzoic acid

Using methods of chemical kinetics and quantum modeling, we investigated the mechanism by which base catalysts affect the regioselectivity of the ring opening of 2‐(chloromethyl)oxirane by benzoic acid. The model reaction was carried out using 2‐(chloromethyl)oxirane as both reagent and solvent at t...

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Bibliographic Details
Published in:International journal of chemical kinetics 2021-03, Vol.53 (3), p.356-368
Main Authors: Bespalko, Yuliia, Sinel'nikova, Marina, Shved, Elena, Bakhalova, Evgeniia
Format: Article
Language:English
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Summary:Using methods of chemical kinetics and quantum modeling, we investigated the mechanism by which base catalysts affect the regioselectivity of the ring opening of 2‐(chloromethyl)oxirane by benzoic acid. The model reaction was carried out using 2‐(chloromethyl)oxirane as both reagent and solvent at temperatures of 303‐333 K. Rate constants and activation parameters of the ring opening were determined for the overall reaction and for the formation of the isomeric “normal” and “abnormal” products. Density functional theory B3LYP/6‐31+G** was used to examine possible reaction pathways. A comparison of experimental measurements and theoretical calculations confirm that the rate‐limiting step is the attack of the benzoate anion on the C1 and C2 positions of 2‐(chloromethyl)oxirane. The present results indicate that the regioselectivity of the 2‐(chloromethyl)oxirane ring opening by benzoic acid depends on the ratio of A2 mechanisms, SN2 and “borderline” SN2 type. This suggests that weak nucleophilic base catalysts can increase the reaction regiospecificity by increasing the contribution of the SN2 pathway.
ISSN:0538-8066
1097-4601
DOI:10.1002/kin.21448