A computational study of the SNAr reaction of 2-ethoxy-3,5-dinitropyridine and 2-methoxy-3,5-dinitropyridine with piperidine

Oluwakemi A. Oloba-Whenu; Idris O. Junaid; Chukwuemeka Isanbor

doi:10.1515/psr-2019-0144

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A computational study of the S_NAr reaction of 2-ethoxy-3,5-dinitropyridine and 2-methoxy-3,5-dinitropyridine with piperidine

Oluwakemi A. Oloba-Whenu , Idris O. Junaid and Chukwuemeka Isanbor

Published/Copyright: October 12, 2020

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From the journal Physical Sciences Reviews Volume 7 Issue 6

Abstract

A computational study of the chemical kinetics and thermodynamics study of the S_NAr between 3,5-dinitroethoxypyridine 1a and 3,5-dinitromethoxypyridine 1b with piperidine 2 in the gas phase is reported using hybrid density functional theory method B3PW91 and 6–31G(d,p) basis set. The reaction was modeled via both the catalyzed and base-catalyzed pathways which proceeded with the initial attack of the nucleophile 2 on the substrates 1 to yield the Meisenheimer complex intermediate that is stabilized with hydrogen bonding. Calculations show that the reaction goes via the formation and decomposition of a Meisenheimer complex, which was observed to be stabilized by hydrogen bonding. Along the uncatalyzed pathway, the decomposition of the Meisenheimer complex was the slow step and requires about 28 kcal/mol. This barrier was reduced to about 14.8 kcal/mol with the intervention of the base catalyst, thus making the formation of the Meisenheimer complex rate determining. All reactions were calculated to be exothermic, about −6.5 kcal/mol and −0.6 kcal/mol, respectively, for the reaction of 1a and 1b with 2.

Keywords: base catalysis; Meisenheimer complex; molecular modeling; nucleophilic aromatic substitution

Corresponding author: Oluwakemi A. Oloba-Whenu, Department of Chemistry, University of Lagos, Akoka, Nigeria, E-mail: ooloba-whenu@unilag.edu.ng

Acknowledgments

The authors of this article are grateful to the Central Research Committee, the University of Lagos, for the mini-research grant to carry out this research work.

Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
Supporting information: Optimized geometries and free energies; computed free energies at the B3PW91/6–31+G(d,p) level are available.

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Published Online: 2020-10-12

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Articles in the same Issue

https://doi.org/10.1515/psr-2019-0144

Keywords for this article

base catalysis; Meisenheimer complex; molecular modeling; nucleophilic aromatic substitution