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Vol. 26 No. 22 (2014): Vol 26 Issue 22

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Theoretical Studies of Reaction Mechanism of 1,3-Indandione with (Z)-N-Methyl-C-Phenylnitrone by Metadynamic Approach

https://doi.org/10.14233/ajchem.2014.17794
Jamal Lasri
Department of Chemistry, College of Science and Arts, King Abdulaziz University, P.O. Box 344 Rabigh 21911, Kingdom of Saudi Arabia ;Centro de Química Física Molecular, Instituto Superior Técnico, University of Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal
Grzegorz Gajewski
Research Center for Applied Sciences, Academia Sinica, 128 Academia Road, Section 2, Nankang 115-29, Taipei, Taiwan

Corresponding Author(s) : Jamal Lasri

jlasri@kau.edu.sa

Asian Journal of Chemistry, Vol. 26 No. 22 (2014): Vol 26 Issue 22

Abstract

DFT-based computational study of the reaction mechanism of the acyclic nitrone (Z)-N-methyl-C-phenylnitrone (1) with 1,3-indandione (2) by using the metadynamic method within the CPMD package was investigated. Two theoretical simulations have been performed to study this reaction. The first one corresponds to the formation of the alkylhydroxylamine intermediate, while the second one concerns the C-N bond cleavage which leads to the elimination of N-methylhydroxylamine and formation of 2-benzylidene-2H-indene-1,3-dione (2'). The gas phase calculations predicted that the reaction is slightly endothermic (+2.71 kcal/mol). The computed energy profile also indicated that the ketone-enol tautomerization in this reaction determines the height of the free energy barrier which is about 30 kcal/mol.

Keywords

Metadynamic method Acyclic nitrones Endiones β-Diketones
Lasri, J., & Gajewski, G. (2014). Theoretical Studies of Reaction Mechanism of 1,3-Indandione with (Z)-N-Methyl-C-Phenylnitrone by Metadynamic Approach. Asian Journal of Chemistry, 26(22), 7785–7788. https://doi.org/10.14233/ajchem.2014.17794
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