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DFT study of the condensation products of 2-chloro-3-formylquinolines with o-aminophenol, o-aminothiophenol and o-phenylenediamine

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Abstract

The reaction mechanism for the synthesis of quinoline-fused benzo/dia/oxa/thia/zepins is investigated using the DFT/B3LYP/6-31G(d) method. DFT conceptual reactivity indices analysis allows classification of o-aminophenol (2, X = O), o-aminothiophenol (2, X = S) and o-phenylenediamine (2, X = N) and R-substituted 2-chloroquinoline-3-carbaldehydes (1 ac) as strong electrophiles, suggesting a polar process. Besides, Parr functions and Fukui indices predict the most reactive sites for observed experimentally product formation, in agreement with the dual descriptor analysis. In the energy aspect, there is no effect of the R (R = CH3, OCH3) substituent on the thermodynamic quantities, whereas the substitution of the X has a remarkable effect. The products (4a–c, X = N) are the most stable, and their cyclizations are the easiest. An extended analysis was performed using the activation strain model/energy decomposition analysis ASM/EDA model. The obtained results indicate that the orbital interaction and electrostatic stabilizations are the principal factors favoring the reaction with X = N. Topological analysis of the electron localization function (ELF) of the bending point structures along the reaction path indicates that the reaction occurs via a non-concerted two-step mechanism.

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Authors and Affiliations

  1. Faculty of Science, Department of Chemistry, University of Msila, BP 166 Ichbilia, 28000, M’sila, Algeria

    Nabila Benabila & Nadjia Latelli

  2. Laboratoire Chimie Des Matériaux Et Des Vivants: Activité, Réactivité, Université El-Hadj, Lakhdar Batna1, 05001, Batna, Algeria

    Nabila Benabila, Hafida Merouani & Nadjia Latelli

  3. Faculty of Technology, Common Core Department, University of Ben Boulaid Batna 2, Batna, Algeria

    Hafida Merouani

  4. Département de Chimie, Université Frères Mentouri, Route de Ain El Bey, 25017, Constantine, Algeria

    Abd Alghani May

  5. University of Lyon, Université Lyon 1 et CNRS UMR 5280, Institut des Sciences Analytiques, 5 rue de la Doua, 69100, Villeurbanne, France

    Christophe Morell, Lynda Merzoud & Henry Chermette

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Contributions

Conceptualization and methodology: were contributed by NB, HM, LM and CM. Investigation was contributed by NB, HM, NL, and HC. Writing—original draft preparation, was contributed by HM. Writing—review & editing, was contributed by CM, LM, HM. Experimental measurements were contributed by NB, NL, HM, AAM. Resources were contributed by NL and CM. Data curation was contributed by NB, HM, NL, LM, and HC. All authors have read and agreed to the published version of the manuscript.

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Correspondence to Hafida Merouani or Henry Chermette.

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All authors have participated in (a) conception and design, or analysis and interpretation of the data; (b) drafting the article or revising it critically for important intellectual content; and (c) approval of the final version. The authors have no affiliation with any organization with a direct or indirect financial interest in the subject matter discussed in the manuscript.

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Benabila, N., Merouani, H., Latelli, N. et al. DFT study of the condensation products of 2-chloro-3-formylquinolines with o-aminophenol, o-aminothiophenol and o-phenylenediamine. Theor Chem Acc 142, 111 (2023). https://doi.org/10.1007/s00214-023-03052-2

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