Theoretical Studies of the Chemical Reactivity of a Series of Coumarin Derivatives by the Density Functional Theory

  • Lamoussa Ouattara Faculty of Fundamental and Applied Sciences (UFR SFA), Laboratoire de Thermodynamique et de Physico-Chimie du Milieu, University NanguiAbrogoua, Abidjan, Côte d'Ivoire
  • Kafoumba BAMBA Faculty of Fundamental and Applied Sciences (UFR SFA), Laboratoire de Thermodynamique et de Physico-Chimie du Milieu, University NanguiAbrogoua, Abidjan, Côte d'Ivoire
  • Mamadou Guy-Richard Kone Faculty of Fundamental and Applied Sciences (UFR SFA), Laboratoire de Thermodynamique et de Physico-Chimie du Milieu, University NanguiAbrogoua, Abidjan, Côte d'Ivoire
  • Jean Stéphane N’dri Faculty of Fundamental and Applied Sciences (UFR SFA), Laboratoire de Thermodynamique et de Physico-Chimie du Milieu, University NanguiAbrogoua, Abidjan, Côte d'Ivoire
  • Affoué Lucie Bede Faculty of Science of Structures of Matter and Technology (UFR SSMT), Laboratoire de Constitution et Réaction de la Matière (LCRM), University Félix Houphouët - Boigny, Abidjan-Cocody, Côte d'Ivoire
  • Kouakou Nobel N’guessan Faculty of Fundamental and Applied Sciences (UFR SFA), Laboratoire de Thermodynamique et de Physico-Chimie du Milieu, University NanguiAbrogoua, Abidjan, Côte d'Ivoire
  • Doh Soro Faculty of Fundamental and Applied Sciences (UFR SFA), Laboratoire de Thermodynamique et de Physico-Chimie du Milieu, University NanguiAbrogoua, Abidjan, Côte d'Ivoire
Keywords: coumarin derivatives, global descriptors, DFT, reactivity

Abstract

The global descriptors of reactivity such as HOMO and LUMO energies, chemical hardness, electrophilicity, softness and dipole moment are theoretically determined for five coumarin derivatives in this paper. The analysis of the determined descriptors allows us to classify the studied molecules according to their reactivities. Thus, compound M3 is qualified to be the most reactive and the least stable with 3.933 eV as its gap energy ΔEgap. It is at the same time the softest, the best electron donor, the most electrophilic and the most polar molecule. The study of thermodynamic parameters shows that all the reactions of formation of studied coumarin derivatives are exothermic and spontaneous with less disorder. Furthermore, Hirschfield population analysis was carried out in order to locate the reactive sites, that are assumed to be the electrophilic and nucleophilic sites of the molecules. It appears that all the reactive sites are located on carbon atoms except those of molecule M3 which are located on oxygen atoms. Compounds M1 and M2 have the same electrophilic site (C15) and the same nucleophilic site (C13) thereby showing that the methyl group does not have any influence on the reactive site. The electrophilic site of the molecule M3 is located on both the identical oxygen atoms O33 and O34 while its nucleophilic site is located on the oxygen atoms O12. The electrophilic sites of compound M4 and M5 are the same and it is located on carbon atom(C11) while the nucleophilic site is located on carbon atom C23 for molecule M4. Concerning the nucleophilic sites of molecule M5 it is located on carbon atom C20. The difference nucleophilic reactive site may be due to the conjugation of activity of both fluorine atom and methyl group on the M5.

References

. D. Arora, Pragi; Arora, Varun; Lamba, H. S.; Wadhwa, “Importance of Heterocyclic Chemistry:,” Int. J. Pharm. Sci. Reserach, vol. 3, no. 09, pp. 2947–2954, 2012.

. P. Duquénois, “Coumarines et dérivés: Réparation dans le règne végétal et biosynthèse,” Pharm. Biol., vol. 7, no. 4, pp. 1107–1120, 1967.

. H. Mossaraf and A. K. Nanda, “A Review on Heterocyclic: Synthesis and Their Application in Medicinal Chemistry of Imidazole Moiety,” Sci. J. Chem., vol. 6, no. 5, pp. 83–94, 2018.

. M. Asif, “Overview of Diverse Pharmacological Activities of Substituted Coumarins : Compounds with Therapeutic Potentials,” vol. 1, no. 1, pp. 1–16, 2014.

. N. B. Patel, “New 4-Thiazolidinones of Nicotinic Acid with 2-Amino-6-methylbenzothiazole and their Biological Activity,” Sci. Pharm., vol. 78, no. 4, pp. 753–765, 2010, [Online]. Available: h.

. L. Ouattara, K. Bamba, M. G.-R. Koné, J. S. N’dri, and K. N. N’Guessan, “Predictive Modeling of Breast Anticancer Activity of a Series of Coumarin Derivatives using Quantum Descriptors,” Chem. Sci. Int. J., vol. 26, no. 4, pp. 1–10, 2019.

. J. B. Foresman and Æ. Frisch, Exploring Chemistry With Electronic Structure Methods Second Edition Gaussian, Inc. Wallingford, CT USA. 1996.pp 3

. M. Kurt, T. R. Sertbakan, and M. Özduran, “An experimental and theoretical study of molecular structure and vibrational spectra of 3- and 4-pyridineboronic acid molecules by density functional theory calculations,” Spectrochim. Acta - Part A Mol. Biomol. Spectrosc., vol. 70, no. 3, pp. 664–673, 2008.

. N. Z. J. S. N’dri, M. G-R. Koné, C.G.Kodjo, A. L. C. Kablan, L. Ouattara, O. Ouattara, “Combining of DFT and QSAR Results to Predict the Antibacterial Activity of a Series of Azetidinones derived from Dapsone as Inhibitors of Bacillus Subtilis and Pseudomonas Aeruginosa,” SDRP J. Comput. Chem. Mol. Model., vol. 2, no. 2, pp. 1–9, 2018.

. C. Ravikumar, I. H. Joe, and V. S. Jayakumar, “Charge transfer interactions and nonlinear optical properties of push-pull chromophore benzaldehyde phenylhydrazone: A vibrational approach,” Chem. Phys. Lett., vol. 460, no. 4–6, pp. 552–558, 2008.

. M. J. Frisch et al., “Gaussian 09, revision A. 02,” Gaussian, Inc., Wallingford, CT, 2009. 1988.

. H. B. Schlegel, “Optimization of equilibrium geometries and transition structures,” J. Comput. Chem., vol. 3, no. 2, pp. 214–218, 1982.

. R. Ditchfield, W. J. Hehre, and J. A. Pople, “Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules,” J. Chem. Phys., vol. 54, no. 2, pp. 724–728, 1971.

. R. Dennington, T. Keith, and J. Millam, “GaussView, Version 5.,” Semichem Inc. , Shawnee Mission, KS. 2016.

. J. W. Ochterski, “Thermochemistry in Gaussian.” pp. 1–19, 2000.

. M.W. Chase, C.A. Davies, J.R. Downey, D.J. Frurip, R.A McDonald and A.N. Syverud "JANAF Thermochemical Tables", 3rd ed. J. Phys. Ref. Data 14 Suppl. No. 1; 1985.

. H. Fujimoto and K. Fukui, “Molecular Orbital Theory of Chemical Reactions,” Adv. Quantum Chem., vol. 6, pp. 177–201, 1972.

. M. Belletête, J. F. Morin, M. Leclerc, and G. Durocher, “A theoretical, spectroscopic, and photophysical study of 2,7-carbazolenevinylene-based conjugated derivatives,” J. Phys. Chem. A, vol. 109, no. 31, pp. 6953–6959, 2005.

. J. I. Aihara, “Reduced HOMO-LUMO Gap as an Index of Kinetic Stability for Polycyclic Aromatic Hydrocarbons,” J. Phys. Chem. A, vol. 103, no. 37, pp. 7487–7495, 1999.

. C. Morell, A. Grand, and A. Toro-Labbé, “New dual descriptor for chemical reactivity,” J. Phys. Chem. A, vol. 109, no. 1, pp. 205–212, 2005.

. P. Bultinck, D. Clarisse, P. W. Ayers, and R. Carbo-Dorca, “The Fukui matrix: A simple approach to the analysis of the Fukui function and its positive character,” Phys. Chem. Chem. Phys., vol. 13, no. 13, pp. 6110–6115, 2011.

. J. Melin, P. W. Ayers, and J. V. Ortiz, “Removing electrons can increase the electron density: A computational study of negative fukui functions,” J. Phys. Chem. A, vol. 111, no. 40, pp. 10017–10019, 2007.

. P. Geerlings, F. De Proft, and W. Langenaeker, “Conceptual density functional theory,” Chem. Rev., vol. 103, no. 5, pp. 1793–1874, 2003.

. W. Yang and R. G. Parr, “Hardness, softness, and the fukui function in the electronic theory of metals and catalysis.,” Proc. Natl. Acad. Sci. U. S. A., vol. 82, no. 20, pp. 6723–6726, 1985.

. R. G. Parr, R. A. Donnelly, M. Levy, and W. E. Palke, “Electronegativity: The density functional viewpoint,” J. Chem. Phys., vol. 68, no. 8, pp. 3801–3807, 1978.

. R. S. Mulliken, “A new electroaffinity scale; Together with data on valence states and on valence ionization potentials and electron affinities,” J. Chem. Phys., vol. 2, no. 11, pp. 782–793, 1934.

. R. G. Pearson, “Recent advances in the concept of hard and soft acids and bases,” J. Chem. Educ., vol. 64, no. 7, p. 561, 1987.

. T. Koopmans, “Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den Einzelnen Elektronen Eines Atoms,” Physica, vol. 1, no. 1–6, pp. 104–113, 1934.

Published
2021-01-02
Issue
Vol 75 No 1 (2021)
Section
Articles

Copyright (c) 2021 American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS)

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Authors who submit papers with this journal agree to the following terms:

  1. Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
  2. Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgement of its initial publication in this journal.
  3. Authors are permitted and encouraged to post their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work (See The Effect of Open Access).
  4. By submitting the processing fee, it is understood that the author has agreed to our terms and conditions which may change from time to time without any notice.
  5. It should be clear for authors that the Editor In Chief is responsible for the final decision about the submitted papers; have the right to accept\reject any paper.  The Editor In Chief will choose any option from the following to review the submitted papers:A. send the paper to two reviewers, if the results were negative by one reviewer and positive by the other one; then the editor may send the paper for third reviewer or he take immediately the final decision by accepting\rejecting the paper. The Editor In Chief will ask the selected reviewers to present the results within 7 working days, if they were unable to complete the review within the agreed period then the editor have the right to resend the papers for new reviewers using the same procedure. If the Editor In Chief was not able to find suitable reviewers for certain papers then he have the right to accept\reject the paper.B. sends the paper to a selected editorial board member(s). C. the Editor In Chief himself evaluates the paper.
  6. Author will take the responsibility what so ever if any copyright infringement or any other violation of any law is done by publishing the research work by the author
  7. Before publishing, author must check whether this journal is accepted by his employer, or any authority he intends to submit his research work. we will not be responsible in this matter.
  8. If at any time, due to any legal reason, if the journal stops accepting manuscripts or could not publish already accepted manuscripts, we will have the right to cancel all or any one of the manuscripts without any compensation or returning back any kind of processing cost.
  9. The cost covered in the publication fees is only for online publication of a single manuscript.