Computational Studies on Keto-Enol Tautomerism of Mesoxaldehyde, 1,2-Bis-Phenyl Hydrazone (MBPH) in the Gas Phase Using HF and DFT Methods, to Investigate the Possibility of Using This Structure for the Synthesis of Different Heterocyclic Compounds, Confirmed by Spectral Tools
In this article, the optimized geometries of six possible tautomers of mesoxaldehyde 2,3-bis-phenyl hydrazone (MBPH) (1) have been studied in the gas phase by ab initio Hartree-Fock (HF) and density Functional theories DFT with different levels of theory, B3LYP, B3PW91, WB97XD, with 6-311G(d,p) basis set. The different conformers of the compound were studied using the B3LYP functional with a 6-311G(d,p) basis set. Optimum molecular geometries, electronic properties, and energetics of these systems have been discussed as the energy gap was determined using HOMO and LUMO energy values. Also, the reactivity descriptors such as Hardness (η), Softness (1/η), electronegativity index (χ), Chemical potential (μ), Electrophilicity (ω = ？？2/2？？), and Nucleophilicity (EHOMO + 9.12), indicate the electrophilic and nucleophilic nature of the different tautomers. The most stable conformer with the minimum energy was identified. This conformer was used for further computations, and electrophilic and nucleophilic regions have been identified with the aid of an MESP plot. The contour map shows electron density flow in the molecule. Thermodynamic properties and tautomeric equilibria between different tautomers were calculated using frequency calculations. Finally, mesoxaldehyde is used as a starting material to synthesize new heterocycles identified by different spectral tools.
References
[1]
Kipnis, A.Y., Yavelov, B.E. and Rowlinson, J.S. (1996) Van der Waals and Molecular Science. Oxford University Press. https://doi.org/10.1093/oso/9780198552109.001.0001
[2]
Katundu, S.M. (2017) Computational Studies of Lactam Tautomers by Using HF and DFT Methods in Gas and Solvent Phase. Master’s Thesis, University of Dodoma.
[3]
Szabo, A. and Ostlund, N.S. (1996) Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory. Courier Corporation. https://scholar.google.com/scholar?cites=11787991376577675180&as_sdt=2005&sciodt=0,5&hl=en
[4]
Hartree, D.R. (1928) The Wave Mechanics of an Atom with a Non-Coulomb Central Field. Part I. Theory and Methods. MathematicalProceedingsoftheCambridgePhilosophicalSociety, 24, 89-110. https://doi.org/10.1017/s0305004100011919
[5]
Lee, C., Yang, W. and Parr, R.G. (1988) Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. PhysicalReviewB, 37, 785-789. https://doi.org/10.1103/physrevb.37.785
[6]
Christopher, J.C. (2002) Essentials of Computational Chemistry. Wiley.
[7]
Jensen, F. (2007) Introduction to Computational Chemistry. 2nd Edition, John Wiley & Sons Ltd.
[8]
Hohenberg, P. and Kohn, W. (1964) Inhomogeneous Electron Gas. PhysicalReview, 136, B864-B871. https://doi.org/10.1103/physrev.136.b864
[9]
Kohn, W., Becke, A.D. and Parr, R.G. (1996) Density Functional Theory of Electronic Structure. TheJournalofPhysicalChemistry, 100, 12974-12980. https://doi.org/10.1021/jp960669l
[10]
Foresman, J.B. and Frisch, E. (1996) Exploring. Chemistry with Electronic Structure Methods. 2nd Edition, Gaussian, Inc.
[11]
Becke, A.D. (1998) A New Inhomogeneity Parameter in Density-Functional Theory. TheJournalofChemicalPhysics, 109, 2092-2098. https://doi.org/10.1063/1.476722
[12]
Tozer, D.J. (1998) Effective Homogeneity of the Exchange-Correlation Energy Functional. Physical Review A, 58, 3524-3527. https://doi.org/10.1103/physreva.58.3524
[13]
Miehlich, B., Savin, A., Stoll, H. and Preuss, H. (1989) Results Obtained with the Correlation Energy Density Functionals of Becke and Lee, Yang and Parr. ChemicalPhysicsLetters, 157, 200-206. https://doi.org/10.1016/0009-2614(89)87234-3
[14]
Senthilkumar, K. and Kolandaivel, P. (2002) Quantum Chemical Studies on Tautomerism of Barbituric Acid in Gas Phase and in Solution. JournalofComputer-AidedMolecularDesign, 16, 263-272. https://doi.org/10.1023/a:1020273219651
[15]
Beytur, M. and Avinca, I. (2021) Molecular, Electronic, Nonlinear Optical and Spectroscopic Analysis of Heterocyclic 3-Substituted-4-(3-Methyl-2-Thienylmethyleneamino)-4,5-Dihydro-1h-1,2,4-Triazol-5-Ones: Experiment and DFT Calculations. HeterocyclicCommunications, 27, 1-16. https://doi.org/10.1515/hc-2020-0118
[16]
March, T.J. (1992) Advanced Organic Chemistry. 4th Edition, Wiley, 330-335.
[17]
El Kadem, H. and Abdel Rahman, M.M.A. (1966) Studies on the Products Obtained by the Periodate Oxidation of the Osazones. Carbohydrate Research, 3, 25-31. https://doi.org/10.1016/S0008-6215(00)82292-2
[18]
Vakili, M., Nekoei, A., Tayyari, S.F., Kanaani, A. and Sanati, N. (2012) Conformation, Molecular Structure, and Intramolecular Hydrogen Bonding of 1,1,1-Trifluoro-5,5-Dimethyl-2,4-Hexanedione. JournalofMolecularStructure, 1021, 102-111. https://doi.org/10.1016/j.molstruc.2012.04.009
[19]
Berenji, A.R., Tayyari, S.F., Rahimizadeh, M., Eshghi, H., Vakili, M. and Shiri, A. (2013) Structure and Vibrational Analysis of Methyl 3-Amino-2-Butenoate. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 102, 350-357. https://doi.org/10.1016/j.saa.2012.10.042
[20]
Gilli, G., Bellucci, F., Ferretti, V. and Bertolasi, V. (1989) Evidence for Resonance-Assisted Hydrogen Bonding from Crystal-Structure Correlations on the Enol Form of the .β.-Diketone Fragment. JournaloftheAmericanChemicalSociety, 111, 1023-1028. https://doi.org/10.1021/ja00185a035
[21]
Gilli, G. and Gilli, P. (2009) The Nature of the Hydrogen Bond: Outline of a Comprehensive Hydrogen. Oxford University Press. https://doi.org/10.1093/acprof:oso/9780199558964.001.0001
[22]
Caricato, M. and Frisch, M.J. (Eds.) (2009) Gaussian 09: IOps Reference. Gaussian.
[23]
Møller, C. and Plesset, M.S. (1934) Note on an Approximation Treatment for Many-Electron Systems. PhysicalReview, 46, 618-622. https://doi.org/10.1103/physrev.46.618
[24]
Becke, A.D. and Roussel, M.R. (1989) Exchange Holes in Inhomogeneous Systems: A Coordinate-Space Model. PhysicalReviewA, 39, 3761-3767. https://doi.org/10.1103/physreva.39.3761
[25]
Azeem, U., Khera, R.A., Naveed, A., Imran, M., Assiri, M.A., Khalid, M., et al. (2021) Tuning of a A-A-D-A-A-Type Small Molecule with Benzodithiophene as a Central Core with Efficient Photovoltaic Properties for Organic Solar Cells. ACSOmega, 6, 28923-28935. https://doi.org/10.1021/acsomega.1c03975
[26]
Khalid, M., Murtaza, S., Gull, K., Abid, S., Imran, M. and Braga, A.A.C. (2024) Influence of Acceptors on the Optical Nonlinearity of 5h-4-Oxa-1,6,9-Trithia-Cyclopenta[b]-As-Indacene-Based Chromophores with a Push-Pull Assembly: A DFT Approach. RSC Advances, 14, 1169-1185. https://doi.org/10.1039/d3ra06673h
[27]
Adeel, M., Khalid, M., Ullah, M.A., Muhammad, S., Khan, M.U., Tahir, M.N., et al. (2021) Exploration of CH⋯F & CF⋯H Mediated Supramolecular Arrangements into Fluorinated Terphenyls and Theoretical Prediction of Their Third-Order Nonlinear Optical Response. RSC Advances, 11, 7766-7778. https://doi.org/10.1039/d0ra08528f
[28]
Ayyash, A.N. (2022) Theoretical Study of Some Spectral Properties of Laser Dye by Using Gaussian Program and Gauss View Depending on Density Function Theory. https://ssrn.com/abstract=4277430
[29]
Zhurko, G.A. and Zhurko, D.A. (2005) ChemCraft: Tool for Treatment of Chemical Data, Lite Version Build 08 (Freeware). https://www.chemcraftprog.com/download.html
[30]
Politzer, P. and Murray, J.S. (1996) Relationships of Electrostatic Potentials to Intrinsic Molecular Properties. In: Theoretical and Computational Chemistry, Elsevier, Vol. 3, 649-660. https://doi.org/10.1016/s1380-7323(96)80056-2
[31]
Rocha, M., Di Santo, A., Ben Altabef, A. and M. Gil, D. (2019) Intermolecular Interactions, Spectroscopic and Theoretical Investigation of 4-aminoacetophenone. InternationalJournalofAdvancedChemistry, 7, 1-12. https://doi.org/10.14419/ijac.v7i1.14703
[32]
Amalanathan, M., Rastogi, V.K., Hubert Joe, I., Palafox, M.A. and Tomar, R. (2011) Density Functional Theory Calculations and Vibrational Spectral Analysis of 3,5-(Dinitrobenzoic Acid). SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 78, 1437-1444. https://doi.org/10.1016/j.saa.2011.01.023
[33]
Vivas-Reyes, R., Núñez-Zarur, F. and Martınez, E. (2008) Electronic Structure and Reactivity Analysis for a Set of Zn-Chelates with Substituted 8-Hydroxyquinoline Ligands and Their Application in OLED. OrganicElectronics, 9, 625-634. https://doi.org/10.1016/j.orgel.2008.04.004
[34]
Karabacak, M. and Kurt, M. (2008) Comparison of Experimental and Density Functional Study on the Molecular Structure, Infrared and Raman Spectra and Vibrational Assignments of 6-Chloronicotinic Acid. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 71, 876-883. https://doi.org/10.1016/j.saa.2008.02.014
[35]
Tayyari, S.F., Zahedi-Tabrizi, M., Azizi-Toupkanloo, H., Hepperle, S.S. and Wang, Y.A. (2010) The Nature of Intramolecular Hydrogen Bond in 2-Nitromalonaldehyde. ChemicalPhysics, 368, 62-65. https://doi.org/10.1016/j.chemphys.2009.12.016
[36]
Belova, N.V., Oberhammer, H., Trang, N.H. and Girichev, G.V. (2014) Tautomeric Properties and Gas-Phase Structure of Acetylacetone. TheJournalofOrganicChemistry, 79, 5412-5419. https://doi.org/10.1021/jo402814c
[37]
Kwiatkowski, J.S., Zielinski, T.J. and Rein, R. (1986) Quantum-Mechanical Prediction of Tautomeric Equilibria. AdvancesinQuantumChemistry, 18, 85-130. https://doi.org/10.1016/s0065-3276(08)60048-9
[38]
Mulliken, R.S. (1955) Electronic Population Analysis on LCAO-MO Molecular Wave Functions. I. TheJournalofChemicalPhysics, 23, 1833-1840. https://doi.org/10.1063/1.1740588
[39]
Balachandran, V. and Parimala, K. (2012) Tautomeric Purine Forms of 2-Amino-6-Chloropurine (N9H10 and N7H10): Structures, Vibrational Assignments, NBO Analysis, Hyperpolarizability, HOMO-LUMO Study Using B3 Based Density Functional Calculations. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 96, 340-351. https://doi.org/10.1016/j.saa.2012.05.050
[40]
Lakshmi, A. and Balachandran, V. (2013) Rotational Isomers, NBO and Spectral Analyses of N-(2-Hydroxyethyl) Phthalimide Based on Quantum Chemical Calculations. JournalofMolecularStructure, 1033, 40-50. https://doi.org/10.1016/j.molstruc.2012.08.002
[41]
Ramalingam, S., Karabacak, M., Periandy, S., Puviarasan, N. and Tanuja, D. (2012) Spectroscopic (Infrared, Raman, UV and NMR) Analysis, Gaussian Hybrid Computational Investigation (MEP Maps/HOMO and LUMO) on Cyclohexanone Oxime. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 96, 207-220. https://doi.org/10.1016/j.saa.2012.03.090
[42]
Arshad, M.N., Mahmood, T., Khan, A.F., Zia-Ur-Rehman M., Asiri, A.M, Khan, I.U. and Nisa, R.U. (2015) Synthesis, Crystal Structure and Spectroscopic Properties of 1,2-Benzothiazine Derivatives: An Experimental and DFT Study. Chinese Journal of Structural Chemistry, 34, 15-25. https://api.semanticscholar.org/CorpusID:101481196%7D
[43]
Arshad, M.N., Asiri, A.M., Alamry, K.A., Mahmood, T., Gilani, M.A., Ayub, K., et al. (2015) Synthesis, Crystal Structure, Spectroscopic and Density Functional Theory (DFT) Study of N-[3-Anthracen-9-yl-1-(4-Bromo-Phenyl)-Allylidene]-n-Benzenesulfonohydrazine. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 142, 364-374. https://doi.org/10.1016/j.saa.2015.01.101
[44]
Fleming, I. and Wiley, J. (1976) Frontier Orbitals and Organic Chemical Reactions. Sons LTD, 879-880.
[45]
Aihara, J. (1999) Reduced HOMO-LUMO Gap as an Index of Kinetic Stability for Polycyclic Aromatic Hydrocarbons. TheJournalofPhysicalChemistryA, 103, 7487-7495. https://doi.org/10.1021/jp990092i
[46]
Ruiz-Morales, Y. (2002) HOMO-LUMO Gap as an Index of Molecular Size and Structure for Polycyclic Aromatic Hydrocarbons (PAHs) and Asphaltenes: A Theoretical Study. I. TheJournalofPhysicalChemistryA, 106, 11283-11308. https://doi.org/10.1021/jp021152e
[47]
Padmaja, L., Ravikumar, C., Sajan, D., Hubert Joe, I., Jayakumar, V.S., Pettit, G.R., et al. (2008) Density Functional Study on the Structural Conformations and Intramolecular Charge Transfer from the Vibrational Spectra of the Anticancer Drug Combretastatin-A2. JournalofRamanSpectroscopy, 40, 419-428. https://doi.org/10.1002/jrs.2145
[48]
Ravikumar, C., Joe, I.H. and Jayakumar, V.S. (2008) Charge Transfer Interactions and Nonlinear Optical Properties of Push-Pull Chromophore Benzaldehyde Phenylhydrazone: A Vibrational Approach. ChemicalPhysicsLetters, 460, 552-558. https://doi.org/10.1016/j.cplett.2008.06.047
[49]
Curtiss, L.A., Redfern, P.C., Raghavachari, K. and Pople, J.A. (1998) Assessment of Gaussian-2 and Density Functional Theories for the Computation of Ionization Potentials and Electron Affinities. TheJournalofChemicalPhysics, 109, 42-55. https://doi.org/10.1063/1.476538
[50]
Sheela, N.R., Muthu, S. and Sampathkrishnan, S. (2014) Molecular Orbital Studies (Hardness, Chemical Potential and Electrophilicity), Vibrational Investigation and Theoretical NBO Analysis of 4-4’-(1h-1,2,4-Triazol-1-Yl Methylene) Dibenzonitrile Based on Abinitio and DFT Methods. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 120, 237-251. https://doi.org/10.1016/j.saa.2013.10.007
[51]
Parr, R.G., Donnelly, R.A., Levy, M. and Palke, W.E. (1978) Electronegativity: The Density Functional Viewpoint. TheJournalofChemicalPhysics, 68, 3801-3807. https://doi.org/10.1063/1.436185
[52]
Parr, R.G. and Pearson, R.G. (1983) Absolute Hardness: Companion Parameter to Absolute Electronegativity. JournaloftheAmericanChemicalSociety, 105, 7512-7516. https://doi.org/10.1021/ja00364a005
[53]
Parr, R. (1989) Density Functional Theory of Atoms and Molecules. Oxford University Press, 101.
[54]
Parr, R.G., Szentpály, L.v. and Liu, S. (1999) Electrophilicity Index. JournaloftheAmericanChemicalSociety, 121, 1922-1924. https://doi.org/10.1021/ja983494x
[55]
Domingo, L.R., Chamorro, E. and Pérez, P. (2008) Understanding the Reactivity of Captodative Ethylenes in Polar Cycloaddition Reactions. A Theoretical Study. TheJournalofOrganicChemistry, 73, 4615-4624. https://doi.org/10.1021/jo800572a
[56]
Jaramillo, P., Domingo, L.R., Chamorro, E. and Pérez, P. (2008) A Further Exploration of a Nucleophilicity Index Based on the Gas-Phase Ionization Potentials. JournalofMolecularStructure: Theochem, 865, 68-72. https://doi.org/10.1016/j.theochem.2008.06.022
[57]
Deuri, S. and Phukan, P. (2012) A DFT Study on Nucleophilicity and Site Selectivity of Nitrogen Nucleophiles. ComputationalandTheoreticalChemistry, 980, 49-55. https://doi.org/10.1016/j.comptc.2011.11.017
[58]
Prabavathi, N. and Senthil Nayaki, N. (2014) The Spectroscopic (FT-IR, Ft-Raman and NMR), First Order Hyperpolarizability and HOMO-LUMO Analysis of 2-Mercapto-4(3h)-Quinazolinone. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 129, 572-583. https://doi.org/10.1016/j.saa.2014.04.041
[59]
Prasad, M.V.S., Chaitanya, K., UdayaSri, N. and Veeraiah, V. (2013) Experimental and Theoretical (HOMO, LUMO, NBO Analysis and NLO Properties) Study of 7-Hydroxy-4-Phenylcoumarin and 5,7-Dihydroxy-4-Phenylcoumarin. JournalofMolecularStructure, 1047, 216-228. https://doi.org/10.1016/j.molstruc.2013.04.066
[60]
Fatma, S., Bishnoi, A. and Verma, A.K. (2015) Synthesis, Spectral Analysis (FT-IR, 1H NMR, 13C NMR and UV-Visible) and Quantum Chemical Studies on Molecular Geometry, NBO, NLO, Chemical Reactivity and Thermodynamic Properties of Novel 2-Amino-4-(4-(Dimethylamino)Phenyl)-5-Oxo-6-Phenyl-5,6-Dihydro-4h-pyrano[3,2-c]Quinoline-3-Carbonitrile. JournalofMolecularStructure, 1095, 112-124. https://doi.org/10.1016/j.molstruc.2015.04.026
[61]
Vitnik, V.D., Vitnik, Ž.J., Banjac, N.R., Valentić, N.V., Ušćumlić, G.S. and Juranić, I.O. (2014) Quantum Mechanical and Spectroscopic (FT-IR, 13C, 1H NMR and UV) Investigations of Potent Antiepileptic Drug 1-(4-Chloro-Phenyl)-3-Phenyl-Succinimide. SpectrochimicaActaPartA: MolecularandBiomolecularSpectroscopy, 117, 42-53. https://doi.org/10.1016/j.saa.2013.07.099
[62]
Çatıkkaş, B., Aktan, E. and Seferoǧlu, Z. (2012) DFT, Ft-Raman, FTIR, NMR, and UV-Vis Studies of a Hetarylazo Indole Dye. InternationalJournalofQuantumChemistry, 113, 683-689. https://doi.org/10.1002/qua.24043
