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Kinetics, thermodynamics and stability constants of aniline oxidative coupling reaction with promethazine: experimental and computational study

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Abstract

A spectrophotometric method was employed to investigate the kinetics and thermodynamics of the oxidative coupling reaction between aniline and promethazine at various temperatures. Experimental and computational techniques, including Fourier transform infrared spectroscopy, ultraviolet–visible spectrophotometry and elemental analysis were used to characterize the resulting product. The kinetic analysis revealed that the reaction followed a first-order model and rate constants were determined across different temperatures ranging from 0.05367 to 0.08947 min−1. Furthermore, the stability constant of the reaction was determined at different temperatures, demonstrating an increase with rising temperature indicating an endothermic nature of the reaction. The activation energy (Ea) and pre-exponential factor (A) were determined as 9.3369 kJ/mol and 2.809 min−1. Thermodynamic analysis unveiled values for activation parameters: entropy (ΔS* = − 0.2447 kJ/mol K), enthalpy (ΔH* =  + 6.826 kJ/mol) and Gibbs free energy (ΔG* =  + 79.7797 kJ/mol). The positive ΔG* and ΔH* values indicated the ability of aniline via oxidative coupling with promethazine to form a product with the process meaning toward being non-spontaneous and endothermic. Additionally, a computational investigation was carried out using density functional theory (DFT) with the B3LYP/DGDZVP basis set to theoretically determine and compare the results with experimental data. The computational results closely matched the experimental data, including thermodynamic parameters, UV–Vis spectrophotometry, IR spectroscopy and molecular orbital energy gap as elucidated by Gaussian software.

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

References

  1. Argese E, Bettiol C, Fasolo M et al (2002) Substituted aniline interaction with submitochondrial particles and quantitative structure-activity relationships. Biochim Biophys Acta—Biomembr 1558:151–160. https://doi.org/10.1016/S0005-2736(01)00424-2

    Article  CAS  Google Scholar 

  2. Miao H, Ma K, Hu S et al (2019) Aerobic oxidative coupling of aniline catalyzed by one-dimensional manganese hydroxide nanomaterials. Synlett 30:552–556. https://doi.org/10.1055/S-0037-1612108

    Article  CAS  Google Scholar 

  3. Ibrahim KA (2014) Synthesis and characterization of some new aromatic diamine monomers from oxidative coupling of anilines and substituted aniline with 4-amino-N, N-dimethyl aniline. Arab J Chem 7:1017–1023. https://doi.org/10.1016/J.ARABJC.2010.12.029

    Article  CAS  Google Scholar 

  4. Anjalin M, Kanagathara N, Suganthi AB (2020) A brief review on aniline and its derivatives. Mater Today Proc 33:4751–4755

    Article  Google Scholar 

  5. Wang K, Li X, Yang K et al (2022) A novel synthetic method of 1, 1, 4, 4-tetramethyl-2-tetrazene (TMTZ) via photocatalytic reaction. FirePhysChem 2:267–271

    Article  Google Scholar 

  6. Kareem MT (2011) Synthesis and characterization of some anilines oxidative coupling products. Tikrit J Pure Sci 16:42–49

    Google Scholar 

  7. Funes-Ardoiz I, Maseras F (2018) Oxidative coupling mechanisms: current state of understanding. ACS Catal 8:1161–1172

    Article  CAS  Google Scholar 

  8. Mallappa D, Res USB (2020) Formulation development and evaluation of promethazine as a lozenge. Am J Pharm Heal 8:18–30

    CAS  Google Scholar 

  9. Ekberg C, Nilsson M, Brown P (2019) Determining stability constants using the AKUFVE technique. Solvent Extr Ion Exch 37:213–225. https://doi.org/10.1080/07366299.2019.1639356

    Article  CAS  Google Scholar 

  10. Shakerzadeh E (2016) Theoretical investigations of interactions between boron nitride nanotubes and drugs. Micro Nano Technol 59–77. https://doi.org/10.1016/B978-0-323-38945-7.00004-3

    Chapter  Google Scholar 

  11. Martin A, Daniel B, Jan ML (2004) Development of novel density functionals for thermochemical kinetics. J Chem Phys 2(2):303431

    Google Scholar 

  12. Bagayoko D (2014) Understanding density functional theory (DFT) and completing it in practice. AIP Adv. https://doi.org/10.1063/1.4903408

    Article  Google Scholar 

  13. Poleshchuk OK, Yureva AG, Filimonov VD, Frenking G (2009) Study of a surface of the potential energy for processes of alkanes free-radical iodination by B3LYP/DGDZVP method. J Mol Struct THEOCHEM 912:67–72. https://doi.org/10.1016/J.THEOCHEM.2009.03.001

    Article  CAS  Google Scholar 

  14. Bobadova-Parvanova P, Jackson KA, Srinivas S et al (2002) Scanning the potential energy surface of iron clusters: a novel search strategy. J Chem Phys 116:3576–3587. https://doi.org/10.1063/1.1445113

    Article  CAS  Google Scholar 

  15. Fouda AS, El-Shafei AA, Elasklany AH, Madkour LH (2010) Inhibition effect of Schiff base compounds on the corrosion of iron in nitric acid and sodium hydroxide solutions. J Corr Sci Eng (JCSE) 13:1–28

    Google Scholar 

  16. Khashi M, Beyramabadi S, Gharib A (2018) Novel Schiff bases of pyrrole: synthesis, experimental and theoretical characterizations, fluorescent properties and molecular docking. Iran J Chem Chem Eng 37:59–72

    CAS  Google Scholar 

  17. Bhat AR, Wagay MH (2017) Synthesis of Schiff’s base derivatives using water as solvent. (A green methodology). Int J Res Appl Sci Eng Technol 5:971–982

    Article  Google Scholar 

  18. Andreani F, Bizzarri PC, Casa CD et al (1991) Ladder oligophenothiazines by direct thionation of N-arylanilino derivatives. J Heterocycl Chem 28:295–299. https://doi.org/10.1002/JHET.5570280215

    Article  CAS  Google Scholar 

  19. Aier M, Baruah S, Puzari A (2022) Spectroscopic investigation (IR and NMR) and HOMO-LUMO analysis of aromatic imines using theoretical approach. J Indian Chem Soc 99:100683

    Article  CAS  Google Scholar 

  20. Isac Paulraj E, Muthu S (2013) Spectroscopic studies (FTIR, FT-Raman and UV), potential energy surface scan, normal coordinate analysis and NBO analysis of (2R,3R,4R,5S)-1-(2-hydroxyethyl)-2-(hydroxymethyl) piperidine-3,4,5-triol by DFT methods. Spectrochim Acta A 108:38–49

    Article  CAS  Google Scholar 

  21. Alghamdi SK, Abbas F, Hussein RK, Alhamzani AG, El-Shamy NT (2023) Spectroscopic characterization (IR, UV-Vis), and HOMO-LUMO, MEP, NLO, NBO Analysis and the antifungal activity for 4-bromo-N-(2-nitrophenyl) benzamide; using DFT modeling and in silico molecular docking. J Mol Struct 1271:134001

    Article  CAS  Google Scholar 

  22. Diya EP, Unni M, Rajimon KJ et al (2023) Synthesis, spectral features, electronic structure studies, and molecular docking analysis of a Schiffbase (E)-1-(4-chlorophenyl)-N-(nitrophenyl)methanimine from 4-chloroaniline and 2-nitrobenzaldehyde. Vietnam J Chem 61:1–16. https://doi.org/10.1002/VJCH.202300001

    Article  Google Scholar 

  23. Kirby ME, Simperler A, Krevor S et al (2018) Computational tools for calculating log β values of geochemically relevant uranium organometallic complexes. J Phys Chem A 122:8007–8019. https://doi.org/10.1021/ACS.JPCA.8B06863

    Article  CAS  PubMed  Google Scholar 

  24. Ghosh B, Roy N, Roy D et al (2021) An extensive investigation on supramolecular assembly of a drug (MEP) with βCD for innovative applications. J Mol Liq 344:117977

    Article  CAS  Google Scholar 

  25. Guin M, Halder S, Chatterjee S, Structure SK (2022) Synthesis, X-ray crystal structure of Cu (II) 1D coordination polymer: in view of Hirshfeld surface, FMO, molecular electrostatic potential (MEP) and natural bond orbital. J Mol Struct 1270:133949

    Article  CAS  Google Scholar 

  26. Ahmed MSM, Mekky AE, Sanad SM (2022) Regioselective cycloaddition synthesis and theoretical calculations of new chromene-pyrazole hybrids: a DFT-based Parr Function, Fukui Function, local. J Mol Struct 1267:133583

    Article  Google Scholar 

  27. Alcolea Palafox M, Gil M, Nez JL, Tardajos G (2002) Study of phenothiazine and N-methyl phenothiazine by infrared, Raman, 1H-, and 13C-NMR spectroscopies. Int J Quantum Chem 89:147–171. https://doi.org/10.1002/QUA.10314

    Article  Google Scholar 

  28. Nandiyanto ABD, Oktiani R, Ragadhita R (2019) How to read and interpret FTIR spectroscope of organic material. Indones J Sci Technol 4:97–118

    Article  Google Scholar 

  29. Li XX, Wang Y, Xu PP, Zhang QZ, Nie K, Hu X, Kong B, Li L, Chen J (2013) Effects of temperature and wavelength choice on in-situ dissolution test of Cimetidine tablets. J Pharm Anal 3:71–74

    Article  CAS  PubMed  Google Scholar 

  30. Elsherif K, Zubi A, Abajja SA et al (2020) Spectrophotometric and conductometric study of formation constant and stoichiometry of Co(II)-salen type ligand complex. Arab J Chem Environ Res. https://doi.org/10.22034/IJNC.2020.116394.1062

    Article  Google Scholar 

  31. Shwan DM, Aziz BK (2023) Enhancing zinc (II) removal from Sulaymaniyah industrial zone sewage using novel adsorbents: a comprehensive study of natural clay, acid/base activated clay, and titanium pillared clay: insights into kinetics and thermodynamics. Reac Kinet Mech Cat. https://doi.org/10.1007/s11144-023-02455-3

    Article  Google Scholar 

  32. Zarrouk A, Hammouti B, Zarrok H, Al-Deyab SS, Messali M (2011) Temperature effect, activation energies and thermodynamic adsorption studies of L-cysteine methyl ester hydrochloride as copper corrosion inhibitor in nitric acid 2M. Int J Electrochem Sci 6:6261–6274

    Article  CAS  Google Scholar 

  33. Sayyah SM, Essawy AA, El-Nggar AM (2015) Kinetic studies and grafting mechanism for methyl aniline derivatives onto chitosan: highly adsorptive copolymers for dye removal from aqueous solutions. React Funct Polym 96:50–60

    Article  CAS  Google Scholar 

  34. Ochterski JW (2000) Thermochemistry in Gaussian. Gaussian Inc Reseach gateate, Wallingford, pp 1–19

    Google Scholar 

  35. Stratmann RE, Scuseria GE, Frisch MJ (1998) An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules. J Chem Phys 109:8218–8224. https://doi.org/10.1063/1.477483

    Article  CAS  Google Scholar 

  36. Xu X, Chen R, Pan R, Zhang D (2020) Pyrolysis kinetics, thermodynamics, and volatiles of representative pine wood with thermogravimetry-Fourier transform infrared analysis. Energy Fuels 34:1859–1869. https://doi.org/10.1021/ACS.ENERGYFUELS.9B03872

    Article  CAS  Google Scholar 

  37. Liu H, Du X, Liang C et al (2010) Morphologies and magnetic properties of cobalt-iron Prussian blue analogues nanoparticles synthesized in microemulsion. Synth React Inorg Met Nano-Metal Chem 40:805–811. https://doi.org/10.1080/15533174.2010.522547

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, College of Science, University of Garmian, Kalar, Sulaymaniyah, 46021, Iraq

    Hayman Saeed Salih

  2. Department of Chemistry, College of Science, University of Sulaimani, Sulaymaniyah, 46001, Iraq

    Hayman Saeed Salih, Mohammad Tahir Kareem & Kareem Jumaa Jibrael

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Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Hayman S. Salih , Mohammad T. Kareem and Kareem J. Jibrael . All Authors contributed on this research equally. All authors read and approved the final manuscript.

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Correspondence to Hayman Saeed Salih.

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Salih, H.S., Kareem, M.T. & Jibrael, K.J. Kinetics, thermodynamics and stability constants of aniline oxidative coupling reaction with promethazine: experimental and computational study. Reac Kinet Mech Cat 136, 3027–3052 (2023). https://doi.org/10.1007/s11144-023-02511-y

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