Kinetics, thermodynamics, and DFT studies of phenols oxidative coupling reactions with 4-amino-N, N-dimethylaniline

Authors

  • Sirwan A. Ahmad Department of Chemistry, College of Science, University of Sulaimani, 46001 Sulaymaniyah, Kurdistan, Iraq. Author
  • Mohammad T. Kareem Department of Chemistry, College of Science, University of Sulaimani, 46001 Sulaymaniyah, Kurdistan, Iraq. Author

DOI:

https://doi.org/10.17656/jzs.10912

Keywords:

Oxidative coupling reaction, Phenol, Stability constant, Rate constants, Thermodynamic parameters

Abstract

A spectrophotometric method has been established for the reaction kinetics of phenol oxidative coupling with 4-amino-N, N-dimethylaniline in the presence of potassium dichromate as an oxidant to form C14H14N2O, known as phenol blue. Optimum conditions for the reaction were investigated: maximum wavelength (λ max), linear range, molar absorptivity, and stability constant. The kinetic models were applied to the reaction, indicating that it is a first-order reaction. The activation energy (Ea) and Arrhenius constant (A) were calculated from the Arrhenius equation as 14.89 kJ·mol−1 and 3.75 × 105 s-1 respectively. Thermodynamic parameters were ΔH* 12.37 Kj·mol−1, ΔG* 5.47 kJ·mol−1 and ΔS* 22.77 J·mol−1·K−1 at 30oC.. Results indicate that the formation of the product phenol blue is non-spontaneous and endothermic in nature. Density function theory (DFT) has been done for the comparison between experimental and theoretical results using the common 6-311G(d,p) basis set. The results are in good agreement with each other, proving the reliability of the method. Finally, some preliminary test has been performed to check possibility of the product as dye.

References

Funes-Ardoiz I, Maseras F. ( 2018). Oxidative coupling mechanisms: current state of understanding. ACS DOI: https://doi.org/10.19061/iochem-bd-1-73

Catalysis. Feb 2;8(2):1161-72.

Son YW, Kwon TH, Lee JK, Pae AN, Lee JY, Cho YS, Min SJ. (2011). A concise synthesis of tetrabenazine:

an intramolecular aza-Prins-type cyclization via oxidative C–H activation. Organic Letters. Dec

;13(24):6500-3.

Wu J, Kozlowski MC. (2022). Catalytic oxidative coupling of phenols and related compounds. ACS DOI: https://doi.org/10.1021/acscatal.2c00318

catalysis. May 18;12(11):6532-49.

Sarhan AA, Bolm C. (2009). Iron (III) chloride in oxidative C–C coupling reactions. Chemical Society DOI: https://doi.org/10.1002/chin.200950240

Reviews. 38(9):2730-44.

Marino JP, Schwartz A. (1979). Selective catechol oxidations with diphenyl selenoxide. Applications to DOI: https://doi.org/10.1002/chin.197949128

phenolic coupling. Tetrahedron Letters. Jan 1;20(35):3253-6.

Syrjänen K, Brunow G. (1998). Oxidative cross-coupling of p-hydroxycinnamic alcohols with dimeric DOI: https://doi.org/10.1002/chin.199908044

arylglycerol β-aryl ether lignin model compounds. The effect of oxidation potentials. Journal of the Chemical

Society, Perkin Transactions 1. (20):3425-30.

Vershinin V, Forkosh H, Ben-Lulu M, Libman A, Pappo D. (2020). Mechanistic insights into the FeCl3-

catalyzed oxidative cross-coupling of phenols with 2-aminonaphthalenes. The Journal of Organic Chemistry.

Dec 9;86(1):79-90.

Paniak TJ, Kozlowski MC. (2020). Aerobic Catalyzed Oxidative Cross-Coupling of N, N-Disubstituted

Anilines and Aminonaphthalenes with Phenols and Naphthols. Organic letters. Feb 12;22(5):1765-70.

Casellato U, Tamburini S, Vigato PA, Vidali M, Fenton DE. (1984). Binuclear oxovanadium (IV)

complexes as catalyst for the oxygenation of the catechols. Inorganica chimica acta. Apr 16;84(1):101-4.

Edwards W, Leukes WD, Rose PD, Burton SG. (1999). Immobilization of polyphenol oxidase on chitosancoated polysulphone capillary membranes for improved phenolic effluent bioremediation. Enzyme and DOI: https://doi.org/10.1016/S0141-0229(99)00116-7

microbial technology. Nov 1;25(8-9):769-73.

Yamada K, Akiba Y, Shibuya T, Kashiwada A, Matsuda K, Hirata M. (2005). Water purification through

bioconversion of phenol compounds by tyrosinase and chemical adsorption by chitosan beads. Biotechnology

progress. 21(3):823-9.

Ashour S. (2013). New kinetic spectrophotometric method for determination of atorvastatin in pure and DOI: https://doi.org/10.4172/2153-2435.1000232

pharmaceutical dosage forms. Pharmaceutica Analytica Acta. 4(5):1-6.

Brooker LG, Sprague RH. (1941). Color and constitution. IV. 1 The absorption of phenol blue. Journal of DOI: https://doi.org/10.1021/ja01856a088

the American Chemical Society. Nov;63(11):3214-5.

Kumar A, Singh S, Mudahar GS, Thind KS. (2006). Molar extinction coefficients of some commonly used DOI: https://doi.org/10.1016/j.radphyschem.2005.12.035

solvents. Radiation Physics and Chemistry. Jul 1;75(7):737-40.

Thakur SV, Farooqui M, Naikwade SD. (2012). Thermodynamic studies of transition metal complexes

with Metformin Hydrochloride drug in 20%(v/v) ethanol-water mixture. Der Chemica Sinica. 3(6):1406-9.

Murzin DY. (2020). Requiem for the rate-determining step in complex heterogeneous catalytic reactions?. DOI: https://doi.org/10.3390/reactions1010004

Reactions. Sep 10;1(1):4.

Schmidt OP, Dechert‐Schmitt AM, Garnsey MR, Wisniewska HM, Blackmond DG. (2019). Kinetic

analysis of catalytic organic reactions using a temperature scanning protocol. ChemCatChem. Aug

;11(16):3808-13.

Schmidt OP, Dechert‐Schmitt AM, Garnsey MR, Wisniewska HM, Blackmond DG. (2019). Kinetic

analysis of catalytic organic reactions using a temperature scanning protocol. ChemCatChem. Aug

;11(16):3808-13.

Fabian Huxoll, Anna Kampwerth, Thomas Seidensticker, Dieter Vogt, Gabriele Sadowski, (2022) “

predicting solvent effects on homogeneity and kinetics of the hydro amino methylation: A thermodynamic

approach using PC-SAFT” Ind. Eng. Chem. Res. 61,5, 2323- 2332.

Pereira F, Xiao K, Latino DA, Wu C, Zhang Q, Aires-de-Sousa J. (2017)Machine learning methods to

predict density functional theory B3LYP energies of HOMO and LUMO orbitals. Journal of chemical

information and modeling. Jan 23;57(1):11-21.

Tanış E. (2022). New optoelectronic material based on biguanide for orange and yellow organic light

emitting diode: A combined experimental and theoretical study. Journal of Molecular Liquids. Jul

;358:119161.

Jaramillo P, Domingo LR, Chamorro E, Pérez P. A (2008). further exploration of a nucleophilicity index

based on the gas-phase ionization potentials. Journal of Molecular Structure: THEOCHEM. Sep 30;865(1-

:68-72.

Deuri S, Phukan P. (2012). A DFT study on nucleophilicity and site selectivity of nitrogen nucleophiles. DOI: https://doi.org/10.1016/j.comptc.2011.11.017

Computational and Theoretical Chemistry. Jan 15;980:49-55.

Tanış E. (2022). New optoelectronic material based on biguanide for orange and yellow organic light DOI: https://doi.org/10.1016/j.molliq.2022.119161

emitting diode: A combined experimental and theoretical study. Journal of Molecular Liquids. Jul

;358:119161.

Udhayakala P, Rajendiran TV, Seshadri S, Gunasekaran S. (2011). Quantum chemical vibrational study,

molecular property and HOMO-LUMO energies of 3-bromoacetophenone for Pharmaceutical application. J.

Chem. Pharm. Res. 3(3):610-25.

Mazurek AH, Szeleszczuk Ł, Pisklak DM. (2020). Periodic DFT calculations—review of applications in DOI: https://doi.org/10.3390/pharmaceutics12050415

the pharmaceutical sciences. Pharmaceutics. May 1;12(5):415.

Ayalew ME. (2022). DFT Studies on Molecular Structure, Thermodynamics Parameters, HOMO-LUMO DOI: https://doi.org/10.4236/jbpc.2022.133003

and Spectral Analysis of Pharmaceuticals Compound Quinoline (Benzo [b] Pyridine). Journal of Biophysical

Chemistry. Aug 19;13(3):29-42.

Chihaia V, Alexiev V, AlMatrouk HS. (2022). Assessment of the Heat Capacity by Thermodynamic

Approach Based on Density Functional Theory Calculations. Applications of Calorimetry. Jun 23:41.

Gunasekaran S, Kumaresan S, Arunbalaji R, Anand G, Srinivasan S. (2008 ). Density functional theory

study of vibrational spectra, and assignment of fundamental modes of dacarbazine. Journal of Chemical

Sciences. May;120:315-24.

Chugunova E, Shaekhov T, Khamatgalimov A, Gorshkov V, Burilov A. (2022). DFT Quantum-Chemical

Calculation of Thermodynamic Parameters and DSC Measurement of Thermostability of Novel Benzofuroxan

Derivatives Containing Triazidoisobutyl Fragments. International Journal of Molecular Sciences. Jan

;23(3):1471.

Published

2023-12-20

How to Cite

Kinetics, thermodynamics, and DFT studies of phenols oxidative coupling reactions with 4-amino-N, N-dimethylaniline. (2023). Journal of Zankoy Sulaimani - Part A, 25(2), 19. https://doi.org/10.17656/jzs.10912