Abstract

This study involved akinetic analysis using a spectrophotometric method by monitoring the formation of an orange azo dye resulting from the reaction of the diazotized metoclopramide reagent ((Z)-5-chloro-4-(chlorodiazenyl)-N-(2-(diethylamino)ethyl)-2-methoxybenzamide) with resorcinol. The reaction was condected at 294 K and a wavelength of λmax=300nm (characteristic of the resulting dye ) in an acidic medium (pH=4.41) under conditions optimized spectrophotometrically. A 1:1 mole ratio of reactants (resorcinol: diazotized metoclopramide reagent) was used, with an aqueous solution concentration of 0.5x 10-3 mol.L-1 for each. Dye formation kinetics were investigated by monitoring formation times using the aforementioned instrument. It was observed that increasing the reagent concetration tenfold (to 5.0 x 10-3 mol.L-1) did not affect the rate constant (k1) of the dye formation reaction show that the reaction follows pseudo-first-order kinetics with respect to resorcinol. This enabled the calculation of the dye formation rate-constant at four temperatures (274, 284. 294 and 304K), with the highest value recorded at 304 K (0.0705 min-1 ) and the lowest at 274 K (0.0599min-1). In addition to calculating the half-lives for the dye formation reaction and determining the time required for the reaction completion (t1/2=9.83 min at 304K, 10.44 min at 294K, 10.93 min at 284K, and 11.57 min at 274K). The study results demonstrated that half-life values are inversely proportional to reaction rate constants as temperature increases under identical conditions. The low activation energy value (Ea=4.107kJ/mol) indicates that the formation reaction proceeds rapidly and spontaneously without the need for catalysts a feature that enhances its industrial economic viability.

References

1. Shakhatreh, M., Jehangir, A., Malik, Z., & Parkman, H. P. (2019). Metoclopramide for the treatment of diabetic gastroparesis. Expert Review of Gastroenterology & Hepatology, 13(8), 711–721. DOI:10.1080/17474124.2019.1645594.
2. De Oliveira Jr, G. S., Castro-Alves, L. J., Chang, R., Yaghmour, E., & McCarthy, R. J. (2012). Systemic metoclopramide to prevent postoperative nausea and vomiting: a meta-analysis without Fujii's studies. British journal of anaesthesia, 109(5), 688-697. DOI:10.1093/bja/aes325 .
3. Parkman, H., Mishra, A., Jacobs, M., Pathikonda, M., Sachdeva, P., Gaughan, J., & Krynetskiy, E. (2012). Clinical Response and Side Effects of Metoclopramide: Associations With Clinical, Demographic, and Pharmacogenetic Parameters. Journal of Clinical Gastroenterology, 46(6), 494–503. DOI:10.1097/MCG.0b013e3182522624.
4. Surawski, R.J. and D.K. Quinn, Metoclopramide and homicidal ideation: a case report and literature review. Psychosomatics, 2011. 52(5): p. 403-409. DOI: 10.1016/j.psym.2011.02.001
5. Vogel, I., Practical organic chemistry. 1974: Citeseer.
6. Abdullah, H.M. and M.T. Tawfiq, Synthesis and Characterization of Some New Azo Dyes Derivatives Via Chalcone and Study Some of Their Biological Activity. Baghdad Science Journal, 2016. 13(1): p. 0122-0122. DOI: 10.21123/bsj.2016.13.1.0122.
7. El‐Mallah, N., et al., Effect of acetonitrile–water mixtures on the reaction of dinitrochlorobenzene and dinitrochlorobenzotrifluoride with hydroxide ion. International Journal of Chemical Kinetics, 2010. 42(8): p. 453- 463. . DOI: 10.1002/kin.20495
8. Mwene-Mbeja, T.M., Chemical stability of pharmaceutical organic compounds. Article American Journal of Biomedical Science & Research, Abstract, 2019. DOI: 10.34297/AJBSR.2019.06.000984
9. Shankarling, G.S., P.P. Deshmukh, and A.R. Joglekar, Process intensification in azo dyes. Journal of environmental chemical engineering, 2017. 5(4): p. 3302-3308. .DOI: 10.1016/j.jece.2017.05.057
10. Marcus, Y., Solvent mixtures: properties and selective solvation. 2002: CRC Press.
11. Altun, Y., Study of solvent composition effects on the protonation equilibria of various anilines by multiple linear regression and factor analysis applied to the correlation between protonation constants and solvatochromic parameters in ethanol–water mixed solvents. Journal of solution chemistry, 2004. 33: p. 479-497. DOI: 10.1023/B:JOSL.0000037772.55748.a3
12. Azzouz, A. and A. Obed Agha, The influence of surfactants and solvents on the stability constant value of some azo dyes formation between oximes and the diazotized Sulphanilic acid salt. Journal of Education and Science, 2005. 17(2): p. 10-16. DOI: 10.33899/edusj.2005.81306
13. Hasan, A.H. and B.A. Jaff, Synthesis and Characterization of Some New Pyrazoline Compounds Derived from Azo Chalcones. Journal of Garmian University, 2019. 6(SCAPAS Conferance): p. 18-25. DOI: 10.24271/garmian.scpas3
14. El-Subruiti, G.M., Kinetics and thermodynamics of solvolysis of a cationic and an anionic chlorocobalt (III) complex in water–ethanol mixtures. Journal of solution chemistry, 2002. 31: p. 415-423. DOI: 10.1023/A:1015863416229
15. Ali Mohsin, A.H., H. Al-Niemi, and M. Mahmoud, Thermodynamic study for the stability of aromatic complexes formation derived from the reaction of 4-dimethyl amino benzaldehyde with diazotized dinitro aniline reagents. Egyptian Journal of Chemistry, 2022. 65(2): p. 421-437. DOI: 10.21608/ejchem.2021.87003.4241
16. Fathalla, M.F., T.S. Kassem, and E.A. Hamed, Kinetics of the reaction between methyl 2, 4-dichloro-3, 5- dinitrobenzoate and piperidine—solvent effect. 2008. DOI: 10.1007/s10953-011-9722-2
17. Fathalla, M.F., Kinetics of the Reaction of 2-Chloro-quinoxaline with Hydroxide Ion in ACN–H 2 O and DMSO– H 2 O Binary Solvent Mixtures. Journal of solution chemistry, 2011. 40: p. 1258-1270. DOI: 10.1007/s10953-011- 9722-2
18. Hamed, E.A., Nucleophilic substitution at the pyridine ring. Kinetics of the reaction of 2‐chloro‐3, 5‐ dinitropyridine with arylthiolates in methanol. International journal of chemical kinetics, 1997. 29(7): p. 515-521. DOI: 10.1002/(SICI)1097-4601(1997)29:7<515::AID-KIN5>3.0.CO;2-X
19. EL Hegazy, F.E.Z.M., et al., Kinetics of the reaction of 2‐chloro‐3, 5‐dinitropyridine with meta‐and para‐ substituted anilines in methanol. Journal of Physical Organic Chemistry, 2000. 13(9): p. 549-554. DOI: 10.1002/1099-1395(200009)13:9<549::AID-POC297>3.3.CO;2-X
20. Mohammed, I.Y. and I.K. Jassism, Synthesis of New Heterocyclic Polymers from Chalcone. Iraqi National Journal of Chemistry, 2017. 17(1).
21. Ahmed, N.G. and H.Y. Ridha, Synthesis of Some New Chalcone Compounds Derived From (Phenyl Quinoxaline Methyl Benzotriazol) of an Expected Biological Activity. Journal of Education and Science, 1970. 28(2): p. 1-22. DOI: 10.33899/edusj.1970.161174
22. Shehata, A.K., et al., Kinetics of the reaction of arylethanediylidene‐bis‐dithiocarbazonoate Ni complexes with morpholine in benzene: Substituent and temperature effects. International Journal of Chemical Kinetics, 2012. 44(1): p. 27-40. DOI: 10.1002/kin.20587
23. Mohsin, A. H. A. (2025). Kinertics Study of The Formation of azo dye derived from a drug (17- (Cycloprpylmethyl)-4,5Α-Epoxy-3, 14-dihydroxymorphinan -6-one). Bani Waleed University Journal of Humanities and Applied Sciences, 10(4), 128-141. DOI:10.58916/jhas.v10i4.979