Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach
Advances in Biochemistry
Volume 4, Issue 1, February 2016, Pages: 1-8
Received: Mar. 6, 2016; Accepted: Mar. 11, 2016; Published: Mar. 24, 2016
Views 4943      Downloads 182
Authors
Ahmed Fawzy, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt
Ishaq Zaafarany, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Ismail Althagafi, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Moataz Morad, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Jabir Alfahmi, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Article Tools
Follow on us
Abstract
The kinetics of oxidation of one of the formamidine derivatives, namely, methylaminopyrazole formamidine (MAPF) by cerium(IV) has been investigated in aqueous perchlorate solutions at a constant ionic strength of 1.2 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction exhibited a first order kinetics with respect to [Ce(IV)], whereas the order with respect to [MAPF] was found to be less than unity. The reaction rate decreased with the increase in acid concentration with a negative less than unit order. The rate of reaction was not affected by increasing either ionic strength or dielectric constant of the medium. Furthermore, addition of cerium(III) product did not affect the reaction rate. The plausible oxidation mechanism involves formation of an intermediate complex between MAPF substrate and the kinetically active species of cerium(IV) in a pre-equilibrium step which decomposes in the slow step to give free radical derived from the substrate and Ce(III). The free radical is attacked by another Ce(IV) species to yield the final oxidation products which were identified by spectral and chemical analyses as methylaminopyrazole, dimethylamine and carbon dioxide. The activation parameters have been evaluated and discussed. The rate law associated with the reaction mechanism was derived.
Keywords
Oxidation, Methylaminopyrazole Formamidine, Cerium(IV), Kinetics, Mechanism
To cite this article
Ahmed Fawzy, Ishaq Zaafarany, Ismail Althagafi, Moataz Morad, Jabir Alfahmi, Oxidation of Formamidines by Cerium(IV) in Aqueous Perchlorate Solutions: A Kinetics and Mechanistic Approach, Advances in Biochemistry. Vol. 4, No. 1, 2016, pp. 1-8. doi: 10.11648/j.ab.20160401.11
Copyright
Copyright © 2016 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
References
[1]
Fawzy A (2016) Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study, Carbohydr. Polym. 138: 356-364.
[2]
Mathur S, Yadav MB, Devra V (2013) Kinetics and mechanism of uncatalyzed and Ag(I) catalyzed oxidation of hydroxylysine by cerium (IV) in acid medium. J. Phys. Chem. Biophys. 3: 5-12.
[3]
Mathur S, Yadav MB, Devra V (2015) Kinetics and mechanism of uncatalyzed and Ag(I) catalyzed oxidation of serine by cerium(IV) in acid medium. Int. J. Res. Phys. Chem. 5: 1-6.
[4]
Thabaj KA, Chimatadar SA, Nandibewoor ST (2006) Mechanistic study of oxidation of palladium(II) by cerium(IV) in aqueous acid. Transition Met. Chem. 31:186-193.
[5]
Bolattin M, Meti M, Nandibewoor ST, Chimatadar SA (2015) Catalytic activity of ruthenium(III) and thermodynamic study of oxidative degradation of chloramphenicol by cerium(IV) in sulfuric acid medium. J. Solution Chem.44: 152-169.
[6]
Hosahalli RV, Savanur AP, Nandibewoor ST, Chimatadar SA (2010) Ruthenium(III)-mediated oxidation of D-mannitol by cerium(IV) in aqueous sulfuric acid medium: A kinetic and mechanistic approach. Int. J. Chem. Kinet. 42: 440-452.
[7]
Das A. K, Islam M, Bayen R (2008) Studies on kinetics and mechanism of oxidation of D-sorbitol and D-mannitol by cerium(IV) in aqueous micellar sulfuric acid media. Int. J. Chem. Kinet. 40: 445–453.
[8]
Adari KK, Nowduri A, Parvataneni V (2008) Kinetics and mechanism of oxidation of L-cystine by cerium(IV) in sulphuric acid medium. ActaChim. Slov.55:425–429.
[9]
Sumathi T, Shanmugasundaram P, Chandramohan G (2011) A kinetic and mechanistic study on the silver(I) catalyzed oxidation of L-Serine by cerium(IV) in sulfuric acid medium. J. Saudi Chem. Soc. in press.
[10]
Fawzy A, Hassan RM, Althagafi I, Morad M (2016) Cerium(IV) oxidation of sulfated polysaccharides in aqueous perchlorate solutions: a kinetic and mechanistic approach, Adv. Mater. Lett., in press.
[11]
Fawzy A, Zaafarany IA, Tirkistani FA, Al-Bonayan A, Aljiffrey FA (2016) Kinetics and mechanistic study of oxidation of pyridine derivative by cerium(IV) in aqueous perchloric acid, Am. J. Phys. Chem., 5: 10-16.
[12]
Hassan RM, Alaraifi A, Fawzy A, Zaafarany IA, Khairou KS, Ikeda Y, Takagi HD (2010) Acid-catalyzed oxidation of some sulfated polysaccharides. Kinetics and mechanism of oxidation of kappa-carrageenan by cerium(IV) in aqueous perchlorate solutions. J. Mol. Cat. A, 332: 138–144.
[13]
Naik DV, Byadagi KS, Nandibewoor ST, ChimatadarSA (2013) Kinetics and mechanistic study of manganese(II)-catalyzed cerium(IV) oxidation of thiamine hydrochloride in aqueous perchloric acid medium by stopped flow technique, Monatshefte für Chemie 144: 1307-1317.
[14]
Byadagi KS, Naik DV, Savanur AP, Nandibewoor ST, Chimatadar SA (2010) Ruthenium(III) mediated oxidation of thiamine hydrochloride by cerium(IV) in perchloric acid medium: a kinetic and mechanistic approach. React. Kinet. Mech. Catal. 99: 53-61.
[15]
Jattinagoudar LN, Byadagi KS, Nandibewoor ST, Chimatadar SA (2015) Kinetics and mechanism of cerium(IV) oxidation of fosfomycin disodium salt: an antibiotic drug in acid perchlorate solutions. Org. Nano Met. Chem. 45:1138-1144.
[16]
Khan F, Kushwaha U, Singh AK (2012) A mechanistic study based on kinetics of the oxidation of diethyl ketone by Ir(III) chloride in aqueous perchloric acid medium when cerium(IV) perchlorate is used as a catalyst. J. Chem. Pharm. Res. 4: 3715-3726.
[17]
Yadav MB, Derva V, Rani A (2009) Kinetics and mechanism of uncatalyzed and silver(I) catalyzed oxidation of lysine by cerium(IV) in acid perchlorate medium. J. Indian Chem. Soc. 86: 600-604.
[18]
Datt N, Nagori RR, Mehrotra RN (1986) Kinetics and mechanisms of oxidations by metal ions. Part VI. Oxidation of α-hydroxy acids by cerium(IV) in aqueous nitric acid. Can. J. Chem. 64: 19-23.
[19]
Leung VSK, Chan TYK, Yeung VTF (1999) Ami-trazpoisining in humans, Clinical Toxicol. 37: 513-514.
[20]
Nakayama A, Sukekawa M, Eguchi Y (1997) Stereo-chemistry and active conformation of a novel insecticide Acetamiprid. Pesticide Sci. 51: 157-164.
[21]
Beeman RW, Matsumura F (1973) Chlordimeform: a pesticide acting upon amine regulatory mechanisms. Nature. 242: 273-274.
[22]
Aziz AA, Knowles CO (1973) Inhibition of monoamine oxidase by the pesticides chlordimeform and related compounds. Nature 242: 417-418.
[23]
SaweczkoP (2001) Interaction of ferrocenoyl-dipeptides with 3-aminopyrazole derivatives: beta-sheet models: A synthetic, spectroscopic, structural, and electrochemical study, Inorg. Chem. 40: 4409-4419.
[24]
Fawzy A, Shaaban MR (2014) Kinetic and mechanistic investigations on the oxidation of N’-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium. Transition Met. Chem. 39: 379-386.
[25]
Hardwick TJ, Robertson E (1951) Ionic species in ceric perchlorate solutions. Can. J. Chem. 29: 818-828.
[26]
Vogel AI (1973) Text book of practical organic chemistry including quantitative organic analysis, 3rd edn, 332 pp. ELBS, Longman.
[27]
Feigl F (1975) Spot tests in organic analysis, 195 pp. Elsevier, New York.
[28]
Sherill MS, King CB, Spooner RC (1943) The oxidation potential of cerous-ceric perchlorates. J. Am. Chem. Soc. 65: 170-179.
[29]
Heidt LJ, Smith ME (1948) Quantum yields of the photochemical reduction of ceric ions by water and evidence for the dimerization of ceric ions. J. Am. Chem. Soc. 70: 2476-2481.
[30]
King EL, Pandow ML (1952) The spectra of cerium(IV) in perchloric acid. Evidence for polymeric species. J. Am. Chem. Soc. 74: 1966-1969.
[31]
Offner HG, Skoog DA (1966) Hydrolysis constant of quadrivalent cerium from spectrometric measurements. Anal. Chem. 38: 1520-1521.
[32]
Chimatadar SA, Madawale SV, Nandibewoor ST (2007) Mechanistic study of iodide catalysed oxidation of L-glutamic acid by cerium(IV) in aqueous sulphuric acid medium. Transition Met. Chem. 32: 634-641.
[33]
Leal JM, Domingo PL, Garcla B, Ibeas S (1993) Alkali metal ion catalysis of the oxidation of L-ascorbic acid by hexacyanoferrate(III) in strongly acidic media. J. Chem. Soc. Faraday Trans. 89: 3571–3577.
[34]
Frost AA, Person RG (1973) Kinetics and mechanism, 147 pp. Wiley Eastern, New Delhi.
[35]
Amis ES (1966) Solvent effect on reaction rates and mechanism, pp. 28, Academic Press, New York.
[36]
Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z. 49: 333–369.
[37]
Fawzy A (2015) Kinetics and mechanistic approach to the oxidative behavior of biological anticancer platinum(IV) complex towards L-asparagine in acid medium and the effect of copper(II) catalyst. Int. J. Chem. Kinet. 47: 1-12.
[38]
Freeman F, Fuselier CO, Armstead CR, Dalton CE, Davidson PA, Karchesfski EM, Krochman DE, Johnson MN, Jones NK. (1981) Permanganate ion oxidations. 13. Soluble manganese(IV) species in the oxidation of 2,4(1H,3H)-pyrimidinediones (uracils). J. Am. Chem. Soc. 103: 1154–1159.
[39]
Hicks KW, Toppen DL, Linck RG (1972) Inner-sphere electron-transfer reactions of vanadium(II) with azidoamine complexes of cobalt(III). Inorg. Chem. 11: 310-315.
[40]
Walling C (1957) Free radical in solutions, (pp. 38). New York: Academic Press.
ADDRESS
Science Publishing Group
1 Rockefeller Plaza,
10th and 11th Floors,
New York, NY 10020
U.S.A.
Tel: (001)347-983-5186