Please enter verification code
Kinetic and Mechanism of Oxidation of Benzazolylformamidines by Permanganate in Alkaline Medium
American Journal of Applied Chemistry
Volume 4, Issue 2, April 2016, Pages: 50-58
Received: Feb. 21, 2016; Accepted: Mar. 6, 2016; Published: Mar. 19, 2016
Views 4711      Downloads 205
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
Ameena Al-Bonayan, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Faten Aljiffrey, Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia
Article Tools
Follow on us
In alkaline medium, the kinetics of oxidation of two substituted benzazolylformamidines, namely N, N-dimethyl-N’-(1H-benzimidazol-2-yl) formamidine (BIF) and N, N-dimethyl-N’-(benzthiazol-2-yl) formamidine (BTF) by permanganate ion has been studied spectrophotometrically at a constant ionic strength of 0.1 mol dm-3 and at 25°C. The reactions exhibited first order kinetics with respect to [permanganate]. Fractional-first order dependences of both reactions on [reductants] and [alkali] were revealed. Increasing either ionic strength or solvent polarity of the medium had no significant effect on the rates. The final oxidation products of BIF and BTF were identified as 2-aminobenzimidazole and 2-aminobenzthiazole, respectively, in addition to dimethylamine and carbon dioxide. Under comparable experimental conditions, the oxidation rate of BIF was higher than that of BTF. The reaction mechanism adequately describing the kinetic results was proposed, and the reaction constants involved in the different steps of the mechanism have been evaluated. The activation parameters with respect to the rate-limiting step of the reactions, along with thermodynamic quantities were computed and discussed.
Permanganate, Oxidation, Benzazolylformamidines, Kinetics, Mechanism
To cite this article
Ahmed Fawzy, Ishaq Zaafarany, Ismail Althagafi, Ameena Al-Bonayan, Faten Aljiffrey, Kinetic and Mechanism of Oxidation of Benzazolylformamidines by Permanganate in Alkaline Medium, American Journal of Applied Chemistry. Vol. 4, No. 2, 2016, pp. 50-58. doi: 10.11648/j.ajac.20160402.13
Copyright © 2016 Authors retain the copyright of this article.
This article is an open access article distributed under the Creative Commons Attribution License ( which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Keri RS, Patil MR, Patil SA, Budagumpi S (2015) A comprehensive review in current developments of benzothiazole based molecules in medicinal chemistry. Eur. J. Med. Chem., 89: 207-251.
Abdul Rouf CT (2014) Bioactive thiazole and benzothiazole derivatives. Eur. J. Med. Chem., 1-17.
Hisamoddin SZK, Priyanka S, Yogesh SP, Patel Nilam PU (2014) Benzothiazole the molecule of diverse biological activities. Pharma Sci. Monitor, 5: 207-225.
Shi B, Chen R, Huang Y (2004) Synthesis of N-(benzothiazol-2-yl-aminodialkyl)-thiophosphate. Gaodeng Xuexiao Huaxue Xuebao, 25: 1458–1460.
Huang ST, Hsei LJ, Chen C (2006) Synthesis and anticancer evaluation of bis(-benzimidazoles), bis(benzoxazoles), and benzothiazoles, Bioorg. Med. Chem., 14: 6106-6119.
Kamal A, Kumar BA, Arifuddin M, Dastidar SG (2006) Synthesis and biological activity of new 4β-N-heteroaryl analogues of podophyllo. Lett. Drug Design. Dis., 3: 205–209.
Yongseog Ch, Young-Kook Sh, Chang-Guo Z, Sungduck L, Hoon Ch (2004) Synthesis and evaluation of antitumor activity of 2- and 6-[(1, 3-benzothiazol-2-yl) aminomethyl]-5, 8-dimethoxy-1, 4-naphthoquinone derivatives, Arch. Pharm. Res. 27: 893–890.
Singh SP, Segal S (1988) Study of fungicidal activities of some benzothiazoles, Ind. J. Chem., 27B: 941-943.
Suresh CH, Rao JH, Jayaveera KN, Subudhi SK (2013) Synthesis and anthelmintic activity of 3-(2-hydrozino benzothiazole)-substituted indole-2-one. Int. J. Pharm., 2: 257-261.
Akhtar T, Hameed S, Al-Masoudi N, Loddo R, Colla P (2008) In vitro antitumor and antiviral activities of new benzothiazole and 1, 3, 4-oxadiazole-2-thione derivatives. Acta Pharm., 58: 135-149.
Abdel-Rahman HM, Morsy MA (2007) Novel benzothiazolyl urea and thiourea derivatives with potential cytotoxic and antimicrobial activities. J. Enz. Inh. Med. Chem., 22: 57–64.
Abdel-Zaher A, Elassar A (2015) Synthesis of benzoazolyl-N, N-dimethylformamidines: complexation and biological activity. Eur. Int. J. Sci. Technol., 4: 88-99.
Arnold DI, Cotton FA, Matonic JH, Murillo SA (1997) Poly[di-μ3-nicotinato-hemi-μ4-oxalato-hemi-μ2-oxalato-neodymium(III) silver(I)] dehydrate, Polyhedron, 16: 1837-1844.
Mitzi DB, Liang K (1997) Synthesis, resistivity, and thermal properties of the cubic perovskite NH2CH=NH2SnI3 and related systems, J. Solid State Chem., 134: 376-382.
Stewart R (1965) Oxidation in Organic Chemistry, Part A (ed.) Wiberg KB, New York, Academic Press.
Jose TP, Nandibewoor ST, Tuwar SM (2005) Mechanism of oxidation of L-histidine by heptavalent manganese in alkaline medium. E-J. Chem., 2: 75-85.
A. Fawzy, S. S. Ashour, M. A. Musleh, Base-catalyzed oxidation of L-asparagine by alkaline permanganate and the effect of alkali-metal ion catalysts: kinetics and mechanistic approach, React. Kinet. Mech. Catal., 111 (2014) 443-460.
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.
Fawzy A, Zaafarany IA, Alfahemi J, Tirkistani FA (2015) Base-catalyzed oxidation of aminotriazole derivative by permanganate ion in aqueous alkaline medium: a kinetic study. Int. J. Inn. Res. Sci. Eng. Tech., 4: 6802-6814.
Asghar BH, Fawzy A (2014) Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese(II). J. Saudi Chem. Soc., in press.
Fawzy A, Ashour SS, Musleh MA (2014) Kinetics and mechanism of oxidation of L-histidine by permanganate ions in sulfuric acid medium. Int. J. Chem. Kinet. 46: 370-381.
Ahmed GA, Fawzy A, Hassan RM (2007) Spectrophotometric evidence for the formation of short-lived hypomanganate(V) and manganate(VI) transient species during the oxidation of K-carrageenan by alkaline permanganate. Carbohydr. Res., 342: 1382-1386.
Zaafarany IA, Fawzy A, Ahmed GA, Ibrahim SA, Hassan RM, Takagi HD (2010) Further evidence for detection of short-lived transient hypomanganate(V) and manganate(VI) intermediates during oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometeric techniques. Carbohydr. Res., 345: 1588-1593.
Hassan RM, Fawzy A, Alarifi A, Ahmed GA, Zaafarany IA, Takagi HD (2011) Base-catalyzed oxidation of some sulfated macromolecules: kinetics and mechanism of formation of intermediate complexes of short-lived manganate (VI) and/or hypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganate. J. Mol. Catal. A, 335: 38-45.
Hassan RM, Dahy A, Ibrahim S, Zaafarany IA, Fawzy A (2012) Oxidation of some macromolecules. Kinetics and mechanism of oxidation of methyl cellulose polysaccharide by permanganate ion in acid perchlorate solutions. Ind. Eng. Chem. Res., 51: 5424–5432.
Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate:  oxidations of arylalkanes in organic solvents. Inorg. Chem., 36: 2069-2078.
Vogel AI (1973) Text book of practical organic chemistry including quantitative organic analysis, 3rd edn, 332 pp. ELBS, Longman.
Feigl F (1975) Spot tests in organic analysis, 195 pp. Elsevier, New York.
Simandi KI, Jaky M, Schelly ZA (1984) Short-lived manganate(VI) and manganate(V) intermediates in the permanganate oxidation of sulfite ion, J. Am. Chem. Soc., 106: 6866-6867; Simandi LI, Jaky M, Savage CR, Schelly ZA (1985) Kinetics and mechanism of the permanganate ion oxidation of sulfite in alkaline solutions. The nature of short-lived Intermediates, J. Am. Chem. Soc., 107: 4220-4224.
Cotton FA, Wilkinson G (1980) Advanced Inorganic Chemistry, pp 747, John Wiley and Sons, New York.
Hassan RM (1993) Alginate polyelectrolyte ionotropic gels. XIV. Kinetics and mechanism of formation of intermediate complex during the oxidation of alginate polysaccharide by alkaline permanganate with a spectrophotometric evidence of manganate(VI) transient species. J. Polym. Sci. A, 31: 51-59.
Panari RG, Chougale RB, Nandibewoor ST (1998) Oxidation of mandelic acid by alkaline potassium permanganate. A kinetic study, J. Phys. Org. Chem., 11: 448-454.
De Oliveira LA, Toma HE, Giesbrecht E (1976) Kinetics of oxidation of free and coordinated dimethylsulfoxide with permanganate in aqueous solution, Inorg. Nucl. Chem. Lett., 2: 195-203.
Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z. 49: 333–369.
Frost AA, Person RG (1973) Kinetics and Mechanism, 147 pp. Wiley Eastern, New Delhi; Amis ES (1966) Solvent effect on reaction rates and mechanism, pp. 28, Academic Press, New York.
Laidler K (1965) Chemical Kinetics. pp 123, McGraw-Hill, New York.
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.
Science Publishing Group
1 Rockefeller Plaza,
10th and 11th Floors,
New York, NY 10020
Tel: (001)347-983-5186