World Journal of Biochemistry and Molecular Biology  
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Permanganate Oxidation of Benzimidazole and Benzthiazole Derivatives in Diluted Sulfuric Acid Medium: Kinetics and Mechanistic Aspects
World Journal of Biochemistry and Molecular Biology
Vol.1 , No. 3, Publication Date: Oct. 11, 2016, Page: 11-19
2392 Views Since October 11, 2016, 576 Downloads Since Oct. 11, 2016
 
 
Authors
 
[1]    

Fawzy A., Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al-Mukarramah, Saudi Arabia; Chemistry Department, Faculty of Science, Assiut University, Assiut, Egypt.

[2]    

Zaafarany I. A., Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al-Mukarramah, Saudi Arabia.

[3]    

Khairou K. S., Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al-Mukarramah, Saudi Arabia.

[4]    

Al-Jahdali B. A., Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al-Mukarramah, Saudi Arabia.

[5]    

Bawazeer T. M., Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al-Mukarramah, Saudi Arabia.

[6]    

Yarkandi N., Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah Al-Mukarramah, Saudi Arabia.

 
Abstract
 

The kinetics of oxidation of N,N-dimethyl-N’-(1H-benzimidazol-2-yl) formamidine (BIF) and N,N-dimethyl-N’-(benzthiazol-2-yl) formamidine (BTF) by permanganate ion in diluted sulfuric acid medium has been investigated spectrophotometrically at a constant ionic strength of 0.2 mol dm-3 and at a temperature of 25°C. The reactions of both organic reductants with permanganate ion showed a first order dependence with respect to [MnO4] and fractional-first order dependences with respect to both hydrogen ion and reductants concentrations. Increasing either ionic strength or dielectric constant of the reactions media had no significant effect on the oxidation rates. Manganese(II) ion was found to auto-catalyze the oxidation reactions with less than unit order dependences. The final oxidation products of BIF and BTF were identified by both spectroscopic and chemical tools 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. A plausible reactions mechanism has been suggested and the reaction constants involved in the mechanism have been evaluated. The activation parameters with respect to the second order rate constants have been computed and discussed.


Keywords
 

Benzimidazole and Benzthiazole Derivatives, Kinetics, Mechanism, Permanganate, Oxidation


Reference
 
[01]    

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.

[02]    

Abdul Rouf CT (2014) Bioactivethiazole and benzothiazole derivatives. Eur. J. Med. Chem., 1-17.

[03]    

Hisamoddin SZK, Priyanka S, Yogesh SP, Patel Nilam PU (2014) Benzothiazole the molecule of diverse biological activities. Pharma Sci. Monitor, 5:207-225.

[04]    

Shi B, Chen R, Huang Y (2004) Synthesis of N-(benzothiazol-2-yl-aminodialkyl)-thiophosphate. Gaodeng Xuexiao Huaxue Xuebao, 25:1458–1460.

[05]    

Huang ST, Hsei LJ, Chen C (2006) Synthesis and anticancer evaluation of bis(-benzimidazoles), bis(benzoxazoles), and benzothiazoles, Bioorg. Med. Chem., 14:6106-6119.

[06]    

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.

[07]    

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.

[08]    

Singh SP, Segal S (1988) Study of fungicidal activities of some benzothiazoles, Ind. J. Chem., 27B: 941-943.

[09]    

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.

[10]    

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.

[11]    

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.

[12]    

Abdel-Zaher A, Elassar A (2015) Synthesis of benzoazolyl-N,N-dimethylformamidines: complexation and biological activity. Eur. Int. J. Sci. Technol., 4: 88-99.

[13]    

Fawzy A, Ashour SS, Musleh MA (2014) 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. 111:443-460.

[14]    

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.

[15]    

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.

[16]    

Fawzy A, Zaafarany, Althagafi I, Al-Bonayan A, Aljiffrey F (2016)Kinetic and mechanism of oxidation of benzazolyl-formamidines by permanganate in alkaline medium. Am. J. Appl. Chem. 4: 50-58.

[17]    

Asghar BH, Fawzy A (2014) Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinyl-formamidines in acidic medium, with autocatalytic behavior of manganese(II). J. Saudi Chem. Soc., in press.

[18]    

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.

[19]    

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.

[20]    

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.

[21]    

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.

[22]    

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) intermediatesduring oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometeric techniques. Carbohydr. Res. 345: 1588-1593.

[23]    

Hassan RM, Fawzy A, Alarifi A, Ahmed GA, Zaafarany IA, Takagi HD (2011) Base-catalyzed oxidationof 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.

[24]    

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.

[25]    

Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate:  oxidations of arylalkanes in organic solvents. Inorg. Chem. 36: 2069-2078.

[26]    

Kini AK, Farokhi SA, Nandibewoor ST (2002) A comparative study of ruthenium(III) catalysed oxidation of L-leucine and L-isoleucine by alkaline permanganate. A kinetic and mechanistic approach. Transition Met. Chem. 27: 532–540.

[27]    

Halligudi LL, Desai SM, Mavalangi AK, Nandibewoor ST (2000) Kinetics of the oxidative degradation of rac-serine by aqueous alkaline permanganate. Monatsh. Chem. 131: 321–332.

[28]    

Verma RS, Reddy JM, Shastry VR (1974) Kinetic study of homogeneous acid-catalyzed oxidation of certain amino-acids by potassium permanganate in moderately concentrated acidic media. J. Chem. Soc. Perkin Trans. 124: 469–473.

[29]    

Mohanty B, Behera J, Acharya S, Mohanty P, Pantaik AK (2013) Metal ion catalyzed oxidation of L-lysine by alkaline permanganate Ion-A kinetic and mechanistic approach. Chem. Sci. Trans. 2: 51–60.

[30]    

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.

[31]    

Vogel AI (1978) A text book of quantitative inorganic analysis. 4th ed, pp. 352, ELBS and Longman, New York.

[32]    

Vogel AI (1973) Text book of practical organic chemistry including quantitative organic analysis, 3rd ed, pp. 332, ELBS and Longman, New York.

[33]    

Feigl F (1975) Spot tests in organic analysis, pp. 195, Elsevier, New York.

[34]    

Frost AA, Person RG (1973) Kinetics and Mechanism, pp. 147, Wiley Eastern, New Delhi.

[35]    

Day MC, Selbin J (1985) Theoretical Inorganic Chemistry, Reinhold Publishing Corporation, New York, pp. 344.

[36]    

Stewart R (1965) Oxidation in Organic Chemistry, Part A (ed.) Wiberg KB, New York, Academic Press.

[37]    

Zimmerman CL. Ph D. (1949) Thesis University of Chicago.

[38]    

Bailey N, Carrington A, Lott T, Symons MCRJ (1960) Structure and reactivity of the oxyanions of transition metals. Part VIII. Acidities and spectra of protonated oxyanions. J. Chem. Soc. 290-297.

[39]    

Carrington A, Symons MCRJ (1963) Structure and reactivity of the oxyanions of transition metals. Chem. Rev. 63:443-460.

[40]    

Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z. 49: 333–369.

[41]    

Amis ES (1966) Solvent effect on reaction rates and mechanism, pp. 28, Academic Press, New York.

[42]    

Laidler K (1965) Chemical Kinetics. Pp. 123, McGraw-Hill, New York.

[43]    

Waters WA (1958) Rev. Chem. Soc. 12, 277-281; Radhakrisshnamurti PS, Rao MD (1977) Ind. J. Chem. 15A: 524–527.

[44]    

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.

[45]    

Weissberger A (1974) In Investigation of rates and mechanism of reactions in techniques of chemistry, (New York: John Wiley & Sons), pp. 421.





 
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