Oxidation Kinetics of Amino Acids by 1-Chlorobenzimidazole in Acid Medium – A Kinetic and Mechanistic Approach
J. Environ. Nanotechnol., Volume 10, No 1 (2021) pp. 08-13
Abstract
In this study, the reaction kinetics of oxidation of amino acids such as glycine, alanine, phenylalanine, tryptophan, leucine and cysteine with 1-Chlorobenzimidazole (CBI) has been studied in an aqueous acetic acid medium. The oxidation kinetic mechanism proposed is consistent with observed kinetic data. The reactions were monitored potentiometrically up to 70 % completion using a platinum-saturated calomel electrode assembly to track the potentials of the reaction mixture containing varying concentrations of the [CBI] / [BI] couple (BI = benzimidazole) at recurring intervals. The reactions were found to be first-order, each with respect to [amino acids] and [oxidant]. The rate of the reaction decreases with the increase in HClO4 and the order in [HClO4] was inverse fractional. The rate of reaction decreases as the dielectric constant of the solvent medium decreases, indicating a dipole-dipole reaction. Electrolytes, such as sodium perchlorate, have no significant effect on reaction rates. The addition of benzimidazole, one of the reaction ingredients, slowed down the reaction rates. When acrylonitrile was applied to the reaction mixture, no polymerization occurred. The thermodynamic parameters were measured after the kinetic runs were carried out at four different temperatures. The results of the reactions have carboxylic acid, ammonia and carbon dioxide. The most-likely reactive species have been identified as HOCl. The kinetic effects that have been derived are compatible with a fitting mechanism.
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Reference
Alhaji, N. M. I. and Mary, S. S. L., Kinetics and mechanism of oxidation of isoleucine by N -bromophthalimide in aqueous perchloric acid medium, E-Journal Chem., 8(4), 1728–1733 (2011a).
https://dx.doi.org/10.1155/2011/917657
Alhaji, N. M. I. and Mary, S. S. L., Kinetics and mechanism of oxidation of glutamic acid by N -bromophthalimide in aqueous acidic medium, E-J. Chem., 8(4), 1472–1477 (2011b).
https://dx.doi.org/10.1155/2011/572603
Bandgar, B. P., Uppalla, L. S. and Sadavarte, V. S., Chemoselective transesterification of β-Keto esters under neutral conditions using NBS as a catalyst, Synlett., 2001(11), 1715–1718 (2001).
https://dx.doi.org/10.1055/s-2001-18082
Bishnoi, M. L. and Banerji, K. K., Kinetics and mechanism of the oxidation of α-amino acids by n-bromoacetamide, Tetrahedron, 41(24), 6047–6050 (1985).
https://dx.doi.org/10.1016/S0040-4020(01)91446-2
Cañibano, V., Rodríguez, J. F., Santos, M., Sanz-Tejedor, M. A., Carreño, M. C., González, G. and García-Ruano, J. L., Mild regioselective halogenation of activated pyridines with N-Bromosuccinimide, Synthesis (Stuttg)., 2001(14), 2175–2179 (2001).
https://dx.doi.org/10.1055/s-2001-18070
Farook, N. A. M., Kinetics of oxidation of 4-Oxoacids by N-Chlorosaccharin in aqueous acetic acid medium, J. Solution Chem., 36(3), 345–356 (2007).
https://dx.doi.org/10.1007/s10953-006-9116-z
Farook, N. A. M., Dameem, G. A. S., Murugesan, A. and Kanagaraj, M., Kinetics of oxidation of some essential amino acids by N-Chlorosaccharin in aqueous acetic acid medium, E-J. Chem., 1(2), 132–136 (2004a).
https://dx.doi.org/10.1155/2004/561690
Farook, N. A. M., Prabaharan, R., Rahini, S., Kumar, R. S., Rajamahendran, G. and Krishnan, B. G., Kinetics of oxidation of some amino acids by N-Chlorosaccharin in aqueous acetic acid medium, E-Jl Chem., 1(2), 127–131 (2004b).
https://dx.doi.org/10.1155/2004/406567
Gowda, B. T., Mahadevappa, D. S., Chloraminometric reactions: kinetics and mechanisms of oxidations of amino-acids by sodium N-chlorotoluene-p-sulphonamide in acid and alkaline media, J. Chem. Soc. Perkin Trans., 2 (3), 323 (1983).
https://dx.doi.org/10.1039/p29830000323
Nanda, N., Sheshadri, B. S. and Mayanna, S. M., Mechanism of oxidation of diazepam by 1-chlorobenzotriazole in acidic medium. A kinetic approach, React. Kinet. Catal. Lett., 67(1), 35–41 (1999).
https://dx.doi.org/10.1007/BF02475824
Patrocı́nio, A. F. and Moran, P. J., Synthesis of acylsilanes via oxidative hydrolysis of 2-silyl-1,3-dithianes mediated by N-bromosuccinimide, J. Organomet. Chem., 603(2), 220–224 (2000).
https://dx.doi.org/10.1016/S0022-328X(00)00181-9
Puttaswamy and Vaz, N., Kinetics of oxidation of acidic amino acids by sodium N-bromobenzenesulphonamide in acid medium: A mechanistic approach, J. Chem. Sci., 113(4), 325–332 (2001).
https://dx.doi.org/10.1007/BF02708651
Rangappa, K. S., Manjunathaswamy, K., Raghavendra, M. P. and Made Gowda, N. M., Kinetics and mechanism of oxidation of neutral ? - Amino acids by sodium N-chloro-p-toluenesulfonamide in acid medium, Int. J. Chem. Kinet., 34(1), 49–55 (2002).
https://dx.doi.org/10.1002/kin.10011
Rani, S. K., Easwaramoorthy, D., Bilal, I. M. and Palanichamy, M., Studies on Mn(II)-catalyzed oxidation of α-amino acids by peroxomonosulphate in alkaline medium-deamination and decarboxylation: A kinetic approach, Appl. Catal. A Gen., 369(1–2), 01–07 (2009).
https://dx.doi.org/10.1016/j.apcata.2009.07.048
Rukmangathan, M., Kumar, V. S. and Ramkumar, B., Reactivity of benzyl alcohol and substituted benzyl alcohols with 1-Chlorobenzimidazole in acid medium – A kinetic and mechanistic approach, IRA-Int. J. Appl. Sci., 3(3), 493-506 (2016).
https://dx.doi.org/10.21013/jas.v3.n3.p20
Rukmangathan, M., Santhoshkumar, V. and Ramkumar, B., Kinetics and mechanism of oxidation of aliphatic primary alcohols with 1-Chlorobenzimidazole in aqueous acetic acid medium, Zeitschrift für Phys Chemie., 230(8), 16-25 (2015).
https://dx.doi.org/10.1515/zpch-2015-0680
Singh, A. K., Jain, B., Negi, R., Katre, Y. and Singh, S. P., Oxidation of valine by N-Bromophthalimide in presence of chloro-complex of Pd(II) as homogenous catalyst: A Kinetic and mechanistic study, Open Catal. J., 2(1), 12–20 (2009a).
https://dx.doi.org/10.2174/1876214X00902010012
Singh, A. K., Jain, B., Negi, R., Katre, Y., Singh, S. P. and Sharma, V. K., A novel oxidation of valine by N-Bromophthalimide in the presence of Ruthenium(III) chloride as a homogeneous catalyst, Catal. Lett., 131(1–2), 98–104 (2009b).