Abstract
The present paper deals with the kinetics and mechanism of homogeneously Ir(III) chloride catalyzed oxidation of Leucine by chloramine-T (CAT) in perchloric acidic medium in the temperature range 30–45 °C. The reaction is carried out in the presence of mercuric acetate as a scavenger for chloride ion. The experimental results show first order kinetics with respect to the oxidant (CAT) and catalyst [Ir(III)] while positive effect with respect to substrate, i.e., Leucine was observed. The reaction shows negligible effect of [Hg(OAc)2], [H+] and ionic strength of the medium. Chloride ion positively influenced the rate of reaction. The various activation parameters were calculated from the rate measurments at different temperatures (30–45 °C). The reaction between chloramine-T and leucine in acid medium shows 1:1 stoichiometry. On the basis of kinetic studies, reaction stoichiometry and product analysis, a suitable mechanism has been proposed and rate law has been derived.
Similar content being viewed by others
References
Puttaswamy, Vaz N, Jagadeesh RV (2008) Mechanistic investigations of oxidation of some dipeptides by sodium-N-Chloro-p-toluenesulfonamide in alkaline medium: a kinetic study. Chin J Chem 26:536–542
Vinod KN, Puttaswamy, Gowda KNN (2009) Mechanistic aspects for the oxidation of sunset yellow dye by chloramine-T in presence of perchloric acid and in sodium hydroxide medium catalyzed by Os(VIII): a spectrophotometric kinetic approach. Inorg Chim Acta 362:2044–2051
Puttaswamy, Anuradha TM, Ramachandrappa R, Gowda NMM (2000) Oxidation of isoniazid by N-haloarenesulfonamides in alkaline medium: a kinetic and mechanistic study. Int J Chem Kinet 32(4):221–230
Jagadeesh RV, Puttaswamy (2006) Mechanistic studies of oxidation of thiols to disulfides by sodium N-Chloro-p-toluenesulfonamide in alkaline medium: a kinetic approach. Ind Eng Chem Res 45:1563–1570
Jagadeesh RV, Puttaswamy (2005) Kinetics of oxidation of pantothenic acid by chloramine-T in perchloric acid and in alkaline medium catalyzed by OsO4: a mechanistic approach. Int J Chem Kint 37(4):201–210
Singh AK, Negi R, Katre Y, Singh SP (2009) Mechanistic study of novel oxidation of paracetamol by chloramine-T using micro-amount of chloro-complex of Ir(III) as a homogeneous catalyst in acidic medium. J Mol Catal A: Chem 302:36–42
Kambo N, Upadhyay SK (2004) Kinetics and mechanism of platinum(IV) catalysed oxidation of some hexoses by alkaline chloramine-T. Ind J Chem 43A:1210–1215
Shukla A, Gupta S, Upadhyay SK (1991) Pd(II) complexes of amino alcohols and their reaction with chloramine-T: a kinetic study. Int J Chem Kinet 23:279–288
Jagadeesh RV, Puttaswamy, Vaz N (2005) Ru(III)-catalyzed oxidation of some N-heterocycles by chloramine-T in hydrochloric acid medium: a kinetic and mechanistic study. J Mol Catal A 229:211–222
Filler R (1963) Oxidations and dehydrogenations with N-bromosuccinimide and related N-haloimides. Chem Rev 63:21–43
Campbell MM, Johnson G (1978) Chloramine-T and related N-halogeno-N-metallo reagents. Chem Rev 78:65–79
Wadhwani M, Jain S (2014) Kinetic study of oxidation of some monosaccharides by Chloramine-T inded by visible light source. Res J Chem Sci 4(7):61–65
Singh AK, Negi R, Jain B, Katre Y, Singh SP, Sharma VK (2011) Pd (II) catalyzed oxidative degradation of paracetamol by chloramine-T in acidic and alkaline media. Ind Eng Chem Res 50:8407–8419
Munavalli DS, Chimatadar SA, Nandibewoor ST (2008) A kinetic and mechanistic study of oxidation of l-lysine by the analytical reagent diperiodatoargentate(III) in aqueous alkaline medium. Trans Met Chem 33:535–542
Ramachandran MS, Vivekanandam TS (1987) Kinetics of oxidation of amino acids by chloramine-T: a reinvestigation on the oxidation of alanine, 2-aminobutyric acid, valine, serine, and threonine. Bull Chem Soc Jpn 60:3397–3404
Singh AK, Singh RK, Srivastava J, Rahman S, Yadav S (2012) Kinetics and mechanistic studies of oxidation of glycine and valine by N-bromosuccinimide using chloro complex of Rh(III) in its nano-concentration range as homogenous catalyst. Ind J Chem 51(A):681–689
Sumathii T, Shanmugasundaram P, Chandramohan G (2011) Silver(I)-catalyzed oxidation of l-Leucine by Cerium(IV) in sulfuric acid medium: a kinetic and mechanistic study. Asian J Chem 23(10):4385–4392
Nelson DL, Cox MM, Lehninger AL (2000) Principles of biochemistry, 3rd edn. Worth Publishing, New York
Combaret L (2005) A leucine-supplemented diet restores the defective postprandial inhibition of proteasome-dependent proteolysis in aged rat skeletal muscle. J Physiol 569(2):489–499
Katre Y, Goyal N, Singh AK (2013) Impact of Micelle Media on the kinetics of oxidation of l-Lysine (an essential amino acid) by N-Bromophthalimide. J Dispers Sci Technol 34:1421–1428
Ramachandran MS, Vivekanandham TS, Nithyanandhan R (1985) Kinetics of oxidation of amino acids by chloramine T: a reinvestigation. J Chem Soc Perkin Trans 2:1507–1511
Singh AK, Negi R, Jain B, Katre Y, Singh SP (2009) Oxidation of valine by N-bromophthalimide in presence of chloro-complex of Pd (II) as homogenous catalyst: a kinetic and mechanistic study. J Open Catal 2:12–20
Kannan RS, Easwaramoorthy D, Vijaya K, Ramachandran MS (2008) Autocatalytic oxidation of β-alanine by peroxomonosulfate in the presence of copper(II) ion. Int J Chem Kinet 40:44–49
Naik KM, Nandibewoor ST (2012) Kinetics and mechanism of oxidation of l-leucine by alkaline diperiodatocuprate(III)—a free radical intervention, deamination and decarboxylation. J Chem Sci 124(4):809–819
Vaz N, Puttaswamy (2003) Ruthenium(III) and osmium(VIII)-catalyzed oxidation of 2-thiouracil by bromamine-B in acid and alkaline media: a kinetic and mechanistic study. Trans Met Chem 28:409–417
Hiremath CV, Kiran TS, Nandibewoor ST (2006) Os(VIII)/Ru(III) catalysed oxidation of aspirin drug by a new oxidant, diperiodatoargentate(III) in aqueous alkaline medium: a comparative kinetic study. J Mol Catal A: Chem 248:163–174
Uma V, Sethuram B, Rao TN (1981) Kinetics of oxidation of isopropanol by IO4 − catalyzed by metal ion. React Kinet Catal Lett 18:283–287
Wen-yu Song, Rong-hui Zhao, Qing-mei Jiang (2005) Catalyzed oxidation of Tetrahydrofurfuryl alcohol by Cerium(iv) in aqueous sulphuric acid medium. Acta Phys Chim Sin 21(08):929–933
Singh AK, Rahmani S, Singh B, Singh RK, Singh M (2004) Mechanism of Ir(III)-catalysed and Hg(II)-co-catalysed oxidation of reducing sugars by N-bromoacetamide in acidic medium. J Phys Org Chem 17(3):249–256
Bai WS, Zhai YQ, Liu HM, Lü HY, Song WY (2008) Kinetics and mechanism of iridium(III) catalyzed oxidation of ethylene glycol by cerium(IV) in sulfuric acid media. Ind J Chem 47A:1194–1198
Singh AK, Sachdev N, Srivastava A, Jain B, Khtre Y (2012) Oxidation of d-glucose by N-bromophthalimide in the presence of chlorocomplex of iridium (III): a kinetic and mechanistic study. Res Chem Intermed 38:507–521
Venkatasubramanian N, Thiagarajan V (1968) The mechanism of oxidation of alcohols by bromine. Tetrahedron Lett 9:1711–1714
Grover N, Kambo N, Upadhyay SK (2002) Kinetics and mechanism of palladium(II) catalysed oxidation of some alpha-aminoacids by chloramine-T in perchloric acid. Ind J Chem 41(15):2482–2488
Gopalakrishanan G, Pai BR, Venkatasubramaniam N (1980) Oxidation of alcohols by N-bromosuccinimide-A curious dependence on initial concentration of the oxidant. Ind J Chem 19B:293
Chang JC, Garner GS (1965) Kinetics of aquation of Aquopentachloroiridate(III) and Chloride anation of Diaquotetrachloroiridate(III) anions. Inorg Chem 4(2):209–215
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Verma, A., Pandey, J. & Srivastava, S. Iridium(III) Catalyzed Oxidation of Leucine by Chloramine-T in Acidic Medium: A Kinetic and Mechanistic Study. Proc. Natl. Acad. Sci., India, Sect. A Phys. Sci. 87, 163–170 (2017). https://doi.org/10.1007/s40010-017-0355-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40010-017-0355-8