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2005 | 3 | 3 | 482-501
Tytuł artykułu

Mechanistic investigations of oxidation of isatins by sodium N-chlorobenzenesulfonamide in alkaline medium: A kinetic study

Treść / Zawartość
Warianty tytułu
Języki publikacji
EN
Abstrakty
EN
Oxidation of isatins (isatin, 5-methylisatin, 5-bromoisatin and 5-nitroisatin) to their anthranilic acids was performed efficiently with sodium N-chlorobenzenesulfonamide or chloramine-B (CAB) in alkaline medium at 35±0.1°C. The reactions follow identical kinetics for all the isatins, being first-order dependence each in [CAB]o and [Isatin]o and inverse fractional-order on [NaOH]. Addition of halide ions and benzenesulfonamide, reduction product of CAB, do not significantly affect the rate. Variation of ionic strength of the medium had no effect on the rate, while the dielectric effect is negative. The solvent isotope effect was studied using D2O. Activation parameters for the overall reaction have been computed. The rates satisfactorily correlate with the Hammett σ relationship and the reaction constant ρ is −0.31 signifies that electron releasing groups accelerate the reaction while the electron withdrawing groups retard the rate. Values of ΔH≠ and ΔS≠ are linearly related and an isokinetic relationship is observed with β=376 K, indicating the reaction is controlled by enthalpy. The stoichiometry of the title reaction is found to be 1∶1. Oxidation products of isatins were identified as their corresponding anthranilic acids and the yields were found to be around 90 %. The observed results have been explained by a plausible mechanism and the related rate law deduced. This method offers several advantages including high yield of the products, short reaction times, easier isolation of products, and stable, cost effective and relatively non-toxic reagents, which make the reaction process simple and smooth.
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Wydawca

Czasopismo
Rocznik
Tom
3
Numer
3
Strony
482-501
Opis fizyczny
Daty
wydano
2005-09-01
online
2005-09-01
Twórcy
autor
  • Department of Post-Graduate Studies in Chemistry, Central College Campus, Bangalore University, 560 001, Bangalore, India, pswamy_chem@yahoo.com
autor
  • Department of Post-Graduate Studies in Chemistry, Central College Campus, Bangalore University, 560 001, Bangalore, India
Bibliografia
  • [1] J.F.M. da Silva, S.J. Garden and A.C. Pinto: “The chemistry of isatins: a review from 1975–1999”, J. Braz. Chem. Soc., Vol. 12(3), (2001), pp. 273–324 and references therein. http://dx.doi.org/10.1590/S0103-50532001000300002[Crossref]
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  • [6] K.K. Banerji, B. Jayaram and D.S. Mahadevappa: “Mechanistic aspects of oxidation by N-metallo-N-haloarylsulfonamides”, J. Sci. Ind. Res., Vol. 46, (1987), pp. 65–76.
  • [7] Puttaswamy, T.M. Anuradha, R. Ramachandrappa and N.M.M. Gowda: “Oxidation of isoniazid by N-haloarenesulfonamidates in alkaline medium: a kinetic and mechanistic study”, Int. J. Chem. Kinet, Vol. 32(4), (2000), pp. 221–230. http://dx.doi.org/10.1002/(SICI)1097-4601(2000)32:4<221::AID-KIN4>3.0.CO;2-1[Crossref]
  • [8] F.F. Hardy and J.P. Johnston: “The interactions of N-bromo-N-sodiobenzesulfonamide (bromamine-B) with p-nitrophenoxide ion”, J. Chem. Soc., Perkin Trans. 2, (1973), pp. 742–746. [Crossref]
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  • [11] Puttaswamy, T.M. Anuradha and K.L. Mahadevappa: “Kinetic analysis of oxidation of dopamine by sodium N-chlorobenzenesulfonamide in perchloric acid medium: a mechanistic approach”, Indian J. Chem. A, Vol. 40, (2001), pp. 514–518.
  • [12] P.G. Stecher (Ed.): The Merck Index, 8th ed., 1968, p. 232.
  • [13] Puttaswamy and D.S. Mahadevappa: “Oxidation of substituted ethanols by sodium-N-bromobenzenesulfonamide: A kinetic study”, J. Phys. Org. Chem., Vol. 2, (1989), p. 660–671. http://dx.doi.org/10.1002/poc.610020809[Crossref]
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  • [17] K. Higuchi, K. Ikeda and A. Hussain: “Mechanism and thermodynamics of chlorine transfer among organochlorinating agents: reversible disproportionation of chloramine-T”, J. Chem. Soc. B., (1967), pp. 546–549; “Mechanism and thermodynamics of chlorine transfer among organochlorinating agents: autocatalytic pathway between N-chlorosuccinimide and chloramine-T”, (1968), pp. 1031–1036.
  • [18] D.S. Mahadevappa, B.T. Gowda and N.M.M. Gowda: “Kinetics and mechanism of oxidation of thiocynate ion by sodium N-chloro-4-methylbenzenesulfonamide in alkaline medium”, Z. Naturforsch, Vol. 34b, (1979), pp. 52–57.
  • [19] D.S. Mahadevappa, M.B.M. Gowda and K.S. Rangappa: “Oxidation of methionine by sodium N-chlorobenzenesulfonamide in aqueous solution: a kinetic study”, Oxid. Commun., Vol. 7(1–2), (1984), pp. 167–180.
  • [20] D.S. Mahadevappa, K.S. Rangappa, N.M.M. Gowda and B.T. Gowda: “Kinetic and mechanistic study of oxidation of arginine, histidine and threonine in alkaline medium by N- chloro-N-sodio-p-toluenesulfonamide”, Int. J. Chem. Kinet., Vol. 14, (1982), pp. 1183–1197. http://dx.doi.org/10.1002/kin.550141103[Crossref]
  • [21] H.M.K. Naidu, B. Yamuna and D.S. Mahadevappa: “Osmium(VIII)-catalyzed reactions of allyl and crotyl alcohols with chloramine-T, chloramine-B, bromamine-T and bromamine-B: kinetic and mechanism of formation of halohydrins in alkaline medium”, Indian J. Chem., Vol. 26A, (1987), pp. 114–117.
  • [22] S.P. Mushran, M.C. Agrawal and B. Prasad: “Mechanism of oxidation by chloramine-T Part-I oxidation of α-hydroxyacids”, J. Chem Soc. B., (1971), pp. 1712–1714 and references therein.
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Typ dokumentu
Bibliografia
Identyfikatory
Identyfikator YADDA
bwmeta1.element.-psjd-doi-10_2478_BF02479277
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