Oxidation of linezolid by permanganate in acidic medium: Pd(II) catalysis, kinetics and pathways

TitleOxidation of linezolid by permanganate in acidic medium: Pd(II) catalysis, kinetics and pathways
Publication TypeJournal Article
Year of Publication2016
AuthorsKulkarni, RM, Hanagadakar, MS, Malladi, RS, Santhakumari, B, Nandibewoor, ST
JournalProgress in Reaction Kinetics and Mechanism
Volume41
Issue3
Pagination245-257
Date PublishedOCT
Type of ArticleArticle
ISSN1468-6783
Abstract

The uncatalysed and Pd(II)-catalysed oxidation of linezolid (LNZ) by permanganate (PMGT) in acidic medium was carried out in the pH range from 3.0 to 6.0. The second order rate constants were found to decrease with increase in pH. The apparent second order rate constants for the uncatalysed reaction were, for example, k `'(app)= 6.32 dm(3) mol(-1) at pH 3.0 and k `'(app). = 2.64 dm(3) mol(-1) s(-1) at pH 6.0 and at 25 +/- 0.2 degrees C and for the Pd(II)-catalysed reaction the total apparent second order rate constants were k `'(app) = 75.5 dm(3) mol(-1) s(-1) at pH 3.0 and k `'(app). = 45.66 dm(3) mol(-1) s(-1) at pH 6.0 and at 25 +/- 0.2 degrees C. The rate constant of the Pd(II)-catalysed reaction was thus ten times higher than for the uncatalysed reaction. The oxidation products of the reaction were identified using high resolution LC-MS. The reaction progresses via formation of a Pd-LNZ complex, which reacts with acidic PMGT to form an intermediate compound, which then decomposes to give oxidised products. The dependence of the rate of reaction on various parameters, such as pH, temperature, [LNZ], [PMGT], [Pd(II)], dielectric constant and ionic strength were studied and activation parameters for the reaction were evaluated and discussed.

DOI10.3184/146867816X14696298762238
Type of Journal (Indian or Foreign)Foreign
Impact Factor (IF)Not Available
Divison category: 
Biochemical Sciences

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