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1.
Raviraj M Kulkarni Dinesh C Bilehal Sharanappa T Nandibewoor 《Analytical sciences》2004,20(4):743-747
The kinetics of oxidation of isoniazid in acidic medium was studied spectrophotometrically. The reaction between QDC and isoniazid in acid medium exhibits (4:1) stoichiometry (QDC:isoniazid). The reaction showed first order kinetics in quinolinium dichromate (QDC) concentration and an order of less than unity in isoniazid (INH) and acid concentrations. The oxidation reaction proceeds via a protonated QDC species, which forms a complex with isoniazid. The latter decomposes in a slow step to give a free radical derived from isoniazid and an intermediate chromium(V), which is followed, by subsequent fast steps to give the products. The reaction constants involved in the mechanism are evaluated. Isoniazid was analyzed by kinetic methods in pure and pharmaceutical formulations. 相似文献
2.
Kini Anand K. Farokhi Sairabanu A. Nandibewoor Sharanappa T. 《Transition Metal Chemistry》2002,27(5):532-540
The kinetics of the RuIII-catalysed oxidation of L-leucine and L-isoleucine by alkaline permanganate were studied and compared, spectrophotometrically using a rapid kinetic accessory. The reaction is first order with respect to [oxidant] and [catalyst] with an apparently less than unit order in [substrate] and [alkali] respectively. The results suggest the formation of a complex between the amino acid and the hydroxylated species of ruthenium(III). The complex reacts further with the alkaline permanganate species in a rate-determining step, resulting in the formation of a free radical, which again reacts with the alkaline permanganate species in a subsequent fast step to yield the products. The reaction constants involved in the mechanism were calculated. There is a good agreement between observed and calculated rate constants under different experimental conditions. The activation parameters with respect to the slow step of the mechanism for both the amino acids were calculated and discussed. Of the two amino acids, leucine is oxidised at a faster rate than isoleucine. 相似文献
3.
Oxidative transformation of ciprofloxacin by alkaline permanganate – A kinetic and mechanistic study
Kiran A. Thabaj Suresh D. KulkarniShivamurti A. Chimatadar Sharanappa T. Nandibewoor 《Polyhedron》2007
This spectroscopic study presents the kinetics and degradation pathways of oxidation of ciprofloxacin by permanganate in alkaline medium at constant ionic strength of 0.04 mol−3. Orders with respect to substrate, oxidant and alkali concentrations were determined. Effect of ionic strength and solvent polarity of the medium on the rate of the reaction was studied. The oxidation products were identified by LC-ESI-MS technique. Product characterization of ciprofloxacin reaction mixtures indicates the formation of three major products corresponding to m/z 263, 306, and 348 (corresponding to full or partial dealkylation of the piperazine ring). The piperazine moiety of ciprofloxacin is the predominant oxidative site to KMnO4. Product analyses showed that oxidation by permanganate results in dealkylation at the piperazine moiety of ciprofloxacin, with the quinolone ring essentially intact. The reaction kinetics and product characterization point to a reaction mechanism that likely begins with formation of a complex between ciprofloxacin and the KMnO4, followed by oxidation at the aromatic N1 atom of piperazine moiety to generate an anilinyl radical intermediate. The radical intermediates subsequently undergo N-dealkylation. Investigations of the reaction at different temperatures allowed the determination of the activation parameters with respect to the slow step of proposed mechanism. The proposed mechanism and the derived rate laws are consistent with the observed kinetics. 相似文献
4.
Kulkarni Raviraj M. Bilehal Dinesh C. Nandibewoor Sharanappa T. 《Transition Metal Chemistry》2003,28(2):199-208
The kinetics of CrIII-catalysed oxidation of L-valine by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction between permanganate and L-valine in alkaline medium exhibits 2:1 stoichiometry (KMnO4:l-valine). The reaction shows first order dependence on [permanganate] and [chromium(III)], and less than unit order dependence each in [L-valine] and alkali concentrations under the experimental conditions. However the order in [L-valine] and [alkali] changes from first order to zero order as the concentrations change from lower to higher respectively. The results suggest the formation of a complex between L-valine and the hydroxylated species of CrIII. The complex reacts further with 1 mol of alkaline permanganate species in a rate-determining step, resulting in the formation of a free radical, which again reacts with 1 mol of alkaline permanganate species in a subsequent fast step to yield the products. The reaction constants involved in the mechanism were evaluated. The activation parameters with respect to the slow step of the mechanism were obtained and discussed. The title reaction has been utilised to analyse chromium(III) in the 26.0 ng cm–3–1.0 g cm–3 range. 相似文献
5.
T. S. Kiran D. C. Hiremath S. T. Nandibewoor 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2007,81(12):2070-2077
The kinetics of oxidation of L-lysine by diperiodatocuprate (III) (DPC) in alkaline medium at a constant ionic strength of
0.15 mol/dm3 was studied spectrophotometrically. The reaction between DPC and L-lysine in an alkaline medium had a 1: 2 stoichiometry
(L-lysine: DPC). The reaction was first order in [DPC] and less than first order in [L-lysine] and [alkali]. The addition
of periodate had no effect on the rate of the reaction. The intervention of free radicals was observed in the reaction. The
oxidation reaction in alkaline medium was shown to proceed via a DPC-L-lysine complex. The main products were identified by
spot test and spectral studies. The reaction constants involved in different steps of the mechanism were calculated. The activation
parameters with respect to the slow step of the mechanism were computed and discussed, and thermodynamic values were also
determined.
The article is published in the original. 相似文献
6.
Veeresh Tegginamath Chanabasayya V. Hiremath Sharanappa T. Nandibewoor 《Journal of Physical Organic Chemistry》2007,20(1):55-64
The oxidation of allyl alcohol by diperiodatoargentate(III) (DPA) is carried out both in the absence and presence of ruthenium(III) catalyst in alkaline medium at 298 K and a constant ionic strength of 1.1 mol dm?3 was studied spectrophotometrically. The oxidation products in both the cases were acrolein and Ag(I), identified by spectral studies. The stoichiometry is same in both the cases, that is, [AA]/[DPA] = 1:1. The reaction shows first order in [DPA] and has less than unit order dependence each in both [AA] and [Alkali] and retarding effect of [IO] in both the catalysed and uncatalysed cases. The order in [Ru(III)] is unity. The active species of DPA is understood to be as monoperiodatoargentate(III) (MPA) in both the cases. The uncatalysed reaction in alkaline medium has been shown to proceed via a MPA–allyl alcohol complex, which decomposes in a rate determining step to give the products. In catalysed reaction, it has been shown to proceed via a Ru(III)‐allyl alcohol complex, which further reacts with one molecule of MPA in a rate determining step to give the products. The reaction constants involved in the different steps of the mechanisms were calculated for both reactions. The catalytic constant (Kc) was also calculated for catalysed reaction at different temperatures. The activation parameters with respect to slow step of the mechanisms were computed and discussed for both the cases. The thermodynamic quantities were also determined for both reactions. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
7.
Ragunatharaddi R. Hosamani Nagaraj P. Shetti Sharanappa T. Nandibewoor 《Journal of Physical Organic Chemistry》2009,22(3):234-240
The kinetics of oxidation of antibiotic drug, ampicillin (AMP) by diperiodatoargentate (III) (DPA) in alkaline medium at a constant ionic strength of 0.25‐mol dm?3 was studied spectrophotometrically. The reaction between DPA and AMP in alkaline medium exhibits 1:2 stoichiometry (AMP:DPA). The reaction is of first order in [DPA] and has less than unit order in both [AMP] and [alkali]. Added periodate retarded the rate of reaction and intervention of free radicals was observed in the reaction. The oxidation reaction in alkaline medium has been shown to proceed via a DPA–AMP complex, which decomposes slowly in a rate‐determining step followed by other fast steps to give the products. The main products were identified by spot test, IR and NMR studies. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to slow step of the mechanism were computed and discussed and thermodynamic quantities were also determined. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
8.
Chimatadar Shivamurti A. Koujalagi Sangappa B. Nandibewoor Sharanappa T. 《Transition Metal Chemistry》2001,26(1-2):241-245
The oxidation of HgI by CeIV has been studied in aqueous H2SO4. A minute amount (10–6 mol dm–3) of OsVIII is sufficient to catalyse the reaction. The active catalyst, substrate and oxidant species are H2OsO5, [Hg2(SO4)HSO4]– and H3Ce(SO4)–
4, respectively. Possible mechanisms are proposed and the reaction constants involved have been determined. 相似文献
9.
10.
Nandibewoor Sharanappa T. Hiremath Gouri A. Timmanagoudar Prakash L. 《Transition Metal Chemistry》2000,25(4):394-399
The oxidation of thiocyanate by periodate has been studied in alkaline media. A micro quantity of RuIII is sufficient to catalyse the reaction. The active catalytic species and oxidant in the reaction are understood to be [Ru(H2O)5OH]2+ and IO−
4. The autocatalysis exhibited by one of the products, cyanate, is attributed to adduct formation between cyanate and periodate.
A composite mechanism and rate law are proposed. The reaction constants involved in the mechanism are evaluated.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献