Ru(III) Catalyzed And Uncatalyzed Oxidative Conversion of 5- Nitroquinoline To Its N-Oxide By Acidified N-Haloamines: A Comparative Kinetic And Mechanistic Approach
Journal Title: IOSR Journal of Applied Chemistry (IOSR-JAC) - Year 2018, Vol 11, Issue 5
Abstract
Kinetics and mechanism Ru(III) catalyzed and uncatalyzed oxidation of 5-nitroquinoline has been carried out in HCl medium at 298 K by N-haloamines (CAT, CAB, BAT and BAB). Under comparable experimental conditions, reactions showed identical kinetics with all the oxidants studied with first order dependence each on [oxidant]o, [substrate]o and [Ru(III)] and fractional-order dependence on [HCl]. Reactions were studied at different temperatures (288-308 K). Activation parameter for both Ru(III) catalyzed and uncatalyzed reactions were computed. Ru(III) catalyzed reactions were found to be 7-9 times faster. Under identical experimental conditions, the rates were higher with bromamines compared to chloramines by a factor of 3 the order: BAB > BAT > CAB > CAT. This is attributable to the difference in electrophilicities of the halo cations, Br+ and Cl+ . Probable mechanism and related rate law have been elucidated.
Authors and Affiliations
T. Naveen Kumar, T. V. Venkatesha
Keywords
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