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|Title:||Structure-reactivity correlation in the aminolysis of 4-fluorophenyl acetate in aqueous medium||Authors:||Rajarathnam, D.
Ananthakrishna Nadar, P.
|Issue Date:||Jun-2002||Citation:||Rajarathnam, D., Jeyakumar, T., Ananthakrishna Nadar, P. (2002-06). Structure-reactivity correlation in the aminolysis of 4-fluorophenyl acetate in aqueous medium. International Journal of Chemical Kinetics 34 (6) : 366-373. ScholarBank@NUS Repository. https://doi.org/10.1002/kin.10065||Abstract:||The reaction of the title substrate with a series of amines of varying pKa, viz. ammonia, ethanolamine, glycine, 1,2-diaminopropane, 1,3-diaminopropane, n-butylamine, piperidine, hydrazine, imidazole, and hydroxylamine is subjected to a kinetic study in aqueous medium, 25°C, ionic strength 0.1 M (KCl). Pseudo-first-order rate coefficients (kobs) are found throughout under amine excess at various pH values for each amine. For amines, excluding hydrazine, ammonia, and hydroxylamine the reaction follows clean second-order kinetics and the plots of (kobs - kH) against free amine concentration are linear at constant pH. The macroscopic nucleophilic substitution rate coefficients (kN) are obtained as the slopes of these plots and found to be pH independent. For hydrazine, ammonia, and hydroxylamine, a rate dependence on more than first power of the amine is observed, accordingly, the rate constants for the assisted paths have been disseminated for these amines besides kN. The Brönsted-type plot (logkN against amine pKa) is linear with a slope value of β = 1.02. The magnitude of the slope value is consistent with a stepwise mechanism through a zwitterionic tetrahedral addition intermediate whose breakdown to products is rate-determining (k2 step). A remarkable reactivity difference is observed among the diamines, the reason for which is discussed in detail. © 2002 Wiley Periodicals, Inc. Int. J. Chem. Kinet.||Source Title:||International Journal of Chemical Kinetics||URI:||http://scholarbank.nus.edu.sg/handle/10635/92350||ISSN:||05388066||DOI:||10.1002/kin.10065|
|Appears in Collections:||Staff Publications|
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