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- W2150289453 abstract "A kinetic and thermodynamic study of the covalent hydration of 4-nitro-6trifluoromethanesulfonylbenzofuroxan, 4, to give the corresponding hydroxy σ-adduct, C-4, in aqueous solution is reported. Analysis of the data obtained in the pH range 0.8–13 has allowed dissection of the observed rates into forward ( k OH 2 ) and reverse ( k , k , k O H 1 2 − + − H 1 -2) rate constants as well as the obtention of pKa values for water addition to the carbocyclic ring. The results reveal that C-4 is the most stable hydroxy σ-adduct known to date (pKa = 2.95) and that its formation arises exclusively from the attack of water molecules between pH 2.5 and 8.5. The related rate constant k is equal to (0.15±0.01) s O H 1 2 , as compared with k = 0.035 s O H 1 2 -1 for the hydration of 4,6-dinitrobenzofuroxan (DNBF, pKa = 3.75). These figures show that substitution of the 6-NO2 group of this latter compound by an SO2CF3 group appreciably increases the electrophilic character of the carbocyclic ring of the benzofuroxan structure. Another manifestation of the activating effect of the SO2CF3 group is that the OH group covalently bonded to the 7-carbon of C-4 undergoes ionization in dilute NaOH solutions (pKa’ = 12.03). Some data pertaining to buffer catalysis and solvent deuterium isotope effects are also reported. From these results, it is concluded that the formation and decomposition of C-4 proceeds through the same mechanisms as those identified in the hydration of DNBF, in particular with OH acting as a general base catalyst and CO acting as a nucleophilic catalyst. − 2 3" @default.
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- W2150289453 date "2002-12-26" @default.
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- W2150289453 title "The super-electrophilic reactivity of 4-nitro-6-trifluoromethanesulfonyl-benzofuroxan in aqueous solution" @default.
- W2150289453 cites W648541693 @default.
- W2150289453 doi "https://doi.org/10.3998/ark.5550190.0003.b16" @default.
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