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• W2053818056 abstract "Eleven p -substituted benzaldoximes ( p -XC 6 H 4 CH=NOH, where X = H, CH 3 , CF 3 , F, Cl, Br, OCH 3 , N(CH 3 ) 2 , COOCH 3 , CN, NO 2 ) have been synthesized and their dissociation constants determined in 10% (v/v) aqueous dioxane at 35 °C. Under the same conditions, the pseudo-first order rate constants k obs of their reactions with p -nitrophenyl acetate (PNPA) were measured at pH values from 7.8 to 10.8 and at concentrations c oxime ranging from 0 to 4.00 × 10 -3 mol l -1 . The kinetic model and mechanism of the said reaction was proposed by means of mathematical statistical modelling of the dependences of k obs on pH and c oxime . The mechanism involves a pre-equilibrium ( k -1 / k 1 ) in which PNPA forms a tetrahedral intermediate (THI) with the deprotonated form of oxime. In the given medium, THI is in equilibrium with the non-reactive conjugated acid THIH (dissociation constant K a,THIH ) which is stabilized by intramolecular hydrogen bond. Depending on pH, the rate-limiting step consists either in formation of THI from educts (pH < p K a,oxime ) or in its spontaneous ( k 2 ) and oxime-catalyzed ( k 3 , general acid catalysis) decomposition to products (pH > p K a,oxime ). Evaluation of substituent effects on dissociation constants ( K a,oxime ) of the oximes showed that there is no direct conjugation between the substituent and the reaction centre (the found reaction constant ρ( K a,oxime ) = 0.91). The transmission coefficient of the transfer of these effects through C=N-O grouping corresponds approximately to one bond. The reaction constants in the Hammett equation obtained from the regression model are: ρ( k -1 K a,THIH / k 1 ) = 1.29, ρ( k 2 K a,THIH ) = 0.20 and ρ( k 3 K a,THIH ) = 0.67. These reaction constants have been discussed with the regard to the reaction mechanism suggested." @default.
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• W2053818056 date "2004-01-01" @default.
• W2053818056 modified "2023-10-11" @default.
• W2053818056 title "Reactivity of p-Substituted Benzaldoximes in the Cleavage of p-Nitrophenyl Acetate: Kinetics and Mechanism" @default.
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• W2053818056 doi "https://doi.org/10.1135/cccc20040397" @default.
• W2053818056 hasPublicationYear "2004" @default.
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