64993-95-9Relevant articles and documents
Kinetics and mechanism of alkaline hydrolysis of Y-substituted phenyl phenyl carbonates
Kim, Song-I,Hwang, So-Jeong,Jung, Eun-Mi,Um, Ik-Hwan
experimental part, p. 2015 - 2018 (2010/12/19)
Second-order rate constants (kOH-) have been measured spectrophotometrically for alkaline hydrolysis of Y-substituted phenyl phenyl carbonates (2a-j) and compared with the kOH- values reported previously for the corresponding reactions of Y-substituted phenyl benzoates (1a-j). Carbonates 2a-j are 8 ~ 16 times more reactive than benzoates 1a-j. The Hammett plots correlated with σ- and σo constants exhibit many scattered points, while the Yukawa-Tsuno plot results in excellent linear correlation with ρ = 1.21 and r = 0.33. Thus, the reaction has been concluded to proceed through a concerted mechanism in which expulsion of the leaving group is advanced only a little. However, one cannot exclude a possibility that the current reaction proceeds through a forced concerted mechanism with a highly unstable intermediate.
REACTIONS OF IMIDIC ACID DERIVATIVES WITH NUCLEOPHILIC REAGENTS. MECHANISM OF THE ALKALINE HYDROLISIS OF ARYL N-ARYLARENECARBOXIMIDATES
Prudchenko, A. P.,Drizhd, L. P.,Savelova, V. A.
, p. 1715 - 1719 (2007/10/02)
In the kinetics of the alkaline hydrolysis of aryl-N-phenylbenzimidates PhC(OArX) =NPh(I) in a water-dioxane mixture (1:1 by volume) and with a constant ionic strength in 0.2 M sodium perchlorate first order is observed in each of the reagents.The Hammett ρ and Bronsted β parameters with variation of the substituent in the leaving group are 1.6 and -0.35 respectively.The products from the hydrolysis of compounds (I) (X = 2,4-(NO2)2, 2-NO2-4-COCH3) are benzoic acid and substituted diphenylamines and, in the case of the derivatives of (I) benzanilide and the corresponding phenol.In spite of the different qualitative composition of the hydrolysis products the data for all the substituents (including the ortho substituents) satisfy the Hammett and Bronsted equations.The results are explained in terms of an addition-elimination stage mechanism with the formation of a tetrahedral intermediate product in the rate-determining stage.