14609-76-8Relevant articles and documents
Nucleophilic Addition to Olefins. 6. Structure-Reactivity Relationships in the Reactions of Substituted Benzylidene Meldrum's Acids with Water, Hydroxide Ion, and Aryl Oxide Ions
Bernasconi, Claude F.,Leonarduzzi, Gianni D.
, p. 5133 - 5142 (1982)
The addition of water to p-methoxybenzylidene Meldrum's Acid (1-OMe), to form an adduct (TOH-, is subject to weak general base catalysis, just as water addition to carbocations studied by Ritchie.This implies a mechanism in which the
Kinetic study on alkaline hydrolysis of Y-substituted phenyl picolinates: Effects of modification of nonleaving group from benzoyl to picolinyl on reactivity and reaction mechanism
Kim, Myung-Joo,Kim, Min-Young,Um, Ik-Hwan
, p. 1138 - 1142 (2015/07/15)
Second-order rate constants (kOH-) for alkaline hydrolysis of Y-substituted phenyl picolinates (6a-6i) have been measured spectrophotometrically. A linear Bronsted-type plot is obtained with βlg = -0.34, which is typical for reactions reported previously to proceed through a stepwise mechanism with formation of an addition intermediate being the rate-determining step (RDS). However, σYo constants result in a much poorer Hammett correlation than σY- constants. Furthermore, the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρY = 0.82 and r = 0.72, indicating that a negative charge develops partially on the O atom of the leaving group in the RDS. Thus, the reactions have been concluded to proceed through a forced concerted mechanism with a highly unstable intermediate 7. Comparison of the current kinetic data with those reported previously for the corresponding reactions of Y-substituted phenyl benzoates has revealed that modification of the nonleaving group from benzoyl to picolinyl causes not only an increase in reactivity but also a change in the reaction mechanism (i.e., from a stepwise mechanism to a forced concerted pathway).
Kinetic and theoretical study on nucleofugality in the phenolysis of 3-nitrophenyl and 4-nitrophenyl 4-cyanophenyl thionocarbonates
Castro, Enrique A.,Ca?ete, Alvaro,Campodónico, Paola R.,Cepeda, Marjorie,Pavez, Paulina,Contreras, Renato,Santos, José G.
, p. 130 - 135 (2013/07/11)
The phenolysis of 3-nitrophenyl 4-cyanophenyl thionocarbonate (1) and 4-nitrophenyl 4-cyanophenyl thionocarbonate (2) are subjected to a kinetic investigation in order to evaluate the nucleofugality of the corresponding leaving groups. For the reaction of 2 only 4-nitrophenoxide is obtained as leaving group. For the reaction of 1 the nucleofugality ratio 3-nitrophenoxide/4-cyanophenoxide is 1/3 from the corresponding T- intermediate. Theoretical calculations confirm the experimental results. From these results it can be concluded that the non-leaving group affects the nucleofugality ratio.
