970-88-7Relevant articles and documents
Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted-Benzenesulfonates and Y-Substituted-Phenyl 4-Nitrobenzenesulfonates with Azide Ion: Regioselectivity and Reaction Mechanism
Moon, Ji-Hyun,Kim, Min-Young,Han, So-Yeop,Um, Ik-Hwan
, p. 1360 - 1365 (2015/07/15)
The second-order rate constants for reactions of 2,4-dinitrophenyl X-substituted-benzenesulfonates (4a-4f) and Y-substituted-phenyl-4-nitrobenzenesulfonates (5a-5f) with N3- ion have been measured spectrophotometrically. The reactions of 4a-4f proceed through S-O and C-O bond fission pathways competitively. Fraction of the S-O bond fission decreases rapidly as the substituent X in the benzenesulfonyl moiety changes from an electron-withdrawing group to an electron-donating group. The Hammett plots for reactions of 4a-4f are linear with ρX=1.87 and 0.56 for the S-O and C-O bond fission, respectively. The fact that the substituent X is further away from the reaction site of the C-O bond fission than that of the S-O bond fission is one reason for the smaller ρX value. The nature of the reaction mechanism (i.e., a stepwise mechanism in which expulsion of the leaving group occurs after the rate-determining step) is also responsible for the smaller ρX value obtained from the C-O bond fission. The Bronsted-type plot for the reactions of 5a-5f is linear with βlg=-0.63, which is typical for reactions reported previously to proceed through a concerted mechanism. Effects of substituents X and Y on regioselectivity and reaction mechanism are discussed in detail.
A kinetic study on nucleophilic displacement reactions of aryl benzenesulfonates with potassium ethoxide: Role of K+ ion and reaction mechanism deduced from analyses of LFERs and activation parameters
Um, Ik-Hwan,Kang, Ji-Sun,Shin, Young-Hee,Buncel, Erwin
, p. 490 - 497 (2013/03/13)
Pseudofirst-order rate constants (kobsd) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates 4a-f and Y-substituted phenyl benzenesulfonates 5a-k with EtOK in anhydrous ethanol. Dissection of k obsd into kEtO- and kEtOK (i.e., the second-order rate constants for the reactions with the dissociated EtO - and ion-paired EtOK, respectively) shows that the ion-paired EtOK is more reactive than the dissociated EtO-, indicating that K + ion catalyzes the reaction. The catalytic effect exerted by K + ion (e.g., the kEtOK/kEtO- ratio) decreases linearly as the substituent X in the benzenesulfonyl moiety changes from an electron-donating group (EDG) to an electron-withdrawing group (EWG), but it is independent of the electronic nature of the substituent Y in the leaving group. The reactions have been concluded to proceed through a concerted mechanism from analyses of the kinetic data through linear free energy relationships (e.g., the Bronsted-type, Hammett, and Yukawa-Tsuno plots). K+ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a cyclic transition state (TS) rather than by increasing the nucleofugality of the leaving group. Activation parameters (e.g., ΔH? and ΔS?) determined from the reactions performed at five different temperatures further support the proposed mechanism and TS structures.