30362-87-9Relevant 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.
Kinetic study on alkaline hydrolysis of Y-substituted phenyl X-substituted benzenesulfonates: Effects of changing nucleophile from azide to hydroxide ion on reactivity and transition-state structure
Moon, Ji-Hyun,Kim, Min-Young,Han, So-Yeop,Um, Ik-Hwan
, p. 1563 - 1568 (2015/08/11)
Second-order rate constants (kOH-) for alkaline hydrolysis of 2,4-dinitrophenyl X-substituted benzenesulfonates (1a-1f) and Y-substituted phenyl 4-nitrobezenesulfonates (2a-2g) have been measured spectrophotometrically. Comparison of kOH/
Competitive Reaction Pathways in the Nucleophilic Substitution Reactions of Aryl Benzenesulfonates with Benzylamines in Acetonitrile
Choi, Jin Heui,Lee, Byung Choon,Lee, Hai Whang,Lee, Ikchoon
, p. 1277 - 1281 (2007/10/03)
The reactions of aryl benzenesulfonates (YC6H4SO2OC6H4Z) with benzylamines (XC6H4CH2NH2) in acetonitrile at 65.0 deg C have been studied. The reactons proceed competitevely by S-O (kS-O) and C-O (kC-O) bond scission, but the former provides the major reaction pathway. On the basis of analysis of the Hammet and Broensted coefficients together with the cross-interaction constants ρXY, ρYZ, and ρXZ, stepwise mechanisms are proposed in which the S-O bond cleavage proceeds by rate-limiting formation of a trigonal-bipyramidal pentacoordinate (TBP-5C) intermediate, whereas the C-O bond scission takes place by rate-limiting expulsion of the sulfonate anion (YC6H4SO3-) from a Meisenheimer-type complex.
Synthesis of aryl esters of protected amino acids from aryl sulfonates
Pudhom, Khanitha,Vilaivan, Tirayut
, p. 5939 - 5942 (2007/10/03)
Aryl esters of Boc- and Fmoc-protected amino acids derived from electron-deficient phenols have been prepared in good yields from aryl 4- nitrobenzenesulfonates in the presence of 1-hydroxy-benzotriazole as catalyst.
Retardation of Hydrolysis of Aryl Arenesulphonate Esters by Quinuclidine through Complex Formation
Suh, Junghun,Suh,, Myung Koo,Cho, Seung Ho
, p. 685 - 688 (2007/10/02)
The hydrolysis of aryl arenesulphonate esters is considerably retarded upon the addition of quinuclidine (Quin).Kinetic and spectral data indicate that the protonated form of Quin forms non-covalent complexes with the sulphonate esters and that the comple
