16728-90-8Relevant articles and documents
Molecular Rearrangements. 19. Thermolysis and Photolysis of N-Arylbenzenesulfonamides
Badr, M. Z. A.,Aly, M. M.,Fahmy, A. M.
, p. 4784 - 4787 (1981)
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Bimolecular Nucleophilic Substitution (SN2) Reactions of Neopentyl Arenesulfonates with Anilines and Benzylamines in Methanol
Koh, Han Joong,Lee, Hai Whang,Lee, Ikchoon
, p. 253 - 258 (2007/10/02)
Bimolecular nucleophilic substitution (SN2) reactions of neopentyl arenesulfonates with anilines and benzylamines in methanol at 55.0 deg C are reported.The tightness of the transition state (TS) is similar to that for other typical SN2 processes at a primary alkyl carbon centre based on the magnitude of the cross-interaction constant ρxz (0.30) between the substituents in the nucleophile (X) and leaving group (Z).The TS variation is in accord with that predicted by the potential energy surface diagram, which in turn is consistent with the positive sign of ρxz; a later TS is obtained with a weaker nucleophile and nucleofuge.Taft's polar substituent constant, ?*, for the trimethylsilyl group is estimated to be -0.48 by using a factor of 1.875 for the fall-off of ?* from the tert-butyl to the neopentyl group and extrapolating from the experimental Taft plot.
Nucleophilic Substitution Reactions of Indan-2-yl Arenesulfonates with Anilines in Methanol
Lee, Ikchoon,Lee, Young Sook,Huh, Chul,Lee, Hai Whang,Lee, Byung Choon
, p. 2415 - 2418 (2007/10/02)
The nucleophilic substitution reactions of (Y)-indan-2-yl (Z)-arenesulfonates with (X)-anilines in methanol at 55.0 deg C are reported.Sign reversals in all three second-order cross-interaction constants, ρXY, ρYZ and ρXZ, are observed at non-interaction points Z = -0.11 (ρXY = 0), X = -0.02 (ρYZ = 0) and Y = 0.43 (ρXZ = 0) respectively, which have been ascribed to an unusually large third-order cross-interaction constant, ρXYZ = -0.53, for the reaction series.An SN2 transition state with a tilted, parallel stacked and displaced structure of the three benzene rings in the nucleophile (X), substrate (Y) and leaving group (Z) is proposed to rationalize the strong three-body coupling manifested by the large ρXYZ value.