Premium
Solvent Effects on the Solvolysis of Some Secondary Tosylates. Applications of Y BnOTs and Y xBnOTs Scales to Mechanistic Studies
Author(s) -
Liu KwangTing,
Lin YenShyi,
Duann YehFang
Publication year - 2003
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.200300009
Subject(s) - solvolysis , chemistry , solvent , computational chemistry , aryl , equation of state , thermodynamics , medicinal chemistry , organic chemistry , hydrolysis , alkyl , physics
The solvolysis of α‐tert ‐butyl‐2‐naphthylmethyl, 9‐fluorenyl, and some 1‐aryl‐1‐ tert ‐butylmethyl tosylates ( 8–10 ) in a variety of solvents were studied. Both the single‐parameter Hammett‐Brown equation and the dual‐parameter Yukawa‐Tsuno equation showed linear correlations. The variation of ρ values was discussed. A new Y xBnOTs scale was developed, and the Y BnOTs scale was expanded. Solvent effects for a number of tosylates were examined. Excellent linear relationships observed from the single‐parameter Grunwald‐Winstein equation (Eqn. 2) for 9‐fluorenyl tosylate ( 10 ) led to the conclusion that the 9‐fluorenyl cation in the solvolysis transition state was unlikely antiaromatic. Anchimeric assistance in the solvolysis of 16–19 was discussed.