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Kinetic Evidence for the Solvent Intervention in the Solvolysis of Tertiary Benzylic Benzoates †
Author(s) -
Liu KwangTing,
Chang LihWei,
Chin ChienPu
Publication year - 2006
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200690230
Subject(s) - chemistry , solvolysis , benzoates , solvent , organic chemistry , kinetic energy , computational chemistry , medicinal chemistry , hydrolysis , physics , quantum mechanics
Rates of solvolyses of 2‐(4‐methylphenyl)‐2‐propyl benzoate ( 2b ), 2‐(4‐methylthiophenyl)‐2‐propyl benzoate ( 3b ) and 2,2‐dimethyl‐1‐(4‐methoxyphenyl)‐1‐phenyl‐1‐propyl benzoate ( 4b ) were measured, respectively, in ten or more different solvent systems. Additional Y BnOPNB and Y xBnOPNB values in binary trifluoroethanol‐water systems were determined. Grunwald‐Winstein type correlation analysis showed that Y BnOPNB values were applicable to benzylic benzoates. The rate ratio, k OPNB / k OBz , was found to be solvent‐dependent in the range of 29 for 4 in ethanol to 4 for 2 in trifluoroethanol‐water. Non‐limiting mechanism, including both nucleophilic and electrophilic solvent assistance, in the solvolysis of 2b was discussed.