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Solvolysis of 2‐aryl‐2‐adamantyl p ‐nitrobenzoates and some tertiary benzylic p ‐nitrobenzoates. Y BnOPNB and Y xBnOPNB scales
Author(s) -
Liu KwangTing,
Chang ChihWei,
Chen HungI,
Chin ChienPu,
Duann YehFang
Publication year - 2000
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(200004)13:4<203::aid-poc230>3.0.co;2-9
Subject(s) - solvolysis , chemistry , reactivity (psychology) , aryl , medicinal chemistry , solvent , solvent effects , reaction rate constant , stereochemistry , computational chemistry , organic chemistry , hydrolysis , alkyl , kinetics , medicine , alternative medicine , physics , pathology , quantum mechanics
Solvolysis rate constants for a number of tertiary benzylic p ‐nitrobenzoate esters in a wide range of solvents were measured. New scales of solvent ionizing power for Grunwald–Winstein‐type correlation analyses, Y BnOPNB from 2‐phenyl‐2‐adamantyl p ‐nitrobenzoate and Y xBnOPNB from 2‐(6‐methoxy‐2‐naphthyl)‐2‐ adamantyl p ‐nitrobenzoate, were developed for the mechanistic study of solvent effects on the solvolytic reactivity of benzylic p ‐nitrobenzoates. The excellent linear log k – Y BnOPNB plot for 2‐(4‐methylphenyl)‐2‐propyl p ‐nitrobenzoate indicated a limiting S N 1 mechanism. The solvolytic transition state for 9‐phenyl‐9‐fluorenyl p ‐nitrobenzoate and that for 1,1‐diphenylethyl p ‐nitrobenzoate were considered to involve extended positive charge delocalizations from the observation of linear relationships between log k and Y xBnOPNB . The ambiguity in the case of 2, 2‐dimethyl‐1‐(4‐methoxyphenyl)‐1‐phenyl‐1‐propyl p ‐nitrobenzoate is discussed. Copyright © 2000 John Wiley & Sons, Ltd.