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Gas‐phase stability of tertiary carbenium ions and rates of solvolysis of tertiary derivatives
Author(s) -
Müller Paul,
Rossier JeanClaude,
Abboud JoseLuis M.
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 - 10.1002/1099-1395(200010)13:10<569::aid-poc274>3.0.co;2-h
Subject(s) - chemistry , solvolysis , carbenium ion , racemization , ion , nucleophile , carbocation , medicinal chemistry , computational chemistry , organic chemistry , hydrolysis , catalysis
The stability of tertiary carbenium ions was determined in the gas phase by ion cyclotron resonance (ICR) and by dissociative proton attachment (DPA). The rate constants for solvolysis of bridgehead derivatives correlate well with the stabilities of bridgehead carbenium ions, as determined by DPA and by ICR, but the ICR data of strained ions do not correlate, indicating rearrangements under the conditions of the ICR experiment. Simple acyclic tertiary derivatives solvolyze faster than predicted on the grounds of the stability of the respective carbenium ions. The effect of nucleophilic solvent participation on the rate of methanolysis of tertiary derivatives was investigated with ( R )‐3‐chloro‐3,7‐dimethyloctane ( 17 ), which reacts with 77% inversion and 23% racemization. Copyright © 2000 John Wiley & Sons, Ltd.