Acidities of 4‐substituted benzoic, bicyclo[2.2.2]oct‐1‐yl and bicyclo[2.2.2]oct‐2‐enyl carboxylic acids
- 1 December 1993
- journal article
- research article
- Published by Wiley in Journal of Physical Organic Chemistry
- Vol. 6 (12) , 685-689
- https://doi.org/10.1002/poc.610061205
Abstract
Experimental gas‐phase acidities are reported for a series of 4‐substituted bicyclo [2.2.2] oct‐1‐yl carboxylic acids and for a limited number of the corresponding bicyclo [2.2.2] oct‐2‐enyl carboxylic acids. Similar acidities are also reported for additional 4‐substituted benzoic acids, allowing a comparison of field and resonance effects between the three series. Ab initio molecular orbital calculations for these series of acids confirm the conclusion that the aromatic acids display direct field and resonance effects, whereas the acidities in the aliphatic series acids are largely determined by direct field effects.Keywords
This publication has 30 references indexed in Scilit:
- The nature of field effects and their fall-off with distance: The acidity of substituted quinuclidinium and bicyclooctylammonium ionsJournal of Physical Organic Chemistry, 1991
- Basicity and acidity of azoles: the annelation effect in azolesJournal of the American Chemical Society, 1988
- Correlation analyses of the aqueous-phase acidities of alcohols and gem-diols, and of carbonyl hydration equilibria using electronic and structural parametersJournal of the Chemical Society, Perkin Transactions 2, 1986
- Elucidation of the Origin of Substituent Effects. Theoretical Investigation of Field Effect in Aliphatic Systems by ab initio Molecular Orbital Calculation Using Simple ModelsBulletin of the Chemical Society of Japan, 1985
- An ab initioLCAO‐MO study of the substituent effect in benzenoid systems: Meta‐ and para‐substituted benzoic acidsInternational Journal of Quantum Chemistry, 1984
- CALCULATION OF NEW INDUCTIVE SUBSTITUENT PARAMETER (τ) FOR GROUP AND THE APPLICATIONChemistry Letters, 1982
- An approach for assessing the relative importance of field and ? inductive contributions to polar substituent effects based on the non-proportionality of field and ? inductive substituent constantsJournal of the Chemical Society, Perkin Transactions 2, 1980
- The Nature and Analysis of Substituent Electronic EffectsPublished by Wiley ,1976
- The Preparation of 1-Carboxy-4-substituted Bicyclo[2.2.2]octanesJournal of the American Chemical Society, 1964
- Electrical Effects of Substituent Groups in Saturated Systems. Reactivities of 4-Substituted Bicyclo [2.2.2]octane-1-carboxylic Acids1Journal of the American Chemical Society, 1953