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Electrical Effects of Substituent Groups in Saturated Systems. Reactivities of 4-Substituted Bicyclo [2.2.2]octane-1-carboxylic Acids

Roberts, John D. and Moreland, Walter T., Jr. (1953) Electrical Effects of Substituent Groups in Saturated Systems. Reactivities of 4-Substituted Bicyclo [2.2.2]octane-1-carboxylic Acids. Journal of the American Chemical Society, 75 (9). pp. 2167-2173. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20151022-140102999

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Abstract

The reactivities of a series of 4-substituted bicyclo[2.2.2]octane-1-carboxylic acids and esters with X = -H, -OH, -CO_2 C_2H_5, -Br and -C≡N have been determined. The apparent ionization constants of the acids in 50% aqueous ethanol at 25º, the reactivities of the acids toward diphenyldiazomethane in ethanol at 30°, and the saponification rates of the ethyl esters were measured and found to parallel one another throughout the series. The order of reactivities with the various substituents at the 4-position was -C≡N > -Br > -CO_2C_2H_5> -OH > -H. Although transmission of electrical effects of substituent groups through the bicyclo[2.2.2]octane ring system is not possible by resonance interaction involving conjugated unsaturation, the magnitudes of the substituent influences were found to be comparable to those observed in m- and p-substituted benzene derivatives. The Kirkwood-Westheimer ellipsoidal cavity model for calculation of electrostatic effects of polar substituent groups on reactivity gives qualitative agreement with the experimental results.


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http://dx.doi.org/10.1021/ja01105a045DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja01105a045PublisherArticle
Additional Information:© 1953 American Chemical Society. Received September 2, 1952. Presented before the Division of Organic Chemistry at the Atlantic City Meeting of the American Chemical Society, September, 1952. U. S. Atomic Energy Commission Predoctoral Fellow, 1951-1952. We are grateful to Professor F. H. Westheimer for many suggestions and helpful discussions regarding the interpretation of the experimental results.
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Atomic Energy CommissionUNSPECIFIED
Record Number:CaltechAUTHORS:20151022-140102999
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20151022-140102999
Official Citation:Electrical Effects of Substituent Groups in Saturated Systems. Reactivities of 4-Substituted Bicyclo [2.2.2]octane-1-carboxylic Acids John D. Roberts and Walter T. Moreland Jr. Journal of the American Chemical Society 1953 75 (9), 2167-2173 DOI: 10.1021/ja01105a045
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ID Code:61439
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:22 Oct 2015 22:07
Last Modified:22 Oct 2015 22:07

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