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Rearrangements in Carbonium Ion-Type Reactions of C^(14)-Labeled Norbornyl Derivatives

Roberts, John D. and Lee, C. C. and Saunders, W. H. (1954) Rearrangements in Carbonium Ion-Type Reactions of C^(14)-Labeled Norbornyl Derivatives. Journal of the American Chemical Society, 76 (18). pp. 4501-4510. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20151022-083817349

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Abstract

The extents of isotope-position rearrangement have been determined in solvolyses of exo- and endo-norbornyl-2,3-C_^(14) p-bromobenzenesulfonates and nitrous acid reactions of exo- and endo-norborny1-3-C^(14)amines. The bridged “norbornonium” ion proposed by Winstein and Trifan as the intermediate in cationic reactions of norbornyl derivatives does not suffice to account for the C^(14)-distributions in the reaction products. The formation of norbornyl derivatives with C^(14) in the 5-and 6-positions along with the observed percentages of rearrangement require 1,3-type hydride shifts which may occur by way of a “nortricyclonium” ion or its equivalent. The extent of rearrangement was found to increase in the solvolytic reactions as nucleophilic character of the solvent decreased. The rearrangement in the amine-nitrous acid reactions was relatively independent of solvent. More rearrangement was observed when the starting norbornyl derivatives had the exo-configuration. Possible interpretations of the experimental results are presented.


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http://dx.doi.org/10.1021/ja01647a001DOIArticle
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Additional Information:© 1954 American Chemical Society. Received February 1, 1954. Preliminary reports of this work were given at the Symposium on Reaction Mechanisms at the 75th Anniversary Meeting of the American Chemical Society, September 7, 1951, and by J. D. Roberts and C. C. Lee, THIS JOURNAL, 73, 5009 (1951). Supported in part by the joint program of the Office of Naval Research and the U. S. Atomic Energy Commission.
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Office of Naval Research (ONR)UNSPECIFIED
Atomic Energy CommissionUNSPECIFIED
Record Number:CaltechAUTHORS:20151022-083817349
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20151022-083817349
Official Citation:Rearrangements in Carbonium Ion-Type Reactions of C14-Labeled Norbornyl Derivatives John D. Roberts, C. C. Lee, and W. H. Saunders Jr. Journal of the American Chemical Society 1954 76 (18), 4501-4510 DOI: 10.1021/ja01647a001
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61404
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:22 Oct 2015 17:58
Last Modified:22 Oct 2015 17:58

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