Rearrangements in Carbonium Ion-Type Reactions of C^(14)-Labeled Norbornyl Derivatives
- Creators
- Roberts, John D.
- Lee, C. C.
- Saunders, W. H.
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.
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.Additional details
- Eprint ID
- 61404
- Resolver ID
- CaltechAUTHORS:20151022-083817349
- Office of Naval Research (ONR)
- Atomic Energy Commission
- Created
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2015-10-22Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field