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Observation by Carbon-13 Nuclear Magnetic Resonance Spectroscopy of Hydride Shifts in C_4H_7^+ Derived from Cyclopropylcarbinol- 1-^(13)C in SbF_5-SO_2CIF-SO_2F_2 Solution

Staral, John S. and Roberts, John D. (1978) Observation by Carbon-13 Nuclear Magnetic Resonance Spectroscopy of Hydride Shifts in C_4H_7^+ Derived from Cyclopropylcarbinol- 1-^(13)C in SbF_5-SO_2CIF-SO_2F_2 Solution. Journal of the American Chemical Society, 100 (25). pp. 8018-8020. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20151007-093103372

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Abstract

The interconversion in carbocationic reactions of cyclobutyl, cyclopropylcarbinyl, and allylcarbinyl derivatives has been the subject of many investigations since its discovery in 1950. Although controversy continues to surround the precise nature of the "nonclassical" C_4H_7^+ cationic intermediate(s) involved in these transformations, the very rapid equilibration of the methylene carbons is well established. At present, opinion is divided as to whether the equilibration process involves rapidly interconverting bicyclobutonium ions (la-c) or "bisected" cyclopropylcarbinyl cations (2a-c). In contrast, no evidence has been reported to indicate that hydride migrations occur in these intermediates. We now report that the ^(13)C NMR spectrum of an isotopically labeled C_4H_7^+ under stable-ion conditions provides unequivocal evidence for slow occurrence of such hydride shifts.


Item Type:Article
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http://dx.doi.org/10.1021/ja00493a046DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00493a046PublisherArticle
Additional Information:© 1978 American Chemical Society. Supported by the National Science Foundation. We thank Professor G. A. Olah of the University of Southern California for the generous use of his facilities to obtain the FT 20-MHz ^(!3)C NMR spectra and Dr. D. J. Donovan and Mr. G. K. S. Prakash for their assistance in recording these spectra.
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Gates and Crellin Laboratories of Chemistry5775
Issue or Number:25
Record Number:CaltechAUTHORS:20151007-093103372
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151007-093103372
Official Citation:Observation by carbon-13 nuclear magnetic resonance spectroscopy of hydride shifts in C4H7+ derived from cyclopropylcarbinol-1-13C in antimony pentafluoride-sulfuryl chloride fluoride-sulfuryl fluoride solution John S. Staral and John D. Roberts Journal of the American Chemical Society 1978 100 (25), 8018-8020 DOI: 10.1021/ja00493a046
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60863
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:07 Oct 2015 22:35
Last Modified:03 Oct 2019 09:01

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