Woods, William G. and Carboni, Rudolph A. and Roberts, John D. (1956) Solvolytic Reactivities of Some 7-Chloronorbornane Derivatives. Journal of the American Chemical Society, 78 (21). pp. 5653-5657. ISSN 0002-7863. doi:10.1021/ja01602a051. https://resolver.caltech.edu/CaltechAUTHORS:20151021-100828851
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Abstract
7-Chloronorbornane, a number of saturated 7-chloronorbornane derivatives and syn-7-chloronorbornene have been found to possess very unreactive chlorine under conditions where exo-norbornyl and cyclopentyl chlorides solvolyze readily. In contrast, anti-7-chloronorbornene (like anti-7-norbornenyl p-toluenesulfonate, Winstein, Woodward and co-workers) is quite reactive and solvolyzes about 55 times more rapidly than exo-norbornyl chloride and about 7 times more rapidly than ɑ-methylallyl chloride in 80% ethanol at 100º. The solvolysis of anti-7-chloronorbornene is probably facilitated through stabilization of the carbocationic transition state by electron delocalization analogous to that predicted theoretically for the cyclopropenyl cation. First-order molecular orbital and steric strain calculations provide support for this formulation. The very low reactivity of syn-7-chloronorbornene and 7-chloronorbornane derivatives may be accounted for on the basis of steric inhibition of hyperconjugation.
| Item Type: | Article | |||||||||
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| Additional Information: | © 1956 American Chemical Society. Received March 12, 1956. Presented at the Dallas Meeting of the American Chemical Society, April, 1956. National Science Foundation Predoctoral Fellow, 1955-1956; U. S. Rubber Co. Predoctoral Fellow, Massachusetts Institute of Technology, 1952-1953. | |||||||||
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| Issue or Number: | 21 | |||||||||
| DOI: | 10.1021/ja01602a051 | |||||||||
| Record Number: | CaltechAUTHORS:20151021-100828851 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20151021-100828851 | |||||||||
| Official Citation: | Solvolytic Reactivities of Some 7-Chloronorbornane Derivatives William G. Woods, Rudolph A. Carboni, and John D. Roberts Journal of the American Chemical Society 1956 78 (21), 5653-5657 DOI: 10.1021/ja01602a051 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 61368 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 21 Oct 2015 19:04 | |||||||||
| Last Modified: | 10 Nov 2021 22:48 |
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