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Solvolytic Reactivities of Some 7-Chloronorbornane Derivatives

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.

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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.

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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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NSF Predoctoral FellowshipUNSPECIFIED
Massachusetts Institute of Technology (MIT)UNSPECIFIED
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Caltech Gates and Crellin Laboratories of Chemistry2089
Issue or Number:21
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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
Deposited By: Ruth Sustaita
Deposited On:21 Oct 2015 19:04
Last Modified:10 Nov 2021 22:48

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