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Published November 1, 1956 | public
Journal Article

Solvolytic Reactivities of Some 7-Chloronorbornane Derivatives

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.

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.

Additional details

Created:
August 19, 2023
Modified:
October 25, 2023