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
- Eprint ID
- 61368
- DOI
- 10.1021/ja01602a051
- Resolver ID
- CaltechAUTHORS:20151021-100828851
- NSF Predoctoral Fellowship
- U.S. Rubber Co.
- Massachusetts Institute of Technology (MIT)
- Created
-
2015-10-21Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Gates and Crellin Laboratories of Chemistry
- Other Numbering System Identifier
- 2089