About this Journal Submit a Manuscript Table of Contents
Organic Chemistry International
Volume 2010 (2010), Article ID 130506, 9 pages
http://dx.doi.org/10.1155/2010/130506
Research Article

On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

1Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901, USA
2Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA

Received 2 February 2010; Accepted 19 April 2010

Academic Editor: Daniel Little

Copyright © 2010 Malcolm J. D'Souza et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl-substituted derivatives have now been reported, where the application of the aromatic ring parameter (I) removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now focused on the application of the hI term for the solvolysis of compounds containing a double bond in the vicinity of any developing carbocation. Available specific rates of solvolysis (plus some new values) at 25°C of cinnamyl chloride, cinnamyl bromide, cinnamoyl chloride, p-chlorocinnamoyl chloride, and p-nitrocinnamoyl chloride are analyzed using the simple and extended (including the hI term) Grunwald-Winstein equations.