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Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media
Chemistry Unit, Grove Building, School of Medicine, Swansea University, Swansea SA2 8PP, Wales, UK
* Author to whom correspondence should be addressed.
Received: 6 July 2011; in revised form: 22 July 2011 / Accepted: 18 July 2011 / Published: 28 July 2011
Abstract: Rate constants and activations parameters are reported for solvolyses of p-Z-substituted benzoyl chlorides (1, Z = OMe, Me, H, and Cl) in 97% w/w hexafluoroisopropanol-water (97H). Additional kinetic data are reported for solvolyses in acetic and formic acids. Plots of log k vs. σp in 97H are consistent with previous research showing that a cationic reaction channel is dominant, even for solvolyses of 1, Z = NO2. A benzoyl cation intermediate was trapped by Friedel-Crafts reaction with 1,3,5-trimethoxybenzene in hexafluoroisopropanol. The results are explained by an SN2-SN1 spectrum of mechanisms with variations in nucleophilic solvent assistance. Ab initio calculations of heterolytic bond dissociation energies of various chloro- and fluoro-substituted and other benzoyl chlorides are correlated with log k for solvolyses.
Keywords: solvolysis; substituent effects; solvent effects; acylium cations
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Bentley, T.W.; Harris, H.C. Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media. Int. J. Mol. Sci. 2011, 12, 4805-4818.
Bentley TW, Harris HC. Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media. International Journal of Molecular Sciences. 2011; 12(8):4805-4818.
Bentley, Thomas William; Harris, Haldon Carl. 2011. "Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media." Int. J. Mol. Sci. 12, no. 8: 4805-4818.