Int. J. Mol. Sci. 2011, 12(8), 4805-4818; doi:10.3390/ijms12084805
Article

Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media

Received: 6 July 2011; in revised form: 22 July 2011 / Accepted: 18 July 2011 / Published: 28 July 2011
(This article belongs to the Special Issue Correlation Analysis Applied to Solvolysis Reactions)
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: 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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MDPI and ACS Style

Bentley, T.W.; Harris, H.C. Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media. Int. J. Mol. Sci. 2011, 12, 4805-4818.

AMA Style

Bentley TW, Harris HC. Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media. International Journal of Molecular Sciences. 2011; 12(8):4805-4818.

Chicago/Turabian Style

Bentley, Thomas William; Harris, Haldon Carl. 2011. "Solvolyses of Benzoyl Chlorides in Weakly Nucleophilic Media." Int. J. Mol. Sci. 12, no. 8: 4805-4818.

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