Next Article in Journal
Evaluation of in Vitro and in Vivo Depigmenting Activity of Raspberry Ketone from Rheum officinale
Next Article in Special Issue
Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects
Previous Article in Journal
Molecular Recognition Effects in Atomistic Models of Imprinted Polymers
Previous Article in Special Issue
Correlation of the Rates of Solvolysis of Neopentyl Chloroformate—A Recommended Protecting Agent
Article Menu

Export Article

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

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 / Revised: 22 July 2011 / Accepted: 18 July 2011 / Published: 28 July 2011
(This article belongs to the Special Issue Correlation Analysis Applied to Solvolysis Reactions)
View Full-Text   |   Download PDF [398 KB, uploaded 19 June 2014]   |  

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. View Full-Text
Keywords: solvolysis; substituent effects; solvent effects; acylium cations solvolysis; substituent effects; solvent effects; acylium cations
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

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.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Int. J. Mol. Sci. EISSN 1422-0067 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top