Journal of the Chemical Society. Perkin transactions II p. 983 - 990 (1985)
Update date:2022-08-29
Topics:
Bentley, T. William
Carter, Gillian E.
Harris, H. Carl
The further development of a convenient, conductimetric method for studying the rates of relatively fast solvolytic reactions in highly aqueous media is described.Rate and product data are reported for solvolyses of benzoyl chloride at 25 deg C in water and in binary aqueous mixtures with acetone, ethanol, methanol, trifluoroethanol, and hexafluoropropan-2-ol.Comparison of these kinetic data with rate data for the SN1 model, 1-adamantyl chloride, reveals sensitivity to solvent nucleophilicity even for highly aqueous media.In constrast with other nucleophilically solvent-assisted processes, the solvent effects are not satisfactorily correlated by one linear free energy relationship.Gas-phase thermochemical data show the feasibility of a direct heterolytic cleavage of the C-Cl bond in benzoyl chloride.Rate-product correlations for hydrolysis and aminolysis in 50percent w/w acetone-water are observed, providing that allowance is made for the medium effect of the added o-nitroaniline.These results are consistent with an SN2 mechanism, not SN1 and/or ion-pair mechanisms previously discussed.Another pathway, dominant in less aqueous media, is much less sensitive to changes in solvent ionizing power, consistent with earlier proposals for a carbonyl addition-elimination mechanism.
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