Abstract
A PREVIOUS investigation1 of the influence of the carboxylate-ion substituent on the kinetics of sol-volysis of organic bromides, RBr, showed that in the two series (R=) there is (where indicated) a change of mechanism from S N2 to S N1 as the CO2—-groups accumulate. We have now investigated the kinetics of the solvolysis of the bromides of two more series (R=), and the results permit consideration of the further series (R=) Throughout series (3), (4) and (5), mechanism S N1 prevails ; and the main interest of the new results relates to the effect of the carboxylate-ion substituent on the unimolecular rate-constants k1, and on their parameters E and B in the Arrhenius equation k1 = B exp — E/RT. The measured reaction is in all cases the heterolysis (ionization) of the CBr-bond. The data are in the accompanying table.
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References
Hughes and Taher, J. Chem. Soc, 956 (1940).
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Dostrovsky and Hughes, J. Chem. Soc, 166 (1946).
Dostrovsky, Hughes and Ingold, J. Chem. Soc, 191 (1946).
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GRIPENBERG, J., HUGHES, E. & INGOLD, C. Effect of Ionic Charges on the Energy and Entropy of Activation of Heterolytic Reactions. Nature 161, 480–481 (1948). https://doi.org/10.1038/161480a0
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DOI: https://doi.org/10.1038/161480a0
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