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The negative sign of the Hammett ρ in this reaction can be rationalized by the formation of an ester in the rate determining step. The rate of an acid-catalyzed esterification is expected to be proportional to the nucleophilicity of the alcohol, which depends upon the electron-donor/acceptor ability of the substituents. See, H. H. Jaffe, Chem. Rev. 1953, 53, 191-261
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The negative sign of the Hammett ρ in this reaction can be rationalized by the formation of an ester in the rate determining step. The rate of an acid-catalyzed esterification is expected to be proportional to the nucleophilicity of the alcohol, which depends upon the electron-donor/acceptor ability of the substituents. See, H. H. Jaffe, Chem. Rev. 1953, 53, 191-261.
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The ampoules were heated in a closed, heavy walled metal reactor, filled with water. Under these conditions explosions of ampoules did not occur
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The ampoules were heated in a closed, heavy walled metal reactor, filled with water. Under these conditions explosions of ampoules did not occur.
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