Determination of gas-phase acidities of dimethylphenols: Combined experimental and theoretical study

  • Paulo J. Amorim Madeira
  • Paulo Jorge Costa
  • Maria Tereza Fernandez
  • José A. Martinho Simões
  • João Paulo Leal
Articles

Abstract

The gas-phase acidities of the six dimethylphenol isomers were determined experimentally, by using the kinetic method, and theoretically, through quantum chemistry calculations. The experimental values, relative to the gas-phase acidity of phenol, are (in kJ mol−1): −1.76 ± 0.76 (2,3-Me2C6H3OH), 1.78 ± 0.29 (2,4-Me2C6H3OH), 0.83 ± 0.58 (2,5-Me2C6H3OH), −4.39 ± 0.89 (2,6-Me2C6H3OH), 5.38 ± 1.08 (3,4-Me2C6H3OH), and 1.88 ± 0.08 (3,5-Me2C6H3OH). This trend was discussed by considering the substituent effects on the thermodynamic stabilities both of the parent phenols and the corresponding phenoxide ions. The above acidity data, the literature values for 2-, 3-, and 4-methylphenol, and the substituent effects analysis allowed to develop a simple empirical method to estimate the acidity of any methyl-substituted phenol.

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Copyright information

© American Society for Mass Spectrometry 2008

Authors and Affiliations

  • Paulo J. Amorim Madeira
    • 1
  • Paulo Jorge Costa
    • 1
  • Maria Tereza Fernandez
    • 1
  • José A. Martinho Simões
    • 1
    • 2
  • João Paulo Leal
    • 1
    • 3
  1. 1.Centro de Química e Bioquímica, Faculdade CiênciasUniversidade de LisboaLisboaPortugal
  2. 2.Instituto de Tecnologia Química e BiológicaUniversidade Nova de LisboaOeirasPortugal
  3. 3.Departamento de QuímicaInstituto Tecnológico e NuclearSacavémPortugal

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