Acid-catalysed hydrolysis of methoxy-substituted trityl trifluoroethyl ethers: A kinetic and computational investigation of leaving group effects

López M. C., Demirtas İ., Maskill H., Mishima M.

Journal of Physical Organic Chemistry, vol.21, no.7-8, pp.614-621, 2008 (SCI-Expanded) identifier

  • Publication Type: Article / Abstract
  • Volume: 21 Issue: 7-8
  • Publication Date: 2008
  • Doi Number: 10.1002/poc.1332
  • Journal Name: Journal of Physical Organic Chemistry
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.614-621
  • Keywords: Acid catalysis, Computational chemistry, Hydrolysis, Trifluoroethyl ether, Trityl cation
  • Ondokuz Mayıs University Affiliated: No


Trityl trifluoroethyl (TFE) ether and its 4-methoxy, 4,4′-dimethoxy-, and 4,4′,4″-trimethoxy-substituted analogues have been prepared; the dimethoxy and trimethoxy compounds undergo ready acid-catalysed hydrolysis at constant ionic strength = 1 mol dm-3 at 25°C. The monomethoxy compound is less reactive and the parent trityl analogue showed minimal reactivity. Using presently reported and literature kinetics results with pKa values of protonated substrates, first-order rate constants covering 12 orders of magnitude have been determined for heterolysis/ dissociation of 11 protonated dimethoxytrityl derivatives DMTrYH+ where YH = H2O, CF3CH2OH, ArNH2 and RNH2. There is a good correlation between logarithms of these rate constants and the pKa values of the conjugate acids (YH 2+) of the nucleofuges YH. Enthalpies and corresponding free energies at 25°C for the dissociation of the specifically solvated ions CH3 - YH(H2O)n+ (YH = MeOH and CF3CH2OH, n = 1; H2O, n = 2; and NH 3, n = 3) have been calculated at the B3LYP/6-31+G* level. Corresponding gas phase calculations have also been carried out for Ph 3C YH(H2O)n+ (YH = H2O, n = 2; MeOH, n = 1; CF3CH2OH, n = 1 and NH3, n = 3) and, in addition, structures for these solvated ions with (YH = H 2O, MeOH and NH3) have been calculated. The specifically solvated ion Ph3C - O(H)CH2CF3(H 2O)+ does not correspond to a stable bonded species in the gas phase, which suggests that acid-catalysed fragmentation of methoxy-substituted analogues of Ph3C - OCH2CF3 in aqueous solution are concerted with proton transfer in which case the hydrolytic cleavage will be general acid catalysed. Copyright © 2008 John Wiley & Sons, Ltd.