Hydrolysis mechanisms for indomethacin and acemethacin in perchloric acid

J Org Chem. 2006 May 12;71(10):3718-26. doi: 10.1021/jo052561k.

Abstract

The acid-catalyzed hydrolysis reactions of the antiinflammatory drugs indomethacin and acemethacin were investigated at 25.0 degrees C in a number of strongly concentrated perchloric acid media. The reaction rates were evaluated by UV measurements, and the intermediate species were detected by UV-vis, 1H NMR, 13C NMR, and mass spectroscopy measurements. A switchover from an A-2 to an A-1 mechanism as a function of the medium acidity is reported for the acid-catalyzed hydrolyses of the amide group of both indomethacin and acemethacin. In the A-2 hydrolysis, two water molecules are involved in the rate-determining step. An analysis of the kinetic data collected for acemethacin by the different techniques used reveals a complex mechanism, indomethacin being a metabolite intermediate species in the hydrolysis of acemethacin. The rate constants for the hydrolysis of the acemethacin ester group were considerably larger compared to those of the amide group.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anti-Inflammatory Agents, Non-Steroidal / chemistry*
  • Hydrolysis
  • Indoles / chemistry*
  • Indomethacin / chemistry*
  • Molecular Structure
  • Perchlorates / chemistry*

Substances

  • Anti-Inflammatory Agents, Non-Steroidal
  • Indoles
  • Perchlorates
  • acemethacin
  • Indomethacin