Hydrolysis of mefenpyrdiethyl: An analytical and DFT investigation

Amina Chnirheb, Mourad Harir, Basem Kanawati, Agnes Fekete, Mohammed El Azzouzi, Norbert Hertkorn, Philippe Schmitt-Kopplin

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

The hydrolysis of the herbicide safener mefenpyrdiethyl (1-(2, 4-dichlorophenyl)-4, 5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylic acid diethyl ester) was investigated in aqueous solutions in the pH range from 2 to 9 and the temperature range from 298 to 323 K. The kinetics of hydrolysis were pseudo first order and were found to be strongly pH and temperature dependent. While near-constant in acidic medium, the hydrolysis rates strongly increased in alkaline pH, and total hydrolysis was observed at pH 11. Two main hydrolysis products, mefenpyrethyl (monoester) and mefenpyr (dicarboxylic acid) were isolated by ultrahigh-pressure liquid chromatography (UHPLC) and characterized using high-resolution Fourier transform ion cyclotron resonance mass spectroscopy (ICR-FT/MS) as well as 1H, 13C and 2D NMR analyses. Additionally, a density functional theory (DFT) investigation explained the stability of the pesticide at pH 7 and the high reactivity of the pesticide in alkaline medium. The key nucleophilic reaction partner is hydroxyl ions instead of neutral water molecules. Furthermore, the calculated activation barrier for hydrolysis in alkaline medium is in agreement with the extrapolated and experimentally determined activation barrier at pH 14.

Original languageEnglish
Pages (from-to)2325-2334
Number of pages10
JournalAnalytical and Bioanalytical Chemistry
Volume398
Issue number5
DOIs
StatePublished - Nov 2010
Externally publishedYes

Keywords

  • Hydrolysis
  • Hydrolysis products
  • Kinetics
  • Mefenpyrdiethyl

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