The present paper deals with the hydrolysis of ethiofencarb [2ethylthiomethyl(phenyl)-N-methylcarbamate] in alkaline solution. The reaction kinetics has been investigated using spectrophotometric and liquid chromatographic techniques. The rate constants were determined following a proposed first-order kinetic model. The positive activation entropy S = = +100.07 J mol −1 K −1 and the absence of general basic catalysis indicated an E1cB hydrolytic mechanism, involving the formation of methyl isocyanate. This result was confirmed by the fact that ethiofencarb fits well into Brönsted and Hammett lines, obtained for a series of substituted N-methylcarbamate whose decomposition in aqueous media was established to follow an E1cB mechanism. C 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: [118][119][120][121][122][123][124] 2013

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The alkaline hydrolysis of landrin (2,3,5-trimethylphenyl-N-methylcarbamate) into 2,3,5-trimethylphenol was examined for various buffers and sodium hydroxide solutions ranging from pH 11.8 to 13.6. This work was carried out by reversed phase liquid chromatography and UV spectrophotometry. The positive activation entropy DS 6 ¼ ¼ þ38:40 J mol À 1 K À 1 and the absence of general basic catalysis indicated an E1cB hydrolytic mechanism involving the formation of methyl isocyanate. This result was confirmed by the finding that landrin fits well into Brönsted and Hammett plots, obtained for a series of substituted Nmethylcarbamates whose decomposition in aqueous media was established to follow an E1cB mechanism.

Degradation via hydrolysis is among the main transformation pathways and particularly for N‐methylcarbamates. Carbamate pesticide hydrolysis is known to proceed through alkaline catalysis, with reaction of the hydroxide ion with the carbonyl function or with abstraction of hydrogen in the α position with respect to the carbonyl. This reaction leads to the formation of methylamine and corresponding phenol. In this respect, the reaction kinetics of 4‐bromo‐3,5‐dimethylphenyl N‐methylcarbamate (BDMC) hydrolysis have been investigated in alkaline solution using a spectrophotometric technique and reversed phase liquid chromatography. The kinetic constants were determined following a proposed pseudo–first‐order kinetic model. The positive activation entropy ΔS≠ = +35.73 J mol−1 K−1 and the absence of general base catalysis indicated an unimolecular elimination conjugate base (E1cB) hydrolytic mechanism involving the formation of methyl isocyanate. This result was confirmed by the fact that BDMC fits well into brönsted and Hammett lines, obtained for a series of substituted N‐methylcarbamate whose decomposition in aqueous media was established to follow an E1cB mechanism.