The mechanisms of hydrolysis of alkyl N-alkylthioncarbamate esters at 100 °C

Abstract

The hydrolysis of ethyl N-ethylthioncarbamate (ETE) at 100 °C was studied in the range of 7 mol/L HCl to 4 mol/L NaOH. The pH–rate profile showed that the hydrolysis occurred through specific acid catalysis at pH < 2, spontaneous hydrolysis at pH 2–6.5, and specific basic catalysis at pH > 6.5. The Hammett acidity plot and the excess acidity plot against X were linear. The Bunnett–Olsen plot gave a negative slope indicating that the conjugate acid was less hydrated than the neutral substrate. It was concluded that the acid hydrolysis occurred by an A1 mechanism. The neutral species hydrolyzed with general base catalysis shown by the Brønsted plot with β = 0.48 ± 0.04. Water acted as a general base catalyst with (pseudo-)first-order rate constant, kN = 3.06 × 10–7 s–1. At pH > 6.5 the rate constants increased, reaching a plateau at high basicity. The basic hydrolysis rate constant of ethyl N,N-diethylthioncarbamate, which must react by a BAc2 mechanism, increased linearly at 1–3 mol/L NaOH with a second-order rate constant, k2 = 2.3 × 10–4 (mol/L)–1 s–1, which was 10 times slower than that expected for ETE. Experiments of ETE in 0.6 mol/L NaOH with an excess of ethylamine led to the formation of diethyl thiourea, presenting strong evidence that the basic hydrolysis occurred by the E1cb mechanism. In the rate-determining step, the E1cb mechanism involved the elimination of ethoxide ion from the thioncarbamate anion, producing an isothiocyanate intermediate that decomposed rapidly to form ethylamine, ethanol, and COS.Key words: alkylthioncarbamate esters, ethyl N-ethylthioncarbamate, ethyl N,N-diethylthioncarbamate, hydrolysis, mechanism.