N-Chlorination of secondary amides. I. Kinetics of N-chlorination of N-methyl acetamide
1969; NRC Research Press; Volume: 47; Issue: 14 Linguagem: Inglês
10.1139/v69-423
ISSN1480-3291
Autores Tópico(s)Synthesis and Catalytic Reactions
ResumoThe rate of N-chlorination of N-methyl acetamide has been studied in acetate buffered hypochlorous acid solutions. The reaction rate is dependent upon pH, chloride ion concentration, and acetic acid concentration. The results fit the following rate expression[Formula: see text]The observed rate constant, k obs , has three components[Formula: see text]The results suggest that the active chlorinating species in the pH range 3.0–6.0 are HOCl, Cl 2 , and CH 3 COOCl, in order of increasing reactivity. The values of the corresponding rate constants at 25 °C are [Formula: see text], and [Formula: see text] l mole −1 min −1 , the last two rate constants being related to k 2 and k 3 through the respective equilibrium constants.At temperatures near room temperature, the N-chlorination reaction has an apparent activation energy of 14 kcal/mole when Cl 2 is the active species, and 5 kcal/mole when CH 3 COOCl is the chlorinating agent.
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