Collect. Czech. Chem. Commun. 1999, 64, 1629-1640

Kinetics and Mechanism of the Formation and Decomposition of Imidazolin-4-ones from 2-(N-Benzoylamino)alkanamides in Aqueous Medium

Miloš Sedlák, Jiří Hanusek, Radim Bína, Jaromír Kaválek and Vladimír Macháček*

Department of Organic Chemistry, University of Pardubice, 532 10 Pardubice, Czech Republic


The cyclization reactions of substituted 2-(N-benzoyl-N-methyl)aminoalkanamides 1a-1g have been studied in aqueous medium. The Hammett reaction constant is ρ = 1.4 for the cyclization reactions of compounds 1a-1e in sodium hydroxide solutions. 2-[N-Methyl- N-(4-nitrobenzoyl)amino]-2-(4-nitrophenyl)propanamide (1g) is cyclized to imidazolinone 2g in aqueous amine buffers of pH 9-11.5; the reaction is subject to specific base catalysis in these media, and the rate-limiting step is the formation of a tetrahedral intermediate. In sodium hydroxide solution, the primary cyclization product is hydrolyzed to give an intermediate M which is subsequently decomposed to sodium 4-nitrobenzoate and 2-methylamino- 2-(4-nitrophenyl)propanamide. At low sodium hydroxide concentration, the rate-limiting step of the opening of imidazoline ring of compound 2g is non-catalyzed decomposition of the intermediate. At higher sodium hydroxide concentrations, the other reaction path begins to make itself felt: hydroxide-ion-catalyzed decomposition of the intermediate. The dependence of observed rate constant of cyclization of compound 1f on sodium hydroxide concentration was used to determine kinetically the value of pKa = 13.5 ± 0.1. The kinetic deuterium isotope effect of cyclization of compounds 1f giving 2f (kCH/kCD = 1.7) was determined in solutions of NaOD in D2O.

Keywords: Reaction kinetics; Mechanism of cyclization; Solvent isotope effect; 2-Phenyl-5-imidazolinones; Imidazolinones; 2-Benzoylaminoalkanamides.