Collect. Czech. Chem. Commun. 1995, 60, 1367-1379

Reactions of 4-Amino-3-penten-2-one and Its NSubstituted Derivatives with Diazonium Ions

Vladimír Macháček, Alexandr Čegan, Aleš Halama, Olga Rožňavská and Vojeslav Štěrba

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


Azo coupling reactions of benzenediazonium salts with substituted 4-amino-3-penten-2-ones take place at the C-3 atom. 1H and 13C NMR spectroscopy has been used to study the structure of both the starting enaminones and coupling products. In CDCl3, 3-(4-chlorophenylhydrazono)-2-(4-methylphenylimino)-4-pentanone exists in hydrazo form whereas 4-amino-3-(4-chlorophenylazo)-3-penten-2-one is present as a mixture of two azo compounds differing probably in the arrangement of the intramolecular hydrogen bond. The azo coupling reaction kinetics have been studied in acetate buffers and methanol-water or tert-butyl alcohol-water mixtures. The coupling rate has been found independent of pH and buffer concentration. The reaction orders with respect to the starting compounds have been determined and the reaction mechanism is suggested. Linear dependence has been found between log kobs and substituent constants according to the Hammett or Yukawa-Tsuno equations.