Collect. Czech. Chem. Commun. 1979, 44, 2401-2408

Kinetics and mechanism of alkaline hydrolysis of (Z)-O-(N-4-nitrophenylcarbamoyl)benzaldoximes in 30% aqueous ethanol

Jaromír Mindl, František Radonský, Jiří Klicnar and Miroslav Večeřa

Department of Organic Chemistry, Institute of Chemical Technology, 532 10 Pardubice


Alkaline hydrolysis of (Z)-O-(N-4-nitrophenylcarbamoyl)benzaldoximes (I), the configuration of which was verified by IR spectra, produces a mixture of Z and E-benzaldoximates II and III, benzonitrile IV, and 4-nitrophenylcarbamate ion (V). In subsequent reactions II and III are hydrolyzed to benzaldehyde VI, and III and IV give finally benzoate VII. The carbamate V is decarboxylated to 4-nitroaniline (VIII). The compound I is hydrolyzed to oxime and 4-nitroaniline (VIII) in neutral medium. The hydrolysis rates of three compounds type I have been measured in 30% aqueous ethanol at pH 4 to 14. Character of the hydrolysis course in alkaline medium corresponds to a reaction of E1cB type. In neutral medium spontaneous hydrolysis with water takes place and the reaction rate is independent of concentration of hydrogen ion.