- Syntheses of N-alkyl, A,N-dialkyl, and N-(4-substituted phenyl) O-ethyl thioncarbamates: A kinetic study
-
The kinetics of the syntheses of N-alkyl, N,N-dialkyl, and N-(4-substituted phenyl) O-ethyl thioncarbamates from sodium ethyl xanthogenacetate, ten alkylamines, and eight substituted anilines were studied at 25, 30, 35, and 40 °C. The reactions were found to follow second-order kinetics. The kinetic (Arrhenius) parameters, such as the activation energy and the frequency factor, as well as the Eyring parameters, such as the standard entropy, the standard Gibbs energy, and the standard enthalpy of activation, were calculated from the second-order rate constants. The mechanism of the reaction was postulated based on the kinetic studies presented and the optimization of the reaction mechanism using the MOPAC PM6 semi-empirical method.
- Milosavljevic, Milutin M.,Marinkovic, Aleksandar D.,Veljkovic, Vlada B.,Milenkovic, Dragan D.
-
experimental part
p. 43 - 49
(2012/07/13)
-
- A synthesis of N-alkyl and N,N-dialkyl O-ethyl thiocarbamates from diethyl dixanthogenate using different oxidants
-
A novel synthesis of N-alkyl and N,N-dialkyl O-ethyl thiocarbamates from diethyl dixanthogenate and primary and secondary amines, using three oxidizing systems, has been developed on the laboratory scale, and the method using sodium hypochlorite has been applied on a semi-industrial scale. The effect of the oxidizing agents, sodium hypochlorite, in-situ-generated peracetic acid, and the manganese(II) acetate/oxygen system on product purity and yield was studied. The results obtained by use of these three methods were compared with those obtained by reaction of sodium ethyl xanthogenacetate and amines, and of sodium ethyl xanthate with amines in the presence of sulfated nickel zeolite catalyst. The reaction mechanism of sodium hypochlorite oxidation has been established on the basis of isolation of reaction intermediates and determination of their structure by use of Fourier-transform infrared, 1H and 13C NMR, and mass spectrometric methods. The suggested sodium hypochlorite and manganese(II) acetate/oxygen systems have many advantages in comparison with commercial and catalytically promoted synthetic methods, because they are new ecologically friendly syntheses. Springer-Verlag 2010.
- Milosavljevic, Milutin M.,Sovrlic, Milica,Marinkovic, Aleksandar D.,Milenkovic, Dragan D.
-
experimental part
p. 749 - 755
(2011/07/08)
-