Direct HPLC diastereo- and enantioseparation of 3-methylcyclohexanone thiosemicarbazone (3-MCET) on a polysaccharide-based chiral stationary phase under normal-phase conditions. The optimized chromatographic system was employed in dynamic HPLC experiments (DHPLC), as well as detection technique in a batch wise approach to determine the rate constants and the corresponding free energy activation barriers of the spontaneous, base- and acid-promoted E/Z diastereomerization of 3-MCET. The stereochemical characterization of four stereoisomers of 3-MCET was fully accomplished by integrating the results obtained by chemical correlation method with those derived by theoretical calculations and experimental investigations of circular dichroism (CD). As a final goal, a deepened analysis of the perturbing effect exercised by the stationary phase on rate constant values measured through DHPLC determinations as a function of the chromatographic separation factor α of the interconverting species was successfully accomplished. This revealed quite small deviations from the equivalent kinetic values obtained by off-column batch wise procedure, and suggested a possible effective correction of rate constants measured by DHPLC approach

3-Methylcyclohexanone thiosemicarbazone: Determination of E/Z isomerization barrier by dynamic high-performance liquid chromatography, configuration assignment and theoretical study of the mechanisms involved by the spontaneous, acid and base catalyzed processes / Carradori, Simone; Cirilli, R.; Dei Cicchi, S.; Ferretti, R.; Menta, Sergio; Pierini, Marco; Secci, Daniela. - In: JOURNAL OF CHROMATOGRAPHY A. - ISSN 0021-9673. - STAMPA. - 1269:(2012), pp. 168-177. [10.1016/j.chroma.2012.08.007]

3-Methylcyclohexanone thiosemicarbazone: Determination of E/Z isomerization barrier by dynamic high-performance liquid chromatography, configuration assignment and theoretical study of the mechanisms involved by the spontaneous, acid and base catalyzed processes

CARRADORI, Simone;MENTA, SERGIO;PIERINI, MARCO;SECCI, DANIELA
2012

Abstract

Direct HPLC diastereo- and enantioseparation of 3-methylcyclohexanone thiosemicarbazone (3-MCET) on a polysaccharide-based chiral stationary phase under normal-phase conditions. The optimized chromatographic system was employed in dynamic HPLC experiments (DHPLC), as well as detection technique in a batch wise approach to determine the rate constants and the corresponding free energy activation barriers of the spontaneous, base- and acid-promoted E/Z diastereomerization of 3-MCET. The stereochemical characterization of four stereoisomers of 3-MCET was fully accomplished by integrating the results obtained by chemical correlation method with those derived by theoretical calculations and experimental investigations of circular dichroism (CD). As a final goal, a deepened analysis of the perturbing effect exercised by the stationary phase on rate constant values measured through DHPLC determinations as a function of the chromatographic separation factor α of the interconverting species was successfully accomplished. This revealed quite small deviations from the equivalent kinetic values obtained by off-column batch wise procedure, and suggested a possible effective correction of rate constants measured by DHPLC approach
2012
01 Pubblicazione su rivista::01a Articolo in rivista
3-Methylcyclohexanone thiosemicarbazone: Determination of E/Z isomerization barrier by dynamic high-performance liquid chromatography, configuration assignment and theoretical study of the mechanisms involved by the spontaneous, acid and base catalyzed processes / Carradori, Simone; Cirilli, R.; Dei Cicchi, S.; Ferretti, R.; Menta, Sergio; Pierini, Marco; Secci, Daniela. - In: JOURNAL OF CHROMATOGRAPHY A. - ISSN 0021-9673. - STAMPA. - 1269:(2012), pp. 168-177. [10.1016/j.chroma.2012.08.007]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/495773
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