The bromination of 5H-dibenz[b,f]azepine-5-carboxamide (carbamazepine) (1) in 1,2-dichloroethane gives only the trans-dibromide 2. The reaction, followed spectrophotometrically, obeys a third-order rate law (second-order in Br2), but the value of k3 changes considerably depending on the monitoring wavelength. It is shown that this is due to the presence of reversibly formed Br3- salt intermediates, that make a more important contribution to the absorbance in the lower wavelength range of the monitored 360-540 nm region. A significant conductivity is also measured during the course of the bromination. Both spectrophotometric and conductimetric measurements are consistent with the presence of Br3- salt intermediates at a maximum concentration amounting to ca. 2% of that of the initial reagents. The structure of dibromide 2, determined by X-ray diffraction, shows a considerable angle strain at carbons bearing bromine. This strain is responsible for an easy spontaneous debromination of 2, as well as for a relatively high barrier for the formation of 2 from the bromonium-tribromide intermediate, that makes possible the accumulation of the intermediate itself during the bromination of 1.

The detection of ionic intermediates during the bromination of 5H-dibenz[b,f]azepine-5 carboxamide in 1,2-dichloroethane.

CHIAPPE, CINZIA;MARCHETTI, FABIO
1992

Abstract

The bromination of 5H-dibenz[b,f]azepine-5-carboxamide (carbamazepine) (1) in 1,2-dichloroethane gives only the trans-dibromide 2. The reaction, followed spectrophotometrically, obeys a third-order rate law (second-order in Br2), but the value of k3 changes considerably depending on the monitoring wavelength. It is shown that this is due to the presence of reversibly formed Br3- salt intermediates, that make a more important contribution to the absorbance in the lower wavelength range of the monitored 360-540 nm region. A significant conductivity is also measured during the course of the bromination. Both spectrophotometric and conductimetric measurements are consistent with the presence of Br3- salt intermediates at a maximum concentration amounting to ca. 2% of that of the initial reagents. The structure of dibromide 2, determined by X-ray diffraction, shows a considerable angle strain at carbons bearing bromine. This strain is responsible for an easy spontaneous debromination of 2, as well as for a relatively high barrier for the formation of 2 from the bromonium-tribromide intermediate, that makes possible the accumulation of the intermediate itself during the bromination of 1.
Bellucci, G; Chiappe, Cinzia; Marioni, F; Marchetti, Fabio
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/198260
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