Active sites for the liquid-phase Beckmann rearrangement of cyclohexanone, acetophenone and cyclododecanone oximes, catalyzed by beta zeolites

摘要

The Beckmann rearrangement of oximes with different molecular sizes, i.e. cyclohexanone, cyclododecanone, and acetophenone oximes, has been studied in liquid phase at 130 degrees C over a series of four Beta zeolites differing in the presence or absence of framework Al and internal silanol groups, When the zeolite does not contain framework Al and internal silanols, no appreciable conversion was observed. The catalyst having internal silanol groups but no framework Al exhibits oxime conversion, but the selectivity to the corresponding amide is low in some cases. In the Beta zeolite without silanol groups but containing framework Al, conversion and selectivity were found to be very high. This superior performance of Bronsted acid sites, compared to silanol groups, shows that the results reported for the vapor phase reaction cannot be extrapolated when the reaction is performed in liquid phase. Finally, as could be anticipated according to the dimensions of the micropores, it is shown that II-Beta zeolites exhibit a much better catalytic performance than H-ZSM-5 zeolite for larger sized oximes. (C) 1998 Academic Press. [References: 34]