Rare earth exchanged Na–Y zeolites,
H-mordenite, K-10 montmorillonite clay and amorphous
silica-alumina were effectively employed for the
continuous synthesis of nitriles. Dehydration of benzaldoxime
and 4-methoxybenzaldoxime were carried
out on these catalysts at 473 K. Benzonitrile (dehydration
product) was obtained in near quantitative yield
with benzaldoxime whereas; 4-methoxybenzaldoxime
produces both Beckmann rearrangement (4-methoxyphenylformamide)
as well as dehydration products
(4-methoxy benzonitrile) in quantitative yields. The
production of benzonitrile was near quantitative under
heterogeneous reaction conditions. The optimal protocol
allows nitriles to be synthesized in good yields
through the dehydration of aldoximes. Time on stream
(TOS) studies show decline in the activity of the catalysts
due to neutralization of acid sites by the basic reactant
and product molecules and water formed during the
dehydration of aldoximes.
Rare earth metal ion exchanged (La3+, Ce3+, RE3+) KFAU-Y zeolites were prepared by simple ion-exchange methods and have
been characterized using different physico-chemical techniques. In this paper a novel application of solid acid catalysts in the dehydration/
Beckmann rearrangement of aldoximes; benzaldoxime and 4-methoxybenzaldoxime is reported. Dehydration/Beckmann
rearrangement reactions of benzaldoxime and 4-methoxybenzaldoxime is carried out in a continuous down flow reactor at
473K. 4-Methoxybenzaldoxime gave both Beckmann rearrangement product (4-methoxyphenylformamide) and dehydration product
(4-methoxybenzonitrile) in high overall yields. The difference in behavior of the aldoximes is explained in terms of electronic
effects. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows
nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream studies show a fast decline in the
activity of the catalyst due to neutralization of acid sites by the basic reactant and product molecules.