Catalytic aldoxime rearrangement

Catalytic Aldoxime Rearrangement and Coupling into Primaiy, Secondaiy and Tertiary Amides... 

In the catalytic hydrogenation of aldoximes with Raney nickel Paul (101) observed a small amount of rearrangement of the aldoxime to the acid amide. Raney nickel induces the rearrangement which takes place... 

Aldoximes are rearranged to amides at 100-150° under the catalytic influence of Raney nickel. The yields of amides from the oximes of acetaldehyde, heptaldehyde, benzaldehyde, and furfural are good (75 96%)> although the reactions are carried out on a small scale only. 

InCls can be used as an efficient reagent for the conversion of aldoximes to nitriles and ketoximes to amides. Benzaldoxime gives benzonitrile, and benzophenone oxime is converted to the Beckmann rearrangement product, benzanilide, in 95% yield (Scheme 8.135) [179]. Sonication of a mixture of a carbonyl compound, an amine, and diethyl phosphite in fhe presence of a catalytic amount of InCls produces a-aminophosphonate (Scheme 8.136) [180]. 

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