The hydrolysis of oximes proceeds easily by heating in the presence of various inorganic acids, and the oximes decompose into the corresponding ketones or aldehydes, and hydroxylamines. The reduction of oximes by sodium metal, sodium amalgam, hydrogenation, or reaction with hydride reagents produces amines. Typically the reduction of aldoximes gives both primary amines and secondary amines; however, reaction conditions can be altered (such as the addition of potassium hydroxide in a 1/30 molar ratio) to yield solely primary amines.
In general, oximes can be changed to the corresponding amide derivatives by treatment with various acids. This reaction is called Beckmann rearrangement. In this reaction, a hydroxyl group is exchanged with the group that is in the anti position of the hydroxyl group. The amide derivatives that are obtained by Beckmann rearrangement can be transformed into a carboxylic acid by means of hydrolysis (base or acid catalyzed). And an amine by Hoffman degradation of the amide in the presence of alkali hypoclorites. Beckmann rearrangement is used for the industrial synthesis of caprolactam (see applications below).
The Ponzio reaction (1906) concerning the conversion of m-nitrobenzaldoxime to m-nitrophenyldinitromethane using dinitrogen tetroxide was the result of research into TNT analogues:
In the Neber rearrangement certain oximes are converted to the corresponding alpha-amino ketones.
Oximes can be dehydrated using acid anhydrides to yield corresponding nitriles.
Certain amidoximes react with benzenesulfonyl chloride to make substituted ureas in the Tiemann rearrangement: