Oximes to amines

Lithium aluminum hydride (LiAlH4) is the most powerful of the hydride reagents. It reduces acid chlorides, esters, lactones, acids, anhydrides, aldehydes, ketones and epoxides to alcohols amides, nitriles, imines and oximes to amines primary and secondary alkyl halides and toluenesulfonates to... 

Reaction CLXXIV. Reduction of Oximes to Amines with Metallic Sodium or Sodium Amalgam. 

Catalytic hydrogenation of oximes to amines requires conditions resembling those for catalytic hydrogenation of nitro compounds and nitriles.20d The catalyst should be as active as possible, e.g., Raney nickel101 (if necessary, platinized), platinum oxide,102 palladium-charcoal,103 palladium-barium sulfate,104 or rhodium-alumina.105 This rhodium catalyst also serves for reduction of an amidoxime to the amidine.106 Hydrogenation may be effected under pressure, but the temperature should be kept as low as possible to avoid formation of secondary amines. 

Sodium Amalgam. Sodium amalgam reduces nitrobenzene to azobenzene as well as to hydrazobenzene knd oximes to amines. The I. G. Farben-industrie, in its development of mercury cells for the production of chlorine and caustic, found that it could lise the intermediate sodium amalgam for the reduction of nitrobenzene to ajzobenzene on a very economical basis. The operation was carried out in batches in nickel reactors, and 50 per cent caustic soda was obtained simultaneously. It was not found feasible to produce hydrazobenzene directly by this method. Hallie has, however, obtained a patent on the reduction of nitrobenzei e to hydrazobenzene using sodium amalgam in aqueous alcohol. 

Pyridones from l-hydroxy-2-pyridones with reduction of oximes to amines... 

Sulphurated borohydrides can reduce oximes to amines the intermediate hydroxylamines are isolable. Sodium borohydride reduces nitriles to amines in high yield in the presence of Raney nickel as catalyst. The titanocene-promoted fixation-reduction of molecular nitrogen has been utilized in the conversion of ketones into amides and acid chlorides into nitriles in an overall reductive deoxygenation, as exemplified in Scheme 109. 

Poly(styryldiphenylphosphine) (8) in carbon tetrachloride converts alcohols to alkyl chlorides up to 20 times faster than does triphenylphosphine, as shown in equation (5). The phosphine oxide by-product is easily separated by filtration, but it cannot be recycled due to concurrent formation of a dichloromethylidinephosphorane. Yields are about 90% from primary and 40-70% from secondary alcohols. Reagent (8) in carbon tetrachloride also dehydrates primary carboxamides and oximes to amines, and secondary carboxamides and oximes to imidoyl chlorides. ... 

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