Catalysis of Organic..

Ostgard et al. 229Table 1. The reaction conditions for the various nitrile hydrogenationsReaction bar °C hours gramsnitrilegramsNH 3ml ofsolvent aBenzonitrile 40 100 3 100 0 2000Benzonitrile 40 100 3 100 15 2000Pynitrile 40 110 5 40 300 1475Pyridine-3-carbonitrile 40 100 3 40 31 2000Valeronitrile 20 120 5 80 15 2000a the solvent was methanol in all casesTable 2. The treatment conditions with the aqueous slurries of the modifiers.°C hours IntendedCatalyst Metal Modifier Mod.amt. a reactionB 113 W Ni formaldehyde 0.839 25 1 BenzonitrileB 113 W Ni carbon dioxide 1.487 25 1 BenzonitrileB 113 W Ni benzaldehyde 0.591 25 1 BenzonitrileB 113 W Ni formaldehyde 0.840 25 0.5 PynitrileB 2112 Z Co formaldehyde 0.840 25 1 PynitrileNi/SiO 2 Ni formaldehyde 0.831 25 1 PynitrileB 113 W Ni carbon monoxide 0.268 25 0,5 PynitrileB 113 W Ni acetone 2.296 25 1 PynitrileB 113 W Ni acetaldehyde 0.908 60 1 PynitrileB 113 W Ni formaldehyde 0.908 25 1 py-3-cn bB 113 W Ni formaldehyde 3.090 25 1 Valeronitrilea Amount of modifier in mmoles of modifier per gram of catalyst.b Pyridine-3-carbonitrileN NH 2NC NPynitrileH 2NNNH 2C N HHH 2NNNH 2HCH NHHDesiredGrewe DiamineUndesiredSecondary AmineNH NN NNNH 2 H 2 NH NH 2NNCH 2 HH N NNHH C - NH 3N N + NH HN3 2 NSchiffs BaseNH 2H 2 NFigure 1. The hydrogenation mechanism of pynitrile and the possible formation ofthe corresponding secondary amine.NNNH 2