ChemInform Abstract: Nickel Catalyzed Amidation of Bromo‐ and Iodobenzene.

Abstract

Abstract The carbonylation of aryl halides in the presence of p -RC 6 H 4 NH 2 (R = H, CH 3 , Cl) or C 6 H 5 NHR (R = CH 3 , C 6 H 5 ) and a catalytic amount of a nickel(II) or nickel(0) tertiary phosphine complex at 150°C or above under carbon monoxide pressures is reported. Amides were obtained in high yields in reactions with p -RC 6 H 4 NH 2 , but with C 6 H 5 NHR compounds the expected N -alkyl benzanilides were not formed, benzanilide in low yield being formed instead. A possible catalytic cycle based on an active Ni o -carbonyl complex is suggested, and the observed deactivation of the catalytic system when the carbon monoxide pressure falls to 6 atm or below, is accounted for in terms of a side reaction which produces an inactive Ni II compound.