Utilization of Carbon-monoxide. I

Reaction of Arylhalogenides with Carbon-monoxide using stabilized Raney-Ni Catalyst

Abstract

Carboxylation reaction of aryl halide by CO and water in the presence of stabilized Raney Ni has been investigated.
It was found that aromatic acid was obtained with good yield from using of an initial pressure at 100 atm and by heating for 1-2 hrs at200-320°C.
For example, 550% benzoic acid from bromobenzene, 20% benzoic acid and 4% terephthalic acid from p-dichloro- or p-dibromobenzene, and 23% 1-naphthalenecarboxylic acid from ac-bromonaphthalene were obtained.
In general, bromobenzene was more reactive than chlorobenzene and using of dihalo-compound showed a tendency accompanied with liberation reaction as above.Although an addition of pyridine was useful for prevention of corrosion of equipment but the purity of formed acid was low and required time for its refining.Also, the reaction in benzene as the solvent or using of alkali catalyst gave lower yield.
Thus, stabilized Raney Ni was good catalyst for such carboxylation reaction and gave better yield of aromatic acid of high purity than using of nickel chloride and nickel formate. It had also a superior property of not requiring to heat at higher temperature.