抄録
Catalytic effect of some metal cyano complexes on the Sandmeyer reaction was examined by determination of benzonitrile using gas-liquid chromatography. The catalytic action of copper- and nickel-cyano complex was effective but the other metal-cyano complexes, such as those of silver, gold, cadmium, cobalt, chromium, iron, manganese, mercury, palladium, platinum, and zinc were weak or negligible. A difference in catalytic action between copper- and nickelcyano complex was seen in the effect of reaction conditions. Good yield of benzonitrile was obtained with the former by all pH ranges in the solution, but with the latter, only in alkaline solution. The Sandmeyer reaction did not run quantitatively and some kind of by-products were obtained. As the main by-product, phenol was detected and determined when the reaction was run in acidic solution. In neutral and alkaline solution, two other acidic products were found. They were separated by alumina column chromatography and recrystallized from methanol-water mixture to yellow microplates, mp 151°, and reddish brown needles, mp 134°. The former was identified as p-hydroxyazobenzene and the latter as 2, 4-bisphenylazophenol.
