遊離アリール基による芳香核置換反応 (第9報)

アニソール, トルエンのp-メチルフェニル化とクロルベンゼンのフエニル化

抄録

The determination, by means of isotope dilution analysis of the molar ratio of p-methyl (¹⁴C)-biphenyl, 2-methoxy-4′-methyl ('4C)-biphenyl, 3-methoxy-4, -melhyl (¹⁴C)-biphenyl, and 4-methoxy-4′-methyl (¹⁴C)-biphenyl formed through the reaction of N-nitroso-p-methyl (¹⁴C)-acetanilide in an equimolar mixture of anisole and benzene, is described. From the results, the partial rate factors of the ortho, meta and para positions of anisole for the homolytic p-methylphenylation were found to be 3.69, 1.09 and 1.52, respectively. Partial rate factors for toluene, 3.27, 1.00 and 1.33 were obtained from the results of experiments in a mixture of toluene and benzene.
A similar experiment on the reaction of N-nitrosoacetanilide-(phenyl-¹⁴C) in a mixture of chlorobenzene and benzene gave partial rate factors of the ortho, meta and para positions of chlorobenzene for the phenylation, 3.09, 1.01 and 1.48, respectively.