Reaction of 4-Bromo-3-Phenanthrols with Anionic Reagents

Substitution Reactions of Phenanthrols. VII

Abstract

The reactions of 4-bromo-3-phenanthrols with anionic reagents in dimethylform amide were investigated. Similar reactions of other related compounds were also examined for comparison.
Upon treatment with lithium chloride (X) at 100°C, 4-bromo-3-phenanthrol (1), 4, 9-dibromo-3-phenanthrol (2), and 2, 4, 9-tribromo-3-phenanthrol (3) were converted almost quantitatively into the corresponding 4-chloro compounds. When treated with sodium nitrite (Y) at 80°C, (1) and (2) gave 4-nitro-3-phenanthrol and 9-bromo-4-nit ro -3-phenanthrol, respectively.
The reactions of 4-chloro-3-phenanthrol (4), 9-bromo-4-chloro-3-phenanthrol (5), 1-bromo-2-phenanthrol (14), or 1-bromo-2-naphthol (17) with (Y) proceeded with difficulty even at a higher temperature, 140°C, and only (4) and (14) gave the corresponding o-hydroxynitro compounds. Attempts to react (14) or (17) with (X) and 9-bromo- or 2, 9-dibromo-3-phenanthrol with (Y) failed to succeed.