1-および4-フェナントロールのアゾカップリング

フェナントロールの置換反応 (第8報)

抄録

The orientation in the azo-coupling reaction of 1-phenanthrol (1) and 4-phenanthrol (8) was determined and compared with that of α-naphthol. In an alkaline aq. ethanolic solution, (1) was coupled with 0.2 moles of benzenediazonium chloride to yield 4-azo (2) (91.8 mol%), 2-azo (3) (7.5 mol%), and 2, 4-disazo (4) (0.5 mol%) compounds. Similarly, (8) gave 1-azo (9) (89.2 mol%), 3-azo (10) (8.0 mol%), and 1, 3-disazo (11) (2.8 mol%) compounds, and α-naphthol gave 4-azo (94.1 mol%) and 2-azo (5.9 mol%) compounds. Thus these two phenanthrols behave quite similarly to each other and also to α-naphthol.
The structures of the products were determined by the following transformations : (3) and (10) were derived from 1, 2-and 3, 4-phenanthrenequinone by the condensation with phenylhydrazine, respectively ; (4), formed from (2) and (3) by the further coupling ; (11), similarly formed from (9) and (10); (2) was converted via 4-amino-1-phenanthrol to its triacetyl derivative by the reduction and successive acetylation ; (9), converted via 1-amino-4-phenatnhrol (characterized as the triacetyl derivative) to 1, 4-phenanthrenequinone by the reduction and successive oxidation.