Abstract
In a mixed solvent of water-acetic acid-propionic acid, 3-phenanthrol was nitrated with an equimolar amount of nitric acid at - 25 - 20°C to obtain a mixture of mononitro compounds containing a small amount of polynitro compounds. The mixture consisted of 9-nitro-3-phenanthrol (2), 4-nitro-3-phenanthrol (3), and 2-nitro -3-phenanthrol (4), the amount of each product being decreased in this order. Further nitration of (3) and (4) in dilute acetic acid at 1112°C gave a common product, 4, 9-dinitro-3-phenanthrol (5). (5) was treated in glacial acetic acid with fuming nitric acid at 15°C to form 2 (?), 4, 9-trinitro-3-phenanthrol in a good yield. (3) is stable under acidic conditions in contrast to unstable 4-bromo-3-phenanthrols.
Through reduction of the methyl ether of (4), the corresponding amine was obtained, as identified using an authentic sample of 3-methoxy-2-phenanthrylamine derived from 3-methoxy-2-phenanthrenecarboxylic acid by the Curtius reaction.
