In a
5-l. flask fitted with a
mechanical stirrer and a
dropping funnel are placed 1 kg. of cracked ice, 1.5 l. of water,
279 g. (3 moles) of a technical grade of aniline, and
458 g. (388 cc., 4.5 moles) of concentrated hydrochloric acid (sp. gr. 1.18). The stirrer is started, and a solution of
109 g. (1.5 moles) of 95 per cent sodium nitrite in 250 cc. of water is added over a period of fifteen minutes. The reaction mixture is then stirred for fifteen minutes, and a solution of
422 g. (3.1 moles) of crystalline sodium acetate dissolved in 800 cc. of water is added over a period of five minutes. A yellow precipitate of
diazoaminobenzene begins to form at once. Stirring is continued for forty-five minutes, keeping the temperature below 20° (Note
1). The yellow
diazoaminobenzene is filtered on a
19-cm. Büchner funnel (Note
2), washed with 5 l. of cold water, and then sucked as dry as possible and spread out on a sheet of paper to dry (Note
3). The product thus obtained is dissolved in
4 l. of boiling ligroin (b.p.
60–90°) (Note
4), filtered, and allowed to cool to room temperature and stand overnight. When crystallization is complete, the yellow crystals are filtered on a 19-cm. Büchner funnel, washed with
500 cc. of cold ligroin (b.p.
60–90°), and dried at room temperature. The yield of yellow crystals melting at
92–94° is
242–251 g. (
82–85 per cent of the theoretical amount) (Note
5). If a product of greater purity is desired, the
diazoaminobenzene is dissolved in
4 l. of boiling ligroin (b.p.
60–90°) and crystallized as before. The recrystallized
diazoaminobenzene weighs
204–218 g. (
69–73 per cent of the theoretical amount) and melts at
94–96° (Note
6) and (Note
7).