Org. Synth. 1948, 28, 80
DOI: 10.15227/orgsyn.028.0080
4-NITRO-1-NAPHTHYLAMINE
[1-Naphthylamine, 4-nitro-]
Submitted by Charles C. Price and Sing-Tuh Voong.
Checked by Richard T. Arnold and Jay S. Buckley, Jr..
1. Procedure
Twenty grams (0.115 mole) of α-nitronaphthalene (Note 1) and 50 g. (0.72 mole) of powdered hydroxylamine hydrochloride are dissolved in 1.2 l. of 95% ethanol contained in a 3-l. flask which is heated in a bath maintained at 50–60°. A filtered solution of 100 g. of potassium hydroxide in 500 g. (630 ml.) of methanol is added gradually with vigorous mechanical stirring (Note 2) over a period of 1 hour. Stirring is continued for an additional hour, and the warm solution is poured slowly into 7 l. of ice water. After the solid has coagulated, it is collected on a filter and washed thoroughly with water. The crude 4-nitro-1-naphthylamine is purified by recrystallization from 500 ml. of 95% ethanol (Note 3). About 12–13 g. (55–60%) of long golden-orange needles, m.p. 190.5–191.5°, is obtained.
2. Notes
1.
The
α-nitronaphthalene, m.p. 56–57°, was obtained from Eastman Kodak Company.
2.
The color changes from yellow to orange, and
potassium chloride separates.
3.
In some experiments a few milliliters of dilute
hydrochloric acid (1:1) or
sulfuric acid (1:1) was added to facilitate the crystallization of the
4-nitro-1-naphthylamine.
3. Discussion
This method is essentially that described by Goldhahn.
1 4-Nitro-1-naphthylamine has also been prepared by the nitration of
α-naphthylamine,
2 acetyl-α-naphthylamine,
3,4 and
ethyl-1-naphthyloxamate,
5,6 by the oxidation of
4-nitroso-1-naphthylamine,
7 and by reaction of
4-chloro-1-nitronaphthalene with
ammonia.
8This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
α-naphthylamine
acetyl-α-naphthylamine
ethanol (64-17-5)
sulfuric acid (7664-93-9)
hydrochloric acid (7647-01-0)
ammonia (7664-41-7)
methanol (67-56-1)
potassium hydroxide (1310-58-3)
Hydroxylamine hydrochloride (5470-11-1)
α-nitronaphthalene (86-57-7)
potassium chloride (7447-40-7)
4-nitro-1-naphthylamine,
1-Naphthylamine, 4-nitro- (776-34-1)
ethyl-1-naphthyloxamate
4-nitroso-1-naphthylamine
4-chloro-1-nitronaphthalene
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