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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.8
This preparation is referenced from:

References and Notes
  1. Goldhahn, J. prakt. Chem., 156, 315 (1940); 157, 96 (1940).
  2. Meldola and Streatfeild, J. Chem. Soc., 63, 1055 (1893).
  3. Lellmann and Remy, Ber., 19, 796 (1886).
  4. Hodgson and Walker, J. Chem. Soc., 1933, 1205.
  5. Lange, Ger. pat. 58,227 [Frdl., 3, 509 (1890–1894)].
  6. Sergievskaya, Russ. pat. 50,696 (1937); J. Gen. Chem. U.S.S.R., 10, 55 (1940)
  7. Vorozhtsov and Kozlov, J. Gen. Chem. U.S.S.R., 9, 587 (1939).
  8. Ger. pat. 117,006 [Frdl., 6, 176 (1900–1902)].

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