芳环直接氨化.pdf

Organic Syntheses, Coll. Vol. 3, p.664 (1955); Vol. 28, p.80 (1948). 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 oxidat