The electrolytic reduction of pheno- and naphtho-morpholones / by Frederic H. Lees and Frank Shedden.

  • Lees, F. H. (Frederic Herbert)
Date:
[1903.]
Catalogue details

Licence: In copyright

Credit: The electrolytic reduction of pheno- and naphtho-morpholones / by Frederic H. Lees and Frank Shedden. Source: Wellcome Collection.

    11/20 (page 758)
    iV-Methylphenomorpholine hydrochloride was obtained from the ether-alcohol mother liquor from the foregoing hydrochloride, by shaking repeatedly with water, rendering the aqueous solution alkaline with sodium carbonate, and extracting with ether. After drying with potassium carbonate, the ethereal solution was concentrated considerably, a little absolute alcohol added, and hydrochloric acid passed in as before. In this way, a crystalline hydrochloride was obtained which melted at 166°, and on recrystallisation from alcohol, in which it was only sparingly soluble in the cold, formed long, glistening needles, which then melted at 167—168° to an emerald-green oil. 0-1204 gave 0*2587 C02 and 0-0728 H,0. C = 58*6 ■ H = 6*7. C9H11ON,HCl requires C = 58*2; H = 6*5 per cent. The melting point of A-methylphenomorpholine hydrochloride is given by Knorr (Ber., 1889, 22, 2098) as 162°. The identity of this product with methylphenomorpholine was fully established as follows. The addition of caustic alkali to a solution of the hydrochloride precipitated an oily base of characteristic odour which was quite insoluble in excess of the reagent. The base was extracted and distilled, when it boiled entirely at 252—254° under a pressure of 769 mm. and was obtained as a colourless oil, which gave the charac¬ teristic oxidation colour reactions of methylphenomorpholine. 0-1017 gave 0-2693 C02 and 0-0682 H20. C = 72-2; H = 75. C9HnON requires C = 72*5; H = 74 per cent. The methiodide was also formed ) it melted at 195—200° with evo¬ lution of methyl iodide. Preparation of 'N-Methyl-fi-naphthomorpholone. a-Nitro-fi-naplithoxyacetic acid, C10H6(NO2)*O*CH2*CO2H, can be a & obtained in two ways, but more conveniently by nitrating /?-naphth- oxyacetic acid. This acid was prepared from /?-naphthol and chloro- acetic acid under conditions which varied somewhat from those given by Spica (Gazzetta, 1886, 16, 441), in that the hot solution of the sodium salts, after the condensation, was not acidified, and subsequently treated with ammonium carbonate and ether to remove /3-napthol, but was allowed to cool, when the sodium salt of the required acid separated in an almost pure state, and in large quantity. /3-Naphthoxyacetic acid (100 grams) was dissolved in glacial acetic acid (600 c.c.), the solution cooled, and 70 c.c. of nitric acid (sp. gr. T42) cautiously added with stirring. On allowing the mixture to remain for 2 hours, the nitro-acid separated, and, after washing with