Derivatives of gallic acid / by Frederick B. Power and Frank Shedden.

  • Frederick Belding Power
Date:
[1902.]
Catalogue details

Licence: In copyright

Credit: Derivatives of gallic acid / by Frederick B. Power and Frank Shedden. Source: Wellcome Collection.

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    Ethyl Dinitrodiacetylg dilate, C6(N02)2(C2H302)2(0H) •002C2H5. By the direct acetylation of ethyl gallate, the ethyl triacetylgallate was first prepared, which has been described by Schiff (Beilstein’s Handbuch, 2, 1922) as a thick yellow oil, which very slowly deposits crystals. No difficulty was experienced, however, in obtaining it in colourless crystals from either acetic acid or alcohol. It melts at 133°. The triacetyl ester was nitrated in the following manner. One hundred grams of the triacetyl ester were added to a cold mixture of 50 c.c. each of nitric acid (sp. gr. 1*42) and sulphuric acid, and 150 c.c. of glacial acetic acid. The mixture, while being kept cool, was allowed to stand for five hours. The product was poured into a litre of water, the yellow, crystalline precipitate filtered off, and the nitro-compound separated from some unchanged ethyl triacetylgallate by treatment with sodium carbonate, in which it readily dissolved. The acid filtrate from the above-mentioned yellow precipitate was extracted several times with ether and the ethereal liquid shaken out with carbonate solution. This was mixed with the main sodium carbonate solution obtained as above and the whole acidified with hydrochloric acid. The separated yellow oil soon formed a crystal¬ line cake, which was collected and recrystallised from chloroform. It formed lemon-yellow needles which melted at 165°. 0-1466 gave 0-2260 C02 and 0-0486 H20. C = 42*0; H = 3 7. 0-1974 „ 13*3 c.c. moist nitrogen at 11° and 744 mm. N = 7'9. Oi3Hi2OnN2 requires C = 41 *9 ; IT = 3-2 ; N = 75 per cent. The substance is strongly acid, dissolving in sodium carbonate with effervescence and forming an orange-red solution. It only dissolves slowly in absolute alcohol, and the solution gives a bluish-green color¬ ation with ferrie chloride. The ethyl triacetylgallate was nitrated in another manner with some¬ what different results. One hundred grams of the substance were mixed in a flask with 100 c.c. of nitric acid (sp. gr. 1 • 42), and, after being kept cool for five hours, the mixture was worked up in the manner already described. By this method, the product consisted of a mixture of the dinitro-ester and the dinitrodiacetyl ester. An attempt was made to form the sodium salt of ethyl dinitro- diacetylgallate by dissolving it in alcohol and adding one atomic pro¬ portion of sodium dissolved in a little alcohol. No precipitate was produced, even after a portion of the alcohol had been evaporated off in a vacuum. On standing for several days, an odour of ethyl acetate was developed, and small, bright red crystals were deposited, which consisted of the sodium salt of ethyl dinitrogdilate.
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