Org. Synth. 1932, 12, 58
DOI: 10.15227/orgsyn.012.0058
[Barbituric acid, 5-nitro-]
Submitted by W. W. Hartman and O. E. Sheppard.
Checked by C. S. Marvel and B. H. Wojcik.
1. Procedure
In a 2-l. flask, equipped with a mechanical stirrer and surrounded by an ice bath, is placed 143 cc. of fuming nitric acid (sp. gr. 1.52). Stirring is started, and 100 g. (0.61 mole) of barbituric acid (p. 60) is added over a period of two hours; the temperature is kept below 40° during the addition. The mixture is stirred for one hour after the barbituric acid has been added, and stirring is continued while 430 cc. of water is added and the solution is cooled to 10°. The mixture is filtered, and the residue is washed with cold water and dried on a glass tray at 60–80° (Note 1). The nitrobarbituric acid is dissolved by adding it to 860 cc. of boiling water in a 2-l. flask and heating the mixture on a boiling water bath while steam is blown in until solution is complete (Note 2). After filtration and cooling overnight, the crystals are removed, washed with cold water, and dried in trays in an oven at 90–95° for two to three hours. The product melts with decomposition at 181–183° when heated rapidly. The yield is 139–141 g. (Note 3). On drying the product at 110–115° for two to three hours, the yield is 90–94 g. (85–90 per cent of the theoretical amount) of an anhydrous compound which melts with decomposition at 176°.
2. Notes
1. Unless the product is dried before recrystallization it is difficult to remove all the nitric acid, and the final product will have a strong odor of nitric acid.
2. If a clear yellow solution is not obtained, Norite should be added before filtering.
3. This yield is slightly above the theoretical yield of 139 g., but this is probably due to a greater degree of hydration than is indicated in the formula.
3. Discussion
Nitrobarbituric acid has been prepared by oxidation of violuric acid,1 and by treatment of barbituric acid with fuming nitric acid2 or concentrated nitric acid.3
This preparation is referenced from:

References and Notes
  1. Ceresole, Ber. 16, 1134 (1883).
  2. Baeyer, Ann. 130, 140 (1864).
  3. Fredholm, Z. anal. Chem. 104, 400 (1936).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

nitric acid (7697-37-2)

Barbituric acid (67-52-7)

Nitrobarbituric acid,
Barbituric acid, 5-nitro- (480-68-2)

violuric acid (87-39-8)