ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 11, p. 1980.
Pleiades Publishing, Ltd., 2007.
Original Russian Text
A.A. Yavolovskii, Yu.E. Ivanov, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 11, p. 1932.
LETTERS
TO THE EDITOR
Synthesis of 5-Amino-6-nitrozopyrimidine-2,4(1H,3H)-dione
A. A. Yavolovskii and Yu. E. Ivanov
Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine,
Lustdorfskaya doroga 86, Odessa, 65080 Ukraine
Received April 6, 2007
DOI: 10.1134/S1070363207110266
6-Amino-5-nitrozouracils I are formed by nitroza-
tion of 6-aminouracils (second stage of the Traube
purine synthesis) [1]. Pyrimidines with nitrogen-
containing substituents in even positions of the ring
are commonly prepared starting from 6-hydroxyami-
nouracil derivatives II. In their turn, the latter com-
pounds are synthesized from 6-chloropyrimidines [2]
or 6-aminouracils [3].
We found that 5-bromo-6-hydroxyaminouracils III
react with sodium azide in absolute methanol at 20 C
to form 5-amino-6-nitrozouracil IV.
O
O
O
H
H
Br
NH2
NO
H
Br2
NaN3
N2
N
N
N
O
NHOH
O
N
H
N
H
O
NHOH
N
H
II
III
IV
Uracil IV is a finely crystalline crimson substance
poorly soluble in water and organic solvents. On
prolonged handling in solution or in the crystal state it
decomposes.
ring accompanied by nitrogen liberation, the reaction
mixture acquired an intensive crimson color. It was
quickly cooled, and the precipitate that formed was
filtered off. Yield 0.40 g (70%), mp >260 C
(decomp.). Mass spectrum (FAB): [M + Na]+ 179,
5-Bromo-6-hydroxyaminopyrimidine-2,4(1H,3H)-
dione (III). To a suspension of 0.7 g of 6-hydroxy-
aminouracil II [3] in 2 ml of acetic acid, a solution of
0.25 ml of bromine in 2 ml of acetic acid was added
in portions under vigorous stirring. The reaction mix-
ture was left in an exhaust hood until the solvent
evaporated. The residue was placed on a filter and
washed with a little acetone. The precipitate was
filtered off and dried in air, yield 0.87 g (80%), mp
>180 C (decomp.). Mass spectrum (FAB): [M + H]+
1
[M + H]+ 157. IR spectrum (Nujol), , cm : 3480
3000, 1720, 1700, 1680, 1620, 1605. Found, %: C
30.78; H 2.52; N 35.95. C4H4N4O3. Calculated, %: C
30.76; H 2.56; N 35.90.
The FAB mass spectra were obtained on a VG
Analytical 7070EQ instrument. The IR spectra were
recorded on a Specord 80 instrument.
REFERENCES
1
223. IR spectrum (Nujol), , cm : 3500 3000, 1710,
1680, 1650, 1640 1500. Found, %: C 21.50; H 1.80;
N 18.80. C4H4BrN3O3. Calculated, %: C 21.53; H
1.79. N 18.83.
1. Traube, W., Chem. Ber., 1900, vol. 33, p. 1371.
2. Pfleiderer, W. and Ferch, H., Justus Liebigs Ann. Chem.,
1958, vol. 615, p. 52.
5-Amino-6-nitrosopyrimidine-2,4(1H,3H)-dione
(IV). Compound III, 0.8 g, was mixed with 0.26 g of
NaN3 and 8 ml of absolute methanol. After short stir-
3. Yavolovskii, A.A., Ivanov, E.I., and Ivanova, R.Yu.,
Zh. Obshch. Khim., 2003, vol. 71, no. 8, p. 1402.
1980