SYNTHESIS OF 2,4-DIOXO-1,2,3,4-TETRAHYDROPYRIMIDIN-5-YL METHACRYLATES
143
(1H, 10-H), 6.12 s (1H, 10-H). 13C NMR spectrum
(CDCl3), dC, ppm: 10.60 (6-CH3), 17.70 (C11), 28.20
(1-CH3), 29.20 (3-CH3), 115.40 (C5), 124.70 (C10),
128.70 (C9), 150.90 (C6), 152.20 (C2), 161.50 (C4),
164.50 (C8). Found, %: C 55.0; H 6.10; N 11.40.
C11H14N2O4. Calculated, %: C 55.46; H 5.92; N 11.76.
pressure to obtain 60 g (83%) of methacrylic anhydride
with bp 8486°C (12 mm).
6-Methyl-2,4-dioxo-1,2,3,4-tetrahydro-
pyrimidin-5-yl methacrylate (V). A small amount (on
a tip of a scalpel) of hydroquinone and 6.0 g (0.039 mol)
of methacrylic anhydride (IV) were added at room
temperature to a mixture of 3.6 g (0.025 mol) of 5-hydr-
oxy-6-methyluracil and 15 ml of pyridine which was
preliminarily dried over KOH and distilled over metallic
sodium. The mixture was stirred for 3050 min and was
left overnight at room temperature. The precipitate
(2.48 g) was filtered off, and pyridine and excess
anhydride IV were distilled off from the filtrate on heating
on an oil bath (180190°C) under reduced pressure
(10 mm). The residue was a yellow crystalline material
which was washed with 50 ml of methanol to isolate an
additional portion (3.2 g) of compound V, Rf 0.64. Over-
all yield 5.3 g (100%), mp 278280°C. The product is
readily soluble in methanol, ethanol, and DMF and in-
3,6-Dimethyl-2,4-dioxo-1,2,3,4-tetrahydro-
pyrimidin-5-yl methacrylate (VII). Methacrylic
anhydride (IV), 5 ml, was added to a mixture of 3.2 g
(0.02 mol) of 3,6-dimethyluracil and 25 ml of pyridine
containing a small amount of hydroquinone, and the
mixture was stirred for 1 h at room temperature and was
left overnight. The crystals were filtered off, and the
filtrate was evaporated to obtain 9.53 g of a liquid residue
which partially crystallized on storage. The crystals were
filtered off and reprecipitated from 15 ml of acetone.
Yield 3.0 g (68%), mp 130132°C, Rf 0.78. IR spectrum,
1
n, cm : 1650, 1720 (C=O, =NC=O), 11301230 (N=),
3200 and 3240 (N1H)], 1380 (ds CH3), 11601210
(ester), 1320 (CN), 830980 (wCH2), 1464 (dCH2),
28802950 (CH2, CH3). UV spectrum (water): lmax
272.35 nm. 1H NMR spectrum (CDCl3), d, ppm: 1.88 s
(3H, C11H3), 2.0 s (3H, 6-CH3), 3.42 s (3H, 3-CH3),
5.90 s (1H, 10-H), 6.12 s (1H, 10-H), 8.47 s (1H, 1-H).
13C NMR spectrum (CDCl3), dC, ppm: 13.27 (6-CH3),
17.70 (C11), 28.20 (3-CH3), 115.90 (C5), 124.70 (C10),
128.70 (C9), 146.50 (C6), 152.20 (C2), 161.50 (C4),
164.70 (C8). Found, %: C 53.10; H 5.60; N 12.77.
C10H12N2O4. Calculated, %: C 53.57; H 5.39; N 12.49.
1
soluble in acetone and chloroform. IR spectrum, n, cm :
16201720 (C=O, =NC=O), 11161238 (N=), 3016
3252 (NH), 1380 (ds CH3), 11601210 (ester), 1312
(CN), 840968 (wCH2), 14001464 (dCH2), 2856
2936 (CH2, CH3). UV spectrum (water): lmax 277.35 nm.
1H NMR spectrum (CDCl3), d, ppm: 1.88 s (3H, C11H3),
2.0 s (3H, 6-CH3), 5.90 s (1H, 10-H), 6.12 s (1H, 10-H),
8.50 s (1H, 1-H), 10.50 s (1H, 3-H). 13C NMR spectrum
(CDCl3), dC, ppm: 12.30 (6-CH3), 17.97 (C11), 116.80
(C5), 124.22 (C10), 128.22 (C9), 143.47 (C6), 151.06 (C2),
158.77 (C4), 164.38 (C8). Found, %: C 50.70; H 4.97;
N 13.60. C9H10N2O4. Calculated, %: C 51.18; H 4.77;
N 13.26.
REFERENCES
1,3,6-Trimethyl-2,4-dioxo-1,2,3,4-tetrahydro-
pyrimidin-5-yl methacrylate (VI). Methacrylic
anhydride (IV), 4.7 g (4 ml), was added under stirring to
a mixture of 3.4 g (0.02 mol) of 1,3,6-trimethyl-5-
hydroxyuracil, 15 ml of pyridine, and a small amount of
hydroquinone, The mixture was stirred for 1 h at room
temperature and was left overnight. Removal of the
solvent left 4.65 g (97%) of compound VI as a light yellow
1. Kamilov,F.Kh.,Lazareva,D.N.,andPlechev,V.V., Pirimidiny
i ikh primenenie v meditsine (Pyrimidines and Their
Application in Medicine), Ufa, 1992, p. 156.
2. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
Moscow: Meditsina, 1985, vol. 2, p. 576.
3. Volodina, V.I., Tarasov, A.I., and Spasskii, S.S., Usp. Khim.,
1970, vol. 39, p. 276.
4. Prochukhan, Yu.A., Gatiyatullina, G.V., Krivonogov, V.P., and
Battalov,E.M., Vestn. Bashkir. Univ., 2001, no. 4, p. 33.
5. Shagidullin, R.R., Chernova,A.V., Doroshkina, G.M., Kata-
ev, V.E., Bazhanova, Z.G., Katsyuba, S.A., Reznik, V.S.,
Mikhailov,A.S.,Giniyatullin,R.Kh.,Pashkurov,N.G.,Efre-
mov,Yu.Ya.,andNafikova,A.A., Russ. J. Gen. Chem., 2002,
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1
thick liquid, Rf 0.8. IR spectrum, n, cm : 1620, 1650,
1670, 1740 (C=O, =NC=O), 11301240 (N=), 3350
(OH), 1380 (dsCH3), 11601210 (ester), 1320 (CN),
830960 (wCH2), 14001464 (dCH2), 28702940 (CH2,
CH3). UV spectrum (ethanol): lmax 278.20 nm. 1H NMR
spectrum (CDCl3), d, ppm: 1.85 s (3H, C11H3), 2.0 s (3H,
6-CH3), 3.30 s (3H, 1-CH3), 3.40 s (3H, 3-CH3), 5.90 s
6. Ivanov, S.P., Cand. Sci. (Chem.) Dissertation, Ufa, 2003.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 1 2005