Reaction of 6-aminouracils with hydrazide nucleophiles [6]

Full text of DOI:10.1023/B:RUGC.0000007670.73042.92

Russian Journal of General Chemistry, Vol. 73, No. 8, 2003, pp. 1326 1327. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 8, 2003,
pp. 1402 1403.
Original Russian Text Copyright
2003 by Yavolovskii, Ivanov, Ivanova.
LETTERS
TO THE EDITOR
Reaction of 6-Aminouracils with Hydrazide Nucleophiles
A. A. Yavolovskii, E. I. Ivanov, and R. Yu. Ivanova
Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa, Ukraine
Received July 26, 2002
Searching for approaches to varying nitrogen-con-
taining functional groups in uracils, we found that 6-
aminouracils Ia and Ib [1] undergo acid-catalyzed
substitution of the exocyclic amino group by hydra-
zides IIa and IIb, semicarbazide (IIc), and thiosemi-
carbazide (IId).
X
O
O
H
N
H
R
NH NH+3
IIa IId
N
O
NH NH
O
NH2
R
N
R
N
R
X
Ia, Ib
IIIa IIIh
I, R = H (a), CH3 (b). II, R = CH3, X = O (a); R = C6H5, X = O (b); R = NH2, X = O (c); R = NH2, X = S (d). III,
R = H, R = CH3, X = O (a); R = CH3, R = CH3, X = O (b); R = H, R = C6H5, X = O (c); R = CH3, R = C6H5, X = O
(d); R = H, R = NH2, X = O (e); R = CH3, R = NH2, X = O (f); R = H, R = NH2, X = S (g); R = CH3, R = NH2, X = S
(h).
The reaction was performed in water (50 ml per
0.01 mol of Ia or Ib) under reflux for 2 (uracil Ia)
or 4 h (uracil Ib). Reagents IIa and IIb were taken in
a double excess with respect to uracils Ia and Ib, as a
mixture of acetate and hydrochloride. Compounds
IIIa IIIf precipitated and were recrystallized from
water. Compounds IIIg and IIIh were first neutralized
with ammonia solution to pH 7 and washed with
boiling ethanol to remove excess thiosemicarbazide.
1,2,3,6-tetrahydropyrimidin-4-yl)benzohydrazide
(IIId), yield 42%, mp >300 C. Found, %: C 55.40;
H 4.60; N 21.53. C12H12N4O3. Calculated, %: C 55.38;
H 4.62; N 21.54. 2-(2,6-Dioxo-1,2,3,6-tetrahydro-
pyrimidin-4-yl)hydrazinocarboxamide (IIIe), yield
82%, mp 270 272 C. Found, %: C 32.40; H 3.80; N
37.82. C5H7N5O3. Calculated, %: C 32.43; H 3.78; N
37.84.
2-(3-Methyl-2,6-dioxo-1,2,3,6-tetrahydro-
pyrimidin-4-yl)hydrazinocarboxamide (IIIf), yield
47%, mp 260 264 C. Found, %: C 36.20; H 4.50; N
35.20. C6H9N5O3. Calculated, %: C 36.18; H 4.52; N
35.18. 2-(2,6-Dioxo-1,2,3,6-tetrahydropyrimidin-4-
yl)hydrazinocarbothiamide (IIIg), yield 45%, mp
240 243 C. Found, %: C 29.90; H 3.50; N 34.80.
C5H7N5O2S. Calculated, %: C 29.85; H 3.48; N 34.83.
2-(3-Methyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-
4-yl)hydrazinocarbothiamide (IIIh), yield 34%, mp
277 280 C. Found, %: C 33.50; H 4.20; N 32.55.
C6H9N5O2S. Calculated, %: C 33.49; H 4.19; N 32.56.
2-(2,6-Dioxo-1,2,3,6-tetrahydropyrimidin-4-yl)-
acetohydrazide (IIIa), yield 52%, mp >300 C.
Found, %: C 39.10; H 4.33; N 30.40. C6H8N4O3.
Calculated, %: C 39.13; H 4.35; N 30.43. 2-(3-Me-
thyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-yl)-
acetohydrazide (IIIb), yield 40%, mp >300 C.
Found, %: C 42.40; H 5.00; N 28.30. C7H10N4O3.
Calculated, %: C 42.42; H 5.05; N 28.28. 2-(2,6-Di-
oxo-1,2,3,6-tetrahydropyrimidin-4-yl)benzohydra-
zide (IIIc), yield 73%, mp >300 C. Found, %: C
53.63; H 4.06; N 22.78. C11H10N4O3. Calculated, %:
C 53.66; H 4.07; N 22.76. 2-(3-Methyl-2,6-dioxo-
Earlier compounds like IIIa IIIh were prepared in
three stages from N-alkylbarbituric acids [2].
1070-3632/03/7308-1326$25.00 2003 MAIK Nauka/Interperiodica

REACTION OF 6-AMINOURACILS WITH HYDRAZIDE NUCLEOPHILES
1327
Purity control was performed by TLC on Silufol
UV-254 plates, eluents CH3OH CHCl3, 1:2 (IIIa,
IIIb, IIIe, IIIh) or CH3OH CHCl3 C6H14, 1:4:1
(IIIc, IIId).
temperature 220 C. The IR spectra were measured in
mineral oil on a Specord-80 instrument.
REFERENCES
1. Geptner, B. and Kreps, L., Zh. Obshch. Khim., 1946,
The structure of compounds IIIa IIIh was proved
by means of mass spectrometry and IR spectroscopy.
The mass spectra were obtained on a Varian MAT-
112 instrument, ionizing energy 70 eV, ion source
vol. 16, no. 2, p.179.
2. Ivashchenko, A.V. and Garicheva, O.N., Khim. Getero-
tsikl. Soedin., 1982, no. 5, p. 579.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 8 2003