NOVAKOV et al.
316
(1H, N3H). Found, %: С 50.47; H 4.30; N 11.62; S 27.00.
M+ 238. C23H29N3O. Calculated, %: С 50.40; H 4.23;
N 11.75; S 26.91. M 238.33.
of acidified probe), diluted with water and extracted with
EtOAc (3 × 75 ml). The organic solutions were combined,
washed with brine, dried with anhydrous MgSO4, and
filtered through a thin bed of silica gel of TLC grade. The
filtrate was concentrated at a reduced pressure; the residue
was crystallized from cyclohexane. Yield 0.76 g (58%),
mp 147–148.5°С. 1H NMR spectrum (CDCl3), δ, ppm:
2.06 s (3H, 5-CH3), 2.09 s (3H, SCH3), 2.71–2.76 m (2H,
CH2CH2SCH3), 3.29–3.34 m (2H, SCH2CH2), 4.00 s (2H,
ThCH2), 6.81 d (1H, H5, Th, J 3.42 Hz), 6.87 d.d (1H, H4,
Th, J1 3.42, J2 1.71 Hz), 7.10 d (1H, H3 Th, J 5.13 Hz).
Found, %: C 50.01; H 5.14; N 9.05; S 30.80. [M]+ 312.
C13H16N2OS3. Calculated, %: C 49.97; H 5.16; N 8.97;
S 30.78. M 312.47.
1H NMR spectra were registered on a spectrometer
Varian-Mercury 300BB (300.73 MHz), internal refer-
ence HMDS. Melting points were measured on a Cole-
Palmer instrument. TLC was carried out on ALUGRAM
Nano-SILG/UV254 plates, eluent hexane–EtOAc–MeOH,
12 : 3 : 1.
5-Methyl-6-(2-thienylmethyl)-2-{[(phenyl-sulfanyl)
methyl]sulfanyl}pyrimidin-4(3Н)-one (Vc). а. A mix-
ture of 1 g (4.2 mmol) of reagent I, 1.08 ml (1.28 g,
8.1 mmol) of reagent IIc, and 10 ml of anhydrous DMF
was stirred for 18 h at room temperature (TLC monitor-
ing), the mixture was diluted with water, the precipitate
was crystallized from MeCN. Yield 0.77 g (51%),
mp 161–163°С. 1H NMR spectrum (DMSO-d6), δ, ppm:
1.91 s (3H, 5-CH3), 3.99 s (2H, ThCH2), 4.75 d (2H,
SCH2S, J 3.42 Hz), 6.86–6.90 m (2H, H4,5 Th), 7.15–
7.21 m (1H, H3 Th), 7.23–7.35 m (5H, Ph), 12.59 br.s
(1H, N3H). Found, %: C 56.70; H 4.49; N 7.81; S 26.58.
[M]+ 360. C17H16N2OS3. Calculated, %: C 56.64; H 4.47;
N 7.77; S 26.68. M 360.52.
5-Methyl-2-{[(methylsulfanyl)methyl]sulfanyl}-
6-(2-thienylmethyl)pyrimidin-4(3Н)-one (Va). b.
A mixture of 1 g (4.2 mmol) of reagent I, 0.4 ml (0.46 g,
4.8 mmol) of reagent IIa, 0.61 g (4.4 mmol) of K2CO3
and 10 ml of anhydrous DMF was stirred for 18 h at
room temperature (TLC monitoring), the mixture was
diluted with water and extracted with EtOAc. The organic
solutions were combined, washed with brine, dried with
anhydrous MgSO4, and filtered through a thin bed of
silica gel of TLC grade. The filtrate was concentrated at
a reduced pressure; the residue was crystallized from cy-
clohexane. Yield 0.87 g (68%), mp 155–156°С. 1H NMR
spectrum NMR spectrum (CDCl3), δ, ppm: 2.06 s (3H,
5-CH3), 2.14 s (3H, SCH3), 4.02 s (2H, ThCH2), 4.31 s
(2H, SCH2S), 6.80–6.90 m (2H, H4,5 Th), 7.08–7.13 m
(1H, H3 Th). Found, %: C 48.11; H 4.70; N 9.51; S 32.23.
[M]+ 298. C12H14N2OS3. Calculated, %: C 48.29; H 4.73;
N 9.39; S 32.23. M 298.45.
Commercial reagents used in the syntheses contained
no less than 95% of the main substance. The purification
and drying of solvents was performed by conventional
procedures [7].
REFERENCES
1 .Novakov, I.A., Orlinson, B.S., and Navrotskii, M.B., Zh. Org.
Khim., 2005, vol. 41, 617; Novakov, I.A., Orlinson, B.S.,
and Navrotskii, M.B., Khim. Geterotsikl. Soedin., 2006,
p. 1418; Novakov, I.A., Orlinson, B.S., Brunilin, R.V.,
Navrotskii, M.B., Savel’ev, E.N., and Novikova, G.A.,
Khim. Geterotsikl. Soedin., 2006, p. 1541; Rakhimov,
A.I., Kameneva, I.Yu., Navrotskii, M.B., Titova, E.S., and
Kudashev, S.V., Zh. Obshch. Khim., 2008, vol. 78, p. 828;
Novakov, I.A., Orlinson, B.S., and Navrotskii, M.B., Zh. Org.
Khim., 2009, vol. 45, p. 325; Mai, A., Artico, M., Rotili, D.,
Novakov, I.A., Orlinson, B.S., Navrotskii, M.B., Eremiichuk,
A.S., and Gordeeva, E.A., Zh. Org. Khim., 2009, vol. 45,
p. 1546; Novakov, I.A., Orlinson, B.S., Brunilin, R.V.,
Navrotskii, M.B., Gordeeva, E.A., Savel’ev, E.N., and
Gerasimov, E.N., Khim. Geterotsikl. Soedin., 2009, p. 1697.
c. Similarly to the procedure b a mixture of reagent
I, K2CO3, and anhydrous DMF was stirred at heating to
90–100°С for 1 h, cooled, and the alkylating agent was
added. Yield 51%.
5-Methyl-2-{[2-(methylsulfanyl)ethyl]sulfanyl}-
6-(2-thienylmethyl)pyrimidin-4(3Н)-one (Vb). d.
Amixture of 1 g (4.2 mmol) of reagent I and a solution of
277 mg (4.2 mmol) of KOH in 20 ml of 95% EtOH was
stirred for 1 h at room temperature, and afterwards 0.5 ml
(0.56 g, 5.0 mmol) of compound IIb was added, the mix-
ture was stirred for 1 h more and was left overnight. Then
the reaction mixture was boiled at stirring till complete
consumption of the initial compound (TLC monitoring
2. Navrotskii, M.B., Khim.-Farm. Zh., 2003, 37, no. 9, 22;
Navrotskii, M.B., Khim.-Farm. Zh., 2004, vol. 38, no. 9,
p. 16; Navrotskii, M.B., Khim.-Farm. Zh., 2005, vol. 39,
no. 9, p. 16; Mai, A., Artico, M., Rotili, D., Tarantino, D.,
Clotet-Codina, I.,Armand-Ugun, M., Ragno, R., Simeoni, S.,
Sbardella, G., Nawrozkij, M.B., Samuele,A., Maga, G., and
Esti, J.A., J. Med. Chem., 2007, vol. 50, p. 5412.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011