SYNTHESIS OF 3-(AMINOOXOETHYL)-6-METHYL-1-(THIETHAN-3-YL)-...
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viscous liquids, crystallizing after 1 day in the cases of
Compounds VIII–XI were prepared similarly
starting from the appropriate N-(2-chloroacetylmethyl)-
amines II–V.
I–III.
1-(Pyrrolidin-1-yl)-2-chloroethanone (I). Yield
1
60%, colorless crystals, mp 42–43°C, Rf 0.50. Н
6-Methyl-3-[2-oxo-2-(piperidin-1-yl)ethyl]-1-
(thiethan-3-yl)pyrimidine-2,4(1H,3H)-dione (VIII).
Yield 66%, mp 229–231°C (EtOH), Rf 0.58. IR spec-
trum, ν, cm–1: 2929 m (С–Н), 1714 s (С2=О), 1699,
1646 s (С4=О, С=О, С=С), 1461, 1437 s (С–N), 1346,
NMR spectrum (СDCl3), δ, ppm: 1.84–1.93 m (2Н,
СН2), 1.96–2.05 m (2Н, СН2), 3.48–3.54 m [4Н,
N(СН2)2], 4.00 s (2Н, СН2СО). Found, %: C 49.02; H
6.75; N 9.76. С6Н10ClNО. Calculated, %: C 48.82; H
6.83; N 9.49.
1
1255 m (С–N). Н NMR spectrum (DMSO-d6), δ,
ppm: 1.41–1.47 m (2Н, CH2), 1.55–1.63 m [4Н,
(CH2)2], 2.08 s (3H, 6-CH3), 3.08–3.14 m [2Н, S(CH)2],
3.39–3.46 m [4H, N(СН2)2], 4.14–4.21 m [2Н, S(CH)2],
4.77 s (2Н, 3-СН2СО), 5.65 s (1Н, Н5), 6.00–6.12 m
(1H, NCH). Found, %: C 55.89; H 6.66; N 13.04.
С15Н21N3О3S. Calculated, %: C 55.71; H 6.55; N 12.99.
1-(Piperidin-1-yl)-2-chloroethanone (II). Yield
68%, colorless needle-shaped crystals, mp 213–215°C,
Rf 0.72. Found, %: C 51.97; H 7.63; N 8.95. С7Н12ClNО.
Calculated, %: C 52.02; H 7.48; N 8.67.
1-(Azepan-1-yl)-2-chloroethanone (III). Yield
1
79%, colorless crystals, mp 193–194°C, Rf 0.63. Н
3-[2-(Azepan-1-yl)-2-oxoethyl]-6-methyl-1-
(thiethan-3-yl)pyrimidine-2,4(1H,3H)-dione (IX).
Yield 75%, mp 173–175°C (PrOH), Rf 0.43. IR spec-
trum, ν, cm–1: 2931 m (С–Н), 1713 s (С2=О), 1698,
1659, 1643 s (С4=О, С=О, С=С), 1454, 1437 s (С–N),
NMR spectrum (СDCl3), δ, ppm: 1.56–1.59 m [4Н,
(СН2)2], 1.72–1.78 m [4Н, (СН2)2], 3.47–3.54 m [4Н,
N(СН2)2], 4.07 s (2Н, СН2СО). Found, %: C 54.77; H
7.86; N 8.04. С8Н14ClNО. Calculated, %: C 54.70; H
8.03; N 7.97.
1
1361, 1281 m (С–N). Н NMR spectrum (СDCl3), δ,
ppm: 1.59–1.62 m [4Н, (CH2)2], 1.72–1.76 m (2Н,
CH2), 1.82–1.86 m (2Н, CH2), 2.14 s (3H, 6-CH3),
3.14–3.19 m [2Н, S(CH)2], 3.48–3.58 m [4Н, N(СН2)2],
4.30–4.36 m [2Н, S(CH)2], 4.65 s (2Н, 3-СН2СО),
5.59 s (1Н, Н5), 6.18–6.30 m (1H, NCH). Found, %: C
56.39; H 6.78; N 12.84. С16Н23N3О3S. Calculated, %:
C 56.95; H 6.87; N 12.45.
1-(Morpholin-4-yl)-2-chloroethanone (IV). Yield
63%, yellow oil, bp 177°C (360 mmHg), Rf 0.75, nD20
1.4878. Found, %: C 43.84; H 5.87; N 8.66. С6Н10ClNО2.
Calculated, %: C 44.05; H 6.16; N 8.56.
N,N-Diethyl-2-chloroacetamide (V). Yield 57%,
yellow oil, bp 159°C (360 mmHg), Rf 0.53, nD20
1
1.4691. Н NMR spectrum (СDCl3), δ, ppm: 1.13 t
6-Methyl-3-[2-(morpholin-4-yl)-2-oxoethyl)]-1-
(thiethan-3-yl)pyrimidine-2,4(1H,3H)-dione (X).
Yield 95%, mp 200–202°C (PrOH), Rf 0.65. IR spec-
trum, ν, cm–1: 2953, 2842 m (С–Н); 1716 s (С2=О),
1641 s (С4=О, С=О, С=С); 1458, 1435 s (С–N); 1353,
(3Н, СН3, J 7.2 Hz), 1.22 t (3Н, СН3, J 7.2 Hz), 3.32–
3.42 m [4Н, N(СН2)2], 4.05 s (2Н, СН2СО). Found, %:
C 48.02; H 8.21; N 9.42. С6Н12ClNО. Calculated, %:
C 48.17; H 8.08; N 9.36.
1
6-Methyl-3-[2-oxo-2-(pyrrolidin-1-yl)ethyl]-1-
(thiethan-3-yl)pyrimidine-2,4(1H,3H)-dione (VII).
A suspension of 0.5 g (2.5 mmol) of VI and 0.52 g
(3.75 mmol) of calcined and milled potassium
carbonate in 12 mL acetonitrile was refluxed during
30 min. Then a solution of 0.44 g (3 mmol) of I in
3 mL of acetonitrile was added to the reaction mixture,
and refluxing was continued during another 7 h. The
hot reaction mixture was filtered, and the solvent was
removed in vacuum. The residue was recrystallized
from isopropanol. Yield 96%, mp 169–170°C, Rf 0.45.
IR spectrum, ν, cm–1: 2961, 2878 m (С–Н), 1717 s
(С2=О), 1655, 1638 s (С4=О, С=О, С=С), 1459, 1430
s (С–N), 1361, 1336 m (С–N). Found, %: C 54.56; H
6.04; N 13.63. С14Н19N3О3S. Calculated, %: C 54.35;
H 6.19; N 13.58.
1243 m (С–N); 1112, 1070 m (С–О–С). Н NMR
spectrum (DMSO-d6), δ, ppm: 2.09 s (3H, 6-CH3),
3.07–3.13 m [2Н, S(CH)2], 3.45–3.64 m [8H, N(СН2)2,
О(СН2)2], 4.14–4.19 m [2Н, S(CH)2], 4.78 s (2Н, 3-
СН2СО), 5.66 s (1Н, Н5), 6.00–6.12 m (1H, NCH).
Found, %: C 51.82; H 5.86; N 12.73. С14Н19N3О4S.
Calculated, %: C 51.68; H 5.89; N 12.91.
N,N-Diethyl-2-[6-methyl-2,4-dioxo-1-(thiethan-
3-yl)-1,2,3,4-tetrahydro-3-yl]acetamide (XI). Yield
96%, mp 122–124°C (i-PrOH–Н2О, 1 : 1), Rf 0.55. IR
spectrum, ν, cm–1: 2962 m (С–Н), 1715 s (С2=О);
1691, 1666, 1642 s (С4=О, С=О, С=С); 1467, 1437 s
(С–N); 1368, 1266 m (С–N). Found, %: C 54.19; H
6.67; N 13.66. С14Н21N3О3S. Calculated, %: C 54.00;
H 6.80; N 13.49.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 8 2014