DYACHENKO et al.
88
spectrum, m/z (Irel, %): 328 (95) [M + 1]+, 265 (14),
264 (100), 109 (11). Found, %: C 69.58; H 3.82;
N 21.14. C19H13N5O. Calculated, %: C 69.72; H 4.00;
N 21.39. M 327.35.
0.71 d (3H, Me, J = 5.01 Hz), 0.92–1.01 m (9H, 3Me),
1.26 m (1H, 7-H), 1.46–1.58 m (4H, CH2, 4-H, 5-H),
1.95 m (1H, CHMe2), 6.02 d (1H, CH=, J = 0.85 Hz),
7.06 d.d (1H, 4'-H, J = 4.11 Hz), 7.32 d.d (1H, 5'-H,
J = 3.08 Hz), 7.51 br.s (2H, NH2), 7.76 t (1H, pyrido-
pyrimidine), 7.88 d (1H, 6'-H), 7.96 d (1H, 3'-H, J =
3.98 Hz), 8.04 d (1H, pyridopyrimidine, J = 4.04 Hz),
8.34 d (1H, pyridopyrimidine, J = 2.14 Hz), 8.57 d
(1H, pyridopyrimidine, J = 1.99 Hz), 9.92 br.s (1H,
NH). Mass spectrum, m/z (Irel, %): 459 (100) [M + 1]+,
338 (28), 262 (10), 95 (11). Found, %: C 67.95;
H 6.42; N 18.14. C26H30N6O2. Calculated, %: C 68.10;
H 6.59; N 18.33. M 458.57.
Compounds XIIa–XIIe (general procedure). Ac-
rylamide Vc, 10 mmol, was dissolved in 15 ml of
DMF, 5.6 ml (10 mmol) of 10% aqueous potassium
hydroxide and 10 mmol of alkyl halide XIa–XIe were
added in succession under stirring at 20°C, and the
mixture was stirred for 2 h, left to stand for 24 h, and
diluted with an equal volume of water. The precipitate
was filtered off, washed in succession with water,
ethanol, and hexane, and recrystallized from butyl
alcohol.
6-Amino-2-oxo-4-phenyl-1-(pyridin-2-yl)-1,2-di-
hydropyridine-3,5-dicarbonitrile (IXa). a. Piperi-
dine, 0.10 ml (10 mmol), was added under stirring at
20°C to a mixture of 1.61 g (10 mmol) of compound
Ia and 0.66 g (10 mmol) of malononitrile in 20 ml of
ethanol, and the mixture was stirred for 30 min and
was left to stand for 24 h. The precipitate was filtered
off, washed with ethanol and hexane, and recrystalliz-
ed from glacial acetic acid. Yield 2.13 g (68%), pink
needles, mp 300°C (decomp.; sublimes at 250°C). IR
spectrum, ν, cm–1: 3354, 3294, 3186 (NH2); 2218
(2E)-2-Cyano-N-ethyl-3-phenyl-N-(1,3-thiazol-2-
yl)prop-2-enamide (XIIa). Yield 2.26 g (80%), yel-
low powder, mp 95–97°C. IR spectrum, ν, cm–1: 2214
(C≡N), 1682 (C=O). 1H NMR spectrum, δ, ppm: 1.37 t
(3H, Me, J = 6.14 Hz), 4.31 q (2H, CH2), 7.20 d (1H,
4-H, J = 2.22 Hz), 7.54–7.61 m (3H, Ph), 7.71 d (1H,
5-H), 8.02–8.09 m (2H, Ph), 8.38 s (1H, CH=). Mass
spectrum, m/z (Irel, %): 284 (100) [M + 1]+. Found, %:
C 63.40; H 4.38; N 14.69. C15H13N3OS. Calculated, %:
C 63.58; H 4.62; N 14.83. M 283.35.
1
(C≡N); 1682 (C=O); 1634 (δNH2). H NMR spectrum,
(2E)-2-Cyano-N-methyl-3-phenyl-N-(1,3-thiazol-
2-yl)prop-2-enamide (XIIb). Yield 2.15 g (80%),
yellow crystals, mp 142–143°C. IR spectrum, ν, cm–1:
2214 (C≡N), 1680 (C=O). 1H NMR spectrum, δ, ppm:
3.55 s (3H, Me), 7.18 d (1H, 4-H, J = 2.25 Hz), 7.54–
7.61 m (3H, Ph), 7.68 d (1H, 5-H), 8.02–8.06 m (2H,
Ph), 8.41 s (1H, CH=). Mass spectrum, m/z (Irel, %):
270 (100) [M + 1]+. Found, %: C 62.25; H 4.00;
N 15.42. C14H11N3OS. Calculated, %: C 62.44; H 4.12;
N 15.60. M 269.33.
δ, ppm: 7.28–7.72 m (7H, Harom, NH2); 7.85–8.16 m
(3H, Harom), 8.63 d (1H, Harom, J = 1.14 Hz). Mass
spectrum, m/z (Irel, %): 314 (100) [M + 1]+. Found, %:
C 68.84; H 3.42; N 22.19. C18H11N5O. Calculated, %:
C 69.00; H 3.54; N 22.35. M 313.32.
b. Piperidine, 0.10 ml (10 mmol), was added at
20°C to a mixture of 1.61 g (10 mmol) of compound
Ia and 1.54 g (10 mmol) of benzylidenemalononitrile
(X) in 20 ml of ethanol, and the mixture was stirred for
1 h and left to stand for 24 h. The precipitate was
filtered off and washed with ethanol and hexane. Yield
2.25 g (72%). The product was identical in the melting
point, chromatographic data, and IR spectrum to
a sample prepared as described above in a.
(2E)-2-Cyano-3-phenyl-N-(phenylcarbamoyl-
methyl)-N-(1,3-thiazol-2-yl)prop-2-enamide (XIIc).
Yield 3.18 g (80%), yellow powder, mp 276–278°C
(sublimes at 205°C). IR spectrum, ν, cm–1: 3302 (NH),
2218 (C≡N), 1678 (C=O). 1H NMR spectrum, δ, ppm:
5.18 s (2H, CH2), 7.07 t (1H, Ph, J = 6.96 Hz), 7.19 d
(1H, 4-H, J = 1.94 Hz), 7.32 t (2H, Ph, J = 6.95 Hz),
7.51–7.59 m (5H, Ph), 7.62 d (1H, Ph, J = 7.12 Hz),
7.68 d (1H, 5-H), 7.89 d (1H, Ph, J = 7.09 Hz), 8.39 s
(1H, CH=), 10.52 br.s (1H, NH). Mass spectrum, m/z
(Irel, %): 389 (100) [M + 1]+. Found, %: C 64.80;
H 4.01; N 14.35. C21H16N4O2S. Calculated, %: C 64.93;
H 4.15; N 14.42. M 388.45.
6-Amino-1-(4-methylpyridin-2-yl)-2-oxo-4-phen-
yl-1,2-dihydropyridine-3,5-dicarbonitrile (IXb) was
synthesized as described above for compound IXa
(method b) from 1.75 g (10 mmol) of N-(4-methyl-
pyridin-2-yl)cyanoacetamide (Ib). Yield 2.19 g (67%),
colorless plates, mp 310–314°C (from AcOH). IR
spectrum, ν, cm–1: 3444, 3295, 3156 (NH2); 2212
1
(C≡N); 1696 (C=O); 1650 (δNH2). H NMR spectrum,
δ, ppm: 2.44 s (3H, Me), 7.31 d (1H, 5-H, J =
2.02 Hz), 7.54–7.61 m (5H, Ph), 7.82 d (1H, 6-H, J =
1.19 Hz), 7.64 br.s (2H, NH2), 8.46 s (1H, 3-H). Mass
(2E)-N-Benzyl-2-cyano-3-phenyl-N-(1,3-thiazol-
2-yl)prop-2-enamide (XIId). Yield 3.00 g (87%),
yellow powder, mp 103–104°C. IR spectrum, ν, cm–1:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007