HETEROCYCLIZATION OF MICHAEL ADDUCTS
249
1Н NMR spectrum, δ, ppm: 0.86 s (3H, CH3), 1.00 s
(3H, CH3), 1.94 d (1H, CH2CO, J 16.2 Hz), 2.16 d (1H,
CH2CO, J 16.2 Hz), 2.40 d (1H, CH2, J 16.7 Hz), 2.49 d
(1H, CH2, J 16.7 Hz), 3.88 s (3H, OCH3), 5.25 s (1H,
CH), 6.10 s (2H, NH2), 7.15 d.t (1Н, C6H4, J 1.6, 7.6 Hz),
7.23 d.t (1Н, C6H4, J 1.3, 7.6 Hz), 7.30 d.d (1Н, C6H4,
J 1.2, 7.9 Hz), 7.45 d.d (1Н, C6H4, J 1.5, 7.8 Hz), 9.95 s
(1H, NH). Mass spectrum, m/z (Irel, %): 410 (6) [M]+,
408 (17) [M]+, 297 (100) [M – 111]+. Found, %: С 64.63;
Н 5.16; N 13.68. C22H21ClN4О2. Calculated, %: C 64.62;
H 5.18; N 13.70. M 408.14.
CH2CO, J 16.3 Hz), 2.23 d (1H, CH2CO, J 16.3 Hz),
2.38 d (1H, CH2, J 17.4 Hz), 2.47 d (1H, CH2, J 17.4 Hz),
3.88 s (3H, OCH3), 5.54 s (1H, CH), 6.74 s (2H, NH2),
6.80 d.d (1Н, С4H3S, J 3.3, 5.0 Hz), 6.84 d (1Н, С4H3S,
J 3.3 Hz), 7.17 d.d (1Н, С4H3S, J 1.2, 5.0 Hz), 9.89 s (1H,
NH). Mass spectrum, m/z (Irel, %): 380 (53) [M]+, 297
(100) [M – 83]+. Found, %: С 63.10; Н 5.32; N 14.75.
C20H20N4О2S. Calculated, %: C 63.14; H 5.30; N 14.73.
M 380.13.
4-Amino-2-[4-(dimethylamino)phenyl]-6-me-
thoxypyridine-3,5-dicarbonitrile (VIIа). Yield 68%,
mp 258–259°С (decomp.). IR spectrum, ν, cm–1: 3343,
4-Amino-5-(3-bromophenyl)-2-methoxy-8,8-di-
methyl-6-oxo-5,6,7,8,9,10-hexahydrobenzo[b][1,8]-
naphthyridine-3-carbonitrile (IVg). Yield 98%,
mp 248–249°С (decomp.). IR spectrum, ν, cm–1: 3411,
3350 (NH2), 3242 (NH), 2210 (C≡N), 1659 (С=О).
1Н NMR spectrum, δ, ppm: 0.82 s (3H, CH3), 1.00 s
(3H, CH3), 2.00 d (1H, CH2CO, J 16.3 Hz), 2.19 d (1H,
CH2CO, J 16.3 Hz), 2.39 d (1H, CH2, J 17.2 Hz), 2.48 d
(1H, CH2, J 17.2 Hz), 3.89 s (3H, OCH3), 5.18 s (1H,
CH), 6.63 s (2H, NH2), 7.16 t (1Н, C6H4, J 7.7 Hz),
7.19 d.t (1Н, C6H4, J 1.4, 7.7 Hz), 7.28 d.t (1Н, C6H4,
J 1.7, 7.6 Hz), 7.60 t (1Н, C6H4, J 1.7 Hz), 9.86 s (1H,
NH). Mass spectrum, m/z (Irel, %): 454 (6) [M]+, 453 (2)
[M]+, 452 (6) [M]+, 297 (100) [M – 155]+. Found, %:
С 58.25; Н 4.64; N 12.33. C22H21BrN4О2. Calculated,
%: C 58.29; H 4.67; N 12.36. M 452.08.
1
3237 (NH2), 2206 (C≡N). Н NMR spectrum, δ, ppm:
3.02 s [6H, (CH3)2N], 4.00 s (3H, OCH3), 6.80 d (2H,
C6H4, J 9.0 Hz), 7.49 s (2H, NH2), 7.86 d (2H, C6H4,
J 9.0 Hz). 13С NMR spectrum, δ, ppm: 54.47 (OCH3),
74.62, 84.20 (С3,5), 113.88, 116.59 (CN), 111.06, 123.15,
130.29, 152.11 (C6H4), 159.83, 162.76, 165.50 (C2,4,6).
Mass spectrum, m/z (Irel, %): 293 (100) [M]+, 249 (5) [M –
44]+. Found, %: С 65.55; Н 5.19; N 23.86. C16H15N5О.
Calculated, %: C 65.52; Н 5.15; N 23.88. M 293.13.
4-Amino-2-(4-hydroxyphenyl)-6-methoxypyridine-
3,5-dicarbonitrile (VIIb) was purified by column
chromatography. Yield 54%, mp 268–269°С (decomp.).
IR spectrum, ν, cm–1: 3348, 3240 (NH2), 2224 (C≡N).
1Н NMR spectrum, δ, ppm: 4.00 s (3H, OCH3), 6.90 d
(2H, C6H4, J 8.7 Hz), 7.56 s (2H, NH2), 7.79 d (2H, C6H4,
J 8.7 Hz), 10.13 s (1Н, ОН). Mass spectrum, m/z (Irel,
%): 266 (100) [M]+, 249 (11) [M – 17]+, 235 (21) [M –
31]+. Found, %: С 63.16; Н 3.82; N 21.06. C14H10N4О2.
Calculated, %: C 63.15; Н 3.79; N 21.04. M 266.08.
4-Amino-5-(3,4-dichlorophenyl)-8,8-dimethyl-2-
methoxy-6-oxo-5,6,7,8,9,10-hexahydrobenzo[b][1,8]-
naphthyridine-3-carbonitrile (IVh). Yield 97%, mp
277–278°С (decomp.). IR spectrum, ν, cm–1: 3412, 3343
(NH2), 3242 (NH), 2208 (C≡N), 1654 (С=О). 1Н NMR
spectrum, δ, ppm: 0.81 s (3H, CH3), 1.00 s (3H, CH3),
2.00 d (1H, CH2CO, J 16.1 Hz), 2.19 d (1H, CH2CO,
J 16.1 Hz), 2.39 d (1H, CH2, J 17.2 Hz), 2.48 d (1H, CH2,
J 17.2 Hz), 3.89 s (3H, OCH3), 5.20 s (1H, CH), 6.66 s
(2H, NH2), 7.14 d.d (1Н, C6H3, J 2.0, 8.4 Hz), 7.46 d (1Н,
C6H3, J 8.4 Hz), 7.66 d (1Н, C6H3, J 2.0 Hz), 9.91 s (1H,
NH). Mass spectrum, m/z (Irel, %): 444 (1) [M]+, 442 (3)
[M]+, 297 (100) [M – 145]+. Found, %: С 59.58; Н 4.53;
N 12.66. C22H20Cl2N4О2. Calculated, %: C 59.60; H 4.55;
N 12.64. M 442.10.
4-Amino-2-(4-hydroxy-3-methoxyphenyl)-6-me-
thoxypyridine-3,5-dicarbonitrile (VIIc). Yield 76%,
mp 266–267°С (decomp.). IR spectrum, ν, cm–1: 3377,
1
3243 (NH2), 2224 (C≡N). Н NMR spectrum, δ, ppm:
3.83 s (3H, 3-CH3O), 4.02 s (3H, 6-CH3O), 6.92 d (1Н,
C6H3, J 8.3 Hz), 7.43 d.d (1Н, C6H3, J 2.1, 8.3 Hz), 7.51 d
(1Н, C6H3, J 2.1 Hz), 7.57 s (2H, NH2), 9.76 s (1Н, ОН).
Mass spectrum, m/z (Irel, %): 296 (44) [M]+. Found, %:
С 60.85; Н 4.06; N 18.93. C15H12N4О3. Calculated, %:
C 60.81; Н 4.08; N 18.91. M 296.09.
4-Amino-8,8-dimethyl-2-methoxy-6-oxo-5-(2-
thienyl)-5,6,7,8,9,10-hexahydrobenzo[b][1,8]naphthy-
ridine-3-carbonitrile (IVi). Yield 93%, mp 311–312°С
(decomp.). IR spectrum, ν, cm–1: 3412, 3343 (NH2), 3242
(NH), 2208 (C≡N), 1654 (С=О). 1Н NMR spectrum, δ,
ppm: 0.91 s (3H, CH3), 1.01 s (3H, CH3), 2.06 d (1H,
ACKNOWLEDGMENTS
The study was carried out in the framework of the basic
part of the State assignment of the Ministry of Education
and Science of the Russian Federation.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 2 2014