HAKOBYAN et al.
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(0.05 mol) of 3 and 5.95 g (0.055 mol) of DMF DMA in
50 mL of xylene was refluxed for 3 h. After cooling, it
was diluted with 30 mL of petroleum ether. The crystals
that formed were filtered off and washed with diethyl
ether. Yield 10.88 g (95%), green crystals, mp 139–
140°C. IR spectrum, ν, cm–1: 1510, 1610 (ring), 2200
(CN). 1H NMR spectrum, δ, ppm: 3.09 s (3H, N–CH3),
3.19 s (3H, N–CH3), 5.73 d (1H, CHallyl, J 12.2 Hz),
7.19 d (1H, CHallyl, J 12.2 Hz), 7.16–7.21 m (1H,
CHarom), 7.29 d.d (1H, CHarom, J 3.6, 1.2 Hz), 7.71 d.d
(1H, CHarom, J 5.1, 1.2 Hz). 13C NMR spectrum, δ, ppm:
37.3 (2C), 45.3, 97.1. 115.6, 115.9, 127.1, 129.1, 130.0,
134.0, 155.8, 161.4. Found, %: C 62.69; H 4.86; N 18.41;
S 14.04. C12H11N3S. Calculated, %: C 62.86; H 4.84;
N 18.33; S 13.98.
and 1 mLof xylene were added to 0.001 mol (0.229 g) of
compound4placedinascrew-cappedampule(inthecase
of 5g, we used 0.0005 molof hexamethylenediamine).
The mixture was heated in an autoclave on a water
bath for 4 h. After cooling, crystal formed and were
filtered off and washed with diethyl ether to obtain the
corresponding amine.
2-(Benzylamino)-4-(thiophen-2-yl)pyridine-3-
carbonitrile (5c). Yield 0.23 g (79%), brown crystals,
mp 132–133°C. IR spectrum, ν, cm–1: 1480 (ring), 1510,
1
1515, 1520 (ring), 2200 (CN), 3390 (NH). H NMR
spectrum, δ, ppm: 4.67 d (1H, CH2N, J 6.0 Hz), 6.71 d
(1H, CH, J 5.3 Hz), 7.12–7.39 m (7H), 7.61 d.d (1H,
3'-CHarom, J 5.1, 1.1 Hz), 7.77 d.d (1H, 5'-CHarom, J 3.8,
1.1 Hz), 8.14 d (1H, CH, J 5.3 Hz). 13C NMR spectrum,
δ, ppm: 44.1, 86.8, 110.6, 116.4, 126.0, 127.0 (2C),
127.5 (2C), 127.7, 128.0, 128.2, 137.7, 139.6, 145.0,
151.5, 159.3. Found, %: C 69.95; H 4.52; N 14.47;
S 11.06. C17H13N3S. Calculated, %: C 70.08; H 4.50;
N 14.42; S 11.00.
N-Substituted 2-amino-4-(thiophen-2-yl)pyridi-
ne-3-carbonitriles 5a and 5b. Compound 4, 0.001 mol
(0.299 g), was added to 50 mLof 30% aqueous ammonia
or methylamine. The mixture was refluxed for 5 h. After
cooling, crystal formed and were filtered off and washed
with diethyl ether to obtain compound 5a or 5b.
2-[(Furan-2-ylmethyl)amino]-4-(thiophen-2-yl)-
pyridine-3-carbonitrile (5d). Yield 0.210 g (75%),
pinkish white crystals, mp 110–111°C. IR spectrum,
ν, cm–1: 1490 (ring), 1510, 1515, 1520 (ring), 2200
2-Amino-4-(thiophen-2-yl)pyridine-3-carbo-
nitrile (5a). Yield 0.170 g (85%), white crystals, mp
130–131°C. IR spectrum, ν, cm–1: 1490 (ring), 1515
1
1
(ring), 2200 (CN), 3300 (NH). H NMR spectrum,
(CN), 3390 (NH). H NMR spectrum, δ, ppm: 4.65 d
δ, ppm: 6.52 br.s (2H, NH2), 6.73 d (1H, 5-CHarom, J
5.3 Hz), 7.19 d.d (1H, 4'-CHarom, J 5.1, 3.7 Hz), 7.60 d.d
(1H, 3'-CHarom, J 5.1, 1.1 Hz), 7.77 d.d (1H, 5'-CHarom, J
3.7, 1.1 Hz), 8.11 d (1H, 6-CHarom, J 5.3 Hz). 13C NMR
spectrum, δ, ppm: 86.9, 110.8, 116.4, 127.7, 127.9,
128.2, 137.7, 144.8, 151.8, 161.2. Found, %: C 59.72;
H 3.50; N 20.79; S 15.99. C10H7N3S. Calculated, %:
C 59.68; H 3.51; N 20.88; S 15.93.
(1H, CH2N, J 5.8 Hz), 6.20 d.d (1H, CHfur, J 3.2, 0.8 Hz),
6.28 d.d (1H, CHfur, J 3.2, 1.9 Hz), 6.76 d (1H, CH, J
5.3 Hz), 7.20 d.d (1H, CHthioph, J 5.1, 3.8 Hz), 7.24 t
(1H, NH, J 5.8 Hz), 7.38 d.d (1H, CHfur, J 1.9, 0.8 Hz),
7.64 d.d (1H, CHthioph, J 5.1, 1.1 Hz), 7.64 d.d (1H,
CHthioph, J 3.8, 1.1 Hz), 8.18 d (1H, CH, J 5.3 Hz). 13C
NMR spectrum, δ, ppm: 37.5, 87.0, 106.2, 109.8, 110.9,
116.2, 127.8, 128.5, 137.6, 128.1, 128.5, 137.6, 140.8,
145.1, 151.4, 152.6, 159.1. Found, %: C 63.95; H 3.95;
N 15.01; S 11.45. C15H11N3OS. Calculated, %: C 64.04;
H 3.94; N 14.94; S 11.40.
2-(Methylamino)-4-(thiophen-2-yl)pyridine-3-
carbonitrile (5b). Yield 0.175 g, (80%), yellowish
crystals, mp 120–121°C. IR spectrum, ν, cm–1: 1480
1
(ring), 1510 (ring), 2200 (CN), 3350 (NH). H NMR
2-(Cyclohexylamino)-4-(thiophen-2-yl)pyridine-
3-carbonitrile (5e). Yield 0.200 g (70%), yellowish
crystals, mp 179–180°C. IR spectrum, ν, cm–1: 1450
(ring), 1510, 1515, 1520 (ring), 2200 (CN), 3390 (NH).
1H NMR spectrum, δ, ppm: 1.16–2.03 m (10H, 5CH2),
3.92–4.07 m (1H, NCH), 5.90 d (1H, NH, J 7.8 Hz),
6.70 d (1H, CH, J 5.2 Hz), 7.19 d.d (1H, CHthioph, J 5.1,
3.7 Hz), 7.63 d.d (1H, CHthioph, J 5.1, 1.1 Hz), 7.74 d.d
(1H, CHthioph, J 3.7, 1.1 Hz), 8.13 d (1H, CH, J 5.2 Hz).
13C NMR spectrum, δ, ppm: 24.7 (2C), 25.1, 32.0
(2C), 49.3, 86.7, 110.3, 116.3, 127.7, 127.9, 128.3,
137.7, 145.0, 151.5, 158.5. Found, %: C 67.67; H 6.08;
spectrum, δ, ppm: 3.45 s (3H, CH3N), 5.97 d (1H,
5-CHarom, J 7.1 Hz), 6.52 br.s (1H, NH), 7.20 d.d (1H,
4'-CHarom, J 5.1, 3.8 Hz), 7.63 d (1H, 6-CHarom, J 7.1 Hz),
7.68 d.d (1H, 3'-CHarom, J 5.1, 1.1 Hz), 7.84 d.d (1H,
13
5'-CHarom, J 3.8, 1.1 Hz). C NMR spectrum, δ, ppm:
38.8, 96.0, 100.6, 116.5, 127.8, 129.1, 129.4, 137.1,
143.5, 146.4, 155.3. Found, %: C 61.51; H 4.19; N 19.43;
S 14.87. C11H9N3S. Calculated, %: C 61.37; H 4.21;
N 19.52; S 14.89.
N-Substituted 2-amino-4-(thiophen-2-yl)pyridi-
ne-3-carbonitriles 5c–5g. Primary amine, 0.001 mol,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020