HETEROCYCLES, Vol. 89, No. 2, 2014
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46), 93 (39), 83 (54), 64 (100). Anal. Calcd for C13H10N6O (266.26); C, 58.64; H, 3.76; N, 31.56%.
Found: C, 58.33; H, 3.54; N, 31.67%.
5-Amino-7-(4-oxo-4H-chromen-3-yl)-2,3-dihydro-1H-1,4-diazepine-6-carbonitrile (15).
A mixture of compound 2 (0.67 g, 3 mmol) and ethylenediamine (0.2 mL, 3 mmol), in absolute EtOH (20
mL) was heated under reflux for 2 h. After cooling, the solid obtained was filtered off and crystallized
from DMF/H2O to give compound 15 as yellow crystals, yield (0.47 g, 70%), mp 283 °C. IR (KBr, cm-1):
3324 (NH2, NH), 3050 (CHarom.), 2929, 2867 (CHaliph.), 2212 (C≡N), 1645 (C=Oγ-pyrone), 1601 (C=N),
1585 (C=C). 1H NMR (DMSO-d6, δ): 3.83 (s, 4H, 2CH2), 5.83 (bs, 2H, NH2 exchangeable with D2O),
6.91−6.99 (m, 2H, Ar-H), 7.18−7.46 (m, 1H, Ar-H), 8.06 (d, 1H, H-5), 8.88 (s, 1H, H-2), 9.91 (bs, 1H,
NH exchangeable with D2O). M/z (I %): 279 (M-1, 24), 182 (23), 140 (29), 94 (41), 64 (82), 55 (100).
Anal. Calcd for C15H12N4O2 (280.29); C, 64.28; H, 4.32; N, 19.99%. Found: C, 64.68; H, 4.60; N,
19.32%.
4-Amino-2-(4-oxo-4H-chromen-3-yl)-1H-1,5-benzodiazepine-3-carbonitrile (16).
A mixture of compound 2 (0.67 g, 3 mmol) and o-phenylendiamine (0.32 g, 3 mmol) in absolute EtOH
(25 mL) was heated under reflux for 2 h. The solid obtained during heating was filtered off and
crystallized from DMF/EtOH to give compound 16 as yellow crystals, yield (0.42 g, 63%), mp 292 °C. IR
(KBr, cm-1): 3319 (NH2, NH), 3052 (CHarom.), 2210 (C≡N), 1633 (C=Oγ-pyrone), 1615 (C=N), 1582 (C=C).
1HNMR (DMSO-d6, δ): 6.89-6.98 (m, 3H, Ar-H), 7.44-7.58 (m, 4H, Ar-H), 7.69 (bs, 2H, NH2
exchangeable with D2O), 7.80 (d, 1H, H-5chromone), 8.30 (bs, 1H, NH exchangeable with D2O), 8.75 (s, 1H,
H-2chromone). 13C NMR (DMSO-d6, δ): 71.5, 116.2, 116.7, 117.3, 119.1, 122.6, 124.3, 126.2, 127.6, 130.8,
133.2, 140.1, 146.1, 151.6, 152.8, 156.8, 183.4. M/z (I %): 328 (M, 88), 311 (69), 299 (63), 256 (25), 208
(100), 152 (25), 121 (63), 93 (38), 65 (75). Anal. Calcd for C19H12N4O2 (328.33); C, 69.51; H, 3.68; N,
17.06%. Found: C, 69.64; H, 3.33; N, 17.00%.
6-Amino-2-oxo-4-(4-oxo-4H-chromen-3-yl)-1,2-dihydropyridine-3,5-dicarbonitrile (17).
A mixture of compound 2 (0.44 g, 2 mmol) and cyanoacetamide (0.17 g, 2 mmol) in absolute EtOH (20
mL) containing two drops of piperidine was heated under reflux for 2 h. The yellow crystals obtained
during heating was filtered off and crystallized from DMF/EtOH to give compound 17 as pale yellow
crystals, yield (0.20 g, 45%), mp > 300 °C. IR (KBr, cm-1): 3385, 3320, 3195 (br, NH2, NH), 3050
(CHarom.), 2217 (2C≡N), 1684 (C=Opyridone), 1663 (C=Oγ-pyrone), 1622 (C= N). 1HNMR (DMSO-d6, δ):
7.51 (t, 1H, H-6chromone, J = 7.8 Hz), 7.62 (d, 1H, H-8chromone, J = 8.7 Hz), 7.77 (t, 1H, H-7chromone, J = 7.8
Hz), 7.88 (d, 1H, H-5chromone, J = 8.4 Hz), 8.25 (s, 1H, NH), 8.56 (s, 1H, NH), 8.97 (s, 1H, NH), 9.26 (s,
1H, H-2chromone). M/z (I %): 304 (M+, 13), 288 (10), 275 (9), 262 (10), 250 (14), 235 (10), 214 (15), 185
(9), 172 (13), 131 (12), 121 (13), 94 (11), 80 (100), 77 (9), 64 (42). Anal. Calcd for C16H8N4O3 (304.27);
C, 63.16; H, 2.65; N, 18.41%. Found: C, 62.89; H, 2.51; N, 18.16%.