A. A. Fadda, E. Abdel-Latif, A. Fekri, and A. R. Mostafa
Vol 000
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(NH), 2216 (C ≡ N), 1692 (broad, C=O). H NMR (δ/
ppm): 7.18–7.62 (m, 5H, Ar-H), 8.05–8.32 (m, 4H, Ar-
H), 11.48 (s, 1H, NH), 12.26 (s, 1H, NH). MS (EI): m/z
(%) = 333 (molecular ion, 31), 208 (base peak, 100.0),
180 (44), 152 (74), 119 (21), 91 (17), 76 (33), 51 (16).
Analysis for C16H11N7O2 (333.10): Calcd: C, 57.66; H,
2123 (C ≡ N), 1692 (C=O). H NMR (δ/ppm): 7.35–8.18
(m, 8H, Ar-H), 8.86 (s, 1H, olefinic CH=C), 11.46 (s,
1H, NH). Analysis for C17H10N5O2Cl (351.05): Calcd: C,
58.05; H, 2.87; N, 19.91%. Found: C, 58.17; H, 2.95; N,
19.98%.
2-Cyano-3-(4-hydroxyphenyl)-N-(4-oxobenzo
[d][1,2,3]
triazin-3(4H)-yl) acrylamide (9d).
Yellow crystals,
3.33; N, 29.42%. Found: C, 57.78; H, 3.41; N, 29.55%.
3-(2-Cyano-2-(4-tolylhydrazono)-acetamido)-4-oxo-4H-
yield = 57%, mp = 293–295°C. IR (v/cmꢀ1): 3221 (NH),
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benzo [d][1,2,3] triazine (7b).
Yellow crystals,
2208 (C ≡ N), 1690 (C=O). H NMR (δ/ppm): 6.88 (d,
yield = 77%, mp = 258–260°C. IR (v/cmꢀ1): 3327, 3230
2H, Ar-H), 7.55–8.25 (m, 6H, Ar-H), 8.71 (s, 1H,
olefinic CH=C), 9.26 (s, 1H, OH), 11.78 (s, 1H, NH).
Analysis for C17H11N5O3 (333.09): Calcd: C, 61.26; H,
3.33; N, 21.01%. Found: C, 61.17; H, 3.24; N, 20.91%.
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(NH), 2214 (C ≡ N), 1704, 1682 (C=O). H NMR (δ/
ppm): 2.31 (s, 3H, CH3), 7.24 (d, 2H, Ar-H), 7.69 (d,
2H, Ar-H), 8.02–8.37 (m, 4H, Ar-H), 12.04 (s, 1H, NH),
12.31 (s, 1H, NH). Analysis for C17H13N7O2 (347.11):
Calcd: C, 58.79; H, 3.77; N, 28.23%. Found: C, 58.63;
Synthesis of 6-amino-4-aryl-2-oxo-1-(4-oxobenzo [d][1,2,3]
triazin-3(4H)-yl)-1,2-dihydropyridine-3,5-dicarbonitrile
derivatives 12a–d.
Method A. A mixture of 9
H, 3.69; N, 28.11%.
3-(2-Cyano-2-(4-anisylhydrazono)-acetamido)-4-oxo-4H-
benzo [d][1,2,3] triazine (7c). Brown crystals, yield = 65%,
(0.002 mol) and malononitrile (10) (0.002 mol, 0.13 g)
has been refluxed for 2 h in 20 mL ethanol containing
five drops of piperidine. The precipitate that separated on
cooling to room temperature was filtered and dried.
mp = 230–232°C. IR (v/cmꢀ1): 3328, 3230 (NH), 2210
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(C ≡ N), 1683 (broad, C=O). H NMR (δ/ppm): 3.77 (s,
3H, OCH3), 6.99 (d, 2H, Ar-H), 7.72 (d, 2H, Ar-H), 8.03
(t, 1H, Ar-H), 8.20 (t, 1H, Ar-H) 8.28–8.36 (m, 2H, Ar-
H), 12.06 (s, 1H, NH), 12.33 (s, 1H, NH). Analysis for
C17H13N7O3 (363.11): Calcd: C, 56.20; H, 3.61; N,
26.99%. Found: C, 56.35; H, 3.69; N, 26.93%.
Method B. To a solution of 3-cyanoacetamido-
benzotriazine derivative 5 (0.002 mol, 0.46 g) in 15 mL
ethanol, different 2-arylidene-malononitrile derivatives 13
(0.002 mol) and five drops piperidine were added. The
reaction mixture was boiled under reflux for 2 h, and the
precipitate that formed was filtered to give the desired
Synthesis of 2-cyano-N-(4-oxobenzo [d][1,2,3]triazin-3(4H)-
yl)-3-phenylacrylamide derivatives 9a–d. To a solution of
3-cyanoacetamido-benzotriazine derivative 5 (0.005 mol,
1.14 g) in 15 mL ethanol, 0.005 mol of different
substituted benzaldehyde 8 (namely, p-tolualdehyde,
pyridine derivatives 12.
6-Amino-2-oxo-1-(4-oxobenzo [d][1,2,3]triazin-3(4H)-yl)-4-
(4-tolyl)-1,2-dihydropyridine-3,5-dicarbonitrile (12a).
Pale
yellow crystals, yield = 48%, mp = 278–280°C. IR (v/
cmꢀ1): 3424, 3365 (NH2), 2205 (C ≡ N), 1676, 1625
p-anisaldehyde,
p-chlorobenzaldehyde,
and
p-
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(C=O). H NMR (δ/ppm): 2.40 (s, 3H, CH3), 7.23–7.38
hydroxybenzaldehyde), and five drops of piperidine were
added. The reaction mixture was refluxed for 2 h, and the
solid that formed on cooling was filtered and dried.
(m, 6H, Ar-H, and NH2), 7.89 (t, 1H, Ar-H), 8.05 (t, 1H,
Ar-H), 8.19–8.26 (m, 2H, Ar-H). Analysis for
C21H13N7O2 (395.11): Calcd: C, 63.79; H, 3.31; N,
24.80%. Found: C, 63.66; H, 3.25; N, 24.71%.
6-Amino-4-(4-anisyl)-2-oxo-1-(4-oxobenzo [d][1,2,3]triazin-
3(4H)-yl)-1,2-dihydropyridine-3,5-dicarbonitrile (12b).
2-Cyano-N-(4-oxobenzo
[d][1,2,3]triazin-3(4H)-yl)-3-(4-
tolyl)-acrylamide (9a).
Beige crystals, yield = 62%,
mp = 290–292°C. IR ( v /cmꢀ1): 3287 (NH), 2123
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(C ≡ N), 1682 (C=O). H NMR (δ/ppm): 2.35 (s, 3H,
Greenish yellow crystals, yield = 50%, mp = 283–285°C.
CH3), 7.31–8.26 (m, 8H, Ar-H), 9.04 (s, 1H, olefinic
CH=C), 11.12 (s, 1H, NH). MS (EI): m/z (%) = 331
(molecular ion, 18), 208 (base peak, 100), 180 (88), 152
(72), 150 (17), 121 (45), 76 (31), 51 (6). Analysis for
C18H13N5O2 (331.11): Calcd: C, 65.25; H, 3.95; N,
IR ( v /cmꢀ1): 3431, 3366 (NH2), 2204 (C ≡ N), 1676,
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1627 (C=O). H NMR (δ/ppm): 3.82 (s, 3H, OCH3), 6.94
(d, 2H, Ar-H), 7.22 (s, 2H, NH2), 7.54 (d, 2H, Ar-H),
7.91 (t, 1H, Ar-H), 8.04 (t, 1H, Ar-H), 8.21–8.28 (m, 2H,
Ar-H). Analysis for C21H13N7O3 (411.11): Calcd: C,
61.31; H, 3.19; N, 23.83%. Found: C, 61.44; H, 3.30; N,
21.14%. Found: C, 65.42; H, 3.99; N, 21.23%.
3-(4-Anisyl)-2-cyano-N-(4-oxobenzo [d][1,2,3]triazin-3(4H)-
yl)-acrylamide (9b).
Yellow crystals, yield = 55%,
23.97%.
mp = 290–292°C. IR ( v /cmꢀ1): 3274 (NH), 2205
6-Amino-4-(4-chlorophenyl)-2-oxo-1-(4-oxobenzo [d][1,2,3]
triazin-3(4H)-yl)-1,2-dihydropyridine-3,5-dicarbonitrile
(12c). Brown powder, yield = 45%, mp = 288–290°C. IR
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(C ≡ N), 1661 (C=O). H NMR (δ/ppm): 3.87 (s, 3H,
OCH3), 7.14 (d, 2H, Ar-H), 7.95–8.35 (m, 6H, Ar-H),
9.16 (s, 1H, olefinic CH=C), 11.68 (s, 1H, NH). Analysis
for C18H13N5O3 (347.10): Calcd: C, 62.24; H, 3.77; N,
20.16%. Found: C, 62.35; H, 3.79; N, 20.22%.
3-(4-Chlorophenyl)-2-cyano-N-(4-oxobenzo [d][1,2,3]triazin-
(v/cmꢀ1): 3335, 3196 (NH2), 2206 (C ≡ N), 1674 (C=O).
1H NMR (δ/ppm): 7.22–7.42 (m, 6H, Ar-H and NH2),
7.87 (t, 1H, Ar-H), 8.06 (t, 1H, Ar-H), 8.18–8.30 (m, 2H,
Ar-H). Analysis for C20H10N7O2Cl (415.06): Calcd: C,
57.77; H, 2.42; N, 23.58%. Found: C, 57.89; H, 2.51; N,
23.67%.
3(4H)-yl) acrylamide (9c).
Pale brown crystals,
yield = 65%, mp = 283–285°C. IR (v/cmꢀ1): 3265 (NH),
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet