552
W. S. Hamama, H. G. El-Gohary, M. Soliman, and H. H. Zoorob
Vol 49
give 18 (45%); mp 208–210ꢂC; white crystals; IR (KBr) ׳
υ
9; (62%); mp 250ꢂC; yellow crystals; IR (KBr) ׳
υ (cmꢁ1),
1
(cmꢁ1), 3397, 3063, 2919, 2790, 1624, 1594, 1476, 1004, 757; H
3389, 3241, 3040, 2978, 2915, 1632, 1593, 1550, 1003, 758;
1H NMR (200 MHz, DMSO-d6): d, 2.18 (s, 6H), 2.24–2.87 (m,
8H), 6.88–8.1 (m, 20H), 9.67 (s, 2H); 13C NMR (200 MHz,
DMSO-d6): d, 170.2, 165.1, 147.8, 144.4, 137.9, 129.1, 124.4,
121.7, 118.6, 118.5, 116.9, 75.4, 48.3; ms: (m/z, %): 605 (M+,
4), 551 (22), 523 (17), 339 (24), 313 (61), 236 (56), 129 (68),
97 (100). Anal. Calcd. for C38H36N8O2 (636.74):C 71.68, H
5.70%. Found: C 71.52, H 5.64%.
10; (40%); mp 122–124ꢂC; pale yellow crystals; IR (KBr) ׳
υ
(cmꢁ1), 3420, 3057, 2926, 1729, 1925, 1595, 1561, 1005, 757;
1H NMR (200 MHz, CDCl3): d, 1.26 (t, J = 4.8 Hz, 3H), 1.84
(q, J = 8.4 Hz, 4H), 2.09 (s, 3H), 2.48 (q, 1H), 3.18 (t, J = 8.4
Hz, 4H), 4.14 (q, J = 4.8 Hz, 2H), 4.74 (s, 1H), (NH, exchange-
able with D2O), 7.06–7.91 (m, 10H); ms: (m/z, %): 432 (M+,
6), 339 (5), 313 (7), 275 (34), 213 (10), 157 (10), 97 (23), 57
(100). Anal. Calcd. for C25H28N4O3 (432.51):C 69.42, H
6.53%. Found: C 69.40, H 6.60%.
NMR (200 MHz, DMSO-d6): d, 2.15 (s, 6H), 7.16–7.90 (m, 10H);
ms: (m/z, %): 346 (M++2, 10), 345 (M++1, 16), 344 (M+, 51), 315
(43), 239 (9), 211 (14), 174 (71), 132 (10), 91 (47), 77 (100).
Anal. Calcd. for C20H16N4O2 (344.37): C 69.76, H 4.68%. Found:
C 69.82, H 4.59%.
6-Amino-4-(4-methoxyphenyl)-2-oxo-1,2-dihydropyridine-
3,5-dicarbonitrile (23). A mixture of arylidine 19 (0.5 g, 1.7
mmol), cyanoacetamide (0.14 g, 1.7 mmol) and TEA (0.4 mL)
in ethanol (20 mL) were refluxed for 15 min then left to stand
at room temperature for two day, the solid precipitate was
filtered, dried and recrystallized from ethanol to give 23 (65%);
mp 205–207ꢂC, [Lit. [32], 205ꢂC (dec)]; white crystals; IR
(KBr) ׳
υ (cmꢁ1), 3446, 3365, 3303, 3172, 2982, 2940, 2207,
1697, 1582, 1509, 1042, 727; 1H NMR (CDCl3): d, 3.89 (s,
3H), 6.96–7.26 (m, 4H), 7.8 (s, 2H), 8.26 (s, 1H); ms: (m/z, %):
266 (M+, 10), 203 (13), 202 (100), 158 (18), 89 (8), 77 (1).
Anal. Calcd. for C14H10N4O2 (266.25): C 63.15, H 3.79%.
Found: C 63.35, H 3.68%.
3-Methyl-4-(3-oxo-3-phenylpropyl)-1-phenyl-1H-pyrazol-5
(4H)-one (12). A mixture of 3-methyl-1-phenyl-1H-pyrazol-5
(4H)-one (1) (0.34 g, 1.95 mmol) and 11 (0.5 g, 1.95 mmol) in
methanol (20 mL) was refluxed over a steam bath for 3 h. The
reaction mixture was left to cool, filtered and the filtrate was
basified. The formed precipitate was filtered, dried and
recrystallized from ethanol to afford 12 (65%); mp 79ꢂC; white
crystals; IR (KBr) ׳
υ (cmꢁ1), 3303, 3061, 2911, 1738, 1686,
1651, 1594, 1573, 1001, 751; 1H NMR (CDCl3): d, 2.04 (s,
3H), 2.25 (q, J = 4.0 Hz, 2H), 2.75 (t, J = 4.0 Hz, 2H), 3.34 (t,
J = 4.0 Hz, 1H), 7.2–8.0 (m, 10H); ms: (m/z, %): 306 (M+, 28),
187 (30), 186 (100), 105 (22), 149 (28), 125 (13), 83 (38), 57
(43). Anal. Calcd. for C19H18N2O2 (306.36): C 74.49, H 5.92%.
Found: C 74.52, H 6.02%.
(3-(4-Methoxyphenyl)-4-methyl-6-phenyl-2,3-dihydropyrazolo
[3,4-c]pyrazol-1(6H)-yl) (pyridin-4-yl)methanone (24).
A
mixture of the arylidine 19 (0.5 g, 1.7 mmol), nicotinic hydrazide
(0.24 g, 1.7 mmol) and triethylamine (0.4 mL) were heated for
15 min then left for two day at room temperature, the solid
precipitate was filtered, dried and recrystallized from ethanol to
furnish 24 (70%); mp 157–159ꢂC; pale yellow crystals; IR (KBr)
׳
υ (cmꢁ1), 3445, 3043, 2993, 1658, 1602, 1551, 1025, 1548,
1408, 1328; 1H NMR (200 MHz, DMSO-d6): d, 2.48 (s, 3H),
3.82 (s, 3H), 7.02–7.83 (m, 13H), 8.41 (s, 1H), 8.79 (s, 1H); ms:
(m/z, %): 412 (M++1, 1), 411 (M+, 5), 276 (1), 275 (1), 185 (4),
135 (5), 133 (100), 106 (26), 78 (17). 106 (26), 78 (17). Anal.
Calcd. for C24H21N5O2 (411.46): C 70.06, H 5.14%. Found:
C 69.84, H 5.09%.
3-Methyl-1,6-diphenyl-1H-pyrazolo[3,4-b]pyridine (14).
A
mixture of 12 (0.5 g, 1.63 mmol) and ammonium carbonate (0.16
g, 1.63 mmol) in acetic acid (10 mL) was refluxed for 8 h, the
solvent was evaporated, the formed residue was neutralized with
diluted ammonium hydroxide, the solid precipitate was filtered
off and recrystallized from ethanol to give 14 (60%); mp 150ꢂC;
red crystals; IR (KBr) ׳
υ (cmꢁ1), 3060, 2921, 1595, 1498, 1003,
755; ms: (m/z, %): 285 (M+, 4), 245 (21), 244 (100), 213 (13),
186 (37), 129 (25), 105 (62), 91 (20), 77 (72). Anal. Calcd. for
C19H15N3 (285.34): C 79.98, H 5.30%. Found: C 79.89, H 5.28%.
5,5a-Dihydro-5-(4-methoxyphenyl)-8-phenyl-1,3,6-trime-
thylpyrazolo[40,30:5,6]pyrido [2,3-d]thiopyrimidine-4(3H)
one (27). A mixture of arylidine 19 (0.5 g, 1.7 mmol), with
6-aminothiouracil (25) (0.22 g, 1.7 mmol) was refluxed in
ethanol (20 mL) in presence of catalytic amount of glacial
acetic acid for 8 h, left to stand at room temperature, water
basified by ammonium hydroxide was added. The solid
precipitate was collected by filtration and crystallized from
ethanol to give 27 (60%); mp 258–260ꢂC; white crystals; IR
(KBr) ׳
υ (cmꢁ1), 3378, 2961, 2924, 1661, 1600, 1542, 1228,
1031, 771; 1H NMR (200 MHz, DMSO-d6): d, 2.50 (s, 3H),
2.69 (d, J = 12.8 Hz, 1H), 2.85 (d, J = 12.8 Hz, 1H), 3.69 (s,
3H), 5.28 (s, 1H), 6.76–7.00 (m, 9H), 7.93 (s, 1H), (NH,
exchangeable with D2O); ms: (m/z, %): 419 (M++2, 3), 385
(6), 278 (4), 263 (100), 262 (8), 233 (2), 232 (12), 108 (9),
107 (3), 77 (16). Anal. Calcd. for C22H19N5O2S (417.48):
C 63.29, H 4.59%. Found: C 63.12, H 4.70%.
5-(4-Methoxyphenyl)-8-phenyl-1,3,6-trimethylpyrazolo[40,30:
5,6]pyrido[2,3-d] pyrimidine-2,4(1H,3H)dione (29). A mixture
of arylidine 28 (0.5 g, 1.7 mmol) with 1,3-dimethyl-6-aminouracil
(26) (0.27 g, 1.7 mmol) was heated in glacial acetic acid (15 mL)
on steam bath for 18 h, the reaction mixture was left to cool, the
formed solid precipitate was collected by filtration, dried and
recrystallized from acetic acid to give 29 (65%); mp 240–242ꢂC;
white crystals; IR (KBr) ׳
υ (cmꢁ1), 3058, 3002, 2918, 1698, 1599,
1503, 1030, 756; ms: (m/z, %): 428 (M++1, 27), 339 (3), 292 (6),
Ethyl 5-amino-3-methyl-1-phenyl-1H-thieno[3,2-c]pyrazole-6-
carboxylate (15).
A mixture of 1 (0.5 g, 2.87 mmol),
ethylcyanoacetate (0.31 g, 2.87 mmol), sulfur (0.09 g, 2.87 mmol)
and triethylamine (0.03 mL, 2.87 mmol) in ethanol (20 mL) was
stirred for 3 h at 40–50ꢂC, the formed precipitate was filtered, dried
and recrystallized from ethanol to afford 15 (45%); mp 120ꢂC; pale
yellow crystals; IR (KBr) ׳
υ (cmꢁ1), 3153, 2919, 1608, 1535, 1000,
764; 1H NMR (200 MHz, DMSO-d6): d, 2.3 (s, 6H), 7.26–7.73 (m,
10H); ms: (m/z, %): 346 (M++2, 3), 345 (M++1, 4), 344 (M+, 11),
314 (8), 239 (2), 211 (4), 174 (34), 91 (43), 77 (12), 76 (100). Anal.
Calcd. for C20H16N4S (344.43):C 69.74, H 4.68%. Found: C 69.65,
H 4.66%.
4(Z)-3-Methyl-4-(3-methyl-5-oxo-1-phenyl-1H-pyrazolo-
4(5H)-ylidene)-1-phenyl-1H-pyrazol-5(4H)-one (18).
A mix-
ture of 1 (0.5 g, 2.87 mmol) and selenium oxide (0.33 g, 2.87
mmol) in ethanol (20 mL) was refluxed for 4 h, the formed black
powder was filtered off and the filtrate was left to cool. The solid
precipitate was filtered, dried and recrystallized from methanol to
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet