Synthesis of Pyrazolinone and Pyrazole Derivatives
J. Chin. Chem. Soc., Vol. 51, No. 5A, 2004 989
9H, Ar-H), 7.80 (d, 1H, CH=CH, J = 16.1 Hz), 7.85 (d, 1H,
CH=CH, J = 16.1 Hz), 8.00 (d, 2H, pyridine H-3 and H-5),
8.85 (d, 2H, pyridine H-2 and H-6). Anal. Calcd. for
C24H18ClN3O (399.88) C, 72.09; H, 4.54; N, 10.51; Cl, 8.87.
Found C, 72.14; H,4.53; N, 10.15; Cl, 8.85%.
Formation of compounds 15 and 16
A mixture of compound 1 (2.8 g, 0.012 mol) in ethanol
(20 mL), compound 12b (0.01 mol) in ethanol (20 mL) and
piperidine (2 mL) was refluxed for 10 h. After cooling, the
precipitate that appeared was collected by filtration and crys-
tallized from ethanol to give 15. The mother liquor which re-
sulted after separation of compound 15 was concentrated and
upon cooling, compound 16 was separated, then collected by
filtration and recrystallized from ethanol to give 16.
Formation of compounds 13 and 14a,b
A mixture of compound 1 (2.8 g, 0.012 mol) in ethanol
(20 mL), appropriate chalcones (0.01 mol) in ethanol (20
mL), and piperidine (2 mL) was refluxed for 6 h. After cool-
ing, the precipitate that appeared was collected by filtration
and crystallized from ethanol to give 13. The mother liquors
which resulted after separation of compound 13 were concen-
trated and upon cooling, compounds 14a,b were separated,
then collected by filtration and recrystallized from ethanol/
water.
4-(5-Chloro-1-phenyl-3-pyridin-4-yl-1H-pyrazol-4-yl)-1,7-
diphenyl-3,5-dipyridin-4-yl-4,7-dihydro-1H-pyrano[2,3-c;
6,5-c¢]dipyrazole (15)
Yield 27%; mp 180-182 °C; IR (KBr) 2840, 1605, 1200
cm-1; 1H NMR (DMSO-d6) d 5.10 (s, 1H, pyran-H), 7.20-8.80
(m, 27H, Ar-H); MS (EI) m/z (rel. intensity) 723 (7, M+ + 1),
698 (9), 589 (10), 523 (20), 424 (32), 320 (45), 276 (40), 198
(60), 69 (100). Anal. Calcd. for C43H28ClN9O (722.21) C,
71.51; H, 3.90; N, 17.45; Cl, 4.91. Found C, 71.76; H, 3.99;
N, 17.30; Cl, 5.20%.
(4-Methoxyphenyl)-1,7-diphenyl-3,5-dipyridin-4-yl-4,7-
dihydro-1H-pyrano[2,3-c; 6,5-c¢]dipyrazole (13)
Yield 34%; mp 230-232 °C; IR (KBr) 2845, 1610, 1203
1
cm-1; H NMR (DMSO-d6) d 3.70 (s, 3H, OCH3), 5.20 (s,
3-(5-Chloro-1-phenyl-3-pyridin-4-yl-1H-pyrazol-4-yl)-3-
(5-hydroxy-1-phenyl-3-pyridin-4-yl-1H-pyrazol-4-yl)-1-(4-
methylphenyl)propan-1-one (16)
1H, pyran-H), 7.30-8.40 (m, 22H, Ar-H). Anal. Calcd. for
C36H26N6O2 (574.64) C, 75.25; H, 4.56; N, 14.62. Found C,
75.67; H, 4.90; N, 14.69%.
Yield 39%; mp 170-172 °C; IR (KBr) 3340, 1660, 1612
1
cm-1; H NMR (CDCl3) d 2.50 (s, 3H, CH3), 6.20 (d, 2H,
3-(5-Hydroxy-1-phenyl-3-pyridin-4-yl-1H-pyrazol-4-yl)-3-
(4-ethoxyphenyl)-1-phenylpropan-1-one (14a)
CHCH2, J = 7.3 Hz), 6.70 (t, 1H, CHCH2, J = 7.3 Hz),
7.40-8.80 (m, 22H, Ar-H), 9.85 (s, 1H, OH). Anal. Calcd. for
C38H29ClN6O2 (637.14) C, 71.63; H, 4.59; N, 13.19; Cl, 5.56.
Found C, 71.50; H, 4.96; N, 13.30; Cl, 5.60%.
Yield 52%; mp 70-72 °C; IR (KBr) 3330, 1660, 1620
1
cm-1; H NMR (CDCl3) d 3.90 (s, 3H, OCH3), 6.10 (d, 2H,
CHCH2, J = 7.2 Hz), 6.60 (t, 1H, CHCH2, J = 7.2 Hz), 7.40-
8.10 (m, 18H, Ar-H), 9.80 (s, 1H, OH); MS (EI) m/z (rel. in-
tensity) 475 (2, M+), 428 (4), 368 (2), 238 (52), 223 (32), 161
(100), 105 (42), 77 (67), 51 (30). Anal. Calcd. for C30H25N3O3
(475.55) C, 75.77; H, 5.30; N, 8.84. Found C, 75.85; H, 5.11;
N, 8.72%.
Received October 20, 2003.
REFERENCES
3-(5-Hydroxy-1-phenyl-3-pyridin-4-yl-1H-pyrazol-4-yl)-3-
(4-ethoxyphenyl)-1-(4-methoxyphenyl)propan-1-one (14b)
Yield 55%; mp 88-90 °C; IR (KBr) 3335, 1665, 1612
1. Gursoy, A.; Demirayak, S.; Capan, G.; Erol, K.; Vural, K.
Eur. J. Med. Chem. 2000, 35, 359.
2. Ergenc, N.; Capan, G.; Demirdamar, R. Arzneimittel
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1
cm-1; H NMR (CDCl3) d 2.40 (s, 3H, CH3), 3.90 (s, 3H,
OCH3), 6.15 (d, 2H, CHCH2, J = 7.0 Hz), 6.70 (t, 1H, CHCH2,
J = 7.0 Hz), 7.30-7.90 (m, 17H, Ar-H), 9.90 (s, 1H, OH); MS
(EI) m/z (rel. intensity) 488 (2, M+-1), 430 (1), 418 (2), 342
(2), 295 (3), 252 (94), 221 (23), 161 (75), 108 (100), 77 (30).
Anal. Calcd. for C31H27N3O3 (489.57) C, 76.05; H, 5.56; N,
8.58. Found C, 76.01; H, 5.82; N, 8.43%.
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