2366 Ilhan et al.
Asian J. Chem.
5-phenyl-1H-pyrazole-3-carboxylic acid chloride (3a) (0.50
g, 1.16 mmol) and N-ethylurea (0.10 g, 1.16 mmol) were
refluxed in xylene (50 mL) for 4 h. The solvent was evaporated
and the remaining oily residue was treated with dry ether to
give a crude product which was recrystallized from n-propanol
and dried on P2O5. m.p.: 223-224 °C, the product was obtained
in 86 % (0.48 g) yield. FT-IR: 3321, 3247 (NH), 1718 (C=O,
N-[4-Benzoyl-1-(2,4-dinitrophenyl)-5-phenyl-1H-
pyrazole-3-carbonyl]-N'-ethylurea (5f): 4-Benzoyl-1-[2,4-
dinitrophenyl]-5-phenyl-1H-pyrazole-3-carboxylic acid
chloride (3b) (0.50 g, 1.05 mmol) and N-ethylurea (0.09 g,
1.05 mmol) were refluxed in xylene (50 mL) for 4 h. The solvent
was evaporated and the remaining oily residue was treated
with dry ether to give a yellow crude product which was recry-
stallized from ethanol and dried on P2O5. m.p.: 195-196 °C,
the product was obtained in 83 % (0.46 g) yield. FT-IR: 3450-
3350 (NH); 1700 (C=O, urea), 1643, 1610 (C=O). 1H NMR
(400 MHz, CDCl3): δ = 9.10, 8.90 (2H, -NH), 8.80-7.20 (m,
13H, Ar-H), 2.80 (CH2), 1.10 (CH3). 13C NMR (400 MHz,
DMSO-d6): δ = 189.19 (t, PhCO), 154.81 (C=O), 146.55 (C=O,
urea), 145.36, 143.38 (-C-NO2), 34.57 (CH2), 12.96 (CH3).
Anal. calcd. for C26H20N6O7 : C, 59.09; H, 3.78; N, 15.91. Found:
C, 58.90; H, 3.66; N, 16.10.
N-[4-Benzoyl-1-(2,4-dinitrophenyl)-5-phenyl-1H-
pyrazole-3-carbonyl]-N'-phenylurea (5g): 4-Benzoyl-1-
[2,4-dinitrophenyl]-5-phenyl-1H-pyrazole-3-carboxylic acid
chloride (3b) (0.50 g, 1.05 mmol) and N-phenylurea (0.14 g,
1.05 mmol) were refluxed in xylene (50 mL) for 4 h. The
solvent was evaporated and the remaining oily residue was
treated with dry ether to give a white crude product which was
recrystallized from ethanol and dried on P2O5. m.p.: 175-176 °C,
the product was obtained in 68 % (0.41 g) yield. FT-IR: 3328-
3198 (NH); 1680 (C=O, urea), 1670, 1639 (C=O). 1H NMR
(400 MHz, CDCl3): δ = 8.80, 8.60 (2H, -NH), 8.20-7.10 (m,
18H, Ar-H). 13C NMR (400 MHz, DMSO-d6):δ =189.43 (t,
PhCO), 155.82 (C=O), 146.24 (C=O, urea), 137.95, 136.73
(-C-NO2). Anal. calcd. for C30H20N6O7 : C, 62.50; H, 3.47; N,
14.58. Found: C, 62.65; H, 3.60; N, 14.45.
N-[4-Benzoyl-1-(4-nitrophenyl)-5-phenyl-1H-pyrazole-
3-carbonyl]-N',N'-dimethylurea (5h): 4-Benzoyl-1-[4-
nitrophenyl]-5-phenyl-1H-pyrazole-3-carboxylic acid chloride
(3a) (0.50 g, 1.16 mmol) and N,N-dimethylurea (0.10 g, 1.16
mmol) were refluxed in xylene (50 mL) for 4 h. The solvent
was evaporated and the remaining oily residue was treated
with dry ether to give a brown crude product which was recry-
stallized from n-propanol and dried on P2O5. m.p.: 209-210
°C, the product was obtained in 77 % (0.44 g) yield. FT-IR:
3394, (NH), 1705 (C=O, urea), 1664, 1620 (C=O). 1H NMR
(400 MHz, CDCl3): δ = 8.20 (1H, -NH), 7.70-7.02 (m, 14H,
Ar-H), 3.23, 2.98 (2CH3). 13C NMR (400 MHz, DMSO-d6): δ
= 190.32 (t, PhCO), 178.52 (C=O), 178.45 (C=O, urea), 159.94
(-C-NO2), 13.59, 13.44 (2CH3). Anal. calcd. for C26H21N5O5 :
C, 64.59; H, 4.34; N, 14.49. Found: C, 64.45; H, 4.02; N, 14.70.
N-[4-Benzoyl-1-(2,4-dinitrophenyl)-5-phenyl-1H-
pyrazole-3-carbonyl]-N',N'-dimethylurea (5k): 4-Benzoyl-
1-[2,4-dinitrophenyl]-5-phenyl-1H-pyrazole-3-carboxylic acid
chloride (3b) (0.50 g, 1.05 mmol) and N,N-dimethylurea (0.09 g,
1.05 mmol) were refluxed in xylene (50 mL) for 4 h. The
solvent was evaporated and the remaining oily residue was
treated with dry ether to give a brown crude product which
was recrystallized from n-propanol and dried on P2O5. m.p.:
164-165 °C, the product was obtained in 82 % (0.45 g) yield.
FT-IR: 3394 (NH); 1703 (C=O, urea), 1643, 1606 (C=O). 1H
NMR (400 MHz, CDCl3): δ = 8.80 (1H, -NH), 8.60-7.20 (m,
13H, Ar-H), 3.00 (2CH3). Anal. Calcd. for C26H20N6O7 : C,
59.09; H, 3.78; N, 15.91. Found: C, 59.34; H, 3.87; N, 15.69.
1
urea), 1693, 1661 (C=O). H NMR (400 MHz, CDCl3): δ =
8.95, 8.27 (2H, -NH), 8.22-7.06 (m, 14H, Ar-H), 3.30 (CH2),
1.20 (CH3). 13C NMR (400 MHz, DMSO-d6): δ =190.48 (t,
PhCO), 161.49 (C=O), 152.51 (C=O, urea), 147.14 (-C-NO2),
34.51 (CH2), 19.80 (CH3). Anal. Calcd. for C26H21N5O5 : C,
64.59; H, 4.34; N, 14.49. Found: C, 64.87; H, 4.20; N, 14.30.
N-[4-Benzoyl-1-(4-nitrophenyl)-5-phenyl-1H-pyrazole-
3-carbonyl]-N'-phenylurea(5c): 4-Benzoyl-1-[4-nitrophenyl]-
5-phenyl-1H-pyrazole-3-carboxylic acid chloride (3a) (0.50 g,
1.16 mmol) and N-phenylurea (0.16 g, 1.16 mmol) were refluxed
in xylene (50 mL) for 4 h. The solvent was evaporated and the
remaining oily residue was treated with dry ether to give a
yellow crude product which was recrystallized from n-propanol
and dried on P2O5. m.p.: 212-213 °C, the product was obtained
in 66 % (0.40 g) yield. FT-IR: 3337, 3263 (NH), 1693 (C=O,
1
urea), 1680, 1670 (C=O). H NMR (400 MHz, CDCl3): δ =
8.68, 8.45 (2H, -NH), 8.25-6.95 (m, 19H, Ar-H). 13C NMR
(400 MHz, DMSO-d6): δ = 189.45 (t, PhCO), 155.81 (C=O),
146.25 (C=O, urea), 143.43 (-C-NO2). Anal. calcd. for
C30H21N5O5: C, 67.79; H, 3.95; N, 13.18. Found: C, 68.10; H,
3.69; N, 13.04.
N-[4-Benzoyl-1-(4-nitrophenyl)-5-phenyl-1H-pyrazole-
3-carbonyl]-N'-ethylthiourea (5d): 4-Benzoyl-1-[4-nitro-
phenyl]-5-phenyl-1H-pyrazole-3-carboxylic acid chloride (3a)
(0.50 g, 1.16 mmol) and N-ethylthiourea (0.12 g, 1.16 mmol)
were refluxed in xylene (50 mL) for 4 h. The solvent was
evaporated and the remaining oily residue was treated with
dry ether to give a orange crude product which was recrysta-
llized from n-propanol and dried on P2O5. m.p.: 195-196 °C,
the product was obtained in 81 % (0.47 g) yield. FT-IR: 3300,
1
3263 (NH), 1672, 1660 (C=O), 1517, (C=S). H NMR (400
MHz, CDCl3): δ = 9.70, 8.45 (2H, -NH), 8.30-7.02 (m, 14H,
Ar-H), 3.70 (CH2), 1.30 (CH3). 13C NMR (400 MHz, DMSO-
d6): δ = 190.11 (t, PhCO), 162.50 (C=O), 149.00 (C=S),
146.91, (-C-NO2), 35.06 (CH2), 26.08 (CH3). Anal. calcd. for
C26H21N5O4S : C, 62.52; H, 4.20; N, 14.03, S, 6.41. Found: C,
62.66; H, 4.17; N, 13.85; S,.6.17.
N-[4-Benzoyl-1-(2,4-dinitrophenyl)-5-phenyl-1H-
pyrazole-3-carbonyl]-N'-methylurea (5e): 4-Benzoyl-1-
[2,4-dinitrophenyl]-5-phenyl-1H-pyrazole-3-carboxylic acid
chloride (3b) (0.50 g, 1.05 mmol) and N-methylurea (0.08 g,
1.05 mmol) were refluxed in xylene (50 mL) for 5 h. The
solvent was evaporated and the remaining oily residue was
treated with dry ether to give a crude product which was recrys-
tallized from ethanol and dried on P2O5. m.p.: 211-212 °C,
the product was obtained in 56 % (0.6 g) yield. FT-IR: 3450-
3350 (NH); 1705 (C=O, urea), 1680, 1670 (C=O). 1H NMR
(400 MHz, CDCl3): δ = 9.10, 9.20 (2H, -NH), 8.1-7.0 (m,
13H, Ar-H), 2,8 (CH3). 13C NMR (400 MHz, DMSO-d6): δ
=189.19 (t, PhCO), 154.81(C=O), 146.55 (C=O, urea), 145.36,
143.38 (-C-NO2), 12.96 (CH3). Anal. calcd. for C25H18N6O7:
C, 58.36; H, 3.50; N, 16.34. Found: C, 58.25; H, 3.61; N, 16.53.