694 JOURNAL OF CHEMICAL RESEARCH 2012
Table 3 Some characteristic data of the compounds 2a–g
Product
M.p./°C
Yield/%
2a
2b
2c
2d
2e
2f
R1=CH3, R2=H, R3=CH3
R1= Cl, R2=H, R3= CH3
R1=COOH, R2=H, R3=CH3
R1=COOCH3, R2=H, R3=CH3
R1=CH3, R2=H, R3=Ph
R1=Cl, R2=H, R3=Ph
134–135 (lit.21134–134.5)
172–174 (lit.21 172–173)
283–285 (lit.21 285)
65
60
67
66
75
70
60
127–128 (lit.21127–127.5)
141–142 (lit.21142–144)
161–163 (lit.21162.5–164)
180–181(lit.22 144–145, lit.23 201–202)
2g
R1=R2=NO2, R3=CH3
1
4-[(1-Benzyl-1H-indol-3-yl)methylene]-1-(2,4-dinitrophenyl)-3-
methyl-1H-pyrazol-5(4H)-one (6): Yield: 80%; m.p. 206–208 °C; νmax
(KBr, cm−1): 1691 (CO), 1523 (NO2), 1333 (NO2); 1H NMR (DMSO-
d6): δ 2.46 (s, 3H, CH3), 5.71 (s, 2H, CH2), 7.28–7.40 (m, 7H, ArH),
7.69–7.71 (m, 1H, ArH), 8.11 (s, 1H, =CH), 8.25 (m, 2H, ArH), 8.60
(dd, 1H, J = 2.4 Hz, J = 8.4 Hz, ArH), 8.76 (d, 1H, J = 2.4 Hz, ArH),
9.72 (s, 1H, indole-CH). ESI-HRMS: Calcd for C26H19N5O5 (MH+):
482.1464; found: 482.1467.
1-(2,4-Dinitrophenly)-3-methyl-4-[(1-methyl-1H-indol-3-yl)meth-
ylene]-1H-pyrazol-5(4H)-one (7): Yield: 82%; m.p. 258–260 °C; νmax
(KBr, cm−1): 1688 (CO), 1534 (NO2), 1329 (NO2); 1H NMR (DMSO-
d6): δ 2.45 (s, 3H, CH3), 4.02 (s, 3H, CH3), 7.41 (m, 2H, ArH), 7.70
(m, 1H, ArH), 8.11 (s, 1H, =CH), 8.23 (brs, 2H, ArH), 8.60 (dd, 1H,
J = 2.4 Hz, J = 8.4 Hz, ArH), 8.75 (d, 1H, J = 2.4 Hz, ArH), 9.57 (s,
1H, =CH). ESI-HRM: Calcd for C20H15N5O5 (MH+): 406.1151; found:
406.1147.
(KBr, cm−1): 1675 (CO); H NMR (DMSO-d6): δ 5.75 (s, 2H, CH2),
7.30–7.39 (m, 9H, ArH), 7.54 (m, 1H, ArH), 7.6–7.66 (m, 3H, ArH),
7.71 (m, 1H, ArH), 7.80 (m, 3H, ArH), 8.12 (s, 1H, =CH), 8.14 (d, 2H,
J = 8.4 Hz, ArH), 10.02 (s, 1H, indolyl-2-CH). ESI-HRMS: Calcd for
C31H22ClN3O (MH+): 488.1530; found: 488.1518 (100%), 490.1498
(35%).
4-[(1H-Indol-3-yl)methylene]-1-(2,4-dinitrophenyl)-3-methyl-1H-
pyrazole-5-one (14): Yield: 86%; m.p. 158–162 °C; νmax (KBr, cm−1):
3357 (NH), 1694 (CO), 1527 (NO2), 1330 (NO2); 1H NMR (DMSO-
d6): δ 2.47 (s, 3H, CH3), 7.35 (m, 2H, ArH), 7.62 (m, 1H, ArH), 8.09
(d, 1H, J = 8.4 Hz, =CH), 8.21 (m, 1H, ArH), 8.27 (s, 1H, ArH), 8.61
(d, 1H, J = 8.4 Hz, ArH), 8.76 (s, 1H, ArH), 9.63 (s, 1H, indolyl-2-
CH), 12.80 (s, 1H, NH). ESI-HRMS: Calcd for C19H13N5O5 (MH+):
392.0995; found: 392.0998.
Methyl 4-{3-methyl-4-[(1-methyl-1H-indol-3-yl)methylene]-5-oxo-
4,5-dihydro-1H-pyrazole-1-yl} benzoate (15): Yield: 80%; m.p. 190–
1
4-[(1H-Indol-3-yl)methylene]-3-methy-1-p-tolyl-1H-pyrazol-5-one
192 °C; νmax (KBr, cm−1): 1712 (ester CO), 1679 (CO); H NMR
(8): Yield: 78%; m.p. 204–206 °C; νmax (KBr, cm−1): 3267 (NH), 1651
(DMSO-d6): δ 2.45 (s, 3H, CH3), 3.86 (s, 3H, OCH3), 4.05 (s, 3H,
CH3), 7.38–7.44 (m, 2H, ArH), 7.69 (d, 1H, J = 7.6 Hz, ArH), 8.04 (d,
2H, J = 8.4 Hz, ArH), 8.15 (s, 1H, =CH), 8.22 (d, 3H, J = 8.4 Hz,
ArH), 9.79 (s, 1H, indolyl-2-CH). ESI-HRMS: Calcd for C22H19N3O3
(MH+): 374.1505; found: 374.1511.
Methyl 4-{4-[[1-(2-tert-butoxy-2-oxoethyl)-1H-indol-3-yl]meth-
ylene]-3-methyl-5-oxo-4,5-dihydro-1H- pyrazol-1-yl}benzoate (16):
Yield: 76%; m.p. 220–222 °C; νmax (KBr, cm−1): 1741 (ester CO), 1708
1
(CO); H NMR (DMSO-d6): δ 2.32 (s, 3H, CH3), 2.41 (s, 3H, CH3),
7.23 (d, 2H, J = 8.4 Hz, ArH), 7.31–7.33 (m, 2H, ArH), 7.59 (m, 1H,
ArH), 7.72 (d, 1H, J = 7.2 Hz, ArH), 7.88 (d, 2H, J = 8.4 Hz, ArH),
8.11 (s, 1H, =CH), 8.16–8.19 (m, 1H, ArH), 9.82 (s, 1H, indolyl-2-
CH), 12.71 (s, 1H, NH). ESI-HRMS: Calcd for C20H17N3O (M+Na+):
338.1269; found: 338.1261.
3-Methyl-4-[(1-methyl-1H-indol-3-yl)methylene]-1-p-tolyl-1H-
pyrazol-5-one (9): Yield: 77%; m.p. 176–178 °C; νmax (KBr, cm−1):
(ester CO), 1682 (CO); H NMR (DMSO-d6): δ 1.45 (s, 9H, 3CH3),
1
1
1668 (CO); H NMR (DMSO-d6): δ 2.32 (s, 3H, CH3), 2.41 (s, 3H,
2.46 (s, 3H, CH3), 3.86 (s, 3H, OCH3), 5.39 (s, 2H, CH3), 7.37–7.40
(m, 2H, ArH), 7.60 (m, 1H, ArH), 8.05 (d, 2H, J = 8.4 Hz, ArH), 8.17
(s, 1H, =CH), 8.24 (m, 3H, ArH), 9.78 (s, 1H, indolyl-2-CH). ESI-
HRMS: Calcd for C27H27N3O5 (MH+): 474.2029; found: 474.2036.
Methyl 4-{4-[(1-benzl-1H-indol-3-yl)methylene]-3-methyl-5-oxo-
4,5-dihydro-1H-pyrazol-1-yl}benzoate (17): Yield: 79%; m.p. 236–
CH3), 4.02 (s, 3H, CH3), 7.23 (d, 2H, J = 8.0 Hz, ArH), 7.37–7.40 (m,
2H, ArH), 7.67 (d, 1H, J = 7.2 Hz, ArH), 7.89 (d, 2H, J = 8.4 Hz,
ArH), 8.08 (s, 1H, =CH), 8.20 (d, 1H, J = 8.4 Hz, ArH), 9.80 (s, 1H,
indolyl=CH). ESI-HRMS: Calcd for C21H19N3O (MH+): 330.1606;
found: 330.1610.
(4Z)-4-[(1-Methyl-1H-indol-3-yl)methylene]-3-phenyl-1-p-tolyl-
1H-pyrazol-5-one (10): Yield: 78%; m.p. 206–208 °C; νmax (KBr,
cm−1): 1674 (CO); 1H NMR (DMSO-d6): δ 2.34 (s, 3H, CH3), 4.06 (s,
3H, CH3), 7.28 (d, 2H, J = 8.4 Hz, ArH), 7.33–7.42 (m, 2H, ArH),
7.59–7.65 (m, 3H, ArH), 7.69 (d, 1H, J= 7.6 Hz, ArH), 7.79 (m, 3H,
ArH), 7.97 (d, 2H, J = 8.4 Hz, ArH), 8.10 (s, 1H, =CH), 9.88 (s, 1H,
indolyl=CH). ESI-HRMS: Calcd for C26H21N3O (MH+): 392.1763;
found: 392.1776.
238 °C; νmax (KBr, cm−1): 1708 (ester CO), 1678 (CO); H NMR
1
(DMSO-d6): δ 2.45 (s, 3H, CH3), 3.85 (s, 3H, OCH3), 5.73 (s, 2H,
CH2), 7.30–7.38 (m, 7H, ArH), 7.69 (m, 1H, ArH), 8.04 (d, 2H, J =
8.4 Hz, ArH), 8.17 (s, 1H, =CH), 8.25 (m, 3H, ArH), 9.93 (s, 1H,
indolyl-2-CH). ESI-HRMS: Calcd for C28H23N3O3 (MH+): 450.1818;
found: 450.1808.
4-{4-[(1H-Indol-3-yl)methylene]-3-methyl-5-oxo-4,5-dihydro-1H-
pyrazol-1-yl}benzoic acid (18): Yield: 80%; m.p. >300 °C; νmax (KBr,
cm−1): 3195 (NH, COOH), 1691 (CO),; 1H NMR (DMSO-d6): δ 2.45
(s, 3H, CH3), 7.32–7.35 (m, 2H, ArH), 7.60–7.62 (m, 1H, ArH), 8.01
(d, 2H, J = 8.4 Hz, ArH), 8.18 (m, 4H, ArH, =CH), 9.81 (s, 1H,
indolyl-2-CH), 12.75 (s, 1H, NH), 12.81 (s, 1H, COOH). ESI-HRMS:
Calcd for C20H15N3O3 (MH+): 346.1192; found: 346.1194.
4-[(1-Benzyl-1H-indol-3-yl)methylene]-3-phenyl-1-p-tolyl-1H-
pyrazol-5-one (11): Yield: 80%; m.p. 210–212 °C; νmax (KBr, cm−1):
1
1673 (CO); H NMR (DMSO-d6): δ 2.34 (s, 3H, CH3), 5.74 (s, 2H,
CH2), 7.28–7.39 (m, 9H, ArH), 7.59–7.65 (m, 3H, ArH), 7.69–7.71
(m, 1H, ArH), 7.78–7.82 (m, 3H, ArH), 7.95 (d, 2H, J = 8.4 Hz, ArH),
8.12 (s, 1H, =CH), 10.03 (s, 1H, indolyl-2-CH). ESI-HRMS: Calcd
for C32H25N3O (MH+): 468.2076; found: 468.2076.
4-[(1H-Indol-3-yl)methylene]-3-phenyl-1-p-tolyl-1H-pyrazol-5-
one (12): Yield: 80%; m.p. 174–176 °C; νmax (KBr, cm−1): 3257 (NH),
1658 (CO); 1H NMR (DMSO-d6): δ 2.34 (s, 3H, CH3), 7.28–7.34 (m,
4H, ArH), 7.57–7.65 (m, 4H, ArH), 7.74–7.81 (m, 3H, ArH), 7.96 (d,
2H, J =8.4 Hz, ArH), 8.13 (s, 1H, =CH), 9.90 (s, 1H, indolyl-2-CH),
12.78 (s, 1H, NH). ESI-HRMS: Calcd for C25H19N3O (MH+): 378.1606;
found: 378.1603.
4-{3-Methyl-4-[(1-methyl-1H-indol-3-yl)methylene]-5-oxo-4,5-
dihydro-1H-pyrazol-1-yl}benzoic acid (19): Yield: 82%; m.p. >300 °C;
νmax (KBr, cm−1): 3409 (COOH), 1685 (CO); H NMR (DMSO-d6):
1
δ 2.44 (s, 3H, CH3), 4.04 (s, 3H, CH3), 7.37–3.43 (m, 2H, ArH), 7.68
(m, 1H, ArH), 8.01–8.05 (m, 3H, ArH), 8.13 (s, 1H, =CH), 8.22 (m,
2H, ArH), 9.78 (s, 1H, indolyl-2-CH), 12.88 (s, 1H, COOH). ESI-
HRMS: Calcd for C21H17N3O3 (MH+): 360.1348; found: 360.1339.
4-{4-[(1-Acetyl-1H-indol-3-yl)methylene]-3-methyl-5-oxo-4,5-
dihydro-1H-pyrazolyl}benzoic acid (20): Yield: 79%; m.p. >300 °C;
1H NMR (DMSO-d6): δ 2.41 (s, 3H, CH3), 3.86 (s, 3H, CH3), 7.34
(dd, 2H, J = 2.4 Hz, J = 7.2 Hz, ArH), 7.60 (m, 1H, CH), 7.93 (d, 2H,
4-[(1-Benzyl-1H-indol-3-yl)methylene]-1-(4-chlorophenyl)-3-
phenyl-1H-pyrazole-5-one (13): Yield: 78%; m.p. 248–250 °C; νmax