6116
J.S. Biradar, B.S. Sasidhar / European Journal of Medicinal Chemistry 46 (2011) 6112e6118
aqueous ethanol and dried. The product obtained was very low
yields. In some cases reaction did not occur.
indole AreH), 7.26 (d, 1H, J ¼ 7.8, indole AreH), 7.40 (d, 1H, J ¼ 7.8,
indole AreH), 7.57e7.65 (m, 5H, Ph AreH), 7.70 (s, 1H, eCH]); MS:
5.1.4.2.2. B) Neat with NH4OAc. Mixture of 2,5-disubstituted
indole-3-carboxaldehyde (1aec) (1 mmol), active methylene
compound (2/4/6/8) (1 mmol) and NH4OAc (1 mmol) were
powdered, mixed and introduced in an open borosil glass vessel.
This was subjected to microwave irradiation for 5e10 min with 50%
microwave power (Table 1). After completion (TLC) the reaction
mixture was brought to room temperature, washed with aqueous
ethanol and dried. The crude product was recrystallised to get the
title compound which was found to be in good purity (TLC) and
yield (Table 1).
m/z
¼
382 [Mþ1]þ 384 [Mþ3]þ (3:1). Anal. Calcd. for
C19H12ClN3O2S (381): C, 59.76; H, 3.17; N, 11.00%. Found: C, 59.77;
H, 3.25; N, 11.06%.
5.1.4.8. 5-((1H-Indol-3-yl)methylene)-dihydro-2-thioxopyrimidine-
4,6(1H,5H)-dione (5c). Yield 65% (Ethanol): mp 176e178 ꢂC; IR
(KBr) (nmax in cmꢀ1): 3411, 2926, 2852, 1719, 1207; 1H NMR (DMSO-
d6 þ CDCl3) in
d ppm: 11.17 (s, 1H, indole NH), 09.99(s, 1H,
pyrimidine NH), 09.90(s, 1H, pyrimidine NH), 7.20 (d, 1H, J ¼ 7.7,
indole AreH), 7.35 (d, 1H, J ¼ 7.7, indole AreH), 7.52e7.70 (m, 2H,
indole AreH), 7.80 (s, 1H, indole AreH), 7.90 (s, 1H, eCH]); MS: m/
z ¼ 272 [Mþ1]þ. Anal. Calcd. for C13H9N3O2S (271): C, 57.55; H, 3.34;
N, 15.49%. Found: C, 57.48; H, 3.37; N, 15.65%.
5.1.4.3. 5-((5-Methyl-2-phenyl-1H-indol-3-yl)methylene)pyrimi-
dine-2,4,6(1H,3H,5H)-trione (3a). Yield 67% (Ethanol); mp
216e218 ꢂC; IR (KBr) (nmax in cmꢀ1) : 3444, 3140, 3052, 1689, 1575;
1H NMR (DMSO-d6 þ CDCl3)
d
(ppm): 11.05 (s, 1H, indole NH),10.08
5.1.4.9. (Z)-5-((5-Methyl-2-phenyl-1H-indol-3-yl)methylene)thiazo-
(s, 1H, pyrimidine NH), 10.06 (s, 1H, pyrimidine NH), 7.10 (s, 1H,
indole AreH), 7.25 (d, 1H, J ¼ 7.8, indole AreH), 7.35 (d, 1H, J ¼ 7.8,
indole AreH), 7.50e7.65 (m, 5H, Ph AreH), 7.80 (s, 1H, eCH]), 2.57
lidine-2,4-dione (7a). Yield 70% (Ethanol): mp 184e186 ꢂC; IR (KBr)
(
nmax in cmꢀ1): 3450, 3134, 3065, 1627, 1574; 1H NMR (DMSO-
d6 þ CDCl3) in
d ppm: 11.40 (s, 1H, indole NH), 09.84 (s, 1H, thia-
(s, 3H, CH3); 13C NMR(DMSO-d6 þ CDCl3)
d
(ppm): 164.1(C]O),
zolidinedione NH), 7.00 (s, 1H, indole AreH), 7.15 (d, 1H, J ¼ 7.6,
indole AreH), 7.27 (d, 1H, J ¼ 7.6, indole AreH), 7.40e7.55 (m, 5H,
Ph AreH), 7.70 (s, 1H, eCH]), 2.60 (s, 3H, CH3); 13C NMR(DMSO-
154.5(C]O) and 148.9, 136.9, 134.8, 132.1, 129.7, 128.8, 126.6, 123.2,
121.7, 116.5, 114.1, 105 and 32; MS: m/z ¼ 346 [Mþ1]þ. Anal. Calcd.
for C20H15N3O3 (345): C, 69.56; H, 4.38; N, 12.17%. Found: C, 69.58;
H, 4.26; N, 12.20%.
d6 þ CDCl3) in
d ppm: 165.6 (C]O), 159.7 (C]O) and 139.9, 136.6,
135.5, 133.3, 132.8, 131.5, 129.6, 126.7, 121.3, 118.7, 116.7, 105.0 and
26; MS: m/z ¼ 335 [Mþ1]þ. Anal. Calcd. for C19H14N2O2S (334): C,
68.24; H, 4.22; N, 08.38%. Found: C, 68.30; H, 4.30; N, 8.40%.
5.1.4.4. 5e((5-Chloro-2-phenyl-1H-indol-3-yl)methylene)pyrimi-
dine-2,4,6(1H,3H,5H)-trione (3b). Yield 61% (Ethanol): mp
230e232 ꢂC; IR (KBr) (nmax in cmꢀ1): 3431, 3156, 2916, 1685, 1584;
5.1.4.10. (Z)-5-((5-Chloro-2-phenyl-1H-indol-3-yl)methylene)thiazo-
lidine-2,4-dione (7b). Yield 68% (Ethanol); mp 195e197 ꢂC; IR
(KBr)(nmax in cmꢀ1): 3334, 3127, 2917, 1632, 1583; 1H NMR (DMSO-
1H NMR (DMSO-d6 þ CDCl3)
d (ppm): 11.38 (s, 1H, indole NH), 10.35
(s, IH, pyrimidine NH), 10.28 (s, IH, pyrimidine NH), 6.90 (s, 1H,
indole AreH), 7.12 (d, 1H, J ¼ 7.8, indole AreH), 7.37 (d, 1H, J ¼ 7.8,
indole AreH), 7.55e7.76 (m, 5H, Ph AreH), 7.90 (s, 1H, eCH]); MS:
m/z ¼ 366 [Mþ1]þ, 368 [Mþ3]þ (3:1); Anal. Calcd. for C19H12ClN3O3
(365): C, 62.39; H, 3.31; N, 09.69%. Found: C, 62.42; H, 3.37; N,
09.55%.
d6 þ CDCl3) in
d ppm: 11.51 (s, 1H, indole NH), 09.91 (s, 1H, thia-
zolidinedione NH), 7.20 (s, 1H, indole AreH), 7.27 (d, 1H, J ¼ 7.6,
indole AreH), 7.41 (d, 1H, J ¼ 7.6, indole AreH), 7.55e7.67 (m, 5H,
Ph AreH), 7.86 (s, 1H, eCH]); MS: m/z ¼ 355 [Mþ1]þ, 357 [Mþ3]þ
(3:1), Anal. Calcd. for C18H11ClN2O2S (354): C, 60.93; H, 3.12; N,
7.90%. Found: C, 60.98; H, 3.24; N, 7.87%.
5.1.4.5. 5-((1H-Indol-3-yl)methylene)pyrimidine-2,4,6(1H,3H,5H)-
trione (3c). Yield 62% (Ethanol): mp 192e194 ꢂC; IR (KBr) (nmax in
cmꢀ1): 3429, 2918, 2849, 1677, 1626; 1H NMR (DMSO-d6 þ CDCl3)
5.1.4.11. (Z)-5-((1H-Indol-3-yl)methylene)thiazolidine-2,4-dione
(7c). Yield 70% (Ethanol); mp 218e220 ꢂC; IR (KBr) (nmax in cmꢀ1):
(d
ppm): 11.30 (s, 1H, indole NH), 09.80 (s, 1H. pyrimidine NH),
3338, 3027, 2916,1637,1567; 1H NMR (DMSO-d6 þ CDCl3) in
d ppm:
09.70 (s, 1H, pyrimidine NH), 7.12 (d, 1H, J ¼ 7.7, indole AreH), 7.33
(d,1H, J ¼ 7.7, indole AreH), 7.50e7.70 (m, 2H, indole AreH), 7.82 (s,
1H, indole AreH), 8.00 (s, 1H, eCH]); MS: m/z ¼ 256 [Mþ1]þ. Anal.
Calcd. for C13H9N3O3 (255): C, 61.18; H, 3.55; N, 16.46%. Found: C,
61.25; H, 3.52; N, 16.67%.
10.71 (s, IH, indole NH), 09.50 (s, 1H, thiazolidinedione NH), 6.50 (d,
1H, J ¼ 7.5, indole AreH), 6.64 (d, 1H, J ¼ 7.5, indole AreH),
6.77e6.95 (m, 2H, indole AreH), 7.12 (s, 1H, indole AreH), 7.40 (s,
1H, eCH]); MS: m/z ¼ 245 [Mþ1]þ. Anal. Calcd. for C12H8N2O2S
(245): C, 59.00; H, 3.30; N, 11.47%. Found: 59.12; H, 3.28; N, 11.56%.
5.1.4.6. 5-((5-Methyl-2-phenyl-1H-indol-3-yl)methylene)-dihydro-
2-thioxopyrimidine-4,6(1H,5H)-dione (5a). Yield 65% (Ethanol): mp
232e234 ꢂC; IR (KBr) nmax in cmꢀ1 : 3433, 3034, 2917, 1684, 1205;
5.1.4.12. (4E)-3-Methyl-4-((5-methyl-2-phenyl-1H-indol-3-yl)meth-
ylene)-1H-pyrazol-5(4H)-one (9a). Yield 75% (Ethanol): mp
235e237 ꢂC; IR (KBr) (nmax in cmꢀ1): 3195, 3050, 2950, 1675, 1600;
1H NMR (DMSO-d6 þ CDCl3) in
d
ppm: 9.91 (s, 1H, indole NH), 9.10
1H NMR (DMSO-d6 þ CDCl3) in
d ppm: 11.50 (s, 1H, indole NH),
(s, 1H, pyrimidine NH), 9.20 (s, 1H, pyrimidine NH), 7.20 (s, 1H,
indole AreH), 7.32 (d, 1H, J ¼ 7.8, indole AreH), 7.50 (d, 1H, J ¼ 7.8,
indole AreH), 7.65e7.82 (m, 5H, Ph AreH), 7.96 (s, 1H, eCH]), 2.55
09.90 (s, 1H, pyrazolone NH), 7.00 (s, 1H, indole AreH), 7.25 (d, 1H,
J ¼ 7.6, indole AreH), 7.45 (d, 1H, J ¼ 7.6, indole AreH), 7.64e8.00
(m, 5H, Ph AreH), 8.20 (s, 1H, eCH]), 2.00 (s, 3H, CH3), 2.40 (s, 3H,
(s, 3H, CH3); 13C NMR(DMSO-d6 þ CDCl3) in
d
ppm: 168.7 (C]S),
CH3); 13C NMR(DMSO-d6 þ CDCl3) in
d ppm: 163.7 (C]O) and
157.0 (C]O) and 152.0, 140.7, 137.3, 136.4, 134.0, 133.1, 132.8, 130.7,
127.8, 121.1, 119.0, 116.4, 106.6 and 29.0; MS: m/z ¼ 362 [Mþ1]þ.
Anal. Calcd. for C20H15N3O2S (361): C, 66.46; H, 4.18; N, 11.63%.
Found C, 66.52; H, 4.22; N, 11.71%.
145.3, 141.5, 133.9, 131.2, 130.3, 129.6, 128.3, 127.6, 126.7, 125.7,
124.5, 123.2, 115.7, 114.2, 104.7, 23.4 and 20.0; MS: m/z ¼ 316
[Mþ1]þ. Anal. Calcd. for C20H17N3O (315): C, 76.17; H, 5.43; N,
13.32%. Found: C, 76.10; H, 5.40; N, 13.40%.
5.1.4.7. 5-((5-Chloro-2-phenyl-1H-indol-3-yl)methylene)-dihydro-2-
thioxopyrimidine-4,6(1H,5H)-dione (5b). Yield 65% (Ethanol): mp
215e216 ꢂC; IR (KBr) (nmax in cmꢀ1): 3132, 3085, 2978, 1700, 1214;
5.1.4.13. (4E)-4-((5-Chloro-2-phenyl-1H-indol-3-yl)methylene)-3-
methyl-1H-pyrazol-5(4H)-one (9b). Yield 66% (Ethanol); mp
270e272 ꢂC; IR (KBr)(nmax in cmꢀ1): 3200, 3150, 2900,1657,1587; 1H
1H NMR (DMSO-d6 þ CDCl3) in
d
ppm: 10.80 (s,1H, indole NH), 9.50
NMR (DMSO-d6 þ CDCl3) in
d ppm: 11.70 (s,1H, indole NH), 09.70 (s,
(s, 1H, pyrimidine NH), 9.55 (s, 1H, pyrimidine NH),7.20 (s, 1H,
1H, pyrazolone NH), 7.00 (s, 1H, indole AreH), 7.22 (d, 1H, J ¼ 7.6,