796
R.A. Rane et al. / European Journal of Medicinal Chemistry 63 (2013) 793e799
obtained from S.D. Fine Pvt. Ltd., SRL, Spectrochem, Aldrich and
some of them were prepared in laboratory and used without
further purification. All melting points (MP) were recorded on
Thermomik Compbell electronics, having oil-heating system and
were uncorrected. Analytical Thin-layer Chromatography (TLC) was
carried out on precoated plates SiO2 (silica gel 60, F 254, Merck).
FTIR spectra were recorded on Perkin Elmer RX I spectrometer
using KBr pellets. All the 1H NMR spectra were recorded on JEOL AL-
300 FT-NMR spectrometer with DMSO-d6 as solvent using tetra-
methyl silane (TMS) as internal reference and 13C (100 MHz)
NMR were recorded on Varian Unity-400 Spectrometer. Mass
spectra were obtained on THERMO FINNINGAN LCQ advantage max
(LCMS).
pyrrole 3H), 6.46e7.58 (m, 3H ArH), 7.63 (d, 1H, eCOCH],
J ¼ 15.0 Hz), 7.86 (d, 2H, ]CHeAr, J ¼ 15.0 Hz); 13C NMR (100 MHz,
DMSO-d6):
d 190.2, 167.8, 162.3, 135.6, 131.2, 130.2, 128.5, 123.3,
118.5, 112.3, 101.3, 100.5, 98.6, 55.6, 55.6, 27.3; Theoretical mass:
425.9340; MS m/z: 426.9420 (Mþ), 427.9422 (M þ 2), 429.9654
(M þ 4).
4.2.5. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(2,5-
dimethoxyphenyl)prop-2-en-1-one (4e)
Yield: 52%; m.p.: 106e108 ꢂC; IR (KBr) Vmax cmꢃ1: 1632 (C]C),
1
1715 (C]O), 3048 (C]CeH aromatic); H NMR (300 MHz, DMSO-
d6):
d 3.53 (s, 3H pyrrole NeCH3), 3.84 (s, 6H OCH3), 6.39 (s, 1H
pyrrole 3H), 6.47e7.42 (m, 3H ArH), 7.66 (d, 1H, eCOCH],
J ¼ 15.6 Hz), 7.72 (d, 2H, ]CHeAr, J ¼ 15.6 Hz); 13C NMR (100 MHz,
4.2. General synthetic procedure for the target compounds (4ae4p)
DMSO-d6): d 190.3, 153.2, 149.6, 135.6, 130.2, 127.6, 121.2, 120.3,
117.9, 116.2, 103.2, 100.6, 98.6, 55.2, 55.2, 27.5; Theoretical mass:
425.9342; MS m/z: 426.9422 (Mþ), 427.9423 (M þ 2), 429.9660
(M þ 4).
In a round bottom flask equipped with sealed mechanical stirrer,
40% sodium hydroxide solution and 5e10 mL methanol were stir-
red in an ice-bath. Then 3a/3b (1 mol) and substituted acetophe-
nones (1 mol) were added to above mixture and stirred for half an
hour. The reaction mixture was then refluxed on water bath till the
yellow precipitate occurred. The reaction mixture was concen-
trated under reduced pressure and to the residue dilute acetic acid
was added slowly till precipitation is complete. The solid precipi-
tated was filtered by vacuum and dried. The obtained solid was
recrystallized using ethanol.
4.2.6. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(2,4-
dichlorophenyl)prop-2-en-1-one (4f)
Yield: 65%; b.p.: 108 ꢂC; IR (KBr) Vmax cmꢃ1: 1625 (C]C), 1719
(C]O), 3052 (C]CeH aromatic); 1H NMR (300 MHz, DMSO-d6):
d
3.63 (s, 3H pyrrole NeCH3), 6.40 (s, 1H pyrrole 3H), 6.72e7.58 (m,
3H ArH), 7.74 (d, 1H, eCOCH], J ¼ 15.3 Hz), 7.82 (d, 2H, ]CHeAr,
J ¼ 15.3 Hz); 13C NMR (100 MHz, DMSO-d6):
d 189.6, 145.2, 135.6,
135.2, 132.5, 131.6, 130.2, 129.6, 127.2, 126.5, 118.5, 100.5, 98.1, 27.9;
Theoretical mass: 433.8355; MS m/z: 434.8435 (Mþ), 435.8436
(M þ 2), 437.8673 (M þ 4).
4.2.1. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(2-hydroxyphenyl)
prop-2-en-1-one (4a)
Yield: 60%; m.p.; 170e172 ꢂC; IR (KBr) Vmax cmꢃ1: 1620 (C]C),
1715 (C]O), 3038 (C]CeH aromatic), 3440 (OH phenol); 1H NMR
4.2.7. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(3-hydroxyphenyl)
prop-2-en-1-one (4g)
(300 MHz, DMSO-d6): d 3.59 (s, 3H pyrrole NeCH3), 5.3 (s,1H phenol
OH), 6.42 (s, 1H pyrrole 3H), 6.7e7.4 (m, 4H ArH), 7.78 (d, 1H, e
Yield: 68%; m.p.: 120e122 ꢂC; IR (KBr) Vmax cmꢃ1: 1620 (C]C),
COCH], J ¼ 15.3 Hz), 7.86 (d, 1H, ]CHeAr, J ¼ 15.3 Hz); 13C NMR
1711 (C]O), 3045 (C]CeH aromatic), 3445 (OH phenol); 1H NMR
(100 MHz, DMSO-d6):
d
192.3, 163.2, 135.6, 135.3, 129.5, 127.5, 121.6,
(300 MHz, DMSO-d6): d 3.55 (s, 3H pyrrole NeCH3), 5.3 (s, 1H
121.1, 117.9, 117.5, 100.2, 98.2, 27.8; Theoretical mass: 381.9072; MS
m/z: 382.9152 (Mþ), 383.9231 (M þ 2), 385.9158 (M þ 4).
phenol OH), 6.37 (s, 1H pyrrole 3H), 6.6e7.42 (m, 4H ArH), 7.72 (d,
1H, eCOCH], J ¼ 15.6 Hz), 7.86 (d, 2H, ]CHeAr, J ¼ 15.6 Hz); 13
C
NMR (100 MHz, DMSO-d6): d 189.5, 165.2, 136.2, 132.5, 131.2, 130.2,
4.2.2. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-phenylprop-2-en-
1-one (4b)
126.5, 123.6, 121.3, 118.6, 117.3, 100.6, 98.6, 27.5; Theoretical mass:
381.9075; MS m/z: 382.9155 (Mþ), 383.9158 (M þ 2), 385.9392
(M þ 4).
Yield: 56%; m.p.: 106e108 ꢂC; IR (KBr) Vmax cmꢃ1: 1622 (C]C),
1714 (C]O), 3049 (C]CeH aromatic); 1H NMR (300 MHz, DMSO-
d6):
d
3.56 (s, 3H pyrrole NeCH3), 6.47 (s, 1H pyrrole 3H), 6.9e7.5
4.2.8. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(2,4-
dihydroxyphenyl)prop-2-en-1-one (4h)
(m, 4H ArH), 7.76 (d, 1H, eCOCH], J ¼ 15.6 Hz), 7.82 (d, 2H, ]CHe
Ar, J ¼ 15.6 Hz); 13C NMR (100 MHz, DMSO-d6):
d
189.5, 137.2, 134.5,
Yield: 50%; m.p.: 118e120 ꢂC; IR (KBr) Vmax cmꢃ1: 1628 (C]C),
133.6, 130.2, 129.6, 128.6, 125.3, 117.5, 100.3, 98.5, 27.9; Theoretical
mass: 365.9130; MS m/z: 366.9210 (Mþ), 367.9289 (M þ 2),
369.9442 (M þ 4).
1712 (C]O), 3048 (C]CeH aromatic), 3442 (OH phenol); 1H NMR
(300 MHz, DMSO-d6):
d 3.65 (s, 3H pyrrole NeCH3), 5.35 (s, 2H
phenol OH), 6.43 (s, 1H pyrrole 3H), 6.6e7.4 (m, 3H ArH), 7.63 (d,
1H, eCOCH], J ¼ 15.0 Hz), 7.76 (d, 2H, ]CHeAr, J ¼ 15.0 Hz); 13C
4.2.3. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(1H-pyrrol-2-yl)
prop-2-en-1-one (4c)
NMR (100 MHz, DMSO-d6): d 189.5, 166.5, 164.3, 135.6, 132.9, 131.2,
127.8, 122.3, 114.3, 111.2, 104.6, 100.3, 98.6, 27.3; Theoretical mass:
397.9040; MS m/z: 398.9120 (Mþ), 399.9122 (M þ 2), 401.9326
(M þ 4).
Yield: 62%; m.p.: 114e116 ꢂC; IR (KBr) Vmax cmꢃ1: 1621 (C]C),
1718 (C]O), 3058 (C]CeH aromatic); 1H NMR (300 MHz, DMSO-
d6):
d 3.62 (s, 3H pyrrole NeCH3), 6.42 (s, 1H pyrrole 3H), 6.9e7.56
(m, 3H pyrrole), 7.78 (d, 1H, eCOCH], J ¼ 15.3 Hz), 7.83 (d, 2H, ]
4.2.9. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(4-hydroxyphenyl)
prop-2-en-1-one (4i)
CHeAr, J ¼ 15.3 Hz), 12.36 (s, 1H pyrrole 1H); 13C NMR (100 MHz,
DMSO-d6):
d
177.2, 136.2, 133.2, 130.5, 129.5, 127.1, 126.5, 121.3,
Yield: 55%; m.p.: 122e124 ꢂC; IR (KBr) Vmax cmꢃ1: 1620 (C]C),
119.6, 111.5, 98.6, 27.5; Theoretical mass: 354.9128; MS m/z:
355.9208 (Mþ), 356.9286 (M þ 2), 358.9442 (M þ 4).
1715 (C]O), 3058 (C]CeH aromatic), 3448 (OH phenol); 1H NMR
(300 MHz, DMSO-d6):
d 3.62 (s, 3H pyrrole NeCH3), 5.36 (s, 1H
phenol OH), 6.46 (s, 1H pyrrole 3H), 6.62e7.53 (m, 4H ArH), 7.64 (d,
4.2.4. 3-(4,5-Dibromo-1-methyl-pyrrol-2-yl)-1-(2,4-
dimethoxyphenyl)prop-2-en-1-one (4d)
1H, eCOCH], J ¼ 15.3 Hz), 7.78 (d, 2H, ]CHeAr, J ¼ 15.3 Hz); 13
C
NMR (100 MHz, DMSO-d6):
d 189.5, 164.6, 135.6, 131.3, 131.3, 130.5,
Yield: 58%; m.p.: 146e148 ꢂC; IR (KBr) Vmax cmꢃ1: 1624 (C]C),
130.2, 127.4, 118.6, 116.5, 116.5, 100.6, 98.6, 27.3; Theoretical mass:
381.9062; MS m/z: 382.9142 (Mþ), 383.9221 (M þ 2), 385.9380
(M þ 4).
1716 (C]O), 3035 (C]CeH aromatic); 1H NMR (300 MHz, DMSO-
d6):
d 3.58 (s, 3H pyrrole NeCH3), 3.86 (s, 6H OCH3), 6.43 (s, 1H