December 2011
1515
Ar–CH3), 5.04 (s, 2H, SO2–CH2), 5.23 (s, 2H, CH2–SO2–NH), 5.54 (br s,
2H, NH2), 6.58 (s, 1H, C5ꢀ–H), 7.11—7.72 (m, 9H, C2ꢀ–H, Ar–H), 8.36 (br s,
1H, NH), 10.22 (br s, 1H, NH–SO2). 13C-NMR (DMSO-d6) d: 21.6 and 21.9
(Ar–CH3), 46.8 (SO2–CH2), 51.4 (CH2–SO2–NH), 102.0 (C-4ꢀ), 116.1 (C-
3ꢀ), 117.8 (C-5ꢀ), 121.5 (C-2ꢀ), 157.9 (C-5), 158.8 (C-3), 126.1, 127.5,
6.64 (s, 1H, C5ꢀ-H), 7.21—7.84 (m, 11H, C2ꢀ-H, Ar–H), 8.75 (br s, 1H, NH),
10.47 (br s, 1H, NH–SO2). 13C-NMR (CDCl3) d: 46.6 (SO2–CH2), 52.0
(CH2–SO2–NH), 104.3 (C-4ꢀ), 110.5 (C-3ꢀ), 117.8 (C-5ꢀ), 121.8 (C-2ꢀ),
155.6 (C-5), 156.3 (C-2), 124.8, 126.2, 127.6, 128.5, 129.1, 130.4, 132.6,
138.2 (aromatic carbons). IR (KBr) cmꢁ1: 3254 (NH), 1629 (CꢄC), 1584
(CꢄN), 1331, 1132 (SO2). Anal. Calcd for C20H18N4O5S2: C, 52.39; H, 3.96;
N, 12.22. Found: C, 52.43; H, 3.95; N, 12.29.
2-(p-Methylphenylaminosulfonylmethyl)-5-(4ꢀ-p-methylphenyl-1ꢀH-
pyrrol-3ꢀ-ylsulfonyl-methyl)-1,3,4-oxadiazole (6b): Yellow solid, yield 66%,
mp 140—142 °C; 1H-NMR (CDCl3) d: 2.22 and 2.28 (s, 6H, Ar–CH3), 4.99
(s, 2H, SO2–CH2), 5.24 (s, 2H, CH2–SO2–NH), 6.56 (s, 1H, C5ꢀ-H), 7.18—
7.88 (m, 9H, C2ꢀ–H, Ar–H), 8.69 (br s, 1H, NH), 10.40 (br s, 1H, NH–SO2).
13C-NMR (CDCl3) d: 21.3 and 21.8 (Ar–CH3), 46.1 (SO2–CH2), 51.4
(CH2–SO2–NH), 103.8 (C-4ꢀ), 109.7 (C-3ꢀ), 116.9 (C-5ꢀ), 121.0 (C-2ꢀ),
155.0 (C-5), 155.9 (C-2), 125.7, 126.5, 127.2, 128.6, 129.3, 130.1, 131.0,
138.8 (aromatic carbons). IR (KBr) cmꢁ1: 3251 (NH), 1625 (CꢄC), 1581
(CꢄN), 1324, 1129 (SO2). Anal. Calcd for C22H22N4O5S2: C, 54.31; H, 4.56;
N, 11.51. Found: C, 54.28; H, 4.57; N, 11.56.
128.4, 129.9, 130.2, 131.4, 132.6, 136.5 (aromatic carbons). IR (KBr) cmꢁ1
:
3428, 3309 (NH2), 3259 (NH), 1626 (CꢄC), 1589 (CꢄN), 1321, 1131
(SO2). Anal. Calcd for C22H24N6O4S2: C, 52.78; H, 4.83; N, 16.79. Found: C,
52.83; H, 4.87; N, 16.87.
4-Amino-3-(p-chlorophenylaminosulfonylmethyl)-5-(4ꢀ-p-chlorophenyl-
1ꢀH-pyrrol-3ꢀ-ylsulfonylmethyl)-1,2,4-triazole (8c): Yellow solid, yield 72%,
1
mp 194—196 °C; H-NMR (DMSO-d6) d: 5.17 (s, 2H, SO2–CH2), 5.36 (s,
2H, CH2–SO2–NH), 5.67 (br s, 2H, NH2), 6.74 (s, 1H, C5ꢀ–H), 7.16—7.81
(m, 9H, C2ꢀ–H, Ar–H), 8.51 (br s, 1H, NH), 10.35 (br s, 1H, NH–SO2). 13C-
NMR (DMSO-d6) d: 47.6 (SO2–CH2), 52.3 (CH2–SO2–NH), 103.3 (C-4ꢀ),
110.8 (C-3ꢀ), 117.0 (C-5ꢀ), 122.4 (C-2ꢀ), 158.0 (C-5), 159.1 (C-3), 126.8,
127.4, 128.6, 129.5, 130.4, 131.2, 132.0, 137.2 (aromatic carbons). IR (KBr)
cmꢁ1: 3445, 3326 (NH2), 3271 (NH), 1629 (CꢄC), 1602 (CꢄN), 1330,
1138 (SO2). Anal. Calcd for C20H18Cl2N6O4S2: C, 44.37; H, 3.35; N, 15.52.
Found: C, 44.34; H, 3.34; N, 15.48.
2-(p-Chlorophenylaminosulfonylmethyl)-5-(4ꢀ-p-chlorophenyl-1ꢀH-
pyrrol-3ꢀ-ylsulfonyl-methyl)-1,3,4-oxadiazole (6c): Yellow solid, yield 73%,
1
General Procedure of Synthesis of 2-(Arylaminosulfonylmethyl)-5-(4ꢀ-
aryl-4ꢀ,5ꢀ-dihydro-1ꢀH-pyrazol-3ꢀ-ylsulfonylmethyl)-1,3,4-oxadiazole
(9a—c)/2-(Arylaminosulfonyl-methyl)-5-(4ꢀ-aryl-4ꢀ,5ꢀ-dihydro-1ꢀH-
pyrazol-3ꢀ-ylsulfonylmethyl)-1,3,4-thiadiazole (10a—c)/4-Amino-3-(aryl-
aminosulfonylmethyl)-5-(4ꢀ-aryl-4ꢀ,5ꢀ-dihydro-1ꢀH-pyrazol-3ꢀ-ylsul-
fonyl-methyl)-1,2,4-triazole (11a—c) To a cooled solution of compound
3/4/5 (5 mmol) in dichloromethane (20 ml), an ice-cold ethereal solution of
diazomethane (40 ml, 0.4 m) and triethylamine (0.12 g) were added. The re-
action mixture was kept at ꢁ20 to ꢁ15 °C for 48 h. The solvent was re-
moved under vacuum and the resultant solid was recrystallized from 2-
propanol.
mp 148—150 °C; H-NMR (CDCl3) d: 5.11 (s, 2H, SO2–CH2), 5.38 (s, 2H,
CH2–SO2–NH), 6.70 (s, 1H, C5ꢀ–H), 7.25—7.74 (m, 9H, C2ꢀ–H, Ar–H), 8.71
(br s, 1H, NH), 10.49 (br s, 1H, NH–SO2). 13C-NMR (CDCl3) d: 46.9
(SO2–CH2), 52.1 (CH2–SO2–NH), 104.8 (C-4ꢀ), 110.9 (C-3ꢀ), 118.3 (C-5ꢀ),
122.1 (C-2ꢀ), 154.9 (C-5), 155.6 (C-2), 126.7, 127.4, 128.8, 130.2, 131.5,
132.4, 134.6, 139.5 (aromatic carbons). IR (KBr) cmꢁ1: 3263 (NH), 1630
(CꢄC), 1587 (CꢄN), 1335, 1137 (SO2). Anal. Calcd for C20H16Cl2N4O5S2:
C, 45.55; H, 3.06; N, 10.62. Found: C, 45.60; H, 3.09; N, 10.67.
2-(Phenylaminosulfonylmethyl)-5-(4ꢀ-phenyl-1ꢀH-pyrrol-3ꢀ-ylsulfonyl-
methyl)-1,3,4-thiadiazole (7a): Yellow solid, yield 70%, mp 156—158 °C;
1H-NMR (CDCl3) d: 5.03 (s, 2H, SO2–CH2), 5.19 (s, 2H, CH2–SO2–NH),
6.68 (s, 1H, C5ꢀ–H), 7.09—7.70 (m, 11H, C2ꢀ–H, Ar–H), 8.35 (br s, 1H, NH),
10.10 (br s, 1H, NH–SO2). 13C-NMR (CDCl3) d: 46.5 (SO2–CH2), 51.0
(CH2–SO2–NH), 102.9 (C-4ꢀ), 109.6 (C-3ꢀ), 117.5 (C-5ꢀ), 121.7 (C-2ꢀ),
158.2 (C-5), 159.6 (C-2), 125.4, 126.1, 127.4, 128.9, 129.5, 130.0, 131.2,
137.9 (aromatic carbons). IR (KBr) cmꢁ1: 3238 (NH), 1624 (CꢄC), 1592
(CꢄN), 1321, 1140 (SO2). Anal. Calcd for C20H18N4O4S3: C, 50.62; H, 3.82;
N, 11.81. Found: C, 50.60; H, 3.81; N, 11.88.
2-(p-Methylphenylaminosulfonylmethyl)-5-(4ꢀ-p-methylphenyl-1ꢀH-
pyrrol-3ꢀ-ylsulfonyl-methyl)-1,3,4-thiadiazole (7b): Pale yellow solid, yield
66%, mp 160—162 °C; 1H-NMR (CDCl3) d: 2.20 and 2.25 (s, 6H, Ar–CH3),
5.01 (s, 2H, SO2–CH2), 5.14 (s, 2H, CH2–SO2–NH), 6.62 (s, 1H, C5ꢀ–H),
7.04—7.65 (m, 9H, C2ꢀ–H, Ar–H), 8.27 (br s, 1H, NH), 10.03 (br s, 1H,
NH–SO2). 13C-NMR (CDCl3) d: 21.5 and 21.9 (Ar–CH3), 45.9 (SO2–CH2),
50.6 (CH2–SO2–NH), 102.3 (C-4ꢀ), 109.0 (C-3ꢀ), 117.0 (C-5ꢀ), 121.2 (C-2ꢀ),
157.9 (C-5), 159.3 (C-2), 125.8, 126.9, 127.5, 128.7, 129.5, 130.2, 132.0,
137.6 (aromatic carbons). IR (KBr) cmꢁ1: 3235 (NH), 1619 (CꢄC), 1584
(CꢄN), 1319, 1128 (SO2). Anal. Calcd for C22H22N4O4S3: C, 52.57; H, 4.41;
N, 11.15. Found: C, 52.62; H, 4.43; N, 11.10.
2-(Phenylaminosulfonylmethyl)-5-(4ꢀ-phenyl-4ꢀ,5ꢀ-dihydro-1ꢀH-pyrazol-
3ꢀ-ylsulfonyl-methyl)-1,3,4-oxadiazole (9a): Pale yellow solid, yield 69%,
mp 137—139 °C; 1H-NMR (CDCl3) d: 3.58 (dd, 1H, HX, JAXꢄ6.5 Hz,
JMXꢄ10.6 Hz), 4.21 (dd, 1H, HM, JAMꢄ12.4 Hz), 4.57 (dd, 1H, HA), 4.96 (s,
2H, SO2–CH2), 5.16 (s, 2H, CH2–SO2–NH), 7.17—7.76 (m, 10H, Ar–H),
10.02 (br s, 1H, NH), 10.57 (br s, 1H, NH–SO2). 13C-NMR (CDCl3) d: 47.2
(SO2–CH2), 52.0 (CH2–SO2–NH), 53.7 (C-5ꢀ), 66.4 (C-4ꢀ), 152.8 (C-3ꢀ),
158.1 (C-5), 158.9 (C-2), 127.7, 128.4, 129.7, 130.6, 131.2, 132.0, 132.9,
135.1 (aromatic carbons). IR (KBr) cmꢁ1: 3255 (NH), 1583 (CꢄN), 1335,
1146 (SO2). Anal. Calcd for C19H19N5O5S2: C, 49.45; H, 4.15; N, 15.17.
Found: C, 49.51; H, 4.17; N, 15.24.
2-(p-Methylphenylaminosulfonylmethyl)-5-(4ꢀ-p-methylphenyl-4ꢀ,5ꢀ-di-
hydro-1ꢀH-pyrazol-3ꢀ-ylsulfonylmethyl)-1,3,4-oxadiazole (9b): Pale yellow
1
solid, yield 67%, mp 146—148 °C; H-NMR (CDCl3) d: 2.22 and 2.26 (s,
6H, Ar–CH3), 3.54 (dd, 1H, HX, JAXꢄ6.2 Hz, JMXꢄ10.4 Hz), 4.12 (dd, 1H,
HM, JAMꢄ12.2 Hz), 4.50 (dd, 1H, HA), 4.88 (s, 2H, SO2–CH2), 5.14 (s, 2H,
CH2–SO2–NH), 7.14—7.67 (m, 8H, Ar–H), 9.93 (br s, 1H, NH), 10.44 (br s,
1H, NH–SO2). 13C-NMR (CDCl3) d: 21.1 and 21.6 (Ar–CH3), 46.6
(SO2–CH2), 51.5 (CH2–SO2–NH), 52.9 (C-5ꢀ), 65.8 (C-4ꢀ), 151.4 (C-3ꢀ),
158.6 (C-5), 159.7 (C-2), 125.8, 126.6, 127.3, 128.4, 129.5, 130.3, 131.2,
134.8 (aromatic carbons). IR (KBr) cmꢁ1: 3257 (NH), 1587 (CꢄN), 1332,
1139 (SO2). Anal. Calcd for C21H23N5O5S2: C, 51.52; H, 4.74; N, 14.31.
Found: C, 51.56; H, 4.77; N, 14.37.
2-(p-Chlorophenylaminosulfonylmethyl)-5-(4ꢀ-p-chlorophenyl-1ꢀH-
pyrrol-3ꢀ-ylsulfonyl-methyl)-1,3,4-thiadiazole (7c): Pale yellow solid, yield
1
71%, mp 175—177 °C; H-NMR (CDCl3) d: 5.13 (s, 2H, SO2–CH2), 5.27
(s, 2H, CH2–SO2–NH), 6.77 (s, 1H, C5ꢀ–H), 7.14—7.68 (m, 9H, C2ꢀ–H,
Ar–H), 8.43 (br s, 1H, NH), 10.22 (br s, 1H, NH–SO2). 13C-NMR (CDCl3)
d: 46.8 (SO2–CH2), 51.8 (CH2–SO2–NH), 103.2 (C-4ꢀ), 110.2 (C-3ꢀ), 117.9
(C-5ꢀ), 122.0 (C-2ꢀ), 158.4 (C-5), 159.0 (C-2), 126.6, 128.7, 129.6, 130.4,
131.5, 132.2, 134.1, 138.5 (aromatic carbons). IR (KBr) cmꢁ1: 3241 (NH),
1627 (CꢄC), 1597 (CꢄN), 1322, 1142 (SO2). Anal. Calcd for
C20H16Cl2N4O4S3: C, 44.20; H, 2.97; N, 10.31. Found: C, 44.24; H, 2.98; N,
10.37.
2-(p-Chlorophenylaminosulfonylmethyl)-5-(4ꢀ-p-chlorophenyl-4ꢀ,5ꢀ-di-
hydro-1ꢀH-pyrazol-3ꢀ-ylsulfonylmethyl)-1,3,4-oxadiazole (9c): Pale yellow
1
solid, yield 73%, mp 152—154 °C; H-NMR (CDCl3) d: 3.63 (dd, 1H, HX,
JAXꢄ6.8 Hz, JMXꢄ10.8 Hz), 4.24 (dd, 1H, HM, JAMꢄ12.8 Hz), 4.59 (dd, 1H,
HA), 5.03 (s, 2H, SO2–CH2), 5.25 (s, 2H, CH2–SO2–NH), 7.21—7.87 (m,
8H, Ar–H), 10.14 (br s, 1H, NH), 10.62 (br s, 1H, NH–SO2). 13C-NMR
(CDCl3) d: 47.9 (SO2–CH2), 52.4 (CH2–SO2–NH), 53.9 (C-5ꢀ), 66.7 (C-4ꢀ),
153.0 (C-3ꢀ), 158.4 (C-5), 159.0 (C-2), 126.7, 127.4, 128.3, 129.0, 130.1,
131.4, 132.7, 136.1 (aromatic carbons). IR (KBr) cmꢁ1: 3269 (NH), 1598
(CꢄN), 1340, 1152, (SO2). Anal. Calcd for C19H17Cl2N5O5S2: C, 43.02; H,
3.23; N, 13.20. Found: C, 43.00; H, 3.22; N, 13.18.
4-Amino-3-(phenylaminosulfonylmethyl)-5-(4ꢀ-phenyl-1ꢀH-pyrrol-3ꢀ-yl-
sulfonylmethyl)- 1,2,4-triazole (8a): Yellow solid, yield 69%, mp 165—
167 °C; 1H-NMR (DMSO-d6) d: 5.09 (s, 2H, SO2–CH2), 5.29 (s, 2H,
CH2–SO2–NH), 5.58 (br s, 2H, NH2), 6.71 (s, 1H, C5ꢀ–H), 7.12—7.76 (m,
11H, C2ꢀ–H, Ar–H), 8.41 (br s, 1H, NH), 10.32 (br s, 1H, NH–SO2). 13C-
NMR (DMSO-d6) d: 47.0 (SO2–CH2), 51.9 (CH2–SO2–NH), 102.1 (C-4ꢀ),
110.4 (C-3ꢀ), 116.7 (C-5ꢀ), 121.9 (C-2ꢀ), 158.2 (C-5), 159.4 (C-3), 126.4,
127.2, 128.3, 129.1, 130.4, 131.4, 132.0, 137.4 (aromatic carbons). IR (KBr)
cmꢁ1: 3439, 3315 (NH2), 3268 (NH), 1632 (CꢄC), 1599 (CꢄN), 1328,
1137 (SO2). Anal. Calcd for C20H20N6O4S2: C, 50.83; H, 4.27; N, 17.78.
Found: C, 50.88; H, 4.24; N, 17.88.
2-(Phenylaminosulfonylmethyl)-5-(4ꢀ-phenyl-4ꢀ,5ꢀ-dihydro-1ꢀH-pyrazol-
3ꢀ-ylsulfonyl-methyl)-1,3,4-thiadiazole (10a): Pale yellow solid, yield 68%,
mp 166—168 °C; 1H-NMR (CDCl3) d: 3.54 (dd, 1H, HX, JAXꢄ5.9 Hz,
JMXꢄ9.8 Hz), 4.26 (dd, 1H, HM, JAMꢄ11.8 Hz), 4.61 (dd, 1H, HA), 4.92 (s,
2H, SO2–CH2), 5.19 (s, 2H, CH2–SO2–NH), 7.19—7.69 (m, 10H, Ar–H),
9.86 (br s, 1H, NH), 10.46 (br s, 1H, NH–SO2). 13C-NMR (CDCl3) d: 47.8
(SO2–CH2), 51.1 (CH2–SO2–NH), 52.8 (C-5ꢀ), 66.8 (C-4ꢀ), 151.4 (C-3ꢀ),
157.9 (C-5), 159.0 (C-2), 125.9, 126.5, 127.6, 128.7, 129.4, 130.2, 133.4,
136.6 (aromatic carbons). IR (KBr) cmꢁ1: 3270 (NH), 1601 (CꢄN), 1325,
4-Amino-3-(p-methylphenylaminosulfonylmethyl)-5-(4ꢀ-p-methylphenyl-
1ꢀH-pyrrol-3ꢀ-ylsulfonylmethyl)-1,2,4-triazole (8b): Yellow solid, yield
74%, mp 172—174 °C; 1H-NMR (DMSO-d6) d: 2.19 and 2.24 (s, 6H,