Supporting Information
Cyclocondensation-Knoevenagel–Michael domino reaction of
phenyl hydrazine, acetoacetate derivatives and aryl aldehydes over
acetic acid functionalized ionic liquid
Ahmad Reza Moosavi-Zare,*a Mohammad Ali Zolfigol,*b Ehsan Noroozizadeh,b Omid Khaledian,b
Behzad Shirmardi Shaghasemib
a
Department of Chemistry, Sayyed Jamaleddin Asadabadi University, Asadabad, 6541835583,
Iran.; E-mail: moosavizare@yahoo.com
b
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran.; E-mail:
mzolfigol@yahoo.com
1
N
N
N
N
OH HO
4-((5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)(phenyl)methyl)-3-methyl-1-phenyl-1Hpyrazol-5-ol
Yellow solid, Mp: 166-169 oC; IR (KBr, cm-1): 3414, 1598, 1580, 1498, 1414, 1368; 1H NMR
(90 MHz, DMSO-d6): δ (ppm) = 2.3 (s, 6H), 4.95 (s, 1H), 7.24-7.49 (m, 11H), 7.6-7.7 (m, 4H),
13.88 (s, 2H).
2
3
Cl
N
N
N
N
OH HO
4-((2-chlorophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3-methyl-1-phenyl1H-pyrazol-5-ol
White solid; m.p. 235-236 ○C (lit. [16] mp 235-236○C); 1H NMR (400 MHz, DMSO-d6): δ
(ppm) 2.27 (s, 6H), 5.12 (s, 1H), 7.23-7.28 (m, 3H), 7.37-7.43 (m, 5H), 7.66-7.68 (m, 4H), 7.74
(s, 2H), 12.69 (s, 1H, OH), 13.95 (s, 1H, OH);
C NMR (DMSO-d6): δ (ppm) 12.33, 32.11,
13
121.09, 126.13, 127.39, 128.54, 129.40, 129.94, 130.69, 132.36, 137.70, 139.92, 146.49; IR
(KBr, cm-1): 3435, 3062, 2912, 1614, 1582, 1560, 1499, 1401, 1368, 1213, 1086, 1033, 837, 746,
690.
4
5
Cl
N
N
N
N
OH HO
4-((4-chlorophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3-methyl-1-phenyl1H-pyrazol-5-ol
White solid, Mp: 214-217 oC; IR (KBr, cm-1): 3414, 1600, 1580, 1487, 1409, 1296, 1198; 1H
NMR (90 MHz, DMSO-d6): δ (ppm) = 2.3 (s, 6H), 4.95 (s, 1H), 7.28-7.49 (m, 10H), 7.68-7.73
(m, 4H), 13.76 (s, 2H).
6
7
NO2
N
N
N
N
OH HO
4-((5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)(2-nitrophenyl)methyl)-3-methyl-1-phenyl1H-pyrazol-5-ol
White solid, Mp: 227-230 oC; IR (KBr, cm-1): 3420, 3070, 2916, 1612, 1557, 1499, 1406, 1373;
1
H NMR (90 MHz, DMSO-d6): δ (ppm) = 2.26 (s, 6H), 5.4 (s, 1H), 7.23-7.59 (m, 14H), 13.12 (s,
2H).
8
9
Br
HO
N
N
N
N
OH HO
4-((5-bromo-2-hydroxyphenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3methyl-1-phenyl-1H-pyrazol-5-ol
White solid, Mp: 258-266 oC; IR (KBr, cm-1): 3070, 1598, 1574, 1500,1409, 1370, 1365, 1307;
1
H NMR (90 MHz, DMSO-d6): δ (ppm) = 2.27 (s, 6H), 5.19 (s, 1H), 6.6-6.7 (m, 1H), 7.11-7.43
(m, 8H), 7.64-7.72 (m, 3H), 13.49 (s, 2H).
10
11
Me
N
N
N
N
OH HO
4-((5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)(p-tolyl)methyl)-3-methyl-1-phenyl-1Hpyrazol-5-ol
White solid, Mp: 200-202 oC; IR (KBr, cm-1): 3422, 30468, 2921, 1601, 1580, 1501, 1456, 1373,
1297; 1H NMR (90 MHz, DMSO): δ (ppm) = 2.29 (s, 9H), 4.85 (s, 1H), 7.08-7.42 (m, 9H), 7.657.73 (m, 4H), 13.84 (s,2H).
12
13
Br
N
N
N
N
OH HO
4-((2-bromophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3-methyl-1-phenyl1H-pyrazol-5-ol
White solid, Mp: 249-252 oC; IR (KBr, cm-1): 3448, 3063, 2912, 2791, 1613, 1560, 1499, 1459,
1309; 1H NMR (90 MHz, DMSO-d6): δ (ppm) = 2.27 (s, 6H), 5.08 (s, 1H), 7.14-7.49 (m, 10H),
7.63-7.71 (m, 4H), 13.52 (s, 2H).
14
15
Br
N
N
N
N
OH HO
4-((4-bromophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3-methyl-1-phenyl1H-pyrazol-5-ol
White solid, Mp: 205-208 oC; IR (KBr, cm-1): 3419, 1600, 1579, 1501, 1481, 1404, 1295, 1198;
1
H NMR (90 MHz, DMSO-d6): δ (ppm) = 2.29 (s, 6H), 4.92 (s, 1H), 7.13-7.48 (m, 10H), 7.637.71 (m, 4H), 13.7 (s, 2H).
16
17
CN
N
N
N
N
OH HO
4-(bis(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)benzonitrile
White solid, Mp: 215-218 oC; IR (KBr, cm-1): 3421, 2921, 2230, 1599, 1580, 1500, 1411, 1295,
1197; 1H NMR (90 MHz, DMSO): δ (ppm) = 2.30 (s, 6H), 5.05 (s, 1H), 7.35-7.42 (m, 9H), 7.647.68 (m, 5H), 13.88 (s,2H).
18
19
NO2
Cl
N
N
N
N
OH HO
4-((2-chloro-3-nitrophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3-methyl-1phenyl-1H-pyrazol-5-ol
White solid, Mp: 230-235 oC; IR (KBr, cm-1): 3454, 3054, 2230, 1598, 1570, 1501, 1368, 1192;
1
H NMR (90 MHz, DMSO-d6): δ (ppm) = 2.31 (s, 6H), 5.07 (s, 1H), 7.30-7.43 (m, 5H), 7.627.80(m, 8H), 13.70 (s, 2H)
20
21
OMe
MeO
N
N
N
N
OH HO
4-((2,5-dimethoxyphenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3-methyl-1phenyl-1H-pyrazol-5-ol
Orang solid, Mp: 134-139 oC; IR (KBr, cm-1): 3472, 1678, 1586, 1493,1373, 1321, 1295, 11253,
1229; 1H NMR (90 MHz, DMSO-d6): δ (ppm) = 2.29 (s, 6H), 3.78-3.88 (d, 7H), 7.15-7.42 (m,
8H), 7.63-7.91(m, 4H), 8.8 (s, 1), 13.70 (s, 2H).
22
23
F
N
N
N
N
OH HO
4-((4-fluorophenyl)(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyl)-3-methyl-1-phenyl1H-pyrazol-5-ol
White solid, Mp: 134-139 oC; IR (KBr, cm-1): 3414,,1600, 1580, 1487; 1H NMR (90 MHz,
DMSO-d6): δ (ppm) = 2.3 (s, 6H), 4.93(s, 1H), 7.02-7.43(m, 11H), 7.64-7.72(m, 4H),
13.70(s,2H)
24
25