5
1
3
1
7
2
1
1
0.0 Hz), 7.72 (d, 1H, J = 10.0 Hz), 7.62 (d,
A
2H
C
, J
C
=
E
1
P
0
T
.0
E
H
D
z), MA
C
NUNM
S
R
C
(
R
D
I
MSO-d , 125 MHz, ppm) δ 156.9, 152.4, 138.4,
P
T
6
.51 (s, 1H), 7.45-7.38 (m, 2H), 7.27-7.26 (m, 3H), 2.30 (s, 3H),
135.7, 131.9, 131.1, 130.6, 130.5, 129.9, 129.4, 128.4, 126.9,
13
+
.14 (s, 3H). C NMR (DMSO-d , 125 MHz, ppm) δ 157.5,
84.7, 12.8. HRMS calc. for C H Cl N NaOS [M + Na]
6
16 12
2
2
52.3, 136.5, 135.8, 133.8, 131.4, 129.9, 129.0, 128.1, 127.2,
372.9940, found 372.9944.
4.2.15 3-tert-butyl-1-phenyl-4-(phenylthio)-1H-pyrazol-5-ol
(4o). Eluent petroleum ether/ethyl acetate (20:1). 121 mg, 73%
yield. H NMR (DMSO-d , 500 MHz, ppm) δ 11.96 (s, br, 1H),
7.78 (d, 2H, J = 10.0 Hz), 7.49 (t, 2H, J = 10.0 Hz), 7.31-7.26 (m,
3H), 7.11 (t, 1H, J = 5.0 Hz), 7.11 (t, 1H, J = 5.0 Hz), 7.05 (d,
1H, J = 10.0 Hz), 1.30 (s, 9H). C NMR (DMSO-d , 125 MHz,
ppm) δ 161.0, 157.0, 139.6, 139.0, 129.4, 129.3, 126.3, 125.1,
125.0, 121.7, 84.3, 34.1, 29.4. HRMS calc. for C H N NaOS
[M + Na] 347.1189, found 347.1183.
4.2.16 3-tert-butyl-1-phenyl-4-(p-tolylthio)-1H-pyrazol-5-ol
27.1, 125.8, 124.5, 122.8, 121.4, 88.0, 20.9, 12.6. HRMS calc.
.
+
for C H N NaOS [M + Na] 369.1032, found 369.1034.
4
ol (4h). Eluent petroleum ether/ethyl acetate (15:1). 124 mg, 79%
yield. H NMR (DMSO-d , 500 MHz, ppm) δ 12.45 (s, br, 1H),
21
18
2
1
.2.8
.
1-(4-chlorophenyl)-3-methyl-4-(phenylthio)-1H-pyrazol-5-
6
1
6
13
7
.83 (d, 2H, J = 10.0 Hz), 7.53 (d, 2H, J = 10.0 Hz), 7.27 (t, 2H,
6
13
J = 10.0 Hz), 7.13-7.09 (m, 3H), 2.14 (s, 3H). C NMR (DMSO-
d6, 125 MHz, ppm) δ 157.5, 152.9, 138.7, 137.5, 130.2, 129.5,
1
C H ClN NaOS [M + Na] 339.0329, found 339.0335.
4
19
20
2
+
29.4, 125.4, 125.3, 122.4, 88.1, 12.8. HRMS calc. for
+
.
16
13
2
.2.9
.
1-(4-chlorophenyl)-4-(4-chlorophenylthio)-3-methyl-1H-
(4p). Eluent petroleum ether/ethyl acetate (20:1). 133 mg, 79%
yield. H NMR (DMSO-d , 500 MHz, ppm) δ 11.92 (s, br, 1H),
7.77 (d, 2H, J = 10.0 Hz), 7.48 (t, 2H, J = 10.0 Hz), 7.29 (t, 1H, J
1
pyrazol-5-ol (4i). Eluent petroleum ether/ethyl acetate (15:1). 131
mg, 75% yield. H NMR (DMSO-d , 500 MHz, ppm) δ 7.81 (d,
6
1
6
2
H, J = 10.0 Hz), 7.53 (d, 2H, J = 10.0 Hz), 7.33 (d, 2H, J = 10.0
= 10.0 Hz), 7.08 (d, 2H, J = 10.0 Hz), 6.94 (d, 2H, J = 10.0 Hz),
13
13
Hz), 7.10 (d, 2H, J = 10.0 Hz), 2.13 (s, 3H). C NMR (DMSO-
d6, 125 MHz, ppm) δ 157.5, 152.8, 137.9, 137.4, 130.2, 130.1,
2.23 (s, 3H), 1.30 (s, 9H). C NMR (DMSO-d , 125 MHz, ppm)
6
δ 160.9, 156.9, 139.1, 137.6, 134.3, 130.0, 129.4, 126.3, 125.1,
1
29.6, 129.4, 129.3, 127.1, 122.4, 87.7, 12.8. HRMS calc. for
121.7, 84.6, 34.1, 29.4. HRMS calc. for C H N NaOS [M + Na
20
22
2
+
+
C H Cl N NaOS [M + Na ] 372.9940, found 372.9944.
] 361.1345, found 361.1348.
4.2.17 3-tert-butyl-4-(4-chlorophenylthio)-1-phenyl-1H-pyrazol-
16
12
2
2
4
1
1
1
.2.10
.
1-(4-chlorophenyl)-4-(4-methoxyphenylthio)-3-methyl-
.
H-pyrazol-5-ol (4j). Eluent petroleum ether/ethyl acetate (10:1).
38 mg, 80% yield. H NMR (DMSO-d , 500 MHz, ppm) δ
5-ol (4q). Eluent petroleum ether/ethyl acetate (20:1). 129 mg,
1
1
72% yield. H NMR (DMSO-d , 500 MHz, ppm) δ 12.03 (s, br,
6
6
2.36 (s, br, 1H), 7.79 (d, 2H, J = 10.0 Hz), 7.53 (d, 2H, J = 10.0
1H), 7.77 (d, 2H, J = 5.0 Hz), 7.49 (t, 2H, J = 10.0 Hz), 7.34 (d,
Hz), 7.10 (d, 2H, J = 10.0 Hz), 6.88 (d, 2H, J = 10.0 Hz), 3.70 (s,
2H, J = 10.0 Hz), 7.30 (t, 1H, J = 5.0 Hz), 7.05 (t, 2H, J = 5.0
13
13
3
1
8
3
4
5
8
1
2
3
1
H), 2.14 (s, 3H). C NMR (DMSO-d , 125 MHz, ppm) δ 158.1,
Hz), 1.30 (s, 9H). C NMR (DMSO-d , 125 MHz, ppm) δ 160.9,
6
6
52.8, 138.0, 137.5, 130.1, 129.4, 128.9, 128.3, 122.4, 115.3+,
157.0, 138.8, 129.9, 129.7, 129.4, 129.3, 126.6, 126.4, 121.7,
+
9.9, 55.6, 12.8. HRMS calc. for C H ClN NaO S [M + Na]
83.9, 34.1, 29.4. HRMS calc. for C H ClN NaOS [M + Na]
17
15
2
2
19 19
2
49.0435, found 349.0436.
.2.11 1-(4-chlorophenyl)-3-methyl-4-(p-tolylthio)-1H-pyrazol-
381.0799, found 381.0783.
4.2.18 3-tert-butyl-4-(naphthalen-1-ylthio)-1-phenyl-1H-
.
.
-ol (4k). Eluent petroleum ether/ethyl acetate (15:1). 137 mg,
pyrazol-5-ol (4r). Eluent petroleum ether/ethyl acetate (20:1).
1
1
3% yield. H NMR (DMSO-d , 500 MHz, ppm) δ 12.39 (s, br,
149 mg, 80% yield. H NMR (DMSO-d , 500 MHz, ppm) δ
6
6
H), 7.82 (d, 2H, J = 10.0 Hz), 7.53 (d, 2H, J = 10.0 Hz), 7.09 (d,
H, J = 10.0 Hz), 7.00 (d, 2H, J = 10.0 Hz), 2.23 (s, 3H), 2.13 (s,
11.98 (s, br, 1H), 7.85-7.81 (m, 4H), 7.77 (d, 1H, J = 5.0 Hz),
7.52-7.40 (m, 5H), 7.31 (t, 1H, J = 10.0 Hz), 7.26 (d, 1H, J =
13
13
H). C NMR (DMSO-d , 125 MHz, ppm) δ 157.3, 152.9,
10.0 Hz), 1.32 (s, 9H). C NMR (DMSO-d , 125 MHz, ppm) δ
6
6
37.6, 135.1, 134.8, 130.1, 129.3, 125.8, 122.4, 88.7, 20.9, 12.8.
160.9, 157.1, 139.1, 137.4, 133.8, 131.3, 129.4, 128.8, 128.1,
127.2, 126.4, 125.6, 124.1, 122.2, 121.8, 84.2, 34.1, 29.4. HRMS
+
HRMS calc. for C H ClN NaOS [M + Na] 353.0486, found
17
15
2
+
3
4
5
6
1
7
53.0489.
.2.12 1-(2-chlorophenyl)-3-methyl-4-(phenylthio)-1H-pyrazol-
calc. for C H N NaOS [M + Na ] 397.1345, found 397.1346.
23
22
2
.
4.2.19. 3-tert-butyl-4-(p-tolylthio)-1-(4-(trifluoromethyl)phenyl)-
-ol (4l). Eluent petroleum ether/ethyl acetate (15:1). 102 mg,
1H-pyrazol-5-ol (4s). Eluent petroleum ether/ethyl acetate (15:1).
1
1
5% yield. H NMR (DMSO-d , 500 MHz, ppm) δ 11.95 (s, br,
146 mg, 72% yield. H NMR (DMSO-d , 500 MHz, ppm) δ
6
6
H), 7.67 (d, 1H, J = 10.0 Hz), 7.57 (dd, 1H, J = 10.0 Hz), 7.54-
.50 (m, 2H), 7.30 (t, 2H, J = 10.0 Hz), 7.14-7.11 (m, 3H), 2.12
12.43 (s, br, 1H), 8.07 (d, 2H, J = 10.0 Hz), 7.85 (d, 2H, J = 5.0
Hz), 7.08 (d, 2H, J = 10.0 Hz), 6.95 (d, 2H, J = 5.0 Hz), 2.22 (s,
13
13
(s, 3H). C NMR (DMSO-d , 125 MHz, ppm) δ 157.0, 152.4,
3H), 1.31 (s, 9H). C NMR (DMSO-d , 125 MHz, ppm) δ 162.0,
6
6
1
1
39.2, 132.0, 131.9, 131.1, 130.6, 130.5, 129.5, 129.1, 128.4,
25.3, 125.1, 84.8, 12.9. HRMS calc. for C H ClN NaOS [M +
157.9, 142.1, 135.7, 134.4, 130.0, 129.1 (q, J = 204.3Hz), 126.6
(q, J = 32.3 Hz), 125.1, 123.6, 85.6, 34.2, 29.2, 20.8, . HRMS
16
13
2
+
+
Na ] 339.0329, found 339.0335.
calc. for C H F N NaOS [M + Na] 429.1219, found 429.1214.
2
1
21
3
2
13a
4
5
6
1
.2.13
.
1-(2-chlorophenyl)-3-methyl-4-(p-tolylthio)-1H-pyrazol-
4.2.20
.
1,3-diphenyl-4-(phenylthio)-1H-pyrazol-5-ol (4t).
-ol (4m). Eluent petroleum ether/ethyl acetate (15:1). 114 mg,
9% yield. H NMR (DMSO-d, 500 MHz, ppm) δ 11.91 (s, br,
Eluent petroleum ether/ethyl acetate (10:1). 120 mg, 70% yield.
1
1
H NMR (DMSO-d , 500 MHz, ppm) δ 12.44 (s, br, 1H), 7.90-
6
H), 7.66 (d, 1H, J = 10.0 Hz), 7.56-7.49 (m, 3H), 7.11 (d, 2H, J
10.0 Hz), 7.01 (d, 2H, J = 10.0 Hz), 2.25 (s, 3H), 2.09 (s, 3H).
7.88 (m, 4H), 7.54 (t, 2H, J = 10.0 Hz), 7.40-7.35 (m, 4H), 7.29
13
=
(t, 2H, J = 5.0 Hz), 7.14-7.11 (m, 3H). C NMR (DMSO-d , 125
6
13
C NMR (DMSO-d , 125 MHz, ppm) δ 156.8, 152.3, 138.4,
MHz, ppm) δ 157.1, 151.9, 150.2, 140.6, 139.1, 138.8, 136.8,
6
1
8
3
4
31.9, 131.1, 130.6, 130.5, 129.9, 129.4, 129.1, 128.4, 126.8+,
129.6, 129.5, 128.7, 127.5, 125.5, 125.2, 115.5, 85.6. HRMS
+
4.7, 21.2, 12.8. HRMS calc. for C H ClN NaOS [M + Na]
calc. for C H N NaOS [M + Na] 367.0876, found 367.0877.
17
15
2
21 16
2
53.0486, found 353.0483.
.2.14 1-(2-chlorophenyl)-4-(4-chlorophenylthio)-3-methyl-1H-
4.2.21
.
4-(naphthalen-1-ylthio)-1,3-diphenyl-1H-pyrazol-5-ol
.
(4u). Eluent petroleum ether/ethyl acetate (10:1). 148 mg, 75%
yield. H NMR (DMSO-d , 500 MHz, ppm) δ 12.51 (s, br, 1H),
1
pyrazol-5-ol (4n). Eluent petroleum ether/ethyl acetate (15:1).
6
1
1
1
7
05 mg, 60% yield. H NMR (DMSO-d , 500 MHz, ppm) δ
7.94-7.91 (m, 4H), 7.85 (t, 2H, J = 10.0 Hz), 7.77 (d, 1H, J =
6
1
3
2.12 (s, br, 1H), 7.66 (dd, 1H, J = 10.0 Hz), 7.57-7.49 (m, 3H),
.36 (d, 2H, J = 10.0 Hz), 7.11 (d, 2H, J = 10.0 Hz), 2.11 (s, 3H).
10.0 Hz), 7.59-7.54 (m, 3H), 7.47-7.32 (m, 7H). C NMR
(DMSO-d , 125 MHz, ppm) δ 157.1, 152.1, 138.8, 136.8, 133.9,
6