ChemMedChem
10.1002/cmdc.201900328
FULL PAPER
(
s, 1H), 9.03 (s, 1H), 8.92 (s, 1H), 8.02 (d, J = 9.0 Hz, 2H), 7.87 (m, 1H),
– 7.76 (m, 1H), 7.57 (t, J = 8.1 Hz, 1H), 7.32 (dd, J = 8.0, 1.7 Hz, 1H), 6.96
(d, J = 1.3 Hz, 1H), 3.89 (s, 3H), 3.09 (s, 3H). 13C NMR (151 MHz, DMSO)
7
3
1
1
.80 (m, 1H), 7.52 (t, J = 9.3 Hz, 1H), 7.34 (d, J = 9.0 Hz, 2H), 6.93 (s, 1H),
.87 (s, 3H). 13C NMR (151 MHz, DMSO) δ 158.0, 157.7, 156.0, 143.6,
42.2, 137.0, 136.0, 135.9, 135.9, 129.5, 128.8, 128.4, 128.3, 127.3, 121.9,
δ 158.3, 158.0, 143.7, 142.5, 140.4, 139.8, 130.7, 127.4, 120.7, 119.4,
+
115.7, 111.5, 92.1, 54.4. HRMS calcd. for C14
H
15
N
4
O
3
S[M + H ] 319.0859,
20.5, 120.2, 119.7, 119.6, 92.1, 54.4. HRMS calcd. for C19
4 3
H14ClFN O S
found 319.0857.
+
[M + H ] 433.0532, found 433.0529.
N-(3-(5-methoxy-2H-pyrazolo[3,4-c]pyridin-2-
2
,3-Dichloro-N-(4-(5-methoxy-2H-pyrazolo[3,4-c]pyridin-2-
yl)phenyl)benzenesulfonamide (8k). Synthesized according to pathway
B, yellow powder, 88 mg in 80% yield; H NMR (600 MHz, DMSO) δ 10.69
1
yl)phenyl)benzenesulfonamide (8d). Synthesized according to pathway
B, yellow powder, 64 mg in 49% yield; H NMR (300 MHz, DMSO) δ 11.19
1
(s, 1H), 9.09 (s, 1H), 8.94 (d, J = 0.5 Hz, 1H), 7.92 (t, J = 2.1 Hz, 1H), 7.83
(dd, J = 5.3, 3.4 Hz, 2H), 7.75 (dd, J = 8.0, 1.7 Hz, 1H), 7.63 – 7.59 (m,
1H), 7.58 – 7.54 (m, 2H), 7.46 (t, J = 8.1 Hz, 1H), 7.21 (dd, J = 8.0, 1.7 Hz,
1H), 6.94 (d, J = 1.3 Hz, 1H), 3.88 (s, 3H). 13C NMR (151 MHz, DMSO) δ
158.0, 143.6, 142.5, 140.2, 139.2, 139.1, 133.1, 130.6, 129.4, 127.3, 126.6,
(s, 1H), 9.02 (d, J = 1.0 Hz, 1H), 8.90 (d, J = 0.8 Hz, 1H), 8.11 (dd, J = 8.0,
1.5 Hz, 1H), 7.98 (d, J = 9.0 Hz, 2H), 7.94 (dd, J = 8.1, 1.5 Hz, 1H), 7.58
(
(
t, J = 8.1 Hz, 1H), 7.31 (d, J = 9.0 Hz, 2H), 6.91 (d, J = 1.3 Hz, 1H), 3.86
s, 3H). 13C NMR (75 MHz, DMSO) δ 158.0, 143.6, 142.2, 138.4, 137.1,
1
35.9, 135.7, 135.3, 134.4, 130.6, 128.9, 128.8, 127.4, 122.0, 120.2, 119.8,
120.6, 119.6, 116.0, 112.0, 92.1, 54.5. HRMS calcd. for C19
H ] 381.1016, found 381.1013.
16 4 3
H N O S [M +
+
+
119.7, 92.1, 54.4. HRMS calcd. for C19
H14Cl
2 4 3
N O S [M + H ] 449.0236,
found 449.0223.
5-Chloro-2-fluoro-N-(3-(5-methoxy-2H-pyrazolo[3,4-c]pyridin-2-
N-(4-(5-Methoxy-2H-pyrazolo[3,4-c]pyridin-2-yl)phenyl)acetamide
8e). Synthesized according to pathway B, yellow powder, 42 mg in 60%
yield; 1H NMR (600 MHz, DMSO) δ 10.26 (s, 1H), 9.04 (s, 1H), 8.95 (s,
yl)phenyl)benzenesulfonamide (8l). Synthesized according to pathway
B, yellow powder, 78 mg in 62% yield; H NMR (600 MHz, DMSO) δ 11.17
(s, 1H), 9.07 (s, 1H), 8.96 (s, 1H), 7.93 (m, 1H), 7.89 (m, 1H), 7.79 (m, 2H),
7.55 – 7.47 (m, 2H), 7.24 (m, 1H), 6.93 (s, 1H), 3.88 (s, 3H). 13C NMR (151
MHz, DMSO) δ 158.1, 157.7, 156.0, 143.7, 142.5, 140.3, 138.1, 135.9,
135.9, 130.8, 129.5, 128.8, 128.3, 128.2, 127.3, 120.6, 119.7, 119.6, 119.5,
1
(
1
1
1
H), 8.03 (d, J = 9.0 Hz, 2H), 7.81 (d, J = 9.0 Hz, 2H), 6.94 (d, J = 1.2 Hz,
H), 3.88 (s, 3H), 2.09 (s, 3H). 13C NMR (151 MHz, DMSO) δ 168.6, 143.6,
42.0, 139.7, 134.6, 127.4, 121.2, 119.9, 119.6, 117.6, 92.1, 54.4, 24.0.
+
4 3
H14ClFN O
S [M + H+]
HRMS calcd. for C15H N O
14 4 2
[M + H ] 283.1190, found 283.1193.
116.4, 112.0, 92.0, 54.4. HRMS calcd. for C19
33.0532, found 433.0531.
4
N-(4-(5-Methoxy-2H-pyrazolo[3,4-c]pyridin-2-yl)phenyl)benzamide
8f). Synthesized according to pathway B, yellow powder, 66 mg in 66%
yield; 1H NMR (600 MHz, DMSO) δ 10.52 (s, 1H), 9.07 (s, 1H), 9.01 (s,
(
2,3-Dichloro-N-(3-(5-methoxy-2H-pyrazolo[3,4-c]pyridin-2-
yl)phenyl)benzenesulfonamide (8m). Synthesized according to pathway
1
1
H), 8.16 – 8.07 (m, 2H), 8.06 – 8.02 (m, 2H), 8.01 – 7.98 (m, 2H), 7.62 (t,
B, pale yellow powder, 96 mg in 74% yield; H NMR (300 MHz, DMSO) δ
J = 7.4 Hz, 1H), 7.56 (t, J = 7.4 Hz, 2H), 6.96 (s, 1H), 3.89 (s, 3H). 13C
11.23 (s, 1H), 9.12 – 9.06 (m, 1H), 8.94 (s, 1H), 8.12 (dd, J = 8.0, 1.6 Hz,
1H), 7.95 – 7.89 (m, 2H), 7.75 (dd, J = 8.0, 1.6 Hz, 1H), 7.57 (t, J = 8.2 Hz,
1H), 7.48 (t, J = 8.2 Hz, 1H), 7.21 (dd, J = 8.2, 1.6 Hz, 1H), 6.93 (s, 1H),
3.87 (s, 3H). 13C NMR (75 MHz, DMSO) δ 158.1, 143.7, 142.6, 140.3,
NMR (151 MHz, DMSO) δ 165.8, 158.0, 143.6, 142.1, 139.6, 135.1, 134.7,
1
31.8, 128.4, 127.7, 127.4, 121.1, 120.9, 120.0, 92.1, 54.4. HRMS calcd.
+
for C20
H N O
16 4 2
[M + H ] 345.1346, found 345.1348.
1
1
4
38.4, 138.2, 135.3, 134.4, 130.9, 130.5, 128.9, 128.8, 127.4, 120.7, 118.8,
16.1, 111.3, 92.1, 54.5. HRMS calcd. for C19
49.0236, found 449.0217.
2 4 3
H14Cl N O
S [M + H+]
5
-Chloro-2-fluoro-N-(4-(5-methoxy-2H-pyrazolo[3,4-c]pyridin-2-
yl)phenyl)benzamide (8g). Synthesized according to pathway B, yellow
powder, 63 mg in 55% yield; H NMR (600 MHz, DMSO) δ 10.80 (s, 1H),
1
9
7
6
1
1
.07 (s, 1H), 9.00 (s, 1H), 8.12 (d, J = 9.0 Hz, 2H), 7.94 (d, J = 9.0 Hz, 2H),
.80 (dd, J = 5.9, 2.7 Hz, 1H), 7.70 – 7.61 (m, 1H), 7.46 (t, J = 9.2 Hz, 1H),
.96 (d, J = 1.2 Hz, 1H), 3.89 (s, 4H). 13C NMR (151 MHz, DMSO) δ 161.5,
58.5, 158.0, 156.8, 143.6, 142.2, 139.0, 135.5, 132.3, 132.3, 131.5, 129.4,
N-(3-(5-Methoxy-2H-pyrazolo[3,4-c]pyridin-2-yl)phenyl)acetamide
(8n). Synthesized according to pathway B, beige powder, 43 mg in 52%
yield; 1H NMR (600 MHz, DMSO) δ 10.29 (s, 1H), 9.08 (s, 1H), 8.96 (s,
1H), 8.49 (d, J = 1.9 Hz, 1H), 7.74 (dd, J = 8.0, 1.6 Hz, 1H), 7.65 – 7.58
(m, 1H), 7.52 (t, J = 8.1 Hz, 1H), 6.95 (s, 1H), 3.88 (s, 3H), 2.10 (s, 3H).
28.4, 127.4, 126.4, 126.3, 121.3, 120.5, 120.1, 118.4, 118.3, 92.1, 54.4.
+
13
HRMS calcd. for C20
H14ClFN O
4 2
[M + H ] 397.0862, found 397.0865.
C NMR (151 MHz, DMSO) δ 168.7, 158.1, 143.7, 142.4, 140.6, 140.0,
1
30.0, 127.3, 120.4, 118.9, 115.0, 111.4, 92.1, 54.4, 24.1. HRMS calcd.
+
for C15
H N O
14 4 2
[M + H ] 283.1190, found 283.1193.
2,3-Dichloro-N-(4-(5-methoxy-2H-pyrazolo[3,4-c]pyridin-2-
yl)phenyl)benzamide (8h). Synthesized according to pathway B, yellow
1
powder, 103 mg in 86% yield; H NMR (600 MHz, DMSO) δ 10.89 (s, 1H),
9
2
N-(3-(5-Methoxy-2H-pyrazolo[3,4-c]pyridin-2-yl)phenyl)benzamide
(8o). Synthesized according to pathway B, yellow powder, 43 mg in 52%
yield; 1H NMR (600 MHz, DMSO) δ 10.55 (s, 1H), 9.10 (s, 1H), 9.00 (s,
1H), 8.70 (s, 1H), 8.04 – 7.99 (m, 2H), 7.91 – 7.88 (m, 1H), 7.84 – 7.80 (m,
1H), 7.61 (m, 4H), 6.97 (s, 1H), 3.89 (s, 3H). 13C NMR (151 MHz, DMSO)
δ 165.8, 158.1, 143.7, 142.4, 140.5, 139.9, 134.5, 131.8, 130.0, 128.4,
.08 (d, J = 1.0 Hz, 1H), 9.01 (s, 1H), 8.14 – 8.11 (m, 2H), 7.96 – 7.92 (m,
H), 7.81 (dd, J = 8.1, 1.5 Hz, 1H), 7.63 (dd, J = 7.6, 1.5 Hz, 1H), 7.53 (dd,
J = 9.7, 6.0 Hz, 1H), 6.97 (d, J = 1.3 Hz, 1H), 3.90 (s, 3H). 13C NMR (151
MHz, DMSO) δ 164.3, 163.0, 158.0, 143.6, 142.2, 139.0, 138.9, 135.4,
32.1, 131.5, 128.8, 128.1, 127.4, 121.4, 120.3, 120.1, 92.1, 54.4. HRMS
1
+
calcd. for C20
H14Cl
N O
2 4 2
[M + H ] 413.0567, found 413.0570.
127.7, 127.3, 120.4, 120.2, 115.6, 112.7, 92.1, 54.4. HRMS calcd. for
+
C H N O
20 16 4 2
[M + H ] 345.1346, found 345.1353.
1-(4-(5-Methoxy-2H-pyrazolo[3,4-c]pyridin-2-yl)phenyl)-3-phenylurea
(
8i). Synthesized according to pathway B, yellow powder, 45 mg in 86%
5-Chloro-2-fluoro-N-(3-(5-methoxy-2H-pyrazolo[3,4-c]pyridin-2-
yl)phenyl)benzamide (8p). Synthesized according to pathway B, light
yellow powder, 56 mg in 49% yield; H NMR (600 MHz, DMSO) δ 10.83 (s,
1H), 9.10 (s, 1H), 9.01 (s, 1H), 8.62 (s, 1H), 7.86 (dd, J = 8.1, 1.6 Hz, 1H),
7.81 (m, 1H), 7.78 – 7.74 (m, 1H), 7.68 (m, 1H), 7.61 (t, J = 8.1 Hz, 1H),
7.46 (m, 1H), 6.97 (s, 1H), 3.89 (s, 3H). 13C NMR (151 MHz, DMSO) δ
161.6, 158.5, 158.0, 156.9, 143.7, 142.5, 140.0, 139.8, 132.4, 132.3, 130.2,
1
yield; H NMR (600 MHz, DMSO) δ 9.46 (s, 1H), 9.20 (s, 1H), 9.04 (s, 1H),
8
2
NMR (151 MHz, DMSO) δ 157.9, 152.5, 143.5, 141.9, 140.4, 139.6, 133.6,
1
for C20
1
.96 (s, 1H), 8.02 (d, J = 9.0 Hz, 2H), 7.69 (d, J = 9.0 Hz, 2H), 7.49 (m,
H), 7.29 (m, 2H), 6.98 (m, 1H), 6.95 (d, J = 1.2 Hz, 1H), 3.89 (s, 3H). 13
C
28.8, 127.4, 121.9, 121.4, 119.8, 118.5, 118.2, 92.1, 54.4. HRMS calcd.
+
H N O
17 5 2
[M + H ] 360.1455, found 360.1461.
1
9
3
29.4, 128.4, 127.4, 126.3, 126.2, 120.5, 119.8, 118.4, 118.3, 116.1, 112.2,
+
2.1, 54.4. HRMS calcd. for C20H14ClFN O
4 2
[M + H ] 397.0862, found
N-(3-(5-Methoxy-2H-pyrazolo[3,4-c]pyridin-2-
97.0868.
yl)phenyl)methanesulfonamide (8j). Synthesized according to pathway
1
B, yellow powder, 71 mg in 77% yield; H NMR (600 MHz, DMSO) δ 10.13
(s, 1H), 9.10 (d, J = 0.9 Hz, 1H), 9.01 (s, 1H), 7.98 (t, J = 2.1 Hz, 1H), 7.84
1
1
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