Molecules 2018, 23, 674
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2
2
.2 Hz, 1H), 7.93 (d, J = 9.3 Hz, 1H), 7.77 (d, J = 7.8 Hz, 2H), 7.62 (t, J = 7.7 Hz, 2H), 7.46 (t, J = 7.4 Hz, 1H),
.69 (s, 3H); 13C-NMR (DMSO-d ):
δ 147.3, 142.2, 141.1, 139.2, 130.3, 127.8, 124.4, 122.9, 122.8, 119.3,
6
+
111.7, 12.1; MS: m/z 253 (M ), calculated m/z 253.09. Anal. Calcd. for C H N O : C, 66.40; H, 4.38;
14
11
3
2
N, 16.59. Found: C, 66.33; H, 4.34; N, 16.42.
1
-(2-Methoxyphenyl)-3-methyl-5-nitro-1H-indazole (11b). Yield: 232 mg (0.82 mmol, 82%) as a light
◦
−1
1
brown solid, m.p. 128–130 C; IR: 2838, 1519, 1338 cm ; H-NMR (DMSO-d ):
δ
8.86 (s, 1H),
6
8
.21 (d, J = 9.3 Hz, 1H), 7.55 (t, J = 8.0 Hz, 1H), 7.49 (d, J = 7.8 Hz, 1H), 7.38–7.28 (overlapping
13
signals, 2H), 7.16 (t, J = 7.7 Hz, 1H), 3.78 (s, 3H), 2.66 (s, 3H); C-NMR (DMSO-d6):
δ
154.0, 146.6, 143.0,
+
1
41.9, 130.8, 128.6, 127.1, 123.2, 122.0, 121.4, 119.0, 113.4, 112.2, 56.2, 12.1; MS: m/z 283 (M ), calculated
m/z 283.10. Anal. Calcd. for C H N O : C, 63.60; H, 4.63; N, 14.83. Found: C, 63.49; H, 4.61; N, 14.88.
15
13
3
3
1
-(3-Methoxyphenyl)-3-methyl-5-nitro-1H-indazole (11c). Yield: 229 mg (0.81 mmol, 81%) as a light
◦
−1
1
brown solid, m.p. 105–106 C; IR: 2836, 1518, 1338 cm ; H-NMR (DMSO-d ):
δ
8.90 (s, 1H),
6
8
7
.29 (d, J = 9.3 Hz, 1H), 7.96 (d, J = 9.3 Hz, 1H), 7.52 (t, J = 8.1 Hz, 1H), 7.34 (d, J = 8.1 Hz, 1H),
13
.28 (s, 1H), 7.04 (d, J = 8.3 Hz, 1H); C-NMR (DMSO-d6):
δ
160.6, 147.3, 142.3, 141.2, 140.3, 131.2, 124.4,
+
1
22.9, 119.3, 114.9, 113.7, 111.9, 108.6, 56.0, 12.1; MS: m/z 283 (M ), calculated m/z 283.10. Anal. Calcd.
for C H N O : C, 63.60; H, 4.63; N, 14.83. Found: C, 63.52; H, 4.55; N, 14.71.
15
13
3
3
1
-(4-Methoxyphenyl)-3-methyl-5-nitro-1H-indazole (11d). Yield: 266 mg (0.94 mmol, 94%) as a tan solid,
◦
−1
1
m.p. 159–160 C. IR: 2836, 1514, 1346 c cm ; H-NMR (DMSO-d ):
δ 8.88 (d, J = 2.2 Hz, 1H),
6
8
3
.26 (dd, J = 9.3, 2.2 Hz, 1H), 7.79 (d, J = 9.3 Hz, 1H), 7.65 (d, J = 8.1 Hz, 2H), 7.15 (d, J = 8.1 Hz, 2H),
.85 (s, 3H), 2.69 (s, 3H); 13C-NMR (DMSO-d ):
δ 158.9, 146.7, 142.0, 141.2, 132.2, 124.8, 123.9, 122.5,
6
+
119.3, 1153, 111.4, 56.0, 12.1; MS: m/z 283 (M ), calculated m/z 283.10. Anal. Calcd. for C H N O :
15
13
3
3
C, 63.60; H, 4.63; N, 14.83. Found: C, 63.57; H, 4.60; N, 14.76.
1
-(4-Bromophenyl)-3-methyl-5-nitro-1H-indazole (11e). Yield: 314 mg, (0.95 mmol, 95%) as a tan solid,
◦
−1
1
m.p. 202–203 C; IR: 1512, 1345 cm ; H-NMR (DMSO-d ):
δ
8.90 (d, J = 2.2 Hz, 1H), 8.31 (dd, J = 9.2,
6
2
.2 Hz, 1H), 7.96 (d, J = 9.2 Hz, 1H), 7.80 (d, J = 8.8 Hz, 2H), 7.75 (d, J = 8.8 Hz, 2H), 2.69 (s, 3H);
13
C-NMR (DMSO-d ):
δ 147.7, 142.4, 141.1, 138.5, 133.1, 124.7, 124.6, 123.0, 120.1, 119.3, 111.8, 12.1;
6
+
MS: m/z 331 (M ), calculated m/z 331.00. Anal. Calcd. for C H BrN O : C, 50.62; H, 3.03; N, 12.65.
14
10
3
2
Found: C, 50.44; H, 2.99; N, 12.73.
1
1
1
7
-(3-Chlorophenyl)-3-methyl-5-nitro-1H-indazole (11f). Yield: 250 mg, (0.87 mmol, 87%) as a tan solid, m.p.
◦
−1 1
35–136 C; IR: 1517, 1339 cm ; H-NMR (DMSO-d6):
δ
8.89 (d, J = 2.2 Hz, 1H), 8.31 (dd, J = 9.3, 2.2 Hz,
H), 7.98 (d, J = 9.3 Hz, 1H), 7.83 (t, J = 2.2 Hz, 1H), 7.78 (d, J = 8.4 Hz, 1H), 7.64 (t, J = 8.1 Hz, 1H),
13
.52 (d, J = 8.0 Hz, 1H), 2.69 (s, 3H); C-NMR (DMSO-d ):
δ 146.8, 141.1, 139.3, 133.4, 130.8, 126.4,
6
+
123.6, 122.0, 121.4, 120.1, 118.2, 110.9; MS: m/z 287 (M ), calculated m/z 287.05. Anal. Calcd.
for C H ClN O : C, 58.45; H, 3.50; N, 14.61. Found: C, 58.58; H, 3.59; N, 14.53.
14
10
3
2
1
2
-(4-Chlorophenyl)-3-methyl-5-nitro-1H-indazole (11g). Yield: 267 mg (0.93 mmol, 93%) as a tan solid, m.p.
◦ −1 1
17–218 C; IR: 1511, 1339 cm ; H-NMR (DMSO-d6): δ 8.91 (d, J = 2.2 Hz, 1H), 8.31 (dd, J = 9.3, 2.2 Hz,
13
1
(
2
5
H), 7.95 (d, J = 9.3 Hz, 1H), 7.82 (d, J = 8.7 Hz, 2H), 7.67 (d, J = 8.7 Hz, 2H), 2.69 (s, 3H); C-NMR
DMSO-d ): 147.7, 1424, 141.1, 138.1, 131.8, 130.2, 124.6, 124.5, 123.0, 119.4, 111.8, 12.1; MS: m/z
87 (M ), calculated m/z 287.05. Anal. Calcd. for C H ClN O : C, 58.45; H, 3.50; N, 14.61. Found: C,
δ
6
+
14
10
3
2
8.42; H, 3.49; N, 14.48.
◦
-(2,4-Dichlorophenyl)-3-methyl-5-nitro-1H-indazole (11h). Yield: 257 mg (0.80 mmol, 80%), m.p. 144–145 C;
1
−1
1
IR: 1516, 1338 cm ; H-NMR (DMSO-d ):
δ
8.92 (d, J = 2.1 Hz, 1H), 8.27 (dd, J = 9.2, 2.1 Hz, 1H)
.01 (d, J = 2.2 Hz, 1H), 7.74 (d, J = 8.5 Hz, 1H), 7.69 (dd, J = 8.5, 2.2 Hz, 1H), 7.44 (d, J = 9.2 Hz, 1H),
.68 (s, 3H); 13C-NMR (DMSO-d6):
147.5, 143.1, 142.4, 135.3, 135.0, 132.0, 131.5, 130.7, 129.3, 123.5, 122.8,
,
6
8
2
δ
+
1
19.3, 111.6, 12.1; MS: m/z 321 (M ), calculated m/z 321.01. Anal. Calcd. for C H Cl N O : C, 52.20;
14 9 2 3 2
H, 2.82; N, 13.04. Found: C, 52.11; H, 2.91; N, 13.09.