10.1002/adsc.201801547
Advanced Synthesis & Catalysis
Hz), 150.1 (d, JC–F = 10.5 Hz), 141.5 (d, JC–F = 6.6 Hz),
127.0 (d, JC–F = 9.6 Hz), 125.0 (d, JC–F = 1.0 Hz), 122.3 (d,
2855, 1630, 1590, 1538, 1507, 1449, 1384, 13634, 1270,
1223, 1189, 1132, 1046, 993, 959, 865, 830 cm-1; HRMS
(orbitrap, ESI) calcd for C15H13F2N2 [M+H]+ 259.1047,
found 259.1041.
JC–F = 19.3 Hz), 122.2 (d, JC–F = 3.3 Hz), 118.8 (d, JC–F
=
11.7 Hz), 118.7 (d, JC–F = 10.6 Hz), 115.9 (d, JC–F = 23.0
Hz), 114.4 (d, JC–F = 29.3 Hz), 110.8 (d, JC–F = 19.8 Hz),
10.0 (d, JC–F = 4.5 Hz), 8.8 (d, JC–F = 3.8 Hz); 19F NMR
(470 MHz, CDCl3) δ -114.0, -120.8; IR (KBr) υ 3126,
3058, 2925, 2856, 2742, 1634, 1584, 1494, 1475, 1394,
1378, 1362, 1311, 1245, 1205, 1159, 1108, 1090, 1064,
1023, 962, 906, 854, 790, 780 cm-1; HRMS (orbitrap, ESI)
calcd for C15H13F2N2 [M+H]+ 259.1047, found 259.1041.
7-Chloro-2-(2-chloro-4-methylphenyl)-5-methyl-2H-
indazole (3j): 29.1 mg (50%); light yellow solid; mp =
115.7–117.0 °C; 1H NMR (400 MHz, CDCl3) 8.21 (s, 1H),
7.58 (d, J = 8.4 Hz, 1H), 7.37 (s, 1H), 7.36 (s, 1H), 7.22 (s,
1H), 7.21 (d, J = 8.4 Hz, 1H), 2.41 (s, 6H); 13C NMR (100
MHz, CDCl3) δ 145.8, 140.7, 135.9, 132.3, 130.7, 128.7,
128.5, 128.3 (two carbons overlap), 125.5, 123.2, 122.5,
117.4, 21.5, 20.9; IR (KBr) υ 3141, 3035, 2969, 2917,
2857, 2731, 1908, 1728, 1633, 1530, 1501, 1453, 1407,
1375, 1330, 1264, 1222, 1262, 1136, 1079, 1032, 1016,
981, 957, 890, 846, 814, 739 cm-1; HRMS (quadrupole, EI)
calcd for C15H12Cl2N2 [M]+ 290.0378, found 290.0384.
2-(2,4-Dimethylphenyl)-5,7-dimethyl-2H-indazole (3f):
45.1 mg (90%); light yellow oil; 1H NMR (400 MHz,
CDCl3) δ 7.92 (s, 1H), 7.31–7.29 (m, 2H), 7.15 (s, 1H),
7.11 (d, J = 8.0 Hz, 1H), 6.95 (s, 1H), 2.63 (s, 3H), 2.41 (s,
3H), 2.39 (s, 3H), 2.18 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 148.4, 138.9, 138.1, 133.8, 131.7, 131.6, 128.2,
127.5, 127.0, 126.4, 123.7, 121.9, 115.6, 21.7, 21.1, 17.7,
17.1; IR (KBr) υ 3120 3014, 2916, 2857, 2731, 1558, 1535,
1509, 1447, 1392, 1377, 1332, 1250, 1202, 1131, 1040,
964, 840, 815, 746 cm-1; HRMS (orbitrap, ESI) calcd for
C17H19N2 [M+H]+ 251.1548, found 251.1543.
4-Fluoro-2-(5-fluoro-2-methylphenyl)-7-methyl-2H-
indazole (3k): 30.0 mg (58%); light yellow solid; mp =
1
84.6–85.1 °C; H NMR (400 MHz, CDCl3) δ 8.15 (s, 1H),
7.33 (dd, J = 8.4, 6.0 Hz, 1H), 7.22 (dd, J = 8.6, 2.6 Hz,
1H), 7.13 (td, J = 8.4, 2.8 Hz, 1H), 6.99 (ddd, J = 7.4, 5.0,
1.0 Hz, 1H), 6.66 (dd, J = 10.4, 7.2 Hz, 1H), 2.60 (s, 3H),
2.23 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.8 (d, JC–F
5-Bromo-2-(4-bromo-2-methylphenyl)-7-methyl-2H-
1
indazole (3g): 54.7 mg (72%); dark yellow oil; H NMR
= 245.1 Hz), 153.9 (d, JC–F = 250.0 Hz), 151.3 (d, JC–F =
(400 MHz, CDCl3) δ 7.98 (s, 1H), 7.71 (s, 1H), 7.52 (s,
1H), 7.46 (dd, J = 8.4, 1.6 Hz, 1H), 7.29 (d, J = 8.0 Hz,
1H), 7.18 (s, 1H), 2.62 (s, 3H), 2.21 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 148.3, 139.1, 136.1, 134.1, 130.2,
129.7, 129.0, 127.9, 123.9, 123.1, 122.7, 119.6, 115.9, 17.7,
16.8; IR (KBr) υ 3117, 3085, 2921, 2852, 2757, 1725,
1614, 1552, 1515, 1489, 1433, 1370, 1317, 1285, 1239,
1180, 1126, 1088, 1069, 1041, 999, 956, 879, 845, 816,
765 cm-1; HRMS (orbitrap, ESI) calcd for C15H13Br2N2
[M+H]+ 378.9445, found 378.3440.
5.3 Hz), 140.5 (d, JC–F = 9.6 Hz), 132.4 (d, JC–F = 8.2 Hz),
129.5 (d, JC–F = 3.6 Hz), 125.1 (d, JC–F = 6.5 Hz), 123.8 (d,
JC–F = 4.7 Hz), 121.9 (d, JC–F = 4.2 Hz), 116.3 (d, JC–F
=
20.5 Hz), 114.1 (d, JC–F = 24.0 Hz), 113.6 (d, JC–F = 20.3
Hz), 104.9 (d, JC–F = 17.2 Hz), 17.3, 16.6; 19F NMR (470
MHz, CDCl3) δ -115.8, -121.8; IR (KBr) υ 3131, 3073,
3040, 2970, 2926, 2855, 2746, 1645, 1612, 1570, 1544,
1508, 1476, 1394, 1348, 1243, 1166, 1118, 1045, 976, 882,
865, 811, 785, 742 cm-1; HRMS (orbitrap, ESI) calcd for
C15H13F2N2 [M+H]+ 259.1047, found 259.1041.
5-Chloro-2-(4-chloro-2-methylphenyl)-7-methyl-2H-
indazole (3h): 39.0 mg (67%); light yellow solid; mp =
104.0–104.8 °C; H NMR (400 MHz, CDCl3) δ 7.99 (s,
4-Chloro-2-(5-chloro-2-methylphenyl)-7-methyl-2H-
indazole (3l): 7.0 mg (12%); orange oil; H NMR (400
1
1
MHz, CDCl3) δ 8.14 (s, 1H), 7.48 (d, J = 2.0 Hz, 1H), 7.38
(dd, J = 8.2, 2.2 Hz, 1H), 7.31 (d, J = 8.4 Hz, 1H), 7.05–
7.00 (m, 2H), 2.61 (s, 3H), 2.24 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 150.0, 140.7, 132.5, 132.4, 131.9, 129.4,
126.9, 126.8, 125.9, 124.2, 122.5, 121.9, 121.7, 17.5, 16.7;
IR (KBr) υ 3127, 3072, 3029, 2924, 2737, 1824, 1732,
1625, 1601, 1573, 1533, 1496, 1445, 1397, 1382, 1339,
1232, 1186, 1132, 1094, 1046, 998, 975,0945, 875, 813,
786 cm-1; HRMS (orbitrap, ESI) calcd for C15H13Cl2N2
[M+H]+ 291.0456, found 291.0450.
1H), 7.54 (s, 1H), 7.38–7.36 (m, 2H), 7.34 (dd, J = 8.4, 2.0
Hz, 1H), 7.08 (s, 1H), 2.63 (s, 3H), 2.22 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 148.0, 138.5, 135.9, 135.1, 131.2,
129.9, 128.1, 127.8, 127.0, 126.8, 124.3, 121.9, 116.2, 17.8,
17.0; IR (KBr) υ 3121, 2923, 2853, 1618, 1519, 1494,
1442, 1372, 1319, 1239, 1183, 1126, 1099, 1075, 1043,
984, 958, 894, 846, 819, 786 cm-1; HRMS (quadrupole, EI)
calcd for C15H12Cl2N2 [M]+ 290.0378, found 290.0379.
5-Fluoro-2-(4-fluoro-2-methylphenyl)-7-methyl-2H-
indazole (3i): 24.3 mg (47%); yellow solid; mp = 107.1–
108.2 °C; 1H NMR (400 MHz, CDCl3) δ 7.98 (s, 1H), 7.39
(dd, J = 8.6, 5.4 Hz, 1H), 7.12 (dd, J = 9.0, 2.2 Hz, 1H),
7.08–6.99 (m, 2H), 6.92 (d, J = 10.0 Hz, 1H), 2.65 (s, 3H),
2.20 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 162.5 (d, JC–F
= 247.3 Hz), 158.6 (d, JC–F = 238.5 Hz), 147.1, 136.9 (d,
JC–F = 8.7 Hz), 136.4 (d, JC–F = 2.7 Hz), 130.7 (d, JC–F = 9.7
Hz), 128.3 (d, JC–F = 9.4 Hz), 124.8 (d, JC–F = 8.5 Hz),
120.7 (d, JC–F = 12.4 Hz), 117.7 (d, JC–F = 22.5 Hz), 117.0
(d, JC–F = 28.5 Hz), 113.4 (d, JC–F = 22.7 Hz), 99.7 (d, JC–F
= 24.1 Hz), 17.8, 17.1 (d, JC–F = 1.0 Hz); 19F NMR (470
MHz, CDCl3) δ -112.5, -119.8; IR (KBr) υ 3059, 2927,
7-Ethyl-2-(2-ethylphenyl)-2H-indazole (3n): 37.1 mg
(74%); yellow sticky oil; H NMR (400 MHz, CDCl3) δ
1
8.07 (s, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.46–7.39 (m, 3H),
7.35–7.30 (m, 1H), 7.14–7.07 (m, 2H), 3.11 (q, J = 7.6 Hz,
2H), 2.55 (q, J = 7.6 Hz, 2H), 1.42 (t, J = 7.6 Hz, 3H), 1.11
(t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 148.8,
140.4, 140.0, 134.1, 129.6, 129.4, 126.9, 126.4, 124.6,
123.2, 122.4, 121.8, 117.6, 24.5, 24.3, 15.0, 14.0; IR (KBr)
υ 3118, 3063, 3033, 2965, 2931, 2872, 2731, 1621, 1582,
1531, 1498, 1456, 1389, 1648, 1261, 1184, 1124, 1050,
959, 945, 862, 805, 750 cm-1; HRMS (orbitrap, ESI) calcd
for C17H19N2 [M+H]+ 251.1548, found 251.1534.
6
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