10.1002/cctc.201601243
ChemCatChem
FULL PAPER
[17]
6-Methyl-1-tosyl-1H-indazole (2an): 128.7 mg, 90% yield from N'-(2-
bromo-4-methyl-benzylidene)-4-methylbenzenesulfonohydrazide; 117.3
3-Methyl-1-(phenylsulfonyl)-1H-indazole (2ba):
126.5 mg, 93%
yield; Yellow solid; m. p. = 134 - 135 oC; 1H NMR (400 MHz, CDCl3): δ
8.10 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 4.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 1H),
7.49 - 7.43 (m, 2H), 7.35 (t, J = 8.0 Hz, 2H), 7.25 (t, J = 8.0 Hz, 1H), 2.45
(s, 3H); 13C NMR (100 MHz, CDCl3): δ 151.0, 141.2, 137.7, 133.9, 129.3,
129.2, 127.5, 126.3, 124.0, 120.7, 113.4, 12.4; IR (KBr): 2958, 1647,
1608, 1524, 1443, 1373, 1292, 1252, 1182, 1124, 974, 756, 721, 681 cm-
1; HRMS (ESI) m/z calculated for C14H12N2O2SNa [M+Na]+: 295.0512;
found 295.0507.
mg,
82%
yield
from
N'-(2-chloro-4-methylbenzylidene)-4-
methylbenzenesulfonohydrazide; White solid; m. p. = 129 - 130 oC; 1H
NMR (400 MHz, CDCl3): δ 8.10 (s, 1H), 8.00 (s, 1H), 7.85 (d, J = 8.0 Hz,
2H), 7.54 (d, J = 8.0 Hz, 1H), 7.23 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz,
1H), 2.54 (s, 3H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 145.3,
141.3, 140.9, 140.1, 134.7, 129.9, 127.5, 126.2, 123.9, 120.8, 112.9,
22.2, 21.7; IR (KBr): 3035, 2920, 2852, 1695, 1595, 1487, 1373, 1311,
870, 816 cm-1; HRMS (ESI) m/z calculated for C15H14N2O2SNa [M+Na]+:
309.0668; found 309.0669.
3-Phenyl-1-(phenylsulfonyl)-1H-indazole (2bb): 148.7 mg, 89% yield;
White solid; m. p. = 186 - 187 oC; 1H NMR (400 MHz, CDCl3): δ 8.29 (d, J
= 8.0 Hz, 1H), 8.03 (d, J = 8.0 Hz, 2H), 7.92 (t, J = 8.0 Hz, 3H), 7.62 -
7.42 (m, 7H), 7.39 (t, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ
151.9, 141.9, 137.7, 134.1, 131.4, 129.7, 129.2, 128.9, 128.3, 127.6,
124.6, 124.4, 121.8, 113.6; IR (KBr): 3062, 2924, 2856, 1065, 1520,
1485, 1444, 1369, 1292, 1254, 1170, 1130, 739, 689 cm-1; HRMS (ESI)
m/z calculated for C19H14N2O2SNa [M+Na]+: 357.0668; found 357.0663.
6-Fluoro-1-tosyl-1H-indazole (2ao):[18]137.9 mg, 95% yield; White solid;
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m. p. = 175 - 176 C; H NMR (400 MHz, CDCl3): δ 8.14 (s, 1H), 7.97 -
7.83 (m, 3H), 7.64 (dd, J = 8.7, 5.1 Hz, 1H), 7.30 - 7.24 (m, 2H), 7.09 (td,
J = 8.8, 2.1 Hz, 1H), 2.37 (s, 3H).; 13C NMR (100 MHz, CDCl3): δ 163.5
(JC-F = 248.0 Hz), 145.8, 141.0, 140.9 (JC-F = 14.0 Hz), 134.4, 130.0,
127.7, 122.8 (JC-F = 11.0 Hz), 122.4, 113.8 (JC-F = 25.0 Hz), 100.1 (JC-F
=
28.0 Hz), 21.7; IR (KBr): 2924, 2852, 1619, 1591, 1481, 1373, 1313,
1242, 1173, 1120, 1070, 943, 856, 673, 582, 539 cm-1; HRMS (ESI) m/z
calculated for C14H11FN2O2SNa [M+Na]+: 313.0417; found 313.0423.
5-Fluoro-3-methyl-1-(phenylsulfonyl)-1H-indazole (2bc): 137.8 mg,
95% yield; White solid; m. p. = 139 - 140 oC; 1H NMR (400 MHz, CDCl3):
δ 8.12 (dd, J = 8.0, 4.0 Hz, 1H), 7.93 (d, J = 8.0 Hz, 2H), 7.55 (t, J = 8.0
Hz, 1H), 7.44 (t, J = 8.0 Hz, 2H), 7.28 (td, J = 8.0, 4.0 Hz, 1H), 7.21 (dd, J
= 8.0, 4.0 Hz, 1H), 2.48 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 159.6 (d,
JC-F = 242.0 Hz), 150.6 (d, JC-F = 5.0 Hz), 137.8, 137.4, 134.2, 129.2,
7-Chloro-1-tosyl-1H-indazole (2ap): 144.4 mg, 94% yield; White solid;
m. p. = 114 - 115 oC; 1H NMR (400 MHz, CDCl3): δ 8.23 (s, 1H), 7.89 (d,
J = 8.3 Hz, 2H), 7.62 (d, J = 7.8 Hz, 1H), 7.51 (d, J = 7.8 Hz, 1H), 7.28 (d,
J = 8.3 Hz, 2H), 7.22 (t, J = 7.8 Hz, 1H), 2.38 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 145.4, 139.8, 137.2, 135.5, 131.4, 129.8, 129.6, 128.3, 125.1,
120.2, 118.8, 21.7; IR (KBr): 3089, 2921, 2854, 1925, 1595, 1502, 1456,
1385, 1335, 1184, 1089, 1041, 953, 819, 673, 569, 538 cm-1; HRMS
(ESI) m/z calculated for Chemical Formula: C14H11ClN2O2SNa [M+Na]+:
329.0122; found 329.0120.
127.5, 126.9 (d, JC-F = 9.0 Hz), 118.1 (d, JC-F = 26.0 Hz), 114.8 (d, JC-F
=
10.0 Hz), 105.6 (d, JC-F = 24.0 Hz), 12.3; IR (KBr): 3076, 2922, 2854,
1620, 1525, 1323, 1277, 1182, 891, 858, 814, 756, 725, 682 cm-1; HRMS
(ESI) m/z calculated for C14H11FN2O2SNa [M+Na]+: 313.0417; found
313.0412.
1-(Phenylsulfonyl)-1H-indazole (2bd): 118.7 mg, 92% yield; White
solid; m. p. = 83 - 84 oC; 1H NMR (400 MHz, CDCl3): δ 8.25 - 8.16 (m,
2H), 7.98 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 8.0 Hz, 1H), 7.56 (q, J = 8.0 Hz,
2H), 7.44 (t, J = 8.0 Hz, 2H), 7.33 (t, J = 8.0 Hz, 1H); 13C NMR (100 MHz,
CDCl3): δ 141.6, 140.3, 137.5, 134.2, 129.4, 129.3, 127.5, 125.9, 124.3,
121.5, 113.1; IR (KBr): 3058, 2852, 1647, 1608, 1579, 1500, 1379, 1311,
1286, 1244, 1182, 1124, 760, 725 cm-1; HRMS (ESI) m/z calculated for
C13H10N2O2SNa [M+Na]+: 281.0355; found 281.0347.
1-Tosyl-1H-[1,3]dioxolo[4,5-f]indazole (2aq):[18] 145.4 mg, 92% yield;
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White solid; m. p. = 188 - 189 C; H NMR (400 MHz, CDCl3): δ 7.97 (s,
1H), 7.83 (d, J = 8.0 Hz, 2H), 7.61 (s, 1H), 7.24 (d, J = 8.0 Hz, 2H), 6.91
(s, 1H), 6.07 (s, 2H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 150.7,
146.4, 145.4, 141.0, 137.1, 134.5, 129.9, 127.6, 120.4, 102.3, 98.2, 93.7,
21.7; IR (KBr): 2920, 2856, 1687, 1626, 1595, 1506, 1467, 1377, 1323,
808 cm-1; HRMS (ESI) m/z calculated for C15H12N2O4SNa [M+Na]+:
339.0410; found 339.0411.
5-Bromo-1-(phenylsulfonyl)-1H-indazole (2be): 157.9 mg, 94% yield;
White solid; m. p. = 93 - 94 oC; 1H NMR (400 MHz, CDCl3): δ 8.16 - 8.08
(m, 2H), 7.98 (d, J = 8.0 Hz, 2H), 7.84 (s, 1H), 7.66 (d, J = 8.0 Hz, 1H),
7.59 (t, J = 8.0 Hz, 1H), 7.48 (t, J = 8.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 140.4, 139.1, 137.3, 134.5, 132.4, 129.4, 127.6, 127.4, 123.9,
117.6, 114.6; IR (KBr): 2922, 2852, 1657, 1633, 1491, 1379, 1296, 1241,
1172, 903, 874, 810, 727, 702, 592, 555 cm-1; HRMS (ESI) m/z
calculated for C13H9BrN2O2SNa [M+Na]+: 358.9460; found 358.9453.
1-Tosyl-1H-benzo[g]indazole (2ar): 148.3 mg, 92% yield; White solid;
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1
m. p. = 112 - 113 C; H NMR (400 MHz, CDCl3): δ 9.42 (d, J = 8.6 Hz,
1H), 8.26 (s, 1H), 7.96 (d, J = 7.6 Hz, 1H), 7.77 - 7.56 (m, 6H), 7.17 (d, J
= 8.1 Hz, 2H), 2.31 (s, 3H).; 13C NMR (100 MHz, CDCl3): δ 145.4, 141.5,
138.9, 134.6, 134.4, 129.8, 129.0, 127.9, 127.4, 127.3, 127.1, 125.9,
124.8, 121.8, 118.1, 21.7.; IR (KBr): 3057, 2922, 2852, 1593, 1375, 1311,
1178, 1092, 1012, 866, 809, 675, 579 cm-1; HRMS (ESI) m/z calculated
for C18H15N2O2S [M+H]+: 323.0849; found 323.0845.
6-Methyl-1-(phenylsulfonyl)-1H-indazole (2bf): 129.2 mg, 95% yield;
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1
3-Methyl-1-tosyl-1H-pyrazolo[3,4-b]pyridine (2as): 139.2 mg, 97%
yield; White solid; m. p. = 168 - 169 oC; 1H NMR (400 MHz, CDCl3): δ
8.71 (dd, J = 4.7, 1.6 Hz, 1H), 8.05 (d, J = 8.4 Hz, 2H), 7.97 (dd, J = 8.0,
1.6 Hz, 1H), 7.32 - 7.23 (m, 3H), 2.56 (s, 3H), 2.36 (s, 3H); 13C NMR (100
MHz, CDCl3): δ 152.3, 150.5, 147.9, 145.4, 135.1, 130.0, 129.8, 128.0,
119.3, 118.0, 21.7, 12.8; IR (KBr): 3444, 1591, 1442, 1379, 1242, 1176,
1119, 1070, 976, 804, 760, 665, 584, 532 cm-1; HRMS (ESI) m/z
calculated for C14H13N3O2SNa [M+Na]+: 310.0621; found 310.0614.
CCDC 1505834 contains the crystallographic data for 2as that can be
White solid; m. p. = 105 - 106 C; H NMR (400 MHz, CDCl3): δ 8.11 (s,
1H), 8.02 - 7.95 (m, 3H), 7.54 (d, J = 8.0 Hz, 2H), 7.44 (t, J = 8.0 Hz, 2H),
7.15 (d, J = 8.0 Hz, 1H), 2.54 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
141.5, 141.0, 140.3, 137.7, 134.1, 129.3, 127.5, 126.3, 123.9, 120.9,
112.9, 22.3; IR (KBr): 3099, 3068, 2922, 2854, 1612, 1485, 1377, 1313,
1180, 895, 810, 756, 725, 682 cm-1; HRMS (ESI) m/z calculated for
C14H12N2O2SNa [M+Na]+: 295.0512; found 295.0507.
1-(Phenylsulfonyl)-1H-[1,3]dioxolo[4,5-g]indazole (2bg): 140.4 mg,
93% yield; White solid; m. p. = 192 - 193 oC; 1H NMR (400 MHz, CDCl3):
δ 8.05 - 7.90 (m, 3H), 7.63 (s, 1H), 7.58 (t, J = 8.0 Hz, 1H), 7.47 (t, J =
8.0 Hz, 2H), 6.93 (s, 1H), 6.08 (s, 2H); 13C NMR (100 MHz, CDCl3): δ
150.8, 146.5, 141.3, 137.5, 137.2, 134.2, 129.3, 127.6, 120.5, 102.4,
obtained
free
of
charge
from
the
CCDC
via
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