10.1002/cctc.201601420
ChemCatChem
FULL PAPER
7.47 (m, 1H), 7.45 (d, J = 8.6 Hz, 1H), 7.41-7.30 (m, 2H), 7.23-7.16
(m, 3H), 7.14 (t, J = 7.8 Hz, 1H), 7.00-6.94 (m, 2H), 5.71 (d, J =
15.3 Hz, 1H), 5.57 (d, J = 15.3 Hz, 1H). 13C NMR (100 MHz,
CDCl3): = 147.9, 135.8, 133.4, 133.0, 132.7, 131.6, 131.5, 129.4,
128.5, 127.7, 126.9, 126.3, 122.6, 122.1, 119.4, 117.6, 117.0,
113.5, 55.1. Elemental analysis: calcd (%) for C21H15N3 (309.36): C
81.53, H 4.89; found: C 81.61, H 5.02.
7.98 (d, J = 8.4 Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H), 7.58-7.50 (m, 2H),
7.46 (d, J = 8.4 Hz, 2H), 7.45-7.30 (m, 3H), 7.20-7.15 (m, 3H), 7.06
(t, J = 8.0 Hz, 1H), 7.01-6.95 (m, 2H), 5.61 (d, J = 14.9 Hz, 1H),
5.38 (d, J = 14.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): = 148.2,
136.2, 134.3, 133.5, 132.2, 129.7, 129.2, 128.3, 128.2, 127.5,
127.3, 126.9, 126.8, 126.3, 126.2, 125.2, 125.1, 122.6, 121.6,
120.3, 117.4, 54.7. Elemental analysis: calcd (%) for C24H18N2
(334.41): C 86.20, H 5.43; found: C 86.14, H 5.50.
2-Benzyl-3-(2-(trifluoromethyl)phenyl)-2H-indazole (19): From
2-benzyl-2H-indazole
(0.270
g,
1.3
mmol)
and
2-
2-Benzyl-3-(pyridin-3-yl)-2H-indazole (23): From 2-benzyl-2H-
indazole (0.270 g, 1.3 mmol) and 3-bromopyridine (0.158 g, 1
mmol), 23 was obtained after purification by flash chromatography
on silica gel (pentane-Et2O, 60-40) in 83% (0.236 g) yield as a
(trifluoromethyl)bromobenzene (0.225 g, 1 mmol), 19 was obtained
after purification by flash chromatography on silica gel (pentane-
Et2O, 95-5) in 76% (0.268 g) yield as a green solid (mp: 142-144
°C). 1H NMR (400 MHz, CDCl3): = 7.89 (d, J = 7.8 Hz, 1H), 7.80
(d, J = 8.8 Hz, 1H), 7.61 (t, J = 7.8 Hz, 1H), 7.56 (t, J = 7.8 Hz, 1H),
7.57-7.20 (m, 5H), 7.17 (d, J = 7.6 Hz, 1H), 7.10-7.02 (m, 3H), 5.57
(d, J = 15.1 Hz, 1H), 5.24 (d, J = 15.1 Hz, 1H). 13C NMR (100 MHz,
CDCl3): = 147.9, 136.0, 133.6, 132.2, 131.6, 130.7 (q, J = 30.3
Hz), 129.8, 128.5, 128.0 (m), 127.8, 127.5, 126.6 (q, J = 5.0 Hz),
126.1, 123.2 (q, J = 273.8 Hz), 122.9, 121.8, 120.0, 117.4, 54.9.
19F{1H} NMR (376 MHz, CDCl3) = -60.2. Elemental analysis:
calcd (%) for C21H15F3N2 (352.35): C 71.58, H 4.29; found: C 71.30,
H 4.18.
yellow solid (mp: 122-124 °C). 1H NMR (400 MHz, CDCl3):
=
8.71 (d, J = 1.6 Hz, 1H), 8.70 (dd, J = 4.8, 1.3 Hz, 1H), 7.81 (d, J =
8.7 Hz, 1H), 7.70 (d, J = 7.9 Hz, 1H), 7.56 (d, J = 8.5 Hz, 1H), 7.43-
7.33 (m, 2H), 7.28-7.21 (m, 3H), 7.14 (t, J = 7.8 Hz, 1H), 7.07 (d, J
= 7.5 Hz, 2H), 5.65 (s, 2H). 13C NMR (100 MHz, CDCl3): = 150.0,
149.7, 148.2, 136.7, 136.3, 132.5, 128.7, 127.8, 126.6, 126.4,
125.9, 123.5, 122.5, 121.7, 119.4, 117.6, 54.6. Elemental analysis:
calcd (%) for C19H15N3 (285.34): C 79.98, H 5.30; found: C 80.12, H
5.14.
3-(2-Benzyl-2H-indazol-3-yl)quinoline (24): From 2-benzyl-2H-
indazole (0.270 g, 1.3 mmol) and 3-bromoquinoline (0.208 g, 1
mmol), 24 was obtained after purification by flash chromatography
on silica gel (pentane-Et2O, 55-45) in 93% (0.311 g) yield as a
2-Benzyl-3-(2-fluorophenyl)-2H-indazole (20): From 2-benzyl-
2H-indazole (0.270 g, 1.3 mmol) and 2-bromofluorobenzene (0.175
g,
1 mmol), 20 was obtained after purification by flash
chromatography on silica gel (pentane-Et2O, 90-10) in 80% (0.242
g) yield as a yellow solid (mp: 108-110 °C). 1H NMR (400 MHz,
CDCl3): = 7.82 (d, J = 8.6 Hz, 1H), 7.53 (d, J = 8.6 Hz, 1H), 7.50-
7.42 (m, 1H), 7.35 (t, J = 7.6 Hz, 2H), 7.30-7.20 (m, 5H), 7.12 (t, J =
7.8 Hz, 1H), 7.08-7.03 (m, 2H), 5.62 (s, 2H). 13C NMR (100 MHz,
CDCl3): = 159.7 (d, J = 249.0 Hz), 148.3, 136.2, 132.0 (d, J = 2.2
Hz), 131.2 (d, J = 8.1 Hz), 129.9, 128.4, 127.6, 127.1, 126.2, 124.4
(d, J = 3.7 Hz), 122.1, 122.0, 119.9, 117.5, 117.3, 116.2 (d, J = 21.6
Hz), 54.9 (d, J = 2.6 Hz). 19F{1H} NMR (376 MHz, CDCl3) = -
112.0. Elemental analysis: calcd (%) for C20H15FN2 (302.34): C
79.45, H 5.00; found: C 79.30, H 4.88.
yellow solid (mp: 186-188 °C). 1H NMR (400 MHz, CDCl3):
=
9.01 (d, J = 2.0 Hz, 1H), 8.20 (d, J = 8.4 Hz, 1H), 8.11 (d, J = 2.0
Hz, 1H), 7.85 (d, J = 8.7 Hz, 1H), 7.82-7.75 (m, 2H), 7.63-7.55 (m,
2H), 7.37 (t, J = 7.8 Hz, 1H), 7.30-7.18 (m, 3H), 7.17-7.10 (m, 3H),
5.68 (s, 2H). 13C NMR (100 MHz, CDCl3): = 150.2, 148.2, 147.5,
136.4, 136.3, 132.6, 130.3, 129.3, 128.6, 127.8, 127.7, 127.3,
127.2, 126.6, 126.4, 122.8, 122.5, 121.9, 119.4, 117.6, 54.6.
Elemental analysis: calcd (%) for C23H17N3 (335.40): C 82.36, H
5.11; found: C 82.40, H 4.98.
2-Benzyl-3-(pyrimidin-5-yl)-2H-indazole (25): From 2-benzyl-2H-
indazole (0.270 g, 1.3 mmol) and 5-bromopyrimidine (0.159 g, 1
mmol), 25 was obtained after purification by flash chromatography
on silica gel (pentane-Et2O, 55-45) in 92% (0.263 g) yield as a
yellow solid (mp: 80-100 °C). 1H NMR (400 MHz, CDCl3): = 9.24
(s, 1H), 8.74 (s, 2H), 7.79 (d, J = 8.7 Hz, 1H), 7.50 (d, J = 8.7 Hz,
1H), 7.33 (t, J = 7.8 Hz, 1H), 7.30-7.20 (m, 3H), 7.13 (t, J = 7.8 Hz,
1H), 7.30-6.99 (m, 2H), 5.60 (s, 2H). 13C NMR (100 MHz, CDCl3):
= 158.1, 156.5, 148.1, 135.8, 128.7, 128.6, 128.0, 126.5, 126.4,
124.5, 123.2, 122.0, 118.7, 117.8, 54.8. Elemental analysis: calcd
(%) for C18H14N4 (286.33): C 75.50, H 4.93; found: C 75.66, H 5.11.
2-Benzyl-3-(2-chlorophenyl)-2H-indazole (21)
2H-indazole (0.270 g, 1.3 mmol) and 2-bromochlorobenzene (0.191
g, mmol), 21 was obtained after purification by flash
:
From 2-benzyl-
1
chromatography on silica gel (pentane-Et2O, 80-20) in 73% (0.232
g) yield as a brown oil. 1H NMR (400 MHz, CDCl3): = 7.82 (d, J =
8.6 Hz, 1H), 7.58 (d, J = 8.6 Hz, 1H), 7.47-7.29 (m, 4H), 7.25 (d, J =
8.0 Hz, 1H), 7.24-7.18 (m, 3H), 7.08 (t, J = 7.8 Hz, 1H), 7.06-7.00
(m, 2H), 5.63 (d, J = 15.0 Hz, 1H), 5.46 (d, J = 15.0 Hz, 1H). 13C
NMR (100 MHz, CDCl3): = 148.1, 136.1, 134.8, 133.0, 132.6,
130.7, 130.0, 128.7, 128.4, 127.7, 127.3, 126.8, 126.1, 122.0,
121.8, 120.0, 117.5, 55.0. Elemental analysis: calcd (%) for
C20H15ClN2 (318.80): C 75.35, H 4.74; found: C 75.50, H 4.57.
1-(4-(2-Hexyl-2H-indazol-3-yl)phenyl)propan-1-one (26): From
2-hexyl-2H-indazole
(0.263
g,
1.3
mmol)
and
4-
bromopropiophenone (0.213 g, 1 mmol), 26 was obtained after
purification by flash chromatography on silica gel (pentane-Et2O,
75-25) in 81% (0.270 g) yield as a yellow oil. 1H NMR (400 MHz,
CDCl3): = 8.11 (d, J = 8.4 Hz, 2H), 7.72 (d, J = 8.4 Hz, 1H), 7.58
(d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 1H), 7.28 (t, J = 7.8 Hz, 1H),
7.06 (t, J = 7.8 Hz, 1H), 4.40 (t, J = 7.4 Hz, 2H), 3.04 (q, J = 7.4 Hz,
2-Benzyl-3-(naphthalen-1-yl)-2H-indazole (22): From 2-benzyl-
2H-indazole (0.270 g, 1.3 mmol) and 1-bromonaphthalene (0.207 g,
1 mmol), 22 was obtained after purification by flash chromatography
on silica gel (pentane-Et2O, 70-30) in 79% (0.264 g) yield as a
yellow oil. 1H NMR (400 MHz, CDCl3): = 8.03 (d, J = 8.4 Hz, 1H),
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