5-bromo-7-(bromomethyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazole → 5-Bromo-7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazole

HRID 913799ノート

反応式

HRID 913799 の反応式
BrC1C=C2C(=C(CBr)C=1)N(COCC[Si](C)(C)C)N=C2.[Br:21][C:22]1[CH:30]=[C:29]([CH2:31]Br)[C:28]2[C:24](=[CH:25][N:26]([CH2:33][O:34][CH2:35][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])[N:27]=2)[CH:23]=1>>[Br:21][C:22]1[CH:30]=[C:29]([CH3:31])[C:28]2[C:24](=[CH:25][N:26]([CH2:33][O:34][CH2:35][CH2:36][Si:37]([CH3:38])([CH3:40])[CH3:39])[N:27]=2)[CH:23]=1

参加物

3

反応物 2

HCID 575461635-bromo-7-(bromomethyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazoleHCID 575462265-bromo-7-(bromomethyl)-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazole

生成物 1

HCID 115809285-Bromo-7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazole

実験手順

5-Bromo-7-(bromomethyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazole and 5-Bromo-7-(bromomethyl)-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazole. A flask was charged with 5-bromo-7-methyl-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazole (2.0 g, 5.86 mmol), N-bromosuccinimide (1.04 g, 5.86 mmol), benzoic peroxyanhydride (0.043 g, 0.18 mmol), and carbon tetrachloride (12 mL). The reaction was heated at reflux overnight. The reaction was concentrated. The resulting residue was suspended in diethyl ether (10 mL). To this was added pentane (20 mL). After stirring for 5 min, the solid was removed by filtration and the mother liquor concentrated. The residue was purified by column chromatography (3%→8% EtOAc/Hex) to give 3 fractions. The fastest eluting fraction was concentrated to give 5-bromo-7-(bromomethyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazole (0.95 g, 39%). The slowest eluting fraction was concentrated to give 5-bromo-7-(bromomethyl)-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazole (420 mg, 17%). 5-Bromo-7-(bromomethyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazole: 1H-NMR (CDCl3, 500 MHz) δ 7.95 (s, 1H), 7.84 (d, J=1.5 Hz, 1H), 7.49 (d, J=1.5 Hz, 1H), 5.98 (s, 2H), 4.93 (s, 2H), 3.50 (t, J=8.2 Hz, 2H), 0.85 (t, J=8.2 Hz, 2H), <0.10 (s, 9H); 13C-NMR (CDCl3, 126 MHz) δ 136.2, 133.5, 132.0, 128.4, 124.6, 123.1, 114.1, 80.4, 66.4, 29.8, 17.9, −1.4. 5-Bromo-7-(bromomethyl)-2-((2-(trimethylsilyl)ethoxy)methyl)-2H-indazole: 1H-NMR (CDCl3, 500 MHz) δ 8.07 (s, 1H), 7.79 (d, J=1.5 Hz, 1H), 7.41 (d, J=1.5 Hz, 1H), 5.72 (s, 2H), 4.84 (s, 2H), 3.64 (t, J=8.2 Hz, 2H), 0.93 (t, J=8.2 Hz, 2H), 0.00 (s, 9H); 13C-NMR (CDCl3, 126 MHz) δ 145.6, 130.2, 129.3, 123.8, 123.4, 122.8, 115.2, 82.1, 67.9, 28.2, 18.0, −1.3.

出典と根拠

ORDレコード
ord-00957191f52a4c97a452e568f82cad79
出典データセット
uspto-grants-2011_09
特許番号
US08026257B2

反応ノート

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