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

HRID 913799노트

반응식

HRID 913799 반응식
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

참가 물질

3

반응물 2

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

생성물 1

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

실험 절차

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.

출처 및 근거

ORD 기록
ord-00957191f52a4c97a452e568f82cad79
출처 데이터셋
uspto-grants-2011_09
특허 번호
US08026257B2

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