Water → 2-(2-Tert-butylphenoxy)-6-chloro-3-nitropyridine

反応式

CC1C=C(C)C=C(C)N=1.[C:10]([C:14]1[CH:30]=[CH:29][CH:28]=[CH:27][C:15]=1[O:16][C:17]1[N:22]=[C:21](O)[CH:20]=[CH:19][C:18]=1[N+:24]([O-:26])=[O:25])([CH3:13])([CH3:12])[CH3:11].O.P(Cl)(Cl)([Cl:34])=O>>[C:10]([C:14]1[CH:30]=[CH:29][CH:28]=[CH:27][C:15]=1[O:16][C:17]1[C:18]([N+:24]([O-:26])=[O:25])=[CH:19][CH:20]=[C:21]([Cl:34])[N:22]=1)([CH3:13])([CH3:12])[CH3:11]

参加物

反応物 4

HCID 962Water

HCID 79532,4,6-Trimethylpyridine

HCID 24813Phosphorus oxychloride

HCID 178440819HCID 178440819、化合物

生成物 1

HCID 598574142-(2-Tert-butylphenoxy)-6-chloro-3-nitropyridine収率 77%

反応条件

温度: 130 °C

実験手順

2,4,6-Trimethylpyridine (1.6 mL) was added dropwise into 136a (2.32 g, 8.0 mmol) in phosphorus oxychloride (3.2 mL) at 0° C. The reaction mixture was heated at 130° C. for 20 h. The reaction was stopped at ˜70% conversion as determined by HPLC. The dark brown solution was poured into water (40 mL) with stirring, and stirred for 15 min. The brown precipitate was filtered, air dried, and purified by SiO2 chromatography (120 g), loaded with a CH2Cl2 and eluted using a gradient of ethyl acetate in hexanes to afford 136b (1.91 g, 77% yield) as an amber colored oil; HPLC purity 100%, 3.95 min (Method A); 1H NMR (500 MHz, CDCl3) δ ppm 8.36 (d, 1H, J, J=10.0 Hz), 7.47 (d, 1H, J=5.0 Hz), 7.23 (m, 2H), 7.16 (d, 1H, J=10.0 Hz), 6.95 (d, 1H, J=10.0 Hz), 1.36 (s, 9H); 13C (125 MHz, CDCl3) δ (ppm), 155.30, 153.23, 150.87, 141.45, 137.72, 133.22, 127.59, 126.91, 125.79, 123.04, 118.39, 34.60, 30.25.