Chlorotrimethylsilane → 2-(2,5-Dimethyl-1H-pyrrol-1-yl)-4-methyl-6-((trimethylsilyl)methyl)pyridine

HRID 73480

反応式

HRID 73480 の反応式
[CH3:1][C:2]1[N:3]([C:8]2[CH:13]=[C:12]([CH3:14])[CH:11]=[C:10]([CH3:15])[N:9]=2)[C:4]([CH3:7])=[CH:5][CH:6]=1.[Li]CCCC.Cl[Si:22]([CH3:25])([CH3:24])[CH3:23]>C1COCC1>[CH3:7][C:4]1[N:3]([C:8]2[CH:13]=[C:12]([CH3:14])[CH:11]=[C:10]([CH2:15][Si:22]([CH3:25])([CH3:24])[CH3:23])[N:9]=2)[C:2]([CH3:1])=[CH:6][CH:5]=1

参加物

5

反応物 3

HCID 6397ChlorotrimethylsilaneHCID 224907362-(2,5-Dimethyl-1H-pyrrol-1-yl)-4,6-dimethylpyridineHCID 178418339Butyllithium

生成物 1

HCID 426256202-(2,5-Dimethyl-1H-pyrrol-1-yl)-4-methyl-6-((trimethylsilyl)methyl)pyridine収率 95%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of 8 (6.0 g, 30 mmol) in THF (100 mL) at 0° C. was added n-BuLi (1.6 M in hexanes, 21 mL, 33 mmol). The solution turned dark red during the addition. After stirring at the same temperature for an additional 2 h, chlorotrimethylsilane (4.2 mL, 33 mmol) was added dropwise to the reaction mixture. The reaction was warmed to room temperature and allowed to stir for an additional 1 h. The resulting bright yellow slurry was partitioned between EtOAc (200 mL) and H2O (100 mL). The organic layer was washed with brine (100 mL), dried over NaSO4, and concentrated. The crude product was purified by flash column chromatography (EtOAc/hexanes, 1:19-1:9) to give 9 (7.7 g, 28.5 mmol, 95%) as a pale yellow oil: 1H NMR (500 MHz, CDCl3) δ 0.10 (s, 9H), 2.13 (s, 6H), 2.39 (s, 3H), 2.41 (s, 3H), 5.89 (s, 2H), 6.78 (s, 1H), 6.85 (s, 1H); 13C NMR (125 MHz, CDCl3) δ−1.5, 13.1, 20.9, 29.8, 106.2, 118.7, 121.9, 128.3, 148.8, 151.5, 161.4; LCQ-MS (M+H+) calcd for C16H25N2Si 273. found 273; LC-TOF-MS (M+H+) calcd for C16H25N2Si 273.17870. found 273.17735.

後処理

  1. additionThe solution turned dark red during the addition
  2. stirringto stir for an additional 1 h
  3. customThe resulting bright yellow slurry was partitioned between EtOAc (200 mL) and H2O (100 mL)
  4. washThe organic layer was washed with brine (100 mL)
  5. dry with materialdried over NaSO4
  6. concentrationconcentrated
  7. customThe crude product was purified by flash column chromatography (EtOAc/hexanes, 1:19-1:9)

出典と根拠

ORDレコード
ord-74bde0d892b6490fa8bef7b615855925
出典データセット
uspto-grants-2014_09
特許番号
US08829187B1

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