Hexane → 2-Acetyl-6-(((tert-butyldimethylsilyl)oxy)methyl)pyridine

HRID 2218950

反応式

HRID 2218950 の反応式
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])[N:3]=1.CCCCCC.[Li]CCCC.[CH3:28][C:29](N(C)C)=[O:30]>CCOCC.C1COCC1>[C:29]([C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][O:9][Si:10]([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11])[N:3]=1)(=[O:30])[CH3:28]

参加物

7

反応物 4

HCID 8058HexaneHCID 31374DimethylacetamideHCID 11483477Pyridine, 2-bromo-6-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-HCID 178418339Butyllithium

生成物 1

HCID 597709522-Acetyl-6-(((tert-butyldimethylsilyl)oxy)methyl)pyridine

試薬・触媒・溶媒 2

HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred solution of 2-Bromo-6-(((tert-butyldimethylsilyl)oxy)methyl)pyridine (1.59 g, 5.26 mmol) in a mixture of ether, hexane and THF (2:1:1, 105 mL) was added n-BuLi (3.29 mL, 5.26 mmol, 1.6 M in hexane solution) dropwise at −78° C. during 5-10 min. To the resulting dark brown solution was dropped anhydrous DMA (0.74 mL, 7.89 mmol) at the same temperature. The reaction mixture was stirred for 30 min and then quenched with water (8 mL) and extracted with EtOAc. The organic layer was washed with water and brine and dried over MgSO4. After purification by column chromatography on silica gel (hexane/EtOAc 98:2) 0.78 g (56%) of the title compound as an oil were obtained. 1H NMR (CDCl3) δ 7.95 (d, 1H, J=7.5 Hz, H-3), 7.88 (t, 1H, J=7.6 Hz, H-4), 7.73 (t, 1H, J=7.6 Hz, H-5), 4.93 (s, 2H, CH2), 2.75 (s, 3H, CH3), 1.03 (s, 9H, (CH3)3C), 0.20 (s, 6H, (Me)2Si); 13C NMR (CDCl3) δ 200.8 (CO), 161.4 (C-6), 153.0 (C-2), 139.4 (C-4), 124.0 (C-5), 118.0 (C-3), 66.4 (CH2), 26.3 ((CH3)3C), 18.8 ((CH3)3C), -4.96 ((Me)2Si).

後処理

  1. customquenched with water (8 mL)
  2. extractionextracted with EtOAc
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried over MgSO4
  5. customAfter purification by column chromatography on silica gel (hexane/EtOAc 98:2) 0.78 g (56%) of the title compound as an oil
  6. customwere obtained

出典と根拠

ORDレコード
ord-4af98cd9957c417b8ae94fdec38ce77e
出典データセット
uspto-grants-2008_08
特許番号
US07414036B2

関連ノート

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