Dimethylformamide → 4-Methoxy-3-(4-methoxy-butyl)-benzaldehyde

HRID 1158447ノート

反応式

HRID 1158447 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[C:4]([CH2:10][CH2:11][CH2:12][CH2:13][O:14][CH3:15])[CH:3]=1.C([Li])CCC.CCCCCC.CN([CH:30]=[O:31])C>C1COCC1>[CH3:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([CH:30]=[O:31])=[CH:3][C:4]=1[CH2:10][CH2:11][CH2:12][CH2:13][O:14][CH3:15]

参加物

6

反応物 4

HCID 6228DimethylformamideHCID 8058HexaneHCID 214586274-Bromo-1-methoxy-2-(4-methoxybutyl)benzeneHCID 178418339Butyllithium

生成物 1

HCID 862481464-Methoxy-3-(4-methoxy-butyl)-benzaldehyde

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

To a solution of 4-bromo-1-methoxy-2-(4-methoxy-butyl)-benzene (8.10 g, 29.7 mmol; described in EP0678 503 B1) in absolute THF (170 mL), cooled to −78° C., is added dropwise over 30 min and under an argon atmosphere a 1.6M solution of n-butyllithium in hexane (20.4 mL, 32.6 mmol). After stirring for 5 min, a mixture of DMF (5.03 mL, 65.2 mmol) in THF (20 mL) is added over 30 min at −78° C. Stirring is continued over 15 min at −78° C., and the reaction mixture is gradually warmed and stirred for an additional hour at room temperature before quenching with 1N HCl. The aqueous layer is extracted with diethyl ether (3×200 mL), the combined organics are dried (Na2SO4) and concentrated. Purification by flash chromatography on silica gel (hexane/AcOEt 4:1) gives the title compound as yellowish oil. TLC, Rf (hexane/AcOEt 4:1)=0.27. MS: 223.2 [M+H]+. 1H-NMR (CDCl3): δ 1.6-1.74 (m, 4H) 2.70 (t, 2H), 3.37 (s, 3H), 3.43 (t, 2H), 3.96 (s, 3H), 6.99 (dd, 1H), 7.73 (d, 1H), 7.76 (dd, 1H), 9.70 (s, 1H) ppm.

後処理

  1. additionis added over 30 min at −78° C
  2. stirringStirring
  3. waitis continued over 15 min at −78° C.
  4. temperaturethe reaction mixture is gradually warmed
  5. stirringstirred for an additional hour at room temperature
  6. custombefore quenching with 1N HCl
  7. extractionThe aqueous layer is extracted with diethyl ether (3×200 mL)
  8. dry with materialthe combined organics are dried (Na2SO4)
  9. concentrationconcentrated
  10. customPurification by flash chromatography on silica gel (hexane/AcOEt 4:1)

出典と根拠

ORDレコード
ord-9c9a82d1a3ac45abb53562a5bfc84a12
出典データセット
uspto-grants-2010_10
特許番号
US07807709B2

反応ノート

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