Methoxymethyl-triphenylphosphonium chloride → 4-(3-Fluoro-4-methylphenyl)-3,3-dimethylbutanal

HRID 1860662ノート

反応式

HRID 1860662 の反応式
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[Cl-].[CH3:12][O:13]C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[F:34][C:35]1[CH:36]=[C:37]([CH2:42][C:43]([CH3:47])([CH3:46])[CH:44]=O)[CH:38]=[CH:39][C:40]=1[CH3:41]>C1COCC1.Cl>[F:34][C:35]1[CH:36]=[C:37]([CH2:42][C:43]([CH3:47])([CH3:46])[CH2:44][CH:12]=[O:13])[CH:38]=[CH:39][C:40]=1[CH3:41]

参加物

6

反応物 3

HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 2733832Lithium HexamethyldisilazideHCID 186241913-(3-Fluoro-4-methylphenyl)-2,2-dimethylpropanal

生成物 1

HCID 186241884-(3-Fluoro-4-methylphenyl)-3,3-dimethylbutanal

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 8028Tetrahydrofuran溶媒3 回

実験手順

Lithium bis(trimethylsilyl)amide solution (55 ml, 55 mmol, 1M in THF) was added to a mixture methoxy methyl triphenyl phosphonium chloride (18.9 g, 55 mmol) in 65 ml THF dropwise at 0° C. and stirred for 15 min and it was added to a mixture of the product of STEP 3 (7.3 g, 34.7 mmol ) in 35 ml THF dropwise at 0° C. After 5 min, the reaction was quenched with H2O. The product was extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with H2O, brine, dried with Na0.2SO4, and concentrated. The residue was purified by chromatography (on silica gel, ethyl acetate/hexane=5/95) to give a yellow liquid in 6.3 g. It was dissolved in 100 ml THF and 100 ml 2N HCl. The reaction was heated at reflux for 30 min and cooled to room temperature. THF was evaporated. The product was extracted with ethyl acetate and washed H2O. The aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with brine, dried with Na2SO4, and concentrated. The residue was purified by chromatography (on silica gel, ethyl acetate/hexane=15/85) to yield a colorless oil in 3.8 g. NMR spectra of the product were consistent for the proposed structure.

後処理

  1. waitAfter 5 min
  2. customthe reaction was quenched with H2O
  3. extractionThe product was extracted with ethyl acetate
  4. extractionThe aqueous layer was extracted with ethyl acetate
  5. washThe combined organic layer was washed with H2O, brine
  6. customdried with Na0.2SO4
  7. concentrationconcentrated
  8. customThe residue was purified by chromatography (on silica gel, ethyl acetate/hexane=5/95)
  9. customto give a yellow liquid in 6.3 g
  10. temperatureThe reaction was heated
  11. temperatureat reflux for 30 min
  12. customTHF was evaporated
  13. extractionThe product was extracted with ethyl acetate
  14. washwashed H2O
  15. extractionThe aqueous layer was extracted with ethyl acetate
  16. washThe combined organic layer was washed with brine
  17. dry with materialdried with Na2SO4
  18. concentrationconcentrated
  19. customThe residue was purified by chromatography (on silica gel, ethyl acetate/hexane=15/85)
  20. customto yield a colorless oil in 3.8 g

出典と根拠

ORDレコード
ord-26b31df7d6fc4919b0f0d9ef56187d65
出典データセット
uspto-grants-2003_03
特許番号
US06531494B1

反応ノート

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