Tetrabutylammonium Fluoride → (E)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate

HRID 2102925ノート

反応式

HRID 2102925 の反応式
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[F:19][C:20]1[CH:32]=[C:31]([CH:33]=O)[CH:30]=[CH:29][C:21]=1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23].[F:35][C:36]([F:53])([F:52])[CH2:37]P(=O)(C1C=CC=CC=1)C1C=CC=CC=1>C1COCC1>[F:19][C:20]1[CH:32]=[C:31](/[CH:33]=[CH:37]/[C:36]([F:53])([F:52])[F:35])[CH:30]=[CH:29][C:21]=1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23]

参加物

5

反応物 3

HCID 2724141Tetrabutylammonium FluorideHCID 11323568Diphenyl(2,2,2-trifluoroethyl)phosphine oxideHCID 86607392tert-Butyl 2-fluoro-4-formylbenzoate

生成物 1

HCID 68704410(E)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate収率 64.7%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

Molecular sieves 4 Å (powder, 24 g) was added to a 1 M solution of TBAF in THF (30 mL, 30 mmol), and the mixture was stirred at room-temperature overnight under an argon atmosphere. To the mixture were added a solution of tert-butyl 2-fluoro-4-formylbenzoate (750 mg, 0.0033 mol) and 2,2,2-trifluoroethyldiphenylphosphine oxide (1.9 g, 0.0067 mol) in THF (30 mL). After the mixture was stirred for 2 h it was filtered. The filtrate was concentrated under vacuum and water (120 mL) was added. The mixture was extracted with AcOEt and the organic extract was washed with brine, dried (Na2SO4), and concentrated under vacuum. The residue was purified by column chromatography on silica gel using AcOEt-hexane (0-15%) as eluent to give (E)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate as a colorless oil (620 mg, 64%), followed by (Z)-tert-butyl 2-fluoro-4-(3,3,3-trifluoroprop-1-enyl)benzoate as a colorless oil (80 mg, 8%).

後処理

  1. stirringAfter the mixture was stirred for 2 h it
  2. filtrationwas filtered
  3. concentrationThe filtrate was concentrated under vacuum and water (120 mL)
  4. additionwas added
  5. extractionThe mixture was extracted with AcOEt
  6. extractionthe organic extract
  7. washwas washed with brine
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated under vacuum
  10. customThe residue was purified by column chromatography on silica gel

出典と根拠

ORDレコード
ord-9261dd154d3447f2b110596b1bd14ae4
出典データセット
uspto-grants-2009_08
特許番号
US07576099B2

反応ノート

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