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

HRID 2102925Notes

Reaction equation

HRID 2102925 reaction equation
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]

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

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%).

Workup

  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

Sources & evidence

ORD record
ord-9261dd154d3447f2b110596b1bd14ae4
Source dataset
uspto-grants-2009_08
Patent number
US07576099B2

Reaction notes

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