Boron trifluoride etherate → HCID 67271716, compound

HRID 599688Notes

Reaction equation

HRID 599688 reaction equation
CO[C:3](=O)[C:4]1[CH:9]=[CH:8][C:7]([F:10])=[CH:6][CH:5]=1.[CH2:12]([Mg]Br)[CH3:13].B(F)(F)F.[CH3:20][CH2:21]OCC>C1COCC1>[CH2:20]([C:3]([C:4]1[CH:9]=[CH:8][C:7]([F:10])=[CH:6][CH:5]=1)=[CH:12][CH3:13])[CH3:21]

Participants

5

Reactant 3

HCID 8000Boron trifluoride etherateHCID 67878Methyl 4-fluorobenzoateHCID 178418443HCID 178418443, compound

Product 1

HCID 67271716HCID 67271716, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 4-fluoro-benzoic acid methyl ester (19.1 g, 114 mmol) in THF (300 mL) at −78° C. is treated with ethylmagnesium bromide (135 mL, 3.0 M). The reaction mixture is allowed to warm to 0° C. over 30 min and quenched with HCl (350 mL, 1.0 M). THF is removed under vacuum, and the residue is extracted with EtOAc (3×100 mL). The organic layer is dried over Na2SO4 and concentrated. The intermediate tertiary alcohol is dissolved in CH2Cl2 (200 mL), cooled to −40° C., and treated with BF3-Et2O (11.5 g, 91.0 mol). The reaction mixture is allowed to warm to 0° C. over 30 min and quenched with water (50 mL). The organic layer is dried over Na2SO4 and concentrated. The residue is purified using silica gel column chromatography (5% EtOAc/Hex) to afford the title compound (16.8 g, 90%).

Workup

  1. customquenched with HCl (350 mL, 1.0 M)
  2. customTHF is removed under vacuum
  3. extractionthe residue is extracted with EtOAc (3×100 mL)
  4. dry with materialThe organic layer is dried over Na2SO4
  5. concentrationconcentrated
  6. dissolutionThe intermediate tertiary alcohol is dissolved in CH2Cl2 (200 mL)
  7. temperaturecooled to −40° C.
  8. temperatureto warm to 0° C. over 30 min
  9. customquenched with water (50 mL)
  10. dry with materialThe organic layer is dried over Na2SO4
  11. concentrationconcentrated
  12. customThe residue is purified

Sources & evidence

ORD record
ord-c71b03c51bae49078572bdc8053eb95e
Source dataset
uspto-grants-2011_03
Patent number
US07897789B2

Reaction notes

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