(Z)-tert-butyl (1-(5-bromo-2-fluorophenyl)-2,2-difluoroethylidene)carbamate → [1-(5-Bromo-2-fluoro-phenyl)-1-difluoromethyl-but-3-enyl]-carbamic acid tert-butyl ester

HRID 81592Notes

Reaction equation

HRID 81592 reaction equation
[C:1]([O:5][C:6](=[O:20])/[N:7]=[C:8](/[C:12]1[CH:17]=[C:16]([Br:18])[CH:15]=[CH:14][C:13]=1[F:19])\[CH:9]([F:11])[F:10])([CH3:4])([CH3:3])[CH3:2].[CH2:21]([Mg]Cl)[CH:22]=[CH2:23]>C1COCC1>[C:1]([O:5][C:6](=[O:20])[NH:7][C:8]([C:12]1[CH:17]=[C:16]([Br:18])[CH:15]=[CH:14][C:13]=1[F:19])([CH:9]([F:10])[F:11])[CH2:23][CH:22]=[CH2:21])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 87096325(Z)-tert-butyl (1-(5-bromo-2-fluorophenyl)-2,2-difluoroethylidene)carbamateHCID 178418473HCID 178418473, compound

Product 1

HCID 66665334[1-(5-Bromo-2-fluoro-phenyl)-1-difluoromethyl-but-3-enyl]-carbamic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of [1-(5-bromo-2-fluoro-phenyl)-2,2-difluoro-eth-(Z)-ylidene]-carbamic acid tert-butyl ester (9.61 g, 27.3 mmol) in 114 ml THF at −75° was added dropwise allylmagnesium chloride solution 2 mol/L in THF (15.0 ml, 30 mmol). The reaction temperature was not allowed to exceed −60° C. After 10 minutes the reaction was quenched with 10% aqueous NH4Cl and extracted with TBME. The organic phase was washed with brine, dried with Na2SO4 and evaporated. The crude product was chromatographed on silica gel with 1-5% TBME/hexane to give 10.39 g of the title compound.

Workup

  1. customto exceed −60° C
  2. customAfter 10 minutes the reaction was quenched with 10% aqueous NH4Cl
  3. extractionextracted with TBME
  4. washThe organic phase was washed with brine
  5. dry with materialdried with Na2SO4
  6. customevaporated
  7. customThe crude product was chromatographed on silica gel with 1-5% TBME/hexane

Sources & evidence

ORD record
ord-f8a3aee291c84bbb8ffabd8314dba44a
Source dataset
uspto-grants-2014_09
Patent number
US08846658B2

Reaction notes

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