tert-butyl (NZ)-N-[2,2,2-trifluoro-1-(2-fluorophenyl)ethylidene]carbamate → [1-(2-Fluoro-phenyl)-1-trifluoromethyl-but-3-enyl]-carbamic acid tert-butyl ester

HRID 81597Notes

Reaction equation

HRID 81597 reaction equation
[C:1]([O:5][C:6](=[O:20])/[N:7]=[C:8](/[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[F:19])\[C:9]([F:12])([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:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[F:19])([C:9]([F:10])([F:11])[F:12])[CH2:23][CH:22]=[CH2:21])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 87096311tert-butyl (NZ)-N-[2,2,2-trifluoro-1-(2-fluorophenyl)ethylidene]carbamateHCID 178418473HCID 178418473, compound

Product 1

HCID 66666093[1-(2-Fluoro-phenyl)-1-trifluoromethyl-but-3-enyl]-carbamic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of [2,2,2-Trifluoro-1-(2-fluoro-phenyl)-eth-(Z)-ylidene]-carbamic acid tert-butyl ester (16.63 g, 57.1 mmol) in 170 mL THF at −75° was added dropwise allylmagnesium chloride solution 2 mol/L in THF (31.4 ml, 62.8 mmol). The reaction temperature was not allowed to exceed −60° C. After 30 minutes, the reaction was quenched with 10% aqueous NH4Cl and extracted with TBME. The organic phase was washed with brine, dried with MgSO4.H2O and evaporated. The crude product was chromatographed on silica gel with hexane/TBME 95/5 to give 18.52 g of the title compound.

Workup

  1. customto exceed −60° C
  2. customthe reaction was quenched with 10% aqueous NH4Cl
  3. extractionextracted with TBME
  4. washThe organic phase was washed with brine
  5. dry with materialdried with MgSO4.H2O
  6. customevaporated
  7. customThe crude product was chromatographed on silica gel with hexane/TBME 95/5

Sources & evidence

ORD record
ord-66a4cefc429b40729f12e28021d0bdfd
Source dataset
uspto-grants-2014_09
Patent number
US08846658B2

Reaction notes

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