Water → t-Butyl 2-(2-fluoro-4-nitrophenyl)acrylate

HRID 2119416Notes

Reaction equation

HRID 2119416 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[CH2:11][C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13].[CH3:19]N(CN(C)C)C.C(OC(=O)C)(=O)C.O>CS(C)=O>[F:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[C:11](=[CH2:19])[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13]

Participants

6

Reactant 4

HCID 962WaterHCID 5829N,N,N',N'-TetramethylmethanediamineHCID 7918Acetic AnhydrideHCID 69838291tert-Butyl 2-(2-fluoro-4-nitrophenyl)acetate

Product 1

HCID 23441579t-Butyl 2-(2-fluoro-4-nitrophenyl)acrylate

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

To a solution of t-butyl 2-fluoro-4-nitrophenylacetate (11.3 g) in dimethyl sulfoxide (70 mL) was added bis(dimethylamino)methane (6.80 g) and acetic anhydride (14.9 g) at room temperature, and the mixture was stirred at the same temperature for 30 min. The mixture was poured to water, and the mixture was extracted with toluene. The organic extracts were washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=9:1) of the residue gave t-butyl 2-(2-fluoro-4-nitrophenyl)acrylate. To a solution of the above t-butyl 2-(2-fluoro-4-nitrophenyl)acrylate and trimethylsulfoxonium iodide (11.7 g) in dimethyl sulfoxide (70 mL) was added potassium t-butoxide (5.96 g) at room temperature, and the mixture was stirred at the same temperature for 1 hour. After quenching the reaction by the addition of 5% hydrochloric acid, the mixture was extracted with ethyl acetate. The organic extracts were washed with 3% sodium thiosulfate solution and brine, dried over anhydrous magnesium sulfate, filtered, and then concentrated in vacuo. Flash chromatography (silica, hexane:ethyl acetate=9:1) of the residue gave t-butyl 1-(2-fluoro-4-nitrophenyl)cyclopropane-1-carboxylate. MS (EI+) m/z: 281 (M+).

Workup

  1. extractionthe mixture was extracted with toluene
  2. washThe organic extracts were washed with water and brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-31ee33e5000c4e0b9b6424ccab13d810
Source dataset
uspto-grants-2004_02
Patent number
US06686363B2

Reaction notes

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