Potassium Carbonate → 2,2-dimethyl-6-fluoro-2H-chromene

HRID 1196052Notes

Reaction equation

HRID 1196052 reaction equation
C(=O)([O-])[O-].[K+].[K+].[F:7][C:8]1[CH:9]=[CH:10][C:11]([OH:16])=[C:12]([CH:15]=1)[CH:13]=O.C(OC(=O)[CH:21]=[C:22]([CH3:24])[CH3:23])C>CN(C)C=O>[CH3:21][C:22]1([CH3:24])[CH:23]=[CH:13][C:12]2[C:11](=[CH:10][CH:9]=[C:8]([F:7])[CH:15]=2)[O:16]1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 12516Ethyl 3,3-dimethylacrylateHCID 27373285-Fluorosalicylaldehyde

Product 1

HCID 108669002,2-dimethyl-6-fluoro-2H-chromene

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

83.1 g (0.2 mol) of potassium carbonate are added, while stirring, to a solution of 28.0 g (0.2 mol) of 5-fluoro-2-hydroxy-benzaldehyde [prepared according to Y. Suzuki and H. Takahashi, Chem. Pharm. Bull. 31, 1751 (1983)] in 500 ml of N,N-dimethylformamide. 36.3 g (0.2 mol) of 3,3-dimethylacrylic acid ethyl ester are added to the resulting viscous suspension. The reaction mixture is then stirred for 16 hours at 150° and, after cooling to room temperature, concentrated by evaporation in vacuo. Water is added to the resulting solid residue and the aqueous mixture is extracted with diethyl ether. The combined ethereal phases are washed in succession with water, 2N hydrochloric acid, 2N sodium hydroxide solution and again with water, dried over sodium sulfate and concentrated by evaporation in vacuo. The resulting oily residue is chromatographed on 1000 g of silica gel (0.040-0.063 mm) with toluene as eluant, yielding 19.5 g (55% of the theoretical yield) of 2,2-dimethyl-6-fluoro-2H-chromene in the form of a light-yellow oil.

Workup

  1. concentrationconcentrated by evaporation in vacuo
  2. additionWater is added to the resulting solid residue
  3. extractionthe aqueous mixture is extracted with diethyl ether
  4. washThe combined ethereal phases are washed in succession with water, 2N hydrochloric acid, 2N sodium hydroxide solution and again with water
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated by evaporation in vacuo
  7. customThe resulting oily residue is chromatographed on 1000 g of silica gel (0.040-0.063 mm) with toluene as eluant
  8. customyielding 19.5 g (55% of the

Sources & evidence

ORD record
ord-c9e555bb9e954991b31caf8769015fa3
Source dataset
uspto-grants-1992_05
Patent number
US05112855

Reaction notes

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