Sodium Acetate → 2-Acetoxy-2',4'-difluoroacetophenone

HRID 1939935Notes

Reaction equation

HRID 1939935 reaction equation
Cl[CH2:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([F:11])=[CH:7][C:6]=1[F:12])=[O:4].[C:13]([O-:16])(=[O:15])[CH3:14].[Na+]>N[C@H](C(O)=O)CC1C=C2C(C=CC=C2)=CC=1.CN(C=O)C>[C:13]([O:16][CH2:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([F:11])=[CH:7][C:6]=1[F:12])=[O:4])(=[O:15])[CH3:14]

Participants

5

Reactant 2

HCID 517045Sodium AcetateHCID 5880832-Chloro-1-(2,4-difluorophenyl)ethanone

Product 1

HCID 152530262-Acetoxy-2',4'-difluoroacetophenoneYield 92.2%

Reagents, catalysts & solvents 2

HCID 1859152-NaphthylalanineCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
20 °C

Procedure

Add 191 g of 2-chloro-2',4'-difluoroacetophenone (Aldrich Chemical Co.) to a mixture of 246 g of sodium acetate, 3 g of Nal, and 3 L of DMF. Stir the mixture at 20° C. for 18 hr. then concentrate it to 1 L. Pour the residue into 6 L of cold dilute aqueous HCl and extract with EtOAc. Wash the extract with brine, dry it over anhydrous Na2SO4, filter the so-formed mixture, and evaporate the filtrate to leave a residue. Chromatograph the residue on silica gel, eluting with CH2Cl2 -hexane to obtain 198 g of the title compound. ##STR35##

Workup

  1. concentrationthen concentrate it to 1 L
  2. additionPour the residue into 6 L of cold dilute aqueous HCl
  3. extractionextract with EtOAc
  4. washWash the
  5. extractionextract with brine
  6. dry with materialdry it over anhydrous Na2SO4
  7. filtrationfilter the so-formed mixture
  8. customevaporate the filtrate
  9. customto leave a residue
  10. washChromatograph the residue on silica gel, eluting with CH2Cl2 -hexane

Sources & evidence

ORD record
ord-702469e02ba34ad896f9ee800f9ceba5
Source dataset
uspto-grants-1997_12
Patent number
US05698557

Reaction notes

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