Bromine → 4-Fluoro-2-hydroxyphenacyl bromide

HRID 2377301Notes

Reaction equation

HRID 2377301 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[C:4]([OH:11])[CH:3]=1.O.[O-2].[O-2].[O-2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.[Al+3].[Al+3].[Br:30]Br>CCOC(C)=O.[Al+3].[Cl-].[Cl-].[Cl-]>[Br:30][CH2:9][C:8]([C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][C:4]=1[OH:11])=[O:10]

Participants

6

Reactant 3

HCID 24408BromineHCID 27373264'-Fluoro-2'-hydroxyacetophenoneHCID 71586775Bentonite

Product 1

HCID 269860714-Fluoro-2-hydroxyphenacyl bromide

Reagents, catalysts & solvents 2

HCID 6451240Aluminum(III) ChlorideCatalystHCID 8857Ethyl AcetateSolvent2×

Procedure

A solution of 1-(4-fluoro-2-hydroxy-phenyl)-ethanone (15.4 g, Aldrich) in EtOAc (100 mL) was treated with AlCl3 (133 mg), stirred at r.t. for 30 min, treated with montmorillonite K10 (2.5 g) stirred an additional 30 min then treated with a solution of bromine (7.05 mL) in EtOAc (100 mL) (added dropwise via addition funnel over 1.5 h). The reaction was stirred at r.t. for 1 h, cooled in a an ice bath and quenched with water added dropwise. The mixture was diluted with EtOAc, filtered through celite and the filtrate was extracted with EtOAc (2×). The combined organic extracts were dried (Na2SO4), concentrated and teh crude product was purified via silica gel chromatography eluting with 5% EtOAc-hexanes to give 3.31 g of the title compound. MS (ESI) m/e 437(2M+H)+.

Workup

  1. stirringstirred an additional 30 min
  2. additionadded dropwise via addition funnel over 1.5 h)
  3. stirringThe reaction was stirred at r.t. for 1 h
  4. temperaturecooled in a an ice bath
  5. customquenched with water
  6. additionadded dropwise
  7. additionThe mixture was diluted with EtOAc
  8. filtrationfiltered through celite
  9. extractionthe filtrate was extracted with EtOAc (2×)
  10. dry with materialThe combined organic extracts were dried (Na2SO4)
  11. concentrationconcentrated
  12. customteh crude product was purified via silica gel chromatography
  13. washeluting with 5% EtOAc-hexanes

Sources & evidence

ORD record
ord-1fa1ee7b37194b8c8769987af75030cd
Source dataset
uspto-grants-2008_12
Patent number
US07468371B2

Reaction notes

Loading…