Sulfuric Acid → HCID 58565018, compound

HRID 554595Notes

Reaction equation

HRID 554595 reaction equation
[CH2:1]([O:3][C:4](=[O:15])[C:5]1[CH:10]=[CH:9][C:8]([Br:11])=[C:7]([CH:12](Br)Br)[CH:6]=1)[CH3:2].[OH:16]S(O)(=O)=O>CCO.O.O1CCOCC1.CCOC(C)=O.[N+]([O-])([O-])=O.[Ag+]>[CH2:1]([O:3][C:4](=[O:15])[C:5]1[CH:10]=[CH:9][C:8]([Br:11])=[C:7]([CH:12]=[O:16])[CH:6]=1)[CH3:2]

Participants

8

Reactant 2

HCID 1118Sulfuric AcidHCID 15939999HCID 15939999, compound

Product 1

HCID 58565018HCID 58565018, compound

Reagents, catalysts & solvents 5

HCID 24470Silver NitrateCatalystHCID 702EthanolSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
60 °C

Procedure

4-Bromo-3-dibromomethyl-benzoic acid ethyl ester (6.4 g, 16 mmol) was dissolved in EtOH (200 mL) and heated to 60° C. Silver nitrate (6.80 g, 40 mmol), prepared as a solution in H2O (50 mL), was added dropwise, resulting in a precipitate. After 1 hour, the mixture was decanted, and the precipitate was washed with EtOH (3×50 mL) and decanted after each wash. The combined EtOH solution was treated with 1N aqueous HCl (40 mL), which resulted in additional precipitate formation. The mixture was filtered, and the filtrate was concentrated and partitioned between EtOAc and H2O. The aqueous layer was separated and extracted with EtOAc, and the combined organic layers were concentrated. The crude material was dissolved in MeOH (100 mL) and treated with 2N aqueous H2SO4 (15 mL) for 1 hour at room temperature. After work-up, the crude material was purified by silica gel chromatography to give a mixture of the aldehyde and the dimethyl acetal. The mixture was dissolved in 1,4-dioxane and treated with 2N aqueous H2SO4 (80 mL), and stirred overnight at room temperature. The solution was diluted with EtOAc and H2O, and the organic layer was separated, dried, and concentrated to give 4-bromo-3-formyl-benzoic acid ethyl ester.

Workup

  1. additionwas added dropwise
  2. customresulting in a precipitate
  3. customthe mixture was decanted
  4. washthe precipitate was washed with EtOH (3×50 mL)
  5. customdecanted after each wash
  6. additionThe combined EtOH solution was treated with 1N aqueous HCl (40 mL), which
  7. customresulted in additional precipitate formation
  8. filtrationThe mixture was filtered
  9. concentrationthe filtrate was concentrated
  10. custompartitioned between EtOAc and H2O
  11. customThe aqueous layer was separated
  12. extractionextracted with EtOAc
  13. concentrationthe combined organic layers were concentrated
  14. dissolutionThe crude material was dissolved in MeOH (100 mL)
  15. additiontreated with 2N aqueous H2SO4 (15 mL) for 1 hour at room temperature
  16. customAfter work-up, the crude material was purified by silica gel chromatography
  17. customto give
  18. customthe organic layer was separated
  19. customdried
  20. concentrationconcentrated

Sources & evidence

ORD record
ord-a2047c182cb746419d7cb47d91f17eca
Source dataset
uspto-grants-2011_11
Patent number
US08049015B2

Reaction notes

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