Sulfuric Acid → 3-(4-Bromo-2-fluorophenyl)-2-propenoic acid

HRID 968066Notes

Reaction equation

HRID 968066 reaction equation
S(=O)(=O)(O)O.[Br:6][C:7]1[CH:13]=[CH:12][C:10](N)=[C:9]([F:14])[CH:8]=1.N([O-])=O.[Na+].NS(O)(=O)=O.[C:24]([OH:28])(=[O:27])[CH:25]=[CH2:26]>O.C/C(/[O-])=C/C(C)=O.C/C(/[O-])=C/C(C)=O.[Pd+2]>[Br:6][C:7]1[CH:13]=[CH:12][C:10]([CH:26]=[CH:25][C:24]([OH:28])=[O:27])=[C:9]([F:14])[CH:8]=1

Participants

8

Reactant 5

HCID 1118Sulfuric AcidHCID 5987Sulfamic AcidHCID 6581Acrylic AcidHCID 1230504-Bromo-2-fluoroanilineHCID 23668193Sodium Nitrite

Product 1

HCID 6883133-(4-Bromo-2-fluorophenyl)-2-propenoic acid

Reagents, catalysts & solvents 2

HCID 5486778Palladium acetylacetonateCatalystHCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

62 ml of sulfuric acid were added to 236 ml of water and the mixture was cooled to 5° C. 57.0 g of 4-bromo-2-fluoroaniline were added at this temperature and a solution of 24.2 g of sodium nitrite in 45 ml of water was added dropwise at 0 to 2° C. in the course of 30 minutes and the mixture was stirred for 20 minutes. 2.8 g of amidosulfonic acid were then added. 5 ml of the diazonium salt solution were added dropwise at 40° C. to 27.5 g of acrylic acid, 0.23 g of palladium(II) acetylacetonate was added and the residual diazonium salt solution was added dropwise in the course of 20 minutes. The mixture was stirred at 40° C. for 4 hours. It was allowed to cool to room temperature and the product was isolated by filtration. After drying, 54.4 g of 4-bromo-2-fluorocinnamic acid were present (74% of theory; melting point: 218° C.).

Workup

  1. additionwas added
  2. stirringThe mixture was stirred at 40° C. for 4 hours
  3. temperatureto cool to room temperature
  4. customthe product was isolated by filtration
  5. customAfter drying

Sources & evidence

ORD record
ord-c50b559d94fc477089c509e87faabfaa
Source dataset
uspto-grants-2005_10
Patent number
US06956129B2

Reaction notes

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