Diethyl 2-((2-bromo-4-chloro-3-fluorophenyl) (hydroxy)methylene)malonate → 1-(2-Bromo-4-chloro-3-fluorophenyl)ethanone

HRID 716632Notes

Reaction equation

HRID 716632 reaction equation
[Br:1][C:2]1[C:7]([F:8])=[C:6]([Cl:9])[CH:5]=[CH:4][C:3]=1[C:10]([OH:22])=[C:11](C(OCC)=O)C(OCC)=O>CC(O)=O.O.OS(O)(=O)=O>[Br:1][C:2]1[C:7]([F:8])=[C:6]([Cl:9])[CH:5]=[CH:4][C:3]=1[C:10](=[O:22])[CH3:11]

Participants

5

Reactant 1

HCID 66698539Diethyl 2-((2-bromo-4-chloro-3-fluorophenyl) (hydroxy)methylene)malonate

Product 1

HCID 666985481-(2-Bromo-4-chloro-3-fluorophenyl)ethanoneYield 84.6%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Procedure

A solution of Intermediate 12B (18.6 g, 47 mmol) in AcOH (200 mL), H2O (150 mL) and H2SO4 (2.0 mL) was stirred at 110° C. for 4 h. Most of the solvent was removed and the residue was diluted with EtOAc (400 mL), washed with H2O (5×20 mL), saturated NaHCO3, 1N NaOH, and brine. The solvent was removed to give Intermediate 12C (10 g, 84% yield) as a low melting solid. 1H NMR (400 MHz, DMSO-d6) δ 7.42 (q, J=6.8, 6.4 Hz, 1H), 7.24 (q, J=6.4, 5.2 Hz, 1H), 2.5 (s, 3H) ppm.

Workup

  1. customMost of the solvent was removed
  2. additionthe residue was diluted with EtOAc (400 mL)
  3. washwashed with H2O (5×20 mL), saturated NaHCO3, 1N NaOH, and brine
  4. customThe solvent was removed

Sources & evidence

ORD record
ord-0a5dfe027048403ca36a69a54b024e74
Source dataset
uspto-grants-2015_11
Patent number
US09192607B2

Reaction notes

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