1-Iodo-3-nitrobenzene → Benzeneacetic acid, α,α-difluoro-3-nitro-, ethyl ester

HRID 1487114Notes

Reaction equation

HRID 1487114 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1.Br[C:12]([F:19])([F:18])[C:13]([O:15][CH2:16][CH3:17])=[O:14]>CS(C)=O.[Cu]>[F:18][C:12]([F:19])([C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1)[C:13]([O:15][CH2:16][CH3:17])=[O:14]

Participants

5

Reactant 2

HCID 125741-Iodo-3-nitrobenzeneHCID 69585Ethyl bromodifluoroacetate

Product 1

HCID 53419335Benzeneacetic acid, α,α-difluoro-3-nitro-, ethyl esterYield 50%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 1-iodo-3-nitrobenzene (1.450 g, 5.82 mmol) and ethyl 2-bromo-2,2-difluoroacetate (1.3 g, 6.40 mmol) in anhydrous DMSO (10 ml) was added Copper powder (0.740 g, 11.64 mmol). The mixture was purged with N2 and heated at 70° C. in a sealed vial for 17 h. After being cooled to room temperature, the reaction mixture was poured into 20% aqueous NH4Cl solution (100 mL) and was extracted with EtOAc (2×100 mL). The organic extract was washed with brine (2×30 mL), dried over Na2SO4 and concentrated. The residue was purified by flash chromatography to obtain ethyl 2,2-difluoro-2-(3-nitrophenyl)acetate (0.714 g).

Workup

  1. customThe mixture was purged with N2
  2. temperatureAfter being cooled to room temperature
  3. additionthe reaction mixture was poured into 20% aqueous NH4Cl solution (100 mL)
  4. extractionwas extracted with EtOAc (2×100 mL)
  5. extractionThe organic extract
  6. washwas washed with brine (2×30 mL)
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated
  9. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-255254e00a9742b492d96822678e522a
Source dataset
uspto-grants-2016_08
Patent number
US09428499B2

Reaction notes

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