Dimethylformamide → Ethyl 2-cyano-4-fluoro-5-nitrophenylacetate

HRID 1930310Notes

Reaction equation

HRID 1930310 reaction equation
Br[C:2]1[CH:7]=[C:6]([F:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14].[CH3:18][N:19](C=O)C>CCOC(C)=O.[C-]#N.[Zn+2].[C-]#N.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[C:18]([C:2]1[CH:7]=[C:6]([F:8])[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])#[N:19]

Participants

6

Reactant 2

HCID 6228DimethylformamideHCID 68984776HCID 68984776, compound

Product 1

HCID 69088377Ethyl 2-cyano-4-fluoro-5-nitrophenylacetateYield 37%

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
160 °C

Procedure

Ethyl 2-(2-bromo-4-fluoro-5-nitrophenyl)acetate (1.0 g, 3.27 mmol) and zinc cyanide (0.77 g, 6.54 mmol) were combined in DMF (8 mL), de-gassed under vacuum and backfilled with argon (4×). Palladium tetrakis(triphenylphosphine) (380 mg, 0.32 mmol) was added and the reaction was heated at 160° C. under microwave for 30 min. The solution was diluted with EtOAc and then the solid was filtered. The filtrate was washed with brine (3×) and dried (Na2SO4), concentrated in vacuo and the residue was purified by silica gel column chromatography to obtain ethyl 2-(2-cyano-4-fluoro-5-nitrophenyl)acetate (0.3 g, 37% yield).

Workup

  1. customde-gassed under vacuum
  2. filtrationthe solid was filtered
  3. washThe filtrate was washed with brine (3×)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-bfc2405b2c30453094522f1a6ce95b22
Source dataset
uspto-grants-2012_05
Patent number
US08188113B2

Reaction notes

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