5-Fluoro-2-iodo-3-nitrotoluene → 4-Fluoro-2-methyl-6-nitrobenzonitrile

HRID 1734615Notes

Reaction equation

HRID 1734615 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5](I)=[C:4]([N+:10]([O-:12])=[O:11])[CH:3]=1.[Cu][C:14]#[N:15]>CN(C)C=O.O.C(OCC)(=O)C>[F:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([C:14]#[N:15])=[C:4]([N+:10]([O-:12])=[O:11])[CH:3]=1

Participants

6

Reactant 2

HCID 541243255-Fluoro-2-iodo-3-nitrotolueneHCID 178418546HCID 178418546, compound

Product 1

HCID 544206034-Fluoro-2-methyl-6-nitrobenzonitrileYield 104.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A stirred mixture of 19.0 grams (0.068 mole) of 4-fluoro-2-nitro-6-methylphenyl iodide and 7.0 grams (0.078 mole) of copper(I) cyanide in 100 mL of N,N-dimethylformamide was heated at 150°-155° C. for 30 minutes. The reaction mixture was then diluted with 400 mL of water and 100 mL of ethyl acetate. The mixture was filtered, and the filtrate was placed in a separatory funnel. The organic layer was separated, and the aqueous layer was washed with 200 mL of ethyl acetate. The combined wash and organic layer was then washed with three 150 mL portions of aqueous 5% lithium chloride. The mixture was dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel. Elution was accomplished using 1:1 methylene chloride:petroleum ether. The product-containing fractions were combined and concentrated under reduced pressure, yielding 12.8 grams of 4-fluoro-2-nitro-6-methylbenzonitrile, mp 61°-63° C. The NMR spectrum was consistent with the proposed structure.

Workup

  1. temperaturewas heated at 150°-155° C. for 30 minutes
  2. filtrationThe mixture was filtered
  3. customthe filtrate was placed in a separatory funnel
  4. customThe organic layer was separated
  5. washthe aqueous layer was washed with 200 mL of ethyl acetate
  6. washThe combined wash
  7. washorganic layer was then washed with three 150 mL portions of aqueous 5% lithium chloride
  8. dry with materialThe mixture was dried with magnesium sulfate
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated under reduced pressure to a residue
  11. washElution
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-a26fc00aad8b4d90a49d3c6393600e57
Source dataset
uspto-grants-1996_07
Patent number
US05534518

Reaction notes

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