Carbon Dioxide → 2-Fluoro-5-(trifluoromethoxy)benzaldehyde

HRID 2113444Notes

Reaction equation

HRID 2113444 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=1.C([Li])(C)(C)C.[C:18](=O)=[O:19].CN(C=O)C>C1COCC1.CCCCC>[F:1][C:2]1[CH:3]=[CH:4][C:5]([O:8][C:9]([F:10])([F:11])[F:12])=[CH:6][C:7]=1[CH:18]=[O:19]

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 6228DimethylformamideHCID 676984-(Trifluoromethoxy)fluorobenzeneHCID 178418306HCID 178418306, compound

Product 1

HCID 27833242-Fluoro-5-(trifluoromethoxy)benzaldehydeYield 53%

Reagents, catalysts & solvents 2

HCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 1-fluoro-4-trifluoromethoxy-benzene (21.0 g, 117 mmol) in THF (233 ml) was cooled to <−70° C. Tert.-butyllithium (86 ml of a 1.5 molar solution in pentane, 129 mmol) was added at such a rate that temperature was kept <−70° C. Stirring in the dry ice bath was continued for 15 min, then DMF (11.6 ml, 150 mmol) was added dropwise keeping temperature <−70° C. After 30 min the reaction mixture was allowed to reach rt, quenched with saturated NH4Cl solution and extracted with ether. The organic phase was washed with brine, concentrated and chromatographed (SiO2, heptane:ethyl acetate=100:0 to 80:2). The title compound (11.0 g, 53%) was obtained as a light yellow oil. 1H-NMR (300 MHz, DMSO): δ=7.60 (t, J=9.2 Hz, 1H), 7.75-7.85 (m, 2H), 10.20 (s, 1H).

Workup

  1. customwas kept <−70° C
  2. customtemperature <−70° C
  3. waitAfter 30 min the reaction mixture was allowed
  4. customto reach rt
  5. customquenched with saturated NH4Cl solution
  6. extractionextracted with ether
  7. washThe organic phase was washed with brine
  8. concentrationconcentrated
  9. customchromatographed (SiO2, heptane:ethyl acetate=100:0 to 80:2)

Sources & evidence

ORD record
ord-6530221df8e146b88a595c730cc7a3c8
Source dataset
uspto-grants-2008_10
Patent number
US07432256B2

Reaction notes

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