Carbon Dioxide → 4-Fluoro-3-methylbenzoic acid

HRID 1953761Notes

Reaction equation

HRID 1953761 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([Mg]Br)=[CH:4][C:3]=1[CH3:10].[C:11](=[O:13])=[O:12]>C1COCC1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:11]([OH:13])=[O:12])=[CH:4][C:3]=1[CH3:10]

Participants

4

Reactant 2

HCID 280Carbon DioxideHCID 178427974HCID 178427974, compound

Product 1

HCID 2428284-Fluoro-3-methylbenzoic acidYield 67%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 4-fluoro-3-methylphenylmagnesium bromide in THF (1.0 M, 250 mL, 250 mmol) was added in a stream over 5 min to a mixture of Dry Ice (10 g) in dry THF (250 mL), and the reaction was allowed to warm to RT and concentrated. The residue was partitioned between water (500 mL) and ether (250 mL), and the layers were separated. The aqueous layer was washed with ether (2×250 mL) and acidified to pH 1 with concentrated hydrochloric acid. The resulting mixture was cooled in an ice bath and filtered. The solid was washed with water and dried to afford the title compound (25.92 g, 67%) as an off-white solid: 1H NMR (400 MHz, CDCl3) δ 7.90-8.02 (m, 2H), 7.09 (t, J=8.9 Hz, 1H), 2.34 (d, J=1.7 Hz, 3H); IR (chloroform) 3400-2300 (broad), 1694 cm-1 ; MS(ES) m/e 155 [M+H+ ; m/e 153 [M-H]-.

Workup

  1. concentrationconcentrated
  2. customThe residue was partitioned between water (500 mL) and ether (250 mL)
  3. customthe layers were separated
  4. washThe aqueous layer was washed with ether (2×250 mL)
  5. temperatureThe resulting mixture was cooled in an ice bath
  6. filtrationfiltered
  7. washThe solid was washed with water
  8. customdried

Sources & evidence

ORD record
ord-5a6a6c1260524157ac2ae9757ac514f0
Source dataset
uspto-grants-2000_09
Patent number
US06117866

Reaction notes

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