Dimethylformamide → 2-Fluoro-N-methyl-4-nitrobenzamide

HRID 1927377Notes

Reaction equation

HRID 1927377 reaction equation
S(Cl)(Cl)=O.[F:5][C:6]1[CH:14]=[C:13]([N+:15]([O-:17])=[O:16])[CH:12]=[CH:11][C:7]=1[C:8](O)=[O:9].[CH3:18][N:19](C=O)C>>[CH3:18][NH:19][C:8](=[O:9])[C:7]1[CH:11]=[CH:12][C:13]([N+:15]([O-:17])=[O:16])=[CH:14][C:6]=1[F:5]

Participants

4

Reactant 3

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 3026792-Fluoro-4-nitrobenzoic acid2×

Product 1

HCID 534406322-Fluoro-N-methyl-4-nitrobenzamideYield 85%

Conditions

Temperature
-5 °C

Procedure

Thionyl chloride (0.15 g, 1.30 mmol) was added slowly to a solution of 2-fluoro-4-nitrobenzoic acid (Formula 37) (0.20 g, 1.10 mmol) in DMF (5 mL) cooled at −5° C. The mixture was stirred for an additional 1 hour at −5° C. Excess methylamine (freshly distilled from its 40% aqueous solution) was added to the reaction medium. The second mixture was stirred for an additional 1 hour. Ethyl acetate (50 mL) was added to the mixture, which was washed with brine (2×50 ml). The organic layer was dried over MgSO4, and concentrated to yield N-Methyl-2-fluoro-4-nitrobenzamide (Formula 38) (0.18 g, 85%) as a yellowish solid. 1H NMR (acetone-d6) δ 3.05 (d, 3H, J=4.3), 6.31 (dd, 1H, J=13.5 and 2.1), 6.40 (dd, 1H, J=8.6 and 2.1), 7.64 (dd, 1H, J=8.6 and 8.6).

Workup

  1. distillationExcess methylamine (freshly distilled from its 40% aqueous solution)
  2. additionwas added to the reaction medium
  3. stirringThe second mixture was stirred for an additional 1 hour
  4. additionEthyl acetate (50 mL) was added to the mixture, which
  5. washwas washed with brine (2×50 ml)
  6. dry with materialThe organic layer was dried over MgSO4
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-472cf65a30af44f7b5fc4ab9befeb4fb
Source dataset
uspto-grants-2012_05
Patent number
US08183274B2

Reaction notes

Loading…