Sodium hydride → 3-Hydroxy-2-methyl-6-nitro-benzoic acid methyl ester

HRID 604279Notes

Reaction equation

HRID 604279 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6](F)[C:5]=1[CH3:14].CS(CCO)(=O)=[O:18].[H-].[Na+]>CN(C=O)C>[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([OH:18])[C:5]=1[CH3:14]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 848342-(Methylsulfonyl)ethanolHCID 59849164Methyl 3-fluoro-2-methyl-6-nitrobenzoate

Product 1

HCID 598492143-Hydroxy-2-methyl-6-nitro-benzoic acid methyl esterYield 89%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirring solution of 3-Fluoro-2-methyl-6-nitro-benzoic acid methyl ester (6 g, 28.2 mmol) and 2-(methylsulfonyl)ethanol (5.2 g, 42.2 mmol) in 47 mL of DMF is added sodium hydride (3.38 g, 84.6 mmol) at 0° C. and the reaction mixture is allowed to warm to room temperature and then stirred for 1.5 hours. The mixture is quenched with 1N HCl solution and partitioned between ethyl acetate. The organic layer is washed with brine and concentrated to dryness and the crude organics purified by flash column chromatography to give 3-Hydroxy-2-methyl-6-nitro-benzoic acid methyl ester (5.3 g) in 89% yields. 1H-NMR (400 MHz, δ, ppm) CDCl3: 2.22 (s, 3H), 3.99 (s, 3H), 6.38 (s, 1H), 6.87 (d, 1H), 7.99 (d, 1H).

Workup

  1. customThe mixture is quenched with 1N HCl solution
  2. custompartitioned between ethyl acetate
  3. washThe organic layer is washed with brine
  4. concentrationconcentrated to dryness
  5. customthe crude organics purified by flash column chromatography

Sources & evidence

ORD record
ord-497a9922d16848e180bb020cb4b145fb
Source dataset
uspto-grants-2011_03
Patent number
US07910585B2

Reaction notes

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