Methyl iodide → Methyl 5-chloro-2-methyl-3-nitrobenzoate

HRID 2208934Notes

Reaction equation

HRID 2208934 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([N+:12]([O-:14])=[O:13])[C:5]([CH3:11])=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8].[C:15](=O)([O-])[O-].[Na+].[Na+].CI>CN(C=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([N+:12]([O-:14])=[O:13])[C:5]([CH3:11])=[C:6]([CH:10]=1)[C:7]([O:9][CH3:15])=[O:8]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 10340Sodium CarbonateHCID 230097625-Chloro-2-methyl-3-nitrobenzoic acid

Product 1

HCID 53399191Methyl 5-chloro-2-methyl-3-nitrobenzoateYield 63%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To stirred solution of 5-chloro-2-methyl-3-nitrobenzoic acid (126 g, 0.59 mol) in DMF (1.0 L) was added sodium carbonate (249 g, 2.34 mol) and methyl iodide (145 mL, 2.34 mol). The reaction mixture was heated at 60° C. for 4 h. On completion, the reaction mixture was filtered and the residue washed with DCM. The aqueous phase was separated and extracted with DCM. The combined organic layers were dried, concentrated under reduced pressure and purified by column chromatography over silica eluting with ethyl acetate:hexane to afford the title compound (85 g, 63%). 1H NMR (DMSO-d6, 400 MHz): δ 8.25 (d, 1H), 8.05 (s, 1H), 3.9 (s, 1H), 2.4 (s, 1H).

Workup

  1. filtrationOn completion, the reaction mixture was filtered
  2. washthe residue washed with DCM
  3. customThe aqueous phase was separated
  4. extractionextracted with DCM
  5. customThe combined organic layers were dried
  6. concentrationconcentrated under reduced pressure
  7. custompurified by column chromatography over silica eluting with ethyl acetate

Sources & evidence

ORD record
ord-f4ce5bea5357492c8bc5a6456109b2f9
Source dataset
uspto-grants-2016_06
Patent number
US09376422B2

Reaction notes

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