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

HRID 2208843Notes

Reaction equation

HRID 2208843 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+].IC>CN(C=O)C.O>[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

6

Reactant 3

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

Product 1

HCID 53399191Methyl 5-chloro-2-methyl-3-nitrobenzoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 5-chloro-2-methyl-3-nitrobenzoic acid (1.17 g, 5.43 mmol) in DMF (11 ml) at room temperature and nitrogen was added Na2CO3 (862 mg, 8.14 mmol) followed by iodomethane (0.51 ml, 8.14 mmol). The reaction mixture was stirred at room temperature for 19 hours before being diluted with deionized water (30 ml) and extracted with EtOAc (3×30 ml). The combined organic phases were washed with saturated NaHCO3(aq) (30 ml), dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by FCC (10 g silica, Isolute cartridge, gradient of eluents; 99:1 Heptane:EtOAc to 95:5 Heptane:EtOAc) to give 900 of the title compound as a pale yellow oil. LC-MS 89%, m/z=no ionisation, 1H NMR (500 MHz, Chloroform-d) δ 8.00 (1H, d, J=2.21 Hz), 7.86 (1H, d, J=2.21 Hz), 3.96 (3H, s), 2.60 (3H, s).

Workup

  1. extractionextracted with EtOAc (3×30 ml)
  2. washThe combined organic phases were washed with saturated NaHCO3(aq) (30 ml)
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by FCC (10 g silica, Isolute cartridge, gradient of eluents; 99:1 Heptane:EtOAc to 95:5 Heptane:EtOAc)

Sources & evidence

ORD record
ord-ff2d0f133ba6496db9b4cff1b060aac0
Source dataset
uspto-grants-2016_06
Patent number
US09376422B2

Reaction notes

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