Methyl iodide → 1,3-Benzenedicarboxylic acid, 5-(methylamino)-, 1,3-dimethyl ester

HRID 2071127Notes

Reaction equation

HRID 2071127 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([C:12]([O:14][CH3:15])=[O:13])[CH:5]=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[H-].[Na+].[CH3:18]I>CN(C=O)C>[CH3:18][NH:1][C:2]1[CH:11]=[C:6]([C:7]([O:9][CH3:10])=[O:8])[CH:5]=[C:4]([CH:3]=1)[C:12]([O:14][CH3:15])=[O:13]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 66831Dimethyl 5-aminoisophthalate

Product 1

HCID 206161311,3-Benzenedicarboxylic acid, 5-(methylamino)-, 1,3-dimethyl esterYield 54%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of dimethyl 5-aminoisophthalate (0.250 g, 1.17 mmol, 1 eq) dissolved in 3 mL anhydrous DMF was added dropwise to a stirred suspension of NaH (60% dispersion in mineral oil, 0.14 g, 3.5 mmol, 3 eq) in 2 mL anhydrous DMF at 0° C. under Ar. MeI (0.23 mL, 0.53 g, 3.7 mmol, 3.2 eq) was added dropwise to the resulting mixture. The reaction was stirred at 0° C. to room temperature overnight. The reaction was poured into ice water to quench. The aqueous mixture was extracted with EtOAc (×2), and the combined organic extracts were washed with water (×3), brine (×1), and dried over Na2SO4. The inorganics were filtered off, and the solvent was removed in vacuo. Purification via flash chromatography on silica gel yielded 0.14 g (0.63 mmol, 54% yield) of dimethyl 5-(methylamino)isophthalate.

Workup

  1. customto quench
  2. extractionThe aqueous mixture was extracted with EtOAc (×2)
  3. washthe combined organic extracts were washed with water (×3), brine (×1)
  4. dry with materialdried over Na2SO4
  5. filtrationThe inorganics were filtered off
  6. customthe solvent was removed in vacuo
  7. customPurification via flash chromatography on silica gel

Sources & evidence

ORD record
ord-e024da9de905441287cd046fffbc5c02
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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