Potassium Iodide → Methyl 6-bromo-3-[(2-ethoxycarbonyl)propan-2-yl]amino-2-nitrobenzoate

HRID 871962Notes

Reaction equation

HRID 871962 reaction equation
[NH2:1][C:2]1[C:3]([N+:13]([O-:15])=[O:14])=[C:4]([C:9]([Br:12])=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].Br[C:17]([CH3:24])(C)[C:18]([O:20][CH2:21][CH3:22])=[O:19].[I-].[K+].[C:27](=O)([O-])[O-].[Cs+].[Cs+]>O.C(OCC)(=O)C>[Br:12][C:9]1[C:4]([C:5]([O:7][CH3:8])=[O:6])=[C:3]([N+:13]([O-:15])=[O:14])[C:2]([NH:1][CH:24]([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH3:27])=[CH:11][CH:10]=1

Participants

7

Reactant 4

HCID 4875Potassium IodideHCID 10796Cesium carbonateHCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl esterHCID 58891824Methyl 3-amino-6-bromo-2-nitrobenzoate

Product 1

HCID 67210813Methyl 6-bromo-3-[(2-ethoxycarbonyl)propan-2-yl]amino-2-nitrobenzoateYield 31%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

The mixture of methyl 3-amino-6-bromo-2-nitrobenzoate (Reference Compound No. 1-(4), 11.6 g, 42.0 mmol), ethyl 2-bromoisobutyrate (60.4 mL, 412 mmol), potassium iodide (7.76 g, 46.2 mmol) and cesium carbonate (56.1 g, 172 mmol) was stirred at 85° C. for 4 days. After the mixture was cooled down, ethyl acetate (500 mL) and water (500 mL) were added thereto, the mixture was partitioned, and then the water layer was extracted with ethyl acetate (300 mL). The organic layer was combined, washed with water (1 L, 2 times) and saturated brine (1 L) successively, dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate) to give the titled reference compound (5.08 g) as an orange oil. (Yield 31%)

Workup

  1. temperatureAfter the mixture was cooled down
  2. customthe mixture was partitioned
  3. extractionthe water layer was extracted with ethyl acetate (300 mL)
  4. washwashed with water (1 L, 2 times) and saturated brine (1 L) successively
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customthe solvent was removed under reduced pressure
  7. customThe obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate)

Sources & evidence

ORD record
ord-5fa380c36c3841538b1a1e43f565ed85
Source dataset
uspto-grants-2015_03
Patent number
US08975256B2

Reaction notes

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