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

HRID 1182759Notes

Reaction equation

HRID 1182759 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

A 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 cooling 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, twice) 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 cooling down
  2. customthe mixture was partitioned
  3. extractionthe water layer was extracted with ethyl acetate (300 mL)
  4. washwashed with water (1 L
  5. dry with materialtwice) and saturated brine (1 L) successively, dried 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-d8cde04499644cc18f59126af469394f
Source dataset
uspto-grants-2014_03
Patent number
US08664221B2

Reaction notes

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