Ethyl Acetate → Methyl 6-bromo-2,2-dimethyl-3-oxo-1,2,3,4-tetrahydroquinoxaline-5-carboxylate

HRID 1038466Notes

Reaction equation

HRID 1038466 reaction equation
[Br:1][C:2]1[C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:6]([N+:12]([O-])=O)[C:5]([NH:15][CH:16]([CH2:18]C(OCC)=O)[CH3:17])=[CH:4][CH:3]=1.[Sn](Cl)Cl.[C:27](OCC)(=[O:29])C.C(=O)([O-])O.[Na+]>C(O)C>[Br:1][C:2]1[C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:6]2[C:5]([NH:15][C:16]([CH3:17])([CH3:18])[C:27](=[O:29])[NH:12]2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 24479Stannous ChlorideHCID 516892Sodium BicarbonateHCID 67210813Methyl 6-bromo-3-[(2-ethoxycarbonyl)propan-2-yl]amino-2-nitrobenzoate

Product 1

HCID 24780709Methyl 6-bromo-2,2-dimethyl-3-oxo-1,2,3,4-tetrahydroquinoxaline-5-carboxylateYield 70%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Methyl 6-bromo-3-[(2-ethoxycarbonyl)propan-2-yl]amino-2-nitrobenzoate (Reference Compound No. 1-(5), 105 mg, 0.26 mmol) was dissolved in anhydrous ethanol (4.5 mL), tin (II) chloride (247 mg, 1.30 mmol) was added thereto, and then the reaction mixture was refluxed for 5 hours. After the reaction mixture was cooled down, ethyl acetate (25 mL) was added thereto, the mixture was neutralized with aqueous sodium hydrogen carbonate solution, and then filtered on celite. After the filtrate was partitioned, the water layer was extracted with ethyl acetate (10 mL, 2 times), the combined organic layer was washed with water (50 mL, 2 times) and saturated brine (50 mL) 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 (56.3 mg) as a pale yellow solid. (Yield 70%)

Workup

  1. temperaturethe reaction mixture was refluxed for 5 hours
  2. temperatureAfter the reaction mixture was cooled down
  3. filtrationfiltered on celite
  4. customAfter the filtrate was partitioned
  5. extractionthe water layer was extracted with ethyl acetate (10 mL, 2 times)
  6. washthe combined organic layer was washed with water (50 mL, 2 times) and saturated brine (50 mL) successively
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customthe solvent was removed under reduced pressure
  9. customThe obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate)

Sources & evidence

ORD record
ord-6c521c6f5c344130a83eca71c48f87dd
Source dataset
uspto-grants-2013_10
Patent number
US08551991B2

Reaction notes

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