Hydrogen Peroxide → Methyl 4-aminocarbonyl-5-(isopropylamino)-2-methylbenzoate

HRID 906161Notes

Reaction equation

HRID 906161 reaction equation
[C:1]([C:3]1[C:12]([NH:13][CH:14]([CH3:16])[CH3:15])=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:17])[CH:4]=1)#[N:2].OO.C(=O)([O-])[O-:21].[K+].[K+]>CS(C)=O>[NH2:2][C:1]([C:3]1[C:12]([NH:13][CH:14]([CH3:15])[CH3:16])=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:17])[CH:4]=1)=[O:21]

Participants

5

Reactant 3

HCID 784Hydrogen PeroxideHCID 11430Potassium CarbonateHCID 67403235Methyl 4-cyano-5-(isopropylamino)-2-methylbenzoate

Product 1

HCID 67402512Methyl 4-aminocarbonyl-5-(isopropylamino)-2-methylbenzoateYield 261.3%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

Methyl 4-cyano-5-(isopropylamino)-2-methylbenzoate (224 mg, 0.96 mmol) was dissolved in DMSO (2 mL) and cooled in a cold water bath. 30% Aqueous hydrogen peroxide (0.2 mL) and potassium carbonate (42.6 mg, 0.31 mmol) was added, and the mixture was stirred at ambient temperature for 1 h. The reaction mixture was partitioned between ethyl acetate and 10% aqueous lithium chloride. The aqueous portion was extracted with ethyl acetate. The combined organic portion was dried over sodium sulfate, then filtered and concentrated to a yellow oil which was purified by column chromatography (silica gel, 15-30% ethyl acetate in hexanes to afford methyl 4-aminocarbonyl-5-(isopropylamino)-2-methylbenzoate (202 mg, 0.81 mmol, 83% yield) as a yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.35 (d, 1H), 7.26 (d, 1H), 7.24-7.22 (m, 2H), 5.70 (br s, 1H), 3.90 (s, 3H), 3.75-3.68 (m, 1H), 2.42 (s, 3H), 1.26-1.24 (m, 6H); MS (EI) for C13H18N2O3: 251 (MH+).

Workup

  1. temperaturecooled in a cold water bath
  2. customThe reaction mixture was partitioned between ethyl acetate and 10% aqueous lithium chloride
  3. extractionThe aqueous portion was extracted with ethyl acetate
  4. dry with materialThe combined organic portion was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated to a yellow oil which
  7. customwas purified by column chromatography (silica gel, 15-30% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-63beafce0f7348b88809e618d54865e4
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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