Dimethylformamide → Tert-butyl 4-(3-((tert-butoxycarbonyl)(methyl)amino)phenyl)-2-nitrobenzoate

HRID 454520Notes

Reaction equation

HRID 454520 reaction equation
[H-].[Na+].[CH3:3]N(C)C=O.[C:8]([O:12][C:13]([NH:15][C:16]1[CH:17]=[C:18]([C:22]2[CH:34]=[CH:33][C:25]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])=[C:24]([N+:35]([O-:37])=[O:36])[CH:23]=2)[CH:19]=[CH:20][CH:21]=1)=[O:14])([CH3:11])([CH3:10])[CH3:9].CI>C(OCC)C.O>[C:8]([O:12][C:13]([N:15]([CH3:3])[C:16]1[CH:17]=[C:18]([C:22]2[CH:34]=[CH:33][C:25]([C:26]([O:28][C:29]([CH3:30])([CH3:31])[CH3:32])=[O:27])=[C:24]([N+:35]([O-:37])=[O:36])[CH:23]=2)[CH:19]=[CH:20][CH:21]=1)=[O:14])([CH3:9])([CH3:10])[CH3:11]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 66990036Tert-butyl 4-(3-(tert-butoxycarbonylamino)phenyl)-2-nitrobenzoate

Product 1

HCID 66991211Tert-butyl 4-(3-((tert-butoxycarbonyl)(methyl)amino)phenyl)-2-nitrobenzoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

Under ice-cooling, 60% sodium hydride (24 mg) was added to an N,N-dimethylformamide (3.0 mL) solution of tert-butyl 4-(3-(tert-butoxycarbonylamino)phenyl)-2-nitrobenzoate (0.17 g), followed by stirring at the same temperature for 15 minutes and then at room temperature for 20 minutes. Methyl iodide (0.037 mL) was added to the reaction mixture under ice-cooling, followed by stirring at room temperature for 1 hour. Water and diethyl ether was added to the reaction mixture, and the organic layer was separated, and the aqueous layer was extracted with diethyl ether. The organic layer and the extract were combined, and the resulting mixture was washed with a 10% aqueous solution of citric acid and a saturated aqueous solution of sodium chloride sequentially and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography [eluent: 95-85% hexane/ethyl acetate] to obtain 0.17 g of tert-butyl 4-(3-((tert-butoxycarbonyl)(methyl)amino)phenyl)-2-nitrobenzoate as a brown oily substance.

Workup

  1. temperatureUnder ice-cooling
  2. waitat room temperature for 20 minutes
  3. temperaturecooling
  4. stirringby stirring at room temperature for 1 hour
  5. customthe organic layer was separated
  6. extractionthe aqueous layer was extracted with diethyl ether
  7. washthe resulting mixture was washed with a 10% aqueous solution of citric acid
  8. dry with materiala saturated aqueous solution of sodium chloride sequentially and dried over anhydrous magnesium sulfate
  9. customThe solvent was evaporated under reduced pressure
  10. customthe obtained residue was purified by silica gel column chromatography [eluent: 95-85% hexane/ethyl acetate]

Sources & evidence

ORD record
ord-13b79364396c464c9c1f2401c7a3ff98
Source dataset
uspto-grants-2013_07
Patent number
US08492582B2

Reaction notes

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