Citric Acid → Methyl 4-(2-((tert-butoxycarbonyl)(methyl)amino)phenyl)-2-nitrobenzoate

HRID 454492Notes

Reaction equation

HRID 454492 reaction equation
[H-].[Na+].[C:3]([O:7][C:8]([NH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[C:17]1[CH:26]=[CH:25][C:20]([C:21]([O:23][CH3:24])=[O:22])=[C:19]([N+:27]([O-:29])=[O:28])[CH:18]=1)=[O:9])([CH3:6])([CH3:5])[CH3:4].CI.[C:32](O)(=O)CC(CC(O)=O)(C(O)=O)O>C(OCC)C.O.CN(C)C=O>[C:3]([O:7][C:8]([N:10]([CH3:32])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[C:17]1[CH:26]=[CH:25][C:20]([C:21]([O:23][CH3:24])=[O:22])=[C:19]([N+:27]([O-:29])=[O:28])[CH:18]=1)=[O:9])([CH3:6])([CH3:4])[CH3:5]

Participants

8

Reactant 4

HCID 311Citric AcidHCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 66989922Methyl 4-(2-(tert-butoxycarbonylamino)phenyl)-2-nitrobenzoate

Product 1

HCID 66990621Methyl 4-(2-((tert-butoxycarbonyl)(methyl)amino)phenyl)-2-nitrobenzoate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

Under ice-cooling, 60% sodium hydride (0.21 g) was added to an N,N-dimethylformamide (15 mL) solution of methyl 4-(2-(tert-butoxycarbonylamino)phenyl)-2-nitrobenzoate (1.3 g), followed by stirring at room temperature for 10 minutes. Then, methyl iodide (0.32 mL) was added thereto under ice-cooling, followed by stirring at room temperature for 1 hour. Water, a 10% aqueous solution of citric acid, and diethyl ether were added to the reaction mixture. The organic layer was separated, washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography [eluent: 95-85% hexane/ethyl acetate] to obtain 1.1 g of methyl 4-(2-((tert-butoxycarbonyl)(methyl)amino)phenyl)-2-nitrobenzoate as a light yellow solid.

Workup

  1. temperatureUnder ice-cooling
  2. temperatureunder ice-cooling
  3. stirringby stirring at room temperature for 1 hour
  4. customThe organic layer was separated
  5. washwashed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customthe solvent was evaporated under reduced pressure
  8. customThe obtained residue was purified by silica gel column chromatography [eluent: 95-85% hexane/ethyl acetate]

Sources & evidence

ORD record
ord-ace8e3bc5abb44e7807a4503e9326236
Source dataset
uspto-grants-2013_07
Patent number
US08492582B2

Reaction notes

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