Citric Acid → HCID 58508546, compound

HRID 454489Notes

Reaction equation

HRID 454489 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].[CH3:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1B(O)O.Br[C:19]1[CH:31]=[CH:30][C:22]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[C:21]([N+:32]([O-:34])=[O:33])[CH:20]=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(OCC)(=O)C.COCCOC.O>[CH3:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[C:19]1[CH:31]=[CH:30][C:22]([C:23]([O:25][C:26]([CH3:28])([CH3:29])[CH3:27])=[O:24])=[C:21]([N+:32]([O-:34])=[O:33])[CH:20]=1

Participants

9

Reactant 4

HCID 311Citric AcidHCID 10340Sodium CarbonateHCID 27339582-Methoxyphenylboronic acidHCID 26369829tert-Butyl 4-bromo-2-nitrobenzoate

Product 1

HCID 58508546HCID 58508546, compoundYield 100.9%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Water (9.0 mL), sodium carbonate (2.6 g), 2-methoxyphenylboronic acid (1.8 g), and bis(triphenylphosphine)palladium(II) dichloride (0.14 g) were added to an ethylene glycol dimethyl ether (30 mL) solution of tert-butyl 4-bromo-2-nitrobenzoate (3.0 g), followed by heating to reflux under a nitrogen atmosphere for 2 hours and 30 minutes. The reaction mixture was cooled to room temperature, and then a 10% aqueous solution of citric acid and ethyl acetate were added thereto. 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: 99-91% hexane/ethyl acetate] to obtain 3.3 g of tert-butyl 4-(2-methoxyphenyl)-2-nitrobenzoate as a light yellow oily substance.

Workup

  1. temperatureby heating
  2. temperatureto reflux under a nitrogen atmosphere for 2 hours and 30 minutes
  3. customThe organic layer was separated
  4. washwashed with a saturated aqueous solution of sodium chloride
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customthe solvent was evaporated under reduced pressure
  7. customThe obtained residue was purified by silica gel column chromatography [eluent: 99-91% hexane/ethyl acetate]

Sources & evidence

ORD record
ord-fb67dc68c1e441b4930aaddebe357f43
Source dataset
uspto-grants-2013_07
Patent number
US08492582B2

Reaction notes

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