Citric Acid → Phenylmethyl 2-[(4-hydroxy-3-nitrophenyl)carbonyl]benzoate

HRID 2367136Notes

Reaction equation

HRID 2367136 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:18]=[CH:17][CH:16]=[CH:15][C:11]=2[C:12]([OH:14])=[O:13])=[O:9])=[CH:4][C:3]=1[N+:19]([O-:21])=[O:20].C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:28](Br)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CN(C=O)C.C(OCC)(=O)C.O>[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:18]=[CH:17][CH:16]=[CH:15][C:11]=2[C:12]([O:14][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)=[O:13])=[O:9])=[CH:4][C:3]=1[N+:19]([O-:21])=[O:20]

Participants

8

Reactant 4

HCID 311Citric AcidHCID 7498Benzyl BromideHCID 10796Cesium carbonateHCID 2257052-(4-Hydroxy-3-nitrobenzoyl)benzoic acid

Product 1

HCID 67045173Phenylmethyl 2-[(4-hydroxy-3-nitrophenyl)carbonyl]benzoateYield 54%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-[(4-hydroxy-3-nitrophenyl)carbonyl]benzoic acid (9.7 g, 30 mmol) in DMF (100 mL) was added cesium carbonate (9.8 g, 30 mmol) and benzyl bromide (3.6 mL, 30 mmol). The reaction mixture was stirred at rt for 4 h. Water, 10% citric acid, and ethyl acetate were added, and then the phases were partitioned. The aqueous phase was extracted with ethyl acetate. The organic extracts were combined, dried over magnesium sulfate, filtered, and concentrated. The residue was purified by flash chromatography (50% hexanes:50% ethyl acetate). The product-containing fractions were combined and concentrated. Impurities were removed from the solid residue by trituration with ether. The desired phenylmethyl 2-[(4-hydroxy-3-nitrophenyl)carbonyl]benzoate was obtained as powdery yellow solid (6.17 g, 16.3 mmol, 54% yield. 1H NMR (400 MHz, CDCl3): 10.89 (s, 1H), 8.25 (d, 1H), 8.16 (dd, 1H), 7.91 (dd, 1H), 7.69 (m, 1H), 7.62 (m, 1H), 7.35 (m, 1H), 7.27-7.23 (m, 3H), 7.20-7.17 (m, 2H), 7.10 (d, 1H), 5.13 (s, 2H); MS (EI) for C21H15NO6: 400 (MNa+).

Workup

  1. customthe phases were partitioned
  2. extractionThe aqueous phase was extracted with ethyl acetate
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by flash chromatography (50% hexanes:50% ethyl acetate)
  7. concentrationconcentrated
  8. customImpurities were removed from the solid residue by trituration with ether

Sources & evidence

ORD record
ord-e65a88f6647e432391723ea37ef19a0b
Source dataset
uspto-grants-2014_04
Patent number
US08697737B2

Reaction notes

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