Toluene → HCID 57423400, compound

HRID 1673334Notes

Reaction equation

HRID 1673334 reaction equation
[C:1]1(C)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:9]1[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[C:11]([N+:19]([O-:21])=[O:20])[CH:10]=1.OB(O)C1C=CC=CC=1.C(=O)([O-])O.[Na+]>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O.C(O)C>[N+:19]([C:11]1[CH:10]=[C:9]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH:18]=[CH:17][C:12]=1[C:13]([O:15][CH3:16])=[O:14])([O-:21])=[O:20]

Participants

9

Reactant 4

HCID 1140TolueneHCID 66827Phenylboronic AcidHCID 516892Sodium BicarbonateHCID 18350461Methyl 4-bromo-2-nitrobenzoate

Product 1

HCID 57423400HCID 57423400, compound

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 178418397HCID 178418397, compoundCatalyst2×HCID 702EthanolSolventHCID 962WaterSolvent2×

Procedure

To a mixed solution of 42 mL of toluene, 16 mL of ethanol and 7.8 mL of water containing 5.2 g of methyl 4-bromo-2-nitrobenzoate, 2.9 g of dihydroxyphenyl borane, 4.2 g of sodium hydrogen carbonate and 1.1 g of tetrakis(triphenylphosphine)-palladium (0) were added sequentially and the resulting mixture was heated to reflux under nitrogen atmosphere for 2 hours. After the reaction mixture was cooled to room temperature, 1.1 g of tetrakis(triphenylphosphine)palladium (0) was added to the reaction mixture and the resulting mixture was heated to reflux under nitrogen atmosphere for 2 hours. After the reaction mixture was cooled to room temperature, 1.1 g of tetrakis(triphenylphosphine)palladium (0) was added to the reaction mixture and the resulting mixture was heated to reflux under nitrogen atmosphere for 2 hours. After the reaction mixture was cooled to room temperature, water was added. The organic layer was separated and dried over anhydrous magnesium sulfate after washed with 1.0 mol/L hydrochloric acid and a saturated sodium chloride aqueous solution sequentially, and the solvent was evaporated under reduced pressure. The obtained residue was purified with silica gel column chromatography [eluent; hexane:ethyl acetate=20:1] to obtain 4.8 g of methyl 2-nitro-4-phenylbenzoate as pale yellow oil.

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux under nitrogen atmosphere for 2 hours
  3. temperaturethe resulting mixture was heated
  4. temperatureto reflux under nitrogen atmosphere for 2 hours
  5. temperatureAfter the reaction mixture was cooled to room temperature
  6. temperaturethe resulting mixture was heated
  7. temperatureto reflux under nitrogen atmosphere for 2 hours
  8. temperatureAfter the reaction mixture was cooled to room temperature
  9. customThe organic layer was separated
  10. dry with materialdried over anhydrous magnesium sulfate
  11. washafter washed with 1.0 mol/L hydrochloric acid
  12. customa saturated sodium chloride aqueous solution sequentially, and the solvent was evaporated under reduced pressure
  13. customThe obtained residue was purified with silica gel column chromatography [eluent; hexane:ethyl acetate=20:1]

Sources & evidence

ORD record
ord-d7dabf45d3864d57a2208456b82eef11
Source dataset
uspto-grants-2011_08
Patent number
US07999132B2

Reaction notes

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