Potassium Phosphate, Tribasic → Methyl(4-cyclopropylphenyl)acetate

HRID 1913421Notes

Reaction equation

HRID 1913421 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8](I)=[CH:7][CH:6]=1.[CH:13]1(B(O)O)[CH2:15][CH2:14]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(OCC)(=O)C.O>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([CH:13]2[CH2:15][CH2:14]2)=[CH:7][CH:6]=1

Participants

9

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 75806TricyclohexylphosphineHCID 2760897Cyclopropylboronic acidHCID 10378700Methyl 4-Iodophenylacetate

Product 1

HCID 66845395Methyl(4-cyclopropylphenyl)acetateYield 69.9%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of methyl(4-iodophenyl)acetate (1.5 g, 5.4 mmol), cyclopropylboronic acid (607 mg, 7.06 mmol), potassium phosphate (4.04 g, 29.7 mmol) and tricyclohexylphosphine (152 mg, 10 mol %) in 25 mL toluene under nitrogen was added water (1.25 mL) and palladium acetate (61 mg, 5 mol %). The mixture was heated to 100° C. for 10 hours. After cooling to room temperature, water and ethyl acetate were added and the mixture was filtered through a Celite® pad to remove insoluble material. The layers were separated and the water layer was washed 2× with ethyl acetate. The combined organic layers were washed with brine and dried over anhydrous magnesium sulfate. Solvent removal gave 1.5 g of a dark yellow paste which was purified by silica chromatography on an ISCO (Teledyne Corp., Thousand Oaks, Calif.) column, eluting with a gradient 0/100 to 30/70 ethyl acetate/heptanes, to give methyl(4-cyclopropylphenyl)acetate as a yellow semi-solid (718 mg, 69%).

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationthe mixture was filtered through a Celite® pad
  3. customto remove insoluble material
  4. customThe layers were separated
  5. washthe water layer was washed 2× with ethyl acetate
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customSolvent removal
  9. customgave 1.5 g of a dark yellow paste which
  10. customwas purified by silica chromatography on an ISCO (Teledyne Corp., Thousand Oaks, Calif.) column
  11. washeluting with a gradient 0/100 to 30/70 ethyl acetate/heptanes

Sources & evidence

ORD record
ord-246116c91c8640b488b939dc3ae42612
Source dataset
uspto-grants-2013_12
Patent number
US08609680B2

Reaction notes

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