Triphenylphosphine → 3-Benzofurancarboxylic acid, methyl ester

HRID 343098Notes

Reaction equation

HRID 343098 reaction equation
[CH3:1][O:2][C:3](=[O:14])[CH:4]=[CH:5][O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])(O)=O.[Na+]>CN(C=O)C.CCOCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:1][O:2][C:3]([C:4]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[O:6][CH:5]=1)=[O:14]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 539113493-(2-Bromo-phenoxy) acrylic acid methyl ester

Product 1

HCID 127770993-Benzofurancarboxylic acid, methyl esterYield 39%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

A stirring solution of 2.43 g (9.45 mmol) of 3-(2-Bromo-phenoxy) acrylic acid methyl ester, prepared as in Intermediate 17, 1.98 g (7.56 mmol, 0.8 equiv) of triphenylphosphine, 794 mg (9.45 mmol, 1.0 equiv) of NaHCO3, and 848 mg (3.78 mmol, 0.4 equiv) of palladium (II) acetate in 25 mL of DMF is heated to 110° C. for 16 h. After cooling to RT, the reaction mixture is diluted with 100 mL of Et2O and extracted with H2O (1×100 mL), dried (MgSO4), and the solvents removed in vacuo. Purification of the crude material by silica gel flash column chromatography afforded 650 mg of the title compound as a yellow oil: 1H NMR (CDCl3, 300 MHz) δ8.22 (s, 1H), 8.06 (m, 1H), 7.55 (m, 1H), 7.37 (m, 2H), 3.95 (s, 3H); Rf =0.50 in hexane/EtOAc 5/1.

Workup

  1. temperatureAfter cooling to RT
  2. extractionextracted with H2O (1×100 mL)
  3. dry with materialdried (MgSO4)
  4. customthe solvents removed in vacuo
  5. customPurification of the crude material by silica gel flash column chromatography

Sources & evidence

ORD record
ord-a00989f0caf94446a548901af76dc4f8
Source dataset
uspto-grants-1999_01
Patent number
US05859007

Reaction notes

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