Triphenylphosphine → 2,4-Dimethyl-5-propionylbenzoic acid

HRID 1487816Notes

Reaction equation

HRID 1487816 reaction equation
I[C:2]1[C:3]([CH3:12])=[CH:4][C:5]([CH3:11])=[C:6]([CH:10]=1)[C:7]([OH:9])=[O:8].[C:13]1(P(C2C=CC=CC=2)C2C=CC=CC=2)[CH:18]=CC=C[CH:14]=1.[Cl-].C([Al+]CC)C.[C]=[O:39]>COCCOC.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>[CH3:11][C:5]1[CH:4]=[C:3]([CH3:12])[C:2]([C:14](=[O:39])[CH2:13][CH3:18])=[CH:10][C:6]=1[C:7]([OH:9])=[O:8]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 16686102Diethyl aluminum chlorideHCID 230918755-Iodo-2,4-dimethylbenzoic acid2×HCID 178418416HCID 178418416, compound

Product 1

HCID 900211532,4-Dimethyl-5-propionylbenzoic acidYield 80%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Into a 100-mL autoclave (30 atm), was placed a solution of 5-iodo-2,4-dimethylbenzoic acid (compound 1.3, 2.00 g, 7.24 mmol) in ethylene glycol dimethyl ether (20 mL). Triphenylphosphine (190 mg, 0.73 mmol), Pd(PPh3)2Cl2 (500 mg, 0.71 mmol) and diethylaluminum chloride (2M, 10.8 mL, 21.6 mmol) were added to the reaction mixture. The resulting mixture was stirred under pressure with carbon monoxide (gas, 30 atm) at 80° C. for 15 h. (CAUTION: Highly toxic gas at high pressure. All necessary safety precautions were performed). After cooling to room temperature, the mixture was carefully purged, then quenched with 20 mL of water. Aqueous HCl (2M) was added carefully to adjust the pH to 5-6 and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were washed with brine (2×100 mL), dried (Na2SO4), filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:40-1:20) as the eluent to yield the title compound as a light yellow solid (1.2 g, 80%).

Workup

  1. customthe mixture was carefully purged
  2. customquenched with 20 mL of water
  3. additionAqueous HCl (2M) was added carefully
  4. extractionthe aqueous layer was extracted with ethyl acetate (100 mL)
  5. washThe combined organic layers were washed with brine (2×100 mL)
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:40-1:20) as the eluent

Sources & evidence

ORD record
ord-6cf838bb870e4c669ec3eb55e5617a74
Source dataset
uspto-grants-2016_08
Patent number
US09428502B2

Reaction notes

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