Methane → 4-Acetyl-2-methylbenzoic acid

HRID 1848279Notes

Reaction equation

HRID 1848279 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][C:3]=1[CH3:11].[C:12](=O)([O-:14])[O-:13].[K+].[K+].C.[C]=O.Cl>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.[Pd].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O.C1(C)C=CC=CC=1>[C:8]([C:5]1[CH:6]=[CH:7][C:2]([C:12]([OH:14])=[O:13])=[C:3]([CH3:11])[CH:4]=1)(=[O:10])[CH3:9]

Participants

11

Reactant 5

HCID 297MethaneHCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 3471241-(4-Bromo-3-methylphenyl)ethanoneHCID 178418416HCID 178418416, compound

Product 1

HCID 534355544-Acetyl-2-methylbenzoic acidYield 90%

Reagents, catalysts & solvents 5

HCID 23938PalladiumCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 812191,3-Bis(diphenylphosphino)propaneCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Procedure

63.9 g (300 mmol) of 4′-bromo-3′-methylacetophenone, 256 g of toluene, 32 g of water, 45.5 g (330 mmol) of potassium carbonate, 9.66 g (30 mmol) of tetra(n-butyl) ammonium bromide, 1.45 g (water content 55.95% by weight) of activated charcoal supported 5% palladium and 0.372 g (0.90 mmol) of 1,3-bis(diphenylphosphino)propane were fed into a pressure-tight reactor, and reaction was performed at 120° for 7 hours by pressurizing with carbon monoxide at 0.8 MPa. After cooling the reaction solution to room temperature, inside of the reactor was purged with nitrogen, and then the pressure was reduced to atmosphere pressure. 224 g of water was added, and stirred for 30 minutes. Catalyst was filtered with Celite and the organic phase was separated. 43.8 g (420 mmol) of 35% hydrochloric acid was added to the water phase. The obtained slurry was filtered, and then dried under reduced pressure to obtain 48.1 g of 4-acetyl-2-methylbenzoic acid as white crystal (yield 90%).

Workup

  1. customwere fed into a pressure-tight reactor
  2. customreaction
  3. custominside of the reactor was purged with nitrogen
  4. addition224 g of water was added
  5. filtrationCatalyst was filtered with Celite
  6. customthe organic phase was separated
  7. filtrationThe obtained slurry was filtered
  8. customdried under reduced pressure

Sources & evidence

ORD record
ord-7043597911674417ab46dd258298f053
Source dataset
uspto-grants-2015_02
Patent number
US08952175B2

Reaction notes

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