Hydrochloric Acid → Methyl 3-acetyl-4-hydroxybenzoate

HRID 572721Notes

Reaction equation

HRID 572721 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[OH:12])[C:5]([O:7][CH3:8])=[O:6].C(N(CC)CC)C.[CH:20]([O:22]CCCC)=[CH2:21].Cl>C(O)C.C(OCC)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C(O[Pd]OC(=O)C)(=O)C.C(Cl)Cl>[C:20]([C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[OH:12])[C:5]([O:7][CH3:8])=[O:6])(=[O:22])[CH3:21]

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 8108Butyl vinyl etherHCID 8471TriethylamineHCID 4778958Methyl 3-bromo-4-hydroxybenzoate

Product 1

HCID 12332833Methyl 3-acetyl-4-hydroxybenzoateYield 82%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
70 °C

Procedure

To a degassed solution of methyl 3-bromo-4-hydroxybenzoate (350 g, 1514.87 mmol) in ethanol (3 L) were added triethylamine (0.528 L, 3787.17 mmol), 1-(vinyloxy)butane (0.588 L, 4544.60 mmol), 1,1′-bis(diphenylphosphino)ferrocene (33.1 g, 60.6 mmol) and diacetoxypalladium (8.50 g, 37.9 mmol) under nitrogen. The mixture was heated at 70° C. overnight. The reaction was cooled down, filtered and the filtrate concentrated. The resulting solid was solubilized with DCM (2 L) and HCl 4N (1.14 L, 4544 mmol) was added under stirring. Stirring was maintained for 2 hrs, the organic phase was separated, dried over magnesium sulfate, filtered and concentrated to afford a solid which was stirred in diethyl ether (5 L) for 2 hrs. The solid was filtered off and the filtrate concentrated to dryness to afford methyl 3-acetyl-4-hydroxybenzoate (240 g, 82%) as a beige powder. Mass spectrum: [M−H]− 193.

Workup

  1. temperatureThe reaction was cooled down
  2. filtrationfiltered
  3. concentrationthe filtrate concentrated
  4. additionwas added
  5. stirringStirring
  6. temperaturewas maintained for 2 hrs
  7. customthe organic phase was separated
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customto afford a solid which
  12. filtrationThe solid was filtered off
  13. concentrationthe filtrate concentrated to dryness

Sources & evidence

ORD record
ord-67722416981a42f4b5e0825437028405
Source dataset
uspto-grants-2015_05
Patent number
US09029374B2

Reaction notes

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