Hydrochloric Acid → 1-Methyl-4-phenoxynaphthalene

HRID 1275421Notes

Reaction equation

HRID 1275421 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([CH3:12])=[CH:4][CH:3]=1.[C:13]1([OH:19])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(=O)([O-])[O-].[K+].[K+].Cl>[Cu]Cl.[Cu].N1C=CC=CC=1>[CH3:12][C:5]1[C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[C:2]([O:19][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:3][CH:4]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 996PhenolHCID 11430Potassium CarbonateHCID 811121-Bromo-4-methylnaphthalene

Product 1

HCID 221195721-Methyl-4-phenoxynaphthaleneYield 33%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 62652Cuprous chlorideCatalystHCID 1049PyridineSolvent

Procedure

To a 3-neck flask fitted with a mechanical stirrer, 600 mL of pyridine (dried over molecular sieve), 100 g of 4-bromo-1-methylnaphthalene, 55.6 g of phenol, 83.7 g of potassium carbonate, 14.9 g of copper(I)chloride, and 2 g copper bronze was added. Under a nitrogen atmosphere, the mixture was refluxed for 72 hours with vigorous stirring. The reaction mixture was cooled and poured into cold dilute hydrochloric acid, and the resulting mixture was extracted with ethyl acetate. The organic layer was washed two times with cold dilute hydrochloric acid, dried over sodium sulfate, and filtered. After removing the solvent under vacuum, the product was flash chromatographed over silica gel with hexane elution. The product was further purified through fractional distillation, obtaining 35 g (33%) of the desired 1-methyl-4-phenoxynaphthalene intermediate at 150° C. at 0.075 torr.

Workup

  1. customTo a 3-neck flask fitted with a mechanical stirrer
  2. temperatureUnder a nitrogen atmosphere, the mixture was refluxed for 72 hours with vigorous stirring
  3. temperatureThe reaction mixture was cooled
  4. extractionthe resulting mixture was extracted with ethyl acetate
  5. washThe organic layer was washed two times with cold dilute hydrochloric acid
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customAfter removing the solvent under vacuum
  9. customchromatographed over silica gel with hexane elution
  10. distillationThe product was further purified through fractional distillation

Sources & evidence

ORD record
ord-198f7b782566487489b4fbc6f495973c
Source dataset
uspto-grants-2000_12
Patent number
US06160175

Reaction notes

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