Trifluoroacetic acid → 3-(2,4-Dihydroxy-phenyl)-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one

HRID 61867

Reaction equation

HRID 61867 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][CH2:8][C:9](=[O:15])[C:10]2([CH3:14])[CH3:13])=[CH:5][CH:4]=1.C[C:17]([CH3:20])([O-:19])[CH3:18].[Na+].F[B-](F)(F)F.[C:27]([PH+](C(C)(C)C)C(C)(C)C)([CH3:30])(C)[CH3:28].FC(F)(F)C(O)=[O:43].P([O-])([O-])(O)=O.[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(Cl)Cl.CO.C1(C)C=CC=CC=1>[OH:43][C:28]1[CH:20]=[C:17]([OH:19])[CH:18]=[CH:30][C:27]=1[CH:8]1[CH2:7][C:6]2[C:11](=[CH:12][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)[C:10]([CH3:13])([CH3:14])[C:9]1=[O:15]

Participants

10

Reactant 5

HCID 6422Trifluoroacetic acidHCID 24450Potassium Phosphate, DibasicHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 130110077-Methoxy-1,1-dimethyl-3,4-dihydronaphthalen-2(1H)-one2×HCID 23676156Sodium t-butoxide

Product 1

HCID 668346193-(2,4-Dihydroxy-phenyl)-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-oneYield 36%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 887MethanolSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
70 °C

Procedure

To 7-methoxy-1,1-dimethyl-3,4-dihydro-1H-naphthalen-2-one (Compound A2, 10 g), 2-bromo-1,3-dihydroxytetrahydropyranbenzene (Compound Z9, 20.98 g), sodium t-butoxide (5.88 g), palladium acetate (550 mg) and tri-t-butylphosphonium tetrafluoroborate (710 mg), toluene (40 mL) was added and the mixture was stirred and heated at 70° C. under nitrogen atmosphere for 6 hr. After cooling, the reaction mixture was added with methanol (38 mL) and trifluoroacetic acid (14.54 mL) at room temperature, and then stirred at room temperature overnight. To the resulting residues, methylene chloride and saturated dipotassium hydrogen phosphate were added and the organic layer was washed with saturated brine. Thereafter, the organic layer was dried over magnesium sulfate. The residues obtained after concentration under reduced pressure were purified by silica gel column chromatography (ethyl acetate/hexane) to obtain the title compound (5.53 g, 36%).

Workup

  1. temperatureAfter cooling
  2. stirringstirred at room temperature overnight
  3. washthe organic layer was washed with saturated brine
  4. dry with materialThereafter, the organic layer was dried over magnesium sulfate
  5. customThe residues obtained
  6. concentrationafter concentration under reduced pressure
  7. customwere purified by silica gel column chromatography (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-0efc1906e96e4b0f843e4ee769e03666
Source dataset
uspto-grants-2016_09
Patent number
US09440922B2

Linked notes

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