Methanol → 6-Bromo-4-tert-butyl-1,1-dimethyl-1,2-dihydronaphthalene

HRID 1599881Notes

Reaction equation

HRID 1599881 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([CH3:14])([CH3:13])[CH2:7][CH2:8][C:9]2=O)=[CH:4][CH:3]=1.[C:15]([Mg]Cl)([CH3:18])([CH3:17])[CH3:16].CO.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1COCC1>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([CH3:14])([CH3:13])[CH2:7][CH:8]=[C:9]2[C:15]([CH3:18])([CH3:17])[CH3:16])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 6101p-Toluenesulfonic acidHCID 107533577-Bromo-4,4-dimethyl-1,2,3,4-tetrahydronaphthalen-1-one2×HCID 178418310HCID 178418310, compound

Product 1

HCID 158960196-Bromo-4-tert-butyl-1,1-dimethyl-1,2-dihydronaphthalene

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

In a flame dried round bottom flask 7-bromo-3,4-dihydro-4,4-dimethylnaphthalen-1(2H)-one (Compound G, 2.0 g, 7.93 mmol) was dissolved in anhydrous THF (50 ml) and 3,4,5,6,-tetrahydro-2(H)-pyrimidinone (DMPU) (11.5 ml, 95.16 mmol) was added, under argon atmosphere. The reaction was then cooled to -20° C. and a solution of t-butyl magnesium chloride (16 ml, 31.7 mmol) (2M in Et2O) was added dropwise and stirred at -20° C. for 2 h and at ambient temperature for 1 h, under argon atmosphere. The reaction was quenched at 0° C. with saturated ammonium chloride solution (20 ml) and extracted with EtOAc (2×50 ml). The combined extract was washed with water (20 ml), brine (20 ml) and dried over MgSO4. The solvent was evaporated under reduced pressure to afford a yellow oil. To this yellow oil were added MeOH (50 ml) and p-tolylsulfonic acid (100 mg). The resultant reaction solution was heated in an oil bath (60° C.) for 3 h. The reaction was cooled and quenched with water (20 ml), extracted with EtOAc (2×50 ml). The combined extract was washed with saturated NaHCO3 (20 ml), water (20 ml), brine (20 ml), and dried over MgSO4. The solvent was concentrated in s vacuo and the title compound was obtained as a colorless oil after purification by flash chromatography (silica, hexane).

Workup

  1. customThe reaction was quenched at 0° C. with saturated ammonium chloride solution (20 ml)
  2. extractionextracted with EtOAc (2×50 ml)
  3. extractionThe combined extract
  4. washwas washed with water (20 ml), brine (20 ml)
  5. dry with materialdried over MgSO4
  6. customThe solvent was evaporated under reduced pressure
  7. customto afford a yellow oil
  8. customThe resultant reaction solution
  9. temperaturewas heated in an oil bath (60° C.) for 3 h
  10. temperatureThe reaction was cooled
  11. customquenched with water (20 ml)
  12. extractionextracted with EtOAc (2×50 ml)
  13. extractionThe combined extract
  14. washwas washed with saturated NaHCO3 (20 ml), water (20 ml), brine (20 ml)
  15. dry with materialdried over MgSO4
  16. concentrationThe solvent was concentrated in s vacuo

Sources & evidence

ORD record
ord-07d7b8e769854c268db0211eff8a1bbf
Source dataset
uspto-grants-1998_04
Patent number
US05741896

Reaction notes

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