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

HRID 1699315Notes

Reaction equation

HRID 1699315 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) (2 M 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 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 vacuo

Sources & evidence

ORD record
ord-19e68b2b62824818aee91050c8b8f855
Source dataset
uspto-grants-2002_02
Patent number
US06344561B2

Reaction notes

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