Reaktion #489988

ord-7e3f510b6ddd4adc937fb3302bc18de4

Lösungsmittel

Reaktionsbedingungen

Temperatur
-78°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Temperaturto warm to room temperature
  2. 2
    workup.ADDITIONwet silica gel (5.0 g/0.5 mL of water) was added
  3. 3
    workup.STIRRINGto stir at room temperature for 10 minutes before it
  4. 4
    Filtrationwas filtered
  5. 5
    WaschenThe silica gel was rinsed with EtOAc
  6. 6
    Einengenthe filtrate was concentrated under vacuum
  7. 7
    SonstigeThe crude residue was purified by silica gel chromatography
  8. 8
    Wascheneluting with 0-20% EtOAc/hexanes

Vorschrift

1-Bromo-4-[(3-methylbut-3-en-1-yl)sulfanyl]benzene (1.05 g, 4.08 mmol) dissolved in dichloromethane (24.0 mL) was cooled to 0° C., and aluminum chloride (0.60 g, 4.49 mmol) was added portionwise. The reaction mixture was stirred at 0° C. for 1 hour and warmed to room temperature for another hour. It was then poured into an Erlenmeyer flask containing a 10% aqueous NaOH solution and ice. The mixture was extracted with dichloromethane (2×, 40.0 mL), and the combined organic layers were dried over Na2SO4, filtered, and concentrated under vacuum. The crude residue was purified by silica gel chromatography eluting with 0-10% EtOAc/Hexanes to give 6-bromo-4,4-dimethyl-3,4-dihydro-2H-thiochromene as a pale-yellow oil. 6-Bromo-4,4-dimethyl-3,4-dihydro-2H-thiochromene (798 mg, 3.10 mmol) in THF (21.0 mL) was cooled to −78° C. and n-BuLi (1.50 mL, 3.72 mmol) was added dropwise. The reaction mixture was stirred at −78° C. for 10 minutes and then DMF (961 μl, 12.4 mmol) was added dropwise via a syringe. The resulting mixture was allowed to warm to room temperature and wet silica gel (5.0 g/0.5 mL of water) was added. The mixture was allowed to stir at room temperature for 10 minutes before it was filtered. The silica gel was rinsed with EtOAc and the filtrate was concentrated under vacuum. The crude residue was purified by silica gel chromatography eluting with 0-20% EtOAc/hexanes to obtain the desired product as a pale-yellow oil.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08742110B2uspto-grants-2014_06