2-Methylthiophene → 1-(5-Methyl-thien-2-yl)3,4-dihydro-4,4-dimethyl-7-bromo-naphthalene

HRID 2608

Reaction equation

HRID 2608 reaction equation
[CH3:1][C:2]1[S:3][CH:4]=[CH:5][CH:6]=1.[Li]CCCC.[CH3:12][C:13]1([CH3:25])[C:22]2[C:17](=[CH:18][C:19]([Br:23])=[CH:20][CH:21]=2)[C:16](=O)[CH2:15][CH2:14]1>C1COCC1.CCOCC.C(OC(=O)C)C>[CH3:1][C:2]1[S:3][C:4]([C:16]2[C:17]3[C:22](=[CH:21][CH:20]=[C:19]([Br:23])[CH:18]=3)[C:13]([CH3:25])([CH3:12])[CH2:14][CH:15]=2)=[CH:5][CH:6]=1

Participants

6

Conditions

Temperature
0 °C

Procedure

To a cold (-78° C.) solution of 2-methylthiophene (800 mg, 8.1 mmol) in THF (10 mL) was added n-BuLi (1.6M solution in hexane, 5 mL). The mixture was stirred for 1.5 hours and transferred to a cold (-78° C.) flask containing 3,4-dihydro-4,4-dimethyl-7-bromo-1(2H)-naphthalenone (Compound A, 1.63 g, 6.5 mmol), in THF (15 mL). The mixture was gradually warmed to 0° C. The reaction mixture was diluted with ether:ethylacetate (1:1, 80 mL), washed with water (10 mL), brine (10 mL), dried with MgSO4 and the solvent was removed by evaporation. The crude material was dissolved in dichloroethane (20 mL) and pTSA (40 mg) was added. The mixture was stirred at ambient temperature for 16 hours and at 50° C. for 4 hours. The reaction mixture was diluted with ether (150 mL), washed with aqueous 10% NaHCO3 (10 mL), brine (10 mL) and dried with MgSO4. Purification by chromatography on silica gel gave 1.35 g of the title compound as a white solid.

Workup

  1. customtransferred to a cold (-78° C.) flask
  2. washwashed with water (10 mL), brine (10 mL)
  3. dry with materialdried with MgSO4
  4. customthe solvent was removed by evaporation
  5. dissolutionThe crude material was dissolved in dichloroethane (20 mL)
  6. additionpTSA (40 mg) was added
  7. stirringThe mixture was stirred at ambient temperature for 16 hours and at 50° C. for 4 hours
  8. additionThe reaction mixture was diluted with ether (150 mL)
  9. washwashed with aqueous 10% NaHCO3 (10 mL), brine (10 mL)
  10. dry with materialdried with MgSO4
  11. customPurification by chromatography on silica gel

Sources & evidence

ORD record
ord-1181981a49704b02b7381620902d58eb
Source dataset
uspto-grants-1998_03
Patent number
US05728846

Linked notes

Loading…