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

HRID 2608

反応式

HRID 2608 の反応式
[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

参加物

6

反応物 3

HCID 111262-MethylthiopheneHCID 107533577-Bromo-4,4-dimethyl-1,2,3,4-tetrahydronaphthalen-1-one2 回HCID 178418339Butyllithium

生成物 1

HCID 186200621-(5-Methyl-thien-2-yl)3,4-dihydro-4,4-dimethyl-7-bromo-naphthalene収率 62.3%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 21584169Diethylether ethylacetate溶媒

反応条件

温度
0 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-1181981a49704b02b7381620902d58eb
出典データセット
uspto-grants-1998_03
特許番号
US05728846

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