Diisopropylamine → 1-Bromo-4-(4-bromophenyl)-3-(4-methoxyphenyl)butan-2-one

HRID 452558

反応式

HRID 452558 の反応式
C(NC(C)C)(C)C.[Li]CCCC.[Br:13][C:14]1[CH:19]=[CH:18][C:17]([CH2:20][CH:21]([C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=2)[C:22](=[O:24])[CH3:23])=[CH:16][CH:15]=1.[Br-:33].[Br-].[Br-].C1([N+](C)(C)C)C=CC=CC=1.C1([N+](C)(C)C)C=CC=CC=1.C1([N+](C)(C)C)C=CC=CC=1>C(OCC)C.C1COCC1.CCOC(C)=O.O>[Br:33][CH2:23][C:22](=[O:24])[CH:21]([C:25]1[CH:26]=[CH:27][C:28]([O:31][CH3:32])=[CH:29][CH:30]=1)[CH2:20][C:17]1[CH:18]=[CH:19][C:14]([Br:13])=[CH:15][CH:16]=1

参加物

9

反応物 4

HCID 7912DiisopropylamineHCID 17977687Phenyltrimethylammonium bromide dibromideHCID 669237034-(4-Bromophenyl)-3-(4-methoxyphenyl)butan-2-oneHCID 178418339Butyllithium

生成物 1

HCID 866508471-Bromo-4-(4-bromophenyl)-3-(4-methoxyphenyl)butan-2-one収率 82.8%

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

Diisopropylamine (0.084 g, 0.83 mmol) was dissolved in anhydrous diethyl ether (7.5 mL) under argon atmosphere and cooled to −78° C. BuLi (0.52 mL, 0.83 mmol) was added dropwise to the solution and the resulting solution was allowed to warm to 0° C. for 10 min, then recooled to −78° C. TMS-Cl (freshly distilled over calcium hydride, 0.11 mL, 0.83 mmol) was added dropwise to the solution at −78° C., after addition, the reaction was allowed to stir for an additional 10 min. The solution was then cooled to −90° C., and 4-(4-bromophenyl)-3-(4-methoxyphenyl)butan-2-one (0.25 g, 0.75 mmol) was added dropwise as a solution in anhydrous diethyl ether. After addition was complete, the solution was allowed to stir for an additional 40 min. The reaction was then warmed to 0° C. and phenyltrimethylammonium tribromide (0.31 mg, 0.83 mmol) was slowly added dropwise as a solution in anhydrous THF (4 mL). The resulting solution was allowed to stir at 25° C. for 1 hour. The mixture was diluted with EtOAc and water, washed with NaCl (×3), dried over sodium sulfate and concentrated in vacuo. The crude product was purified using silica gel chromatography (0-30% EtOAc in hexanes gradient) to afford 256 mg of 1-bromo-4-(4-bromophenyl)-3-(4-methoxyphenyl)butan-2-one as a viscous oil.

後処理

  1. temperatureto warm to 0° C. for 10 min
  2. customrecooled to −78° C
  3. distillationTMS-Cl (freshly distilled over calcium hydride, 0.11 mL, 0.83 mmol)
  4. additionwas added dropwise to the solution at −78° C.
  5. additionafter addition
  6. temperatureThe solution was then cooled to −90° C.
  7. additionAfter addition
  8. stirringto stir for an additional 40 min
  9. temperatureThe reaction was then warmed to 0° C.
  10. stirringto stir at 25° C. for 1 hour
  11. washwashed with NaCl (×3)
  12. dry with materialdried over sodium sulfate
  13. concentrationconcentrated in vacuo
  14. customThe crude product was purified

出典と根拠

ORDレコード
ord-e34228de24764d1881609c1a56dad532
出典データセット
uspto-grants-2013_07
特許番号
US08492387B2

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