Isopropenyl acetate → 1-(4-Methoxy-2-methylphenyl)-2-propanone

HRID 69322

反応式

HRID 69322 の反応式
C([Sn](CCCC)(CCCC)OC)CCC.Br[C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][C:18]=1[CH3:25].C([O:29][C:30]([CH3:32])=[CH2:31])(=O)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[F-].[K+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:24][O:23][C:20]1[CH:21]=[CH:22][C:17]([CH2:31][C:30](=[O:29])[CH3:32])=[C:18]([CH3:25])[CH:19]=1

参加物

8

反応物 5

HCID 7916Isopropenyl acetateHCID 80271Tri-o-tolylphosphineHCID 1179151-Bromo-4-methoxy-2-methylbenzeneHCID 522689Potassium FluorideHCID 16683411Tributyltin methoxide

生成物 1

HCID 247214921-(4-Methoxy-2-methylphenyl)-2-propanone

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒2 回

実験手順

Four batches of this experiment were carried out (4×250 g substrate). Tributyl(methoxy)stannane (400 g, 1.24 mol), 1-bromo-4-methoxy-2-methylbenzene (250 g, 1.24 mol), prop-1-en-2-yl acetate (187 g, 1.87 mol), palladium(II) acetate (7.5 g, 33 mmol) and tris(2-methylphenyl)phosphane (10 g, 33 mmol) were stirred together in toluene (2 L) at 100° C. for 18 hours. After cooling to room temperature, the reaction mixture was treated with aqueous potassium fluoride solution (4 M, 400 mL) and stirred for 2 hours at 40° C. The resulting mixture was diluted with toluene (500 mL) and filtered through Celite; the filter pad was thoroughly washed with ethyl acetate (2×1.5 L). The organic phase from the combined filtrates was dried over sodium sulfate, filtered, and concentrated in vacuo. Purification via silica gel chromatography (Gradient: 0% to 5% ethyl acetate in petroleum ether) provided the product as a yellow oil. Combined yield: 602 g, 3.38 mol, 68%. LCMS m/z 179.0 [M+H+]. 1H NMR (400 MHz, CDCl3) δ 7.05 (d, J=8.3 Hz, 1H), 6.70-6.77 (m, 2H), 3.79 (s, 3H), 3.65 (s, 2H), 2.22 (s, 3H), 2.14 (s, 3H).

後処理

  1. filtrationfiltered through Celite
  2. washthe filter pad was thoroughly washed with ethyl acetate (2×1.5 L)
  3. dry with materialThe organic phase from the combined filtrates was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customPurification via silica gel chromatography (Gradient: 0% to 5% ethyl acetate in petroleum ether)

出典と根拠

ORDレコード
ord-26c3853413ed4f609f020779bb13ff9a
出典データセット
uspto-grants-2014_09
特許番号
US08822494B2

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