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Sodium Acetate → (E)-(3-Fluoro-6H-dibenzo[b,e]oxepin-11-ylidene)-acetic acid ethyl ester

HRID 244342
ノート
印刷プレビュー

反応式

HRID 244342 の反応式
[CH2:1]([O:3][C:4](=[O:23])[CH:5]=[CH:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[CH2:13][O:14][C:15]1[CH:20]=[C:19]([F:21])[CH:18]=[CH:17][C:16]=1Br)[CH3:2].C([O-])(=O)C.[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN1CCCC1=O.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:1]([O:3][C:4](=[O:23])/[CH:5]=[C:6]1/[C:16]2[CH:17]=[CH:18][C:19]([F:21])=[CH:20][C:15]=2[O:14][CH2:13][C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]/1=2)[CH3:2]
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 2

HCID 517045Sodium AcetateHCID 671334433-[2-(2-Bromo-5-fluoro-phenoxymethyl)-phenyl]-acrylic acid ethyl ester

生成物 1

HCID 67333776(E)-(3-Fluoro-6H-dibenzo[b,e]oxepin-11-ylidene)-acetic acid ethyl ester収率 87%

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide触媒HCID 167845palladium(II) acetate触媒
HCID 962
Water
溶媒
HCID 13387N-methyl-2-pyrrolidone溶媒

実験手順

Heat a mixture of 3-[2-(2-bromo-5-fluoro-phenoxymethyl)-phenyl]-acrylic acid ethyl ester (94 g, 0.25 mol), sodium acetate (30 g, 0.37 mol), tetra-n-butylammonium bromide (81 g, 0.25 mol), and palladium (II) acetate (1.7 g, 7 mmol, 3 mol %) in N-methylpyrrolidinone (850 mL) at 100-110° C. for 6 h. Cool to room temperature, dilute with water (1 L), filter through diatomaceous earth, and wash with ethyl acetate (2 L). Transfer the filtrate to a separatory funnel, add water (500 mL) and separate the layers. Wash the organic layer with water (2×1.5 L), dry over anhydrous sodium sulfate, filter through a silica pad, wash with ethyl acetate (1.5 L) and concentrate to dryness. To the residual solid add hexanes (1 L), refrigerate for 2 h, filter, rinse with hexanes (500 mL), and dry at 50° C./20 mm Hg to obtain the title compound (64.3 g, 87%). LC-MS m/z 299.0 [M+H]+.

後処理

  1. temperatureHeat
  2. filtrationfilter through diatomaceous earth
  3. washwash with ethyl acetate (2 L)
  4. additionTransfer the filtrate to a separatory funnel, add water (500 mL)
  5. customseparate the layers
  6. washWash the organic layer with water (2×1.5 L)
  7. dry with materialdry over anhydrous sodium sulfate
  8. filtrationfilter through a silica pad
  9. washwash with ethyl acetate (1.5 L)
  10. concentrationconcentrate to dryness
  11. additionTo the residual solid add hexanes (1 L)
  12. filtrationfilter
  13. washrinse with hexanes (500 mL)
  14. customdry at 50° C./20 mm Hg

出典と根拠

ORDレコード
ord-19a5d2e15abd4cee88bfdefc244aece0
出典データセット
uspto-grants-2014_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08658638B2

反応ノート

読み込み中…

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