Dimethylformamide → 4-Acetyl-2-chloro-5-hydroxybenzonitrile

HRID 626833ノート

反応式

HRID 626833 の反応式
Br[C:2]1[C:7]([Cl:8])=[CH:6][C:5]([C:9](=[O:11])[CH3:10])=[C:4]([OH:12])[CH:3]=1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.[CH3:55][N:56](C)C=O>[C-]#N.[Zn+2].[C-]#N.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:9]([C:5]1[C:4]([OH:12])=[CH:3][C:2]([C:55]#[N:56])=[C:7]([Cl:8])[CH:6]=1)(=[O:11])[CH3:10]

参加物

6

反応物 3

HCID 6228DimethylformamideHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 595641771-(4-Bromo-5-chloro-2-hydroxyphenyl)ethanone

生成物 1

HCID 866975254-Acetyl-2-chloro-5-hydroxybenzonitrile収率 72%

試薬・触媒・溶媒 2

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒

反応条件

温度
120 °C

実験手順

1-(4-bromo-5-chloro-2-hydroxyphenyl)ethanone (6.2 g, 25 mmol) was combined with zinc cyanide (4.4 g, 37 mmol) in N,N-dimethylformamide (40 mL) degassed with nitrogen and tris(dibenzylideneacetone)dipalladium(0) (0.38 g, 0.42 mmol) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (0.57 g, 0.99 mmol) were added. The reaction was degassed with nitrogen and heated to 120° C. and monitored by LC/MS. After heating for 2 hrs, the reaction was allowed to cool to room temperature, diluted with ethyl acetate, and filtered to remove the solids. The organic layer was washed with water, brine, dried over magnesium sulfate and concentrated in vacuo to give the crude product. The product was purified by FCC on silica gel eluting hexane:ethyl acetate gradient to give 4-acetyl-2-chloro-5-hydroxybenzonitrile as a yellow crystalline solid (3.5 g, 72%).

後処理

  1. additionwere added
  2. customThe reaction was degassed with nitrogen
  3. temperatureAfter heating for 2 hrs
  4. temperatureto cool to room temperature
  5. additiondiluted with ethyl acetate
  6. filtrationfiltered
  7. customto remove the solids
  8. washThe organic layer was washed with water, brine
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated in vacuo
  11. customto give the crude product
  12. customThe product was purified by FCC on silica gel
  13. washeluting hexane

出典と根拠

ORDレコード
ord-888e931804f44f959a9cc959d6523252
出典データセット
uspto-grants-2016_04
特許番号
US09309251B2

反応ノート

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