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

HRID 626833노트

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HRID 626833 반응식
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]

참가 물질

6

반응물 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

생성물 1

HCID 866975254-Acetyl-2-chloro-5-hydroxybenzonitrile수율 72%

시약·촉매·용매 2

HCID 11186Zinc cyanide (Zn(CN)2)촉매HCID 9811564Bis(dibenzylideneacetone)palladium촉매

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온도
120 °C

실험 절차

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%).

후처리

  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

출처 및 근거

ORD 기록
ord-888e931804f44f959a9cc959d6523252
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09309251B2

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