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N,N,N',N'-Tetramethylethylenediamine → 4-Acetyl-2-fluorobenzonitrile

HRID 500133
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인쇄 미리보기

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HRID 500133 반응식
C[N:2](C)[CH2:3][CH2:4]N(C)C.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.BrC1[CH:57]=[CH:56][C:55]([C:58](=[O:60])[CH3:59])=[CH:54][C:53]=1[F:61]>CN(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:58]([C:55]1[CH:56]=[CH:57][C:4]([C:3]#[N:2])=[C:53]([F:61])[CH:54]=1)(=[O:60])[CH3:59]
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참가 물질

7

반응물 3

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 228319141-(4-Bromo-3-fluorophenyl)ethan-1-one

생성물 1

HCID 224816534-Acetyl-2-fluorobenzonitrile

시약·촉매·용매 3

HCID 11186Zinc cyanide (Zn(CN)2)촉매
HCID 9811564
Bis(dibenzylideneacetone)palladium
촉매
HCID 6228Dimethylformamide용매

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온도
160 °C

실험 절차

N,N,N′,N′-Tetramethylethylenediamine (0.667 mL, 4.42 mmol), zinc cyanide (1.46 g, 12.4 mmol), tris(dibenzylideneacetone)dipalladium(0) (54.05 mg, 0.059 mmol) and (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine) (124.3 mg, 0.215 mmol) was added successively to a solution of 1-(4-bromo-3-fluorophenyl)ethanone (4.34 g, 20.0 mmol) in N,N-dimethylformamide (15 mL) in a microwave tube. The tube was sealed and degassed three times, and heated to 160° C. under microwave irradiation with a 240 s hold time, and 300 Watt maximum power input. After cooling, the reaction mixture was filtered through a pad of Celite with a thin layer of silica gel in the middle using dichloromethane as the eluant. The combined filtrates were concentrated under reduced pressure. The residue was purified by chromatography on silica gel with ethyl acetate in hexanes (0-40%) to give the desired product. (3.20 g, 98.1%).

후처리

  1. customThe tube was sealed
  2. customdegassed three times
  3. temperatureAfter cooling
  4. filtrationthe reaction mixture was filtered through a pad of Celite with a thin layer of silica gel in the middle
  5. concentrationThe combined filtrates were concentrated under reduced pressure
  6. customThe residue was purified by chromatography on silica gel with ethyl acetate in hexanes (0-40%)

출처 및 근거

ORD 기록
ord-77ff4e5b5c7244ae8e31d1c30552ca0c
출처 데이터셋
uspto-grants-2010_08
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US07767675B2

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