Dimethylformamide → 6-Methylbenzofuran-2-carbonitrile

HRID 1773214노트

반응식

HRID 1773214 반응식
Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][C:7]([CH3:10])=[CH:6][C:5]=1[OH:11].C([O-])([O-])=O.[Na+].[Na+].[CH3:19][N:20](C=O)C>[Cu]I.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:10][C:7]1[CH:8]=[CH:9][C:4]2[CH:3]=[C:2]([C:19]#[N:20])[O:11][C:5]=2[CH:6]=1

참가 물질

7

반응물 3

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 1184526172-(2,2-Dibromovinyl)-5-methylphenol

생성물 1

HCID 289100396-Methylbenzofuran-2-carbonitrile

시약·촉매·용매 3

HCID 11776Triphenylphosphine촉매HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 167845palladium(II) acetate촉매

반응 조건

온도
80 °C

실험 절차

To a 500 mL 3-neck flask was added 2-(2,2-dibromovinyl)-5-methylphenol (17.7 g, 60.6 mmol), CuI (1.16 g, 6.06 mmol), Na2CO3 (12.85 g, 121 mmol) and DMF (120 mL). The reaction was heated to 80° C. for 6 hr. After 6 hr the r×n was cooled to RT and anhydrous K4Fe(CN)6 (4.47 g, 12.12 mmol), Pd(OAc)2 (2.04 g, 3.03 mmol) and PPh3 (0.32 g, 1.21 mmol) were added to the reaction and the reaction was flushed with nitrogen for 10 min. The reaction was then heated to 120° C. for 18 hr. After 18 hr the r×n was cooled to RT and diluted with EtOAc. The reaction mixture was filtered through a silica plug to remove solids and flushed with EtOAc. The collected filtrates were diluted with water and brine and extracted with EtOAc×2. The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude mixture was purified via silica gel FCC, 100% Heptane-20% EtOAc/80% Heptane to give a yellow solid, 6-methylbenzofuran-2-carbonitrile (5.1 g). 1H NMR (400 MHz, DMSO-d6) δ 2.47 (s, 3H), 7.27 (ddd, J=8.2, 1.4, 0.7 Hz, 1H), 7.57 (s, 1H), 7.71 (d, J=8.1 Hz, 1H), 8.05 (d, J=1.0 Hz, 1H).

후처리

  1. temperatureAfter 6 hr the r×n was cooled to RT
  2. customthe reaction was flushed with nitrogen for 10 min
  3. temperatureThe reaction was then heated to 120° C. for 18 hr
  4. temperatureAfter 18 hr the r×n was cooled to RT
  5. additiondiluted with EtOAc
  6. filtrationThe reaction mixture was filtered through a silica plug
  7. customto remove solids
  8. customflushed with EtOAc
  9. additionThe collected filtrates were diluted with water and brine
  10. extractionextracted with EtOAc×2
  11. washThe combined organic layers were washed with brine
  12. dry with materialdried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated under reduced pressure
  15. customThe crude mixture was purified via silica gel FCC, 100% Heptane-20% EtOAc/80% Heptane

출처 및 근거

ORD 기록
ord-37df925819094586b0813c89acf91423
출처 데이터셋
uspto-grants-2016_02
특허 번호
US09255093B2

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