Tris(1,1-dimethylethyl)phosphine → 4-(2-Fluoro-5-nitrophenyl)nicotinonitrile

HRID 586281노트

반응식

HRID 586281 반응식
Br[C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[CH:4][CH:3]=1.[F:10][C:11]1[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][C:12]=1B1OC(C)(C)C(C)(C)O1.[F-].[K+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>O1CCCC1.O1CCOCC1.O.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]>[F:10][C:11]1[CH:16]=[CH:15][C:14]([N+:17]([O-:19])=[O:18])=[CH:13][C:12]=1[C:2]1[C:7]([C:8]#[N:9])=[CH:6][N:5]=[CH:4][CH:3]=1

참가 물질

9

반응물 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 522689Potassium FluorideHCID 38332972-Fluoro-5-nitrophenylboronic acid, pinacol esterHCID 223295224-Bromopyridine-3-carbonitrile

생성물 1

HCID 223295054-(2-Fluoro-5-nitrophenyl)nicotinonitrile

시약·촉매·용매 4

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 962Water용매HCID 8028Tetrahydrofuran용매HCID 312751,4-Dioxane용매

실험 절차

A mixture of 4-bromonicotinonitrile (1.00 g, 5.46 mmol), 2-(2-fluoro-5-nitrophenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (1.90 g, 7.10 mmol) and potassium fluoride (1.05 g, 18.03-mmol) in tetrahydrofuran (50 ml) was degassed with nitrogen for 30 min then treated with tris(dibenzylideneacetone)dipalladium(0) (0.05 g, 0.05 mmol) followed by tri-tert-butylphosphine (0.60 ml of a 0.2 M solution in 1,4-dioxane, 0.11 mmol) and then the reaction was stirred at ambient temperature for 30 min before heating at 50° C. for 1 h to complete the coupling. The slurry-like reaction mixture was then diluted with water (100 ml) and stirred at ambient temperature for 90 min. The resulting solid was collected by filtration, washed with water then with isohexane, and finally dried under vacuum over phosphorus pentoxide, to afford 4-(2-fluoro-5-nitrophenyl)-nicotinonitrile as a white solid: 1H NMR (400 MHz, CDCl3) δ 7.44-7.52 (2H, m), 8.38-8.47 (2H, m), 8.95 (1H, d, J 5 Hz), 9.06 (1H, s).

후처리

  1. customwas degassed with nitrogen for 30 min
  2. temperaturebefore heating at 50° C. for 1 h
  3. customThe slurry-like reaction mixture
  4. stirringstirred at ambient temperature for 90 min
  5. filtrationThe resulting solid was collected by filtration
  6. washwashed with water
  7. dry with materialwith isohexane, and finally dried under vacuum over phosphorus pentoxide

출처 및 근거

ORD 기록
ord-8b1f45702a7c47658f2380cc90e6d24b
출처 데이터셋
uspto-grants-2005_08
특허 번호
US06936608B2

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