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

HRID 586281ノート

反応式

HRID 586281 の反応式
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

参加物

9

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 4

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒HCID 312751,4-Dioxane溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-8b1f45702a7c47658f2380cc90e6d24b
出典データセット
uspto-grants-2005_08
特許番号
US06936608B2

反応ノート

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