Tris(1,1-dimethylethyl)phosphine → 3'-Amino-4,2',6'-trifluorobiphenyl-2-carbonitrile

HRID 891855

反応式

HRID 891855 の反応式
Br[C:2]1[C:3]([F:10])=[C:4]([NH2:9])[CH:5]=[CH:6][C:7]=1[F:8].[F:11][C:12]1[CH:13]=[CH:14][C:15](B2OC(C)(C)C(C)(C)O2)=[C:16]([CH:19]=1)[C:17]#[N:18].[F-].[K+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>O1CCCC1.O.O1CCOCC1.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]>[NH2:9][C:4]1[C:3]([F:10])=[C:2]([C:15]2[C:16]([C:17]#[N:18])=[CH:19][C:12]([F:11])=[CH:13][CH:14]=2)[C:7]([F:8])=[CH:6][CH:5]=1

参加物

9

反応物 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 522689Potassium FluorideHCID 137327463-Bromo-2,4-difluoroanilineHCID 221807905-Fluoro-2-(tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile

生成物 1

HCID 222400973'-Amino-4,2',6'-trifluorobiphenyl-2-carbonitrile収率 106.4%

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

反応条件

温度
50 °C

実験手順

A solution of 3-bromo-2,4-difluorophenylamine (from Example 2, step b) (5.2 g, 25 mmol) and 5-fluoro-2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)benzonitrile (7.10 g, 28.8 mmol) in tetrahydrofuran (95 ml) and water (5 ml) was treated with potassium fluoride (4.8 g, 82.5 mmol) and this mixture was degassed with nitrogen for 10 min before adding tris(dibenzylideneacetone)dipalladium(0) (460 mg, 0.5 mmol) and tri-tert-butylphosphine (2.5 ml of a 0.2 M solution in 1,4-dioxane, 0.5 mmol). The reaction was then heated at 50° C. for 2 h then cooled to ambient temperature. The mixture was poured into ice-cold 0.5 N sodium hydroxide (750 ml), stirred for 10 min and the solid collected by filtration. This was triturated with water and dried to afford 3′-amino-4,2′,6′-trifluorobiphenyl-2-carbonitrile as a grey powder (6.6 g), which was used without further purification: 1H NMR (360 MHz, CDCl3) δ 3.74 (2H, br s), 6.79–6.89 (2H, m), 7.36–7.42 (1H, m), 7.45–7.51 (2H, m).

後処理

  1. customthis mixture was degassed with nitrogen for 10 min
  2. temperaturethen cooled to ambient temperature
  3. filtrationthe solid collected by filtration
  4. customThis was triturated with water
  5. customdried

出典と根拠

ORDレコード
ord-ccdd763186ed48778098b1d8695a0f8d
出典データセット
uspto-grants-2006_02
特許番号
US07005431B2

関連ノート

読み込み中…