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

HRID 891855

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HRID 891855 반응식
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

참가 물질

9

반응물 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

생성물 1

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

시약·촉매·용매 4

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

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온도
50 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-ccdd763186ed48778098b1d8695a0f8d
출처 데이터셋
uspto-grants-2006_02
특허 번호
US07005431B2

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