2-Bromobenzonitrile → 2'-Fluoro-5'-nitrobiphenyl-2-carbonitrile

HRID 2183862Notes

Reaction equation

HRID 2183862 reaction equation
Br[C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[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:3]([C:4]#[N:5])=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

9

Reactant 4

HCID 162722-BromobenzonitrileHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 522689Potassium FluorideHCID 38332972-Fluoro-5-nitrophenylboronic acid, pinacol ester

Product 1

HCID 114478612'-Fluoro-5'-nitrobiphenyl-2-carbonitrileYield 100%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 2-bromobenzonitrile (34.6 g, 190 mmol), 2-(2-fluoro-5-nitrophenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (76.1 g, 285 mmol) and potassium fluoride (36.4 g, 627 mmol) in tetrahydrofuran (600 ml) was degassed with nitrogen for 30 min then treated with tris(dibenzylideneacetone)dipalladium(0) (1.74 g, 1.9 mmol) followed by tri-tert-butylphosphine (38 ml of a 0.1M solution in 1,4-dioxane, 3.8 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 (3 l) 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 2′-fluoro-5′-nitrobiphenyl-2-carbonitrile as a beige solid (46 g, 100%): δH (360 MHz, CDCl3) 7.37-7.42 (1H, m), 7.53 (1H, d, J 8), 7.59 (1H, td, J 8 and 1), 7.75 (1H, td, J 8 and 1), 7.83 (1H, dd, J 8 and 1), 8.35-8.39 (2H, m).

Workup

  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

Sources & evidence

ORD record
ord-0ed8c5e72ba244f98584a3c8fa2fcd2c
Source dataset
uspto-grants-2005_05
Patent number
US06900215B2

Reaction notes

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