2-Bromo-4-fluorobenzonitrile → 5,2'-Difluoro-5'-nitrobiphenyl-2-carbonitrile

HRID 586243Notes

Reaction equation

HRID 586243 reaction equation
Br[C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].[F-].[K+].[F:13][C:14]1[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][C:15]=1B1OC(C)(C)C(C)(C)O1>O1CCCC1>[F:10][C:8]1[CH:9]=[C:2]([C:15]2[CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[CH:18]=[CH:19][C:14]=2[F:13])[C:3]([C:4]#[N:5])=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 1189392-Bromo-4-fluorobenzonitrileHCID 522689Potassium FluorideHCID 38332972-Fluoro-5-nitrophenylboronic acid, pinacol ester

Product 1

HCID 222852855,2'-Difluoro-5'-nitrobiphenyl-2-carbonitrile

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A suspension of 2-bromo-4-fluorobenzonitrile (2.50 g, 12.5 mmol), potassium fluoride (2.40 g, 41.3 mmol) and 2-(2-fluoro-5-nitrophenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (4.67 g, 17.5 mmol) in tetrahydrofuran (50 ml) was degassed with nitrogen for 30 min. Tris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine (0.2 M solution in 1,4-dioxane, 3.7 ml) were added and the mixture stirred at ambient temperature for 15 min then at 50° C. for 18 h. After cooling to ambient temperature, the resulting dark suspension was poured onto 0.5 M sodium hydroxide solution (500 ml) and stirred vigorously for 2 h. The dark solid was collected by filtration, washed with water (100 ml) and isohexane (50 ml) and left to air dry which gave the title compound as a brown/black solid: 1H NMR (360 MHz, CDCl3) δ 7.25-7.33 (2H, m), 7.40-7.44 (1H, m), 7.86 (1H, dd, J 9, 6 Hz), 8.35-8.42 (2H, m).

Workup

  1. customwas degassed with nitrogen for 30 min
  2. additionTris(dibenzylideneacetone)dipalladium(0) and tri-tert-butylphosphine (0.2 M solution in 1,4-dioxane, 3.7 ml) were added
  3. waitat 50° C. for 18 h
  4. temperatureAfter cooling to ambient temperature
  5. additionthe resulting dark suspension was poured onto 0.5 M sodium hydroxide solution (500 ml)
  6. stirringstirred vigorously for 2 h
  7. filtrationThe dark solid was collected by filtration
  8. washwashed with water (100 ml) and isohexane (50 ml)
  9. waitleft to air
  10. customdry which

Sources & evidence

ORD record
ord-fcd738926fa945efa7eced095249e9c0
Source dataset
uspto-grants-2005_08
Patent number
US06936608B2

Reaction notes

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