Benzonitrile, 4-chloro-3-nitro- → 2-Nitrobiphenyl-4-carbonitrile

HRID 539471Notes

Reaction equation

HRID 539471 reaction equation
Cl[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[C:13]1(B(O)O)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.O.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>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].C1(C)C=CC=CC=1>[N+:10]([C:3]1[CH:4]=[C:5]([C:6]#[N:7])[CH:8]=[CH:9][C:2]=1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)([O-:12])=[O:11]

Participants

8

Reactant 4

HCID 13655Benzonitrile, 4-chloro-3-nitro-HCID 66827Phenylboronic AcidHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 22031701Potassium phosphate, tribasic, monohydrate

Product 1

HCID 104893112-Nitrobiphenyl-4-carbonitrileYield 72.3%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

4-chloro-3-nitrobenzonitrile (10 g, 54.8 mmol), phenylboronic acid (8.68 g, 71.2 mmol), Pd2dba3 (1.002 g, 1.096 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-Phos) (1.797 g, 4.38 mmol) were charged into a 500 mL 3-neck flask. Toluene (250 mL) was then charged into the reaction mixture followed by potassium phosphate tribasic monohydrate (35.3 g, 153 mmol) dissolved in 60 mL of water. This mixture was degassed with nitrogen then heated at reflux overnight. The reaction mixture was cooled to room temperature then partitioned with water. The toluene layer was dried over magnesium sulfate, filtered, and dried under vacuum. This crude residue was passed through a silica gel column using 15-35% ethyl acetate/hexanes as the eluent. The product fractions were combined and solvents were removed under vacuum. This crude product was triturated with ethyl acetate/hexanes. The product, 2-nitro-[1,1′-biphenyl]-4-carbonitrile, (8.87 g, 39.6 mmol, 72.2% yield) was isolated via filtration as a yellow solid.

Workup

  1. customThis mixture was degassed with nitrogen
  2. temperaturethen heated
  3. temperatureat reflux overnight
  4. customthen partitioned with water
  5. dry with materialThe toluene layer was dried over magnesium sulfate
  6. filtrationfiltered
  7. customdried under vacuum
  8. customsolvents were removed under vacuum
  9. customThis crude product was triturated with ethyl acetate/hexanes

Sources & evidence

ORD record
ord-2a75b486fa7649da9c1444ded6540ee3
Source dataset
uspto-grants-2014_10
Patent number
US08871361B2

Reaction notes

Loading…