Triphenylphosphine → 3-(4-Methylphenyl)benzonitrile

HRID 1954481Notes

Reaction equation

HRID 1954481 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([Mg]Cl)=[CH:4][CH:3]=1.Br[C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][CH:18]=1)[C:14]#[N:15].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:11]2[CH:18]=[CH:17][CH:16]=[C:13]([C:14]#[N:15])[CH:12]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 233813-BromobenzonitrileHCID 178426149HCID 178426149, compound

Product 1

HCID 13939093-(4-Methylphenyl)benzonitrileYield 89%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

4-methylphenylmagnesium chloride (49 g, 20% solution in tetrahydrofuran) is added dropwise over eight hours to a refluxing solution of 3-bromobenzonitrile (10 g), palladium (II) acetate (2.4 g) and triphenylphosphine (5.8 g) in tetrahydrofuran (200 ml). [HPLC: yield 89-91%]. After cooling to room temperature tetrahydrofuran is removed under vacuum. The residue is taken up in toluene/water (3:1) (200 ml ) and the aqueous phase separated off. The solvent is removed by distillation and the crude product purified by column chromatrography (Kieselgel 60; n-hezane/acetone 3:1) to give 4'-methylbiphenyl-3-carbonitrile as a solid, m.pt. 59-61° C. 1H NMR (CDCl3): 2.41(s,3H), 7.29(d,2H), 7.46(d,2H), 7.49-7.63(m,2H) 7.77-7.85(m,2H).

Workup

  1. customis removed under vacuum
  2. customthe aqueous phase separated off
  3. customThe solvent is removed by distillation
  4. customthe crude product purified by column chromatrography (Kieselgel 60; n-hezane/acetone 3:1)

Sources & evidence

ORD record
ord-cf7603185a594b088e17346efaff9279
Source dataset
uspto-grants-2000_09
Patent number
US06121480

Reaction notes

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