Pyridine → 2-Cyano-4'-methylbiphenyl

HRID 1769402Notes

Reaction equation

HRID 1769402 reaction equation
N1C=CC=CC=1.Br[C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=1.Cl[C:16]1[CH:23]=[CH:22][CH:21]=[CH:20][C:17]=1[C:18]#[N:19].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Ni](Cl)Cl.[Zn].C1(C)C=CC=CC=1>[C:18]([C:17]1[CH:20]=[CH:21][CH:22]=[CH:23][C:16]=1[C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=1)#[N:19]

Participants

8

Reactant 4

HCID 1049PyridineHCID 78054-BromotolueneHCID 11776TriphenylphosphineHCID 133912-Chlorobenzonitrile

Product 1

HCID 1455122-Cyano-4'-methylbiphenylYield 57%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24385Nickel DichlorideCatalystHCID 1140TolueneSolvent

Procedure

Into a 1 l four necked flask, 500 ml of dry pyridine, 44.3 g (0.259 mol) of 4-bromotoluene, 35.6 g (0.259 mol) of 2-chlorobenzonitrile, 3.24 g (0.025 mol) of anhydrous nickel chloride, 13.1 g (0.05 mol) of triphenylphosphine and 67.6 g (1.034 mol) of zinc powder were charged under a nitrogen atmosphere and stirred at room temperature for 30 minutes. The temperature was raised to 80° C., and the mixture was reacted for 6 hours. Then, 400 ml of toluene was added thereto, and the solid was filtered off while it was still hot. The toluene layer was analyzed by gas chromatography. The results are shown in Table 1. Then, pyridine and toluene were recovered under reduced pressure. Then, 500 ml of toluene was added to the residue, and the solid was filtered off while it was still hot and washed with 100 ml of toluene. The warm toluene layer was washed with 300 ml of 5% hydrochloric acid, then with 300 ml of a 5% sodium hydrogencarbonate aqueous solution and further twice with 300 ml of warm water. The toluene layer was concentrated to obtain 54 g of a crude product. This product was distilled to obtain 28.4 g (yield: 57%, purity: 97.4%) of white crystals of 2-cyano-4'-methyl-1,1'-biphenyl.

Workup

  1. temperatureThe temperature was raised to 80° C.
  2. customthe mixture was reacted for 6 hours
  3. filtrationthe solid was filtered off while it
  4. customThen, pyridine and toluene were recovered under reduced pressure
  5. additionThen, 500 ml of toluene was added to the residue
  6. filtrationthe solid was filtered off while it
  7. washwashed with 100 ml of toluene
  8. washThe warm toluene layer was washed with 300 ml of 5% hydrochloric acid
  9. concentrationThe toluene layer was concentrated
  10. customto obtain 54 g of a crude product
  11. distillationThis product was distilled

Sources & evidence

ORD record
ord-ec73ee1b0c4f405c9cdeabd8f51f6669
Source dataset
uspto-grants-1995_01
Patent number
US05380910

Reaction notes

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