Toluene → 3-(4-Methylphenyl)pyridine-2-carbonitrile

HRID 864462Notes

Reaction equation

HRID 864462 reaction equation
[C:1]([C:3]1[C:8](Br)=[CH:7][CH:6]=[CH:5][N:4]=1)#[N:2].[C:10]1([CH3:19])[CH:15]=[CH:14][C:13](B(O)O)=[CH:12][CH:11]=1.C1(C)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(O)C>[C:1]([C:3]1[C:8]([C:13]2[CH:14]=[CH:15][C:10]([CH3:19])=[CH:11][CH:12]=2)=[CH:7][CH:6]=[CH:5][N:4]=1)#[N:2]

Participants

7

Reactant 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 79799Tolylboronic acidHCID 8176943-Bromopyridine-2-carbonitrile

Product 1

HCID 153301703-(4-Methylphenyl)pyridine-2-carbonitrileYield 34%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolvent

Procedure

Under nitrogen, 13.91 g (76 mmol) of 2-cyano-3-bromopyridine from step 2 and 11.41 g (84 mmol) of 4-tolylboronic acid from step 3 were treated with 2.65 g (2.3 mmol) of tetrakis (triphenylphosphine)palladium zero, 155 mL of toluene, 60 mL of ethanol, and 77 mL of 2M aqueous sodium carbonate. The reaction mixture was heated to reflux and vigorously stirred overnight. The product crystallized from the reaction mixture after several days at ambient temperature. Filtration provided 5.02 g (34%) of 2-cyano-3-(4-tolyl)pyridine as a colorless solid: mp 136°-138° C.; NMR (CDCl3) δ2.44 (s, 3H), 7.34 (d, J=8 Hz, 2H), 7.47 (d, J=8 Hz, 2H), 7.56 (dd, J=8 and 5 Hz, 1H), 7.85 (dd, J=8 and 2 Hz, 1H), 8.68 (dd, J=5 and 2 Hz, 1H); MS (70 eV) m/e (rel intensity) 194 (100).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux and vigorously stirred overnight
  3. customThe product crystallized from the reaction mixture after several days at ambient temperature
  4. filtrationFiltration

Sources & evidence

ORD record
ord-bad5dce4d57b4be6936e064a688339ab
Source dataset
uspto-grants-1996_10
Patent number
US05563139

Reaction notes

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