Potassium Carbonate → 3-Methyl-2-(1H-1,2,4-triazol-1-yl)-5-vinylbenzonitrile

HRID 1502760Notes

Reaction equation

HRID 1502760 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH3:15])[C:5]([N:10]2[CH:14]=[N:13][CH:12]=[N:11]2)=[C:6]([CH:9]=1)[C:7]#[N:8].C(=O)([O-])[O-].[K+].[K+].[C:22]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:23]=1>C1(C)C=CC=CC=1>[CH3:15][C:4]1[C:5]([N:10]2[CH:14]=[N:13][CH:12]=[N:11]2)=[C:6]([CH:9]=[C:2]([CH:22]=[CH2:23])[CH:3]=1)[C:7]#[N:8]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 711383195-Bromo-3-methyl-2-(1H-1,2,4-triazol-1-yl)benzonitrile

Product 1

HCID 866752183-Methyl-2-(1H-1,2,4-triazol-1-yl)-5-vinylbenzonitrileYield 1,043.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 5-bromo-3-methyl-2-(1H-1,2,4-triazol-1-yl)benzonitrile (0.6 g, 2.3 mmol), potassium carbonate (0.95 g, 6.87 mmol), vinyl boronic anhydride (0.82 g, 3.43 mmol) and triphenylphosphine (0.13 g, 0.114 mmol) in toluene (20.0 mL) were stirred and degassed with argon for 30 min. The reaction mixture was heated to reflux for 18 h. The reaction mixture was cooled to ambient temperature, diluted with water and extracted with ethyl acetate (2×100 mL). The combined ethyl acetate layer was washed with brine, dried over Na2SO4 and concentrated under reduced pressure to afford the crude compound that was purified by flash column chromatography (SiO2, 100-200 mesh; eluting with 30% ethyl acetate/pet ether) to afford the title compound as a pink solid (0.25 g, 52%): 1H NMR (400 MHz, CDCl3) δ 8.33 (s, 1H), 8.22 (s, 1H), 7.67 (s, 1H), 7.60 (s, 1H), 6.75 (dd, J=17.6, 10.8 Hz, 1H), 5.92 (d, J=17.6, 1H), 5.52 (d, J=10.8 Hz, 1H), 2.21 (s, 3H), ESIMS m/z 211.35 ([M+H]+); IR (thin film) 2236, 1511 cm−1.

Workup

  1. customdegassed with argon for 30 min
  2. temperatureThe reaction mixture was heated
  3. temperatureto reflux for 18 h
  4. additiondiluted with water
  5. extractionextracted with ethyl acetate (2×100 mL)
  6. washThe combined ethyl acetate layer was washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customto afford the crude compound that
  10. customwas purified by flash column chromatography (SiO2, 100-200 mesh; eluting with 30% ethyl acetate/pet ether)

Sources & evidence

ORD record
ord-19ef84d2d0044f6e9d700d9698cc402c
Source dataset
uspto-grants-2015_12
Patent number
US09210927B2

Reaction notes

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