Acetonitrile → 2-(4-bromophenyl)benzonitrile

HRID 1865064Notes

Reaction equation

HRID 1865064 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:16]=[CH:15][CH:14]=[CH:13][C:9]=2[C:10]([NH2:12])=O)=[CH:4][CH:3]=1.C(#N)C.C(N(CC)CC)C.FC(F)(F)C(OC(=O)C(F)(F)F)=O>FC(F)(F)C(OC(=O)C(F)(F)F)=O.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:16]=[CH:15][CH:14]=[CH:13][C:9]=2[C:10]#[N:12])=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 6342AcetonitrileHCID 8471TriethylamineHCID 9845Trifluoroacetic anhydrideHCID 15982087HCID 15982087, compound

Product 1

HCID 13943922-(4-bromophenyl)benzonitrileYield 94.5%

Reagents, catalysts & solvents 2

HCID 9845Trifluoroacetic anhydrideCatalystHCID 962WaterSolvent

Conditions

Temperature
3 °C

Procedure

Add 2-(4-bromophenyl)benzamide (12.0 g, 0.04345 moles, preparation 60), acetonitrile (120 mL), and triethylamine (9.23 grams, 0.0912 moles) to a 250 mL 3-neck round-bottom flask equipped with a magnetic stirrer, internal temperature probe, ice-water bath, and addition funnel. Cool the contents of the 250 mL 3-neck round-bottom flask to 3° C. Add trifluoroacetic anhydride (9.6 grams, 0.0456 moles) to the reaction mixture via the addition funnel over 5 minutes. The reaction mixture warms to 12-15° C. Remove the ice-water bath, and allow the reaction mixture to warm to 20° C. and stir the mixture for 45 minutes. Add additional trifluoroacetic anhydride (0.8 g, 0.0038 moles) and stir the reaction mixture at 22° C. for 75 minutes. Add water (120 mL) and cool the resulting suspension to 3° C. Stir the suspension at 3° C. for 15 minutes. Collect the precipitate by filtration and rinse the filter cake three times with 15 mL of 30% acetonitrile and 70% water. Vacuum (15-25 mm) dry the filter cake at 45° C. to provide the title compound (10.6 g, 0.041 moles) in 94.5% yield. 1H NMR (CDCl3, 500.0 MHz): δ 7.75 (app. d, 1H, J=8); 7.64 (td, 1H, J=1.5, 7.5); 7.61 (app. d, 2H, J=8.5); 7.5-7.4 (m, 4H).

Workup

  1. customequipped with a magnetic stirrer
  2. customwarms to 12-15° C
  3. customRemove the ice-water bath
  4. temperatureto warm to 20° C.
  5. stirringstir the reaction mixture at 22° C. for 75 minutes
  6. stirringStir the suspension at 3° C. for 15 minutes
  7. customCollect the precipitate
  8. filtrationby filtration
  9. washrinse the filter cake three times with 15 mL of 30% acetonitrile and 70% water
  10. customVacuum (15-25 mm) dry the filter cake at 45° C.

Sources & evidence

ORD record
ord-38cd32bf45e646a191e6efe8d91b7d76
Source dataset
uspto-grants-2009_12
Patent number
US07625932B2

Reaction notes

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