HCID 53821226, compound → Methyl 3-cyano-4-isobutylbenzoate

HRID 423319Notes

Reaction equation

HRID 423319 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1OS(C(F)(F)F)(=O)=O)[C:6]([O:8][CH3:9])=[O:7])#[N:2].Br[Zn][CH2:23][CH:24]([CH3:26])[CH3:25]>O1CCCC1>[C:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1[CH2:23][CH:24]([CH3:26])[CH3:25])[C:6]([O:8][CH3:9])=[O:7])#[N:2]

Participants

4

Reactant 2

HCID 53821226HCID 53821226, compoundHCID 178448255HCID 178448255, compound

Product 1

HCID 59316752Methyl 3-cyano-4-isobutylbenzoateYield 22.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To methyl 3-cyano-4-{[(trifluoromethyl)sulfonyl]oxy}benzoate (D25) (1.5 g, 4.85 mmol) was added bromo(2-methylpropyl)zinc (48.5 ml, 24.25 mmol) in tetrahydrofuran (50 ml) under argon. To the solution was then added 1,1′-bis(diphenylphosphino)ferrocenedichloro palladium(II) dichloromethane complex (0.355 g, 0.485 mmol) and the reaction heated to reflux for 6 h. The mixture was quenched with water (2 mL) and then filtered through celite, washing with ethyl acetate. The solvent was removed in vacuo. The residue was partitioned between ethyl acetate (50 mL) and water (50 mL) and the organic phase dried (phase separator) and the solvent removed in vacuo. The residue was purified by silica chromatography, eluting 0-15% EtOAc in iso-hexane over 40 min. Two batches were collected, one of which was the title compound as a colourless oil (233 mg, 1.072 mmol). δH (CDCl3, 400 MHz): 8.28 (1H, d), 8.15 (1H, dd), 7.38 (1H, d), 3.94, 3H, s), 2.78 (2H, d), 2.02 (1H, m), 0.96 (6H, d).

Workup

  1. temperatureadded 1,1′-bis(diphenylphosphino)ferrocenedichloro palladium(II) dichloromethane complex (0.355 g, 0.485 mmol) and the reaction heated
  2. temperatureto reflux for 6 h
  3. customThe mixture was quenched with water (2 mL)
  4. filtrationfiltered through celite
  5. washwashing with ethyl acetate
  6. customThe solvent was removed in vacuo
  7. customThe residue was partitioned between ethyl acetate (50 mL) and water (50 mL)
  8. customthe organic phase dried (phase separator)
  9. customthe solvent removed in vacuo
  10. customThe residue was purified by silica chromatography
  11. washeluting 0-15% EtOAc in iso-hexane over 40 min
  12. customTwo batches were collected

Sources & evidence

ORD record
ord-1fb5fb175a3448dcbd27b8e4f3c44854
Source dataset
uspto-grants-2012_01
Patent number
US08101775B2

Reaction notes

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