Acetonitrile → 4-Bromo-2-hydroxybenzonitrile

HRID 2228642Notes

Reaction equation

HRID 2228642 reaction equation
FC1C=C[C:7]([Br:10])=[CH:6][C:3]=1C#N.[C:11]([O-:14])(=O)[CH3:12].[K+].C1OCCOCCOCCOCCOCCOC1.[OH-].[Na+].[CH3:36][C:37]#[N:38]>>[OH:14][C:11]1[CH:12]=[C:7]([Br:10])[CH:6]=[CH:3][C:36]=1[C:37]#[N:38]

Participants

6

Reactant 5

HCID 6342AcetonitrileHCID 14798Sodium HydroxideHCID 2855718-Crown-6HCID 517044Potassium AcetateHCID 27249005-Bromo-2-fluorobenzonitrile

Product 1

HCID 129669614-Bromo-2-hydroxybenzonitrileYield 81%

Procedure

A mixture of 2-fluoro-5-bromobenzonitrile (30 g, 152.3 mmole), potassium acetate (222.4 g, 228.5 mmole), and 18-crown-6 ether (60.4 g, 288.5 mmole) in MeCN (400 mL) was heated at reflux in 36 h. The mixture was cooled, added 2.5 N NaOH (200 mL), stirred at RT overnight. The mixture was extracted with ether (discarded). The aqueous layer was acidified with 6N HCl, extracted with EtOAc, dried over MgSO4, concentrated, purified by flash column chromatography (40% EtOAc/Hex) to give a light yellow foam (24.45 g, 81%). 1H-NMR (300 MHz, DMSO-d6): δ7.13 (dd, J=1.7, 8.3 Hz, 1H), 7.17 (d, J=1.7 Hz, 1H), 7.61 (d, J=8.3 Hz, 1H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux in 36 h
  3. temperatureThe mixture was cooled
  4. extractionThe mixture was extracted with ether (discarded)
  5. extractionextracted with EtOAc
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. custompurified by flash column chromatography (40% EtOAc/Hex)

Sources & evidence

ORD record
ord-3b86e109a0a547669f6f7bae59c0e693
Source dataset
uspto-grants-2002_07
Patent number
US06417215B1

Reaction notes

Loading…