Hydrogen Peroxide → 5-Cyano-2-fluorobenzoic acid

HRID 1397384Notes

Reaction equation

HRID 1397384 reaction equation
[C:1]([C:3]1[CH:4]=[CH:5][C:6]([F:11])=[C:7]([CH:10]=1)[CH:8]=[O:9])#[N:2].OO.Cl([O-])=[O:15].[Na+]>O.C(#N)C>[C:1]([C:3]1[CH:4]=[CH:5][C:6]([F:11])=[C:7]([CH:10]=1)[C:8]([OH:15])=[O:9])#[N:2]

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 109097255-Cyano-2-fluorobenzaldehydeHCID 23668197Sodium Chlorite

Product 1

HCID 27784625-Cyano-2-fluorobenzoic acidYield 90.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent

Procedure

NaH2PO4 (87 mg, 0.724 mmol) in water (3.5 mL) was added to a solution of 5-cyano-2-fluorobenzaldehyde (500 mg, 3.35 mmol) in acetonitrile (7 mL), followed by 30% H2O2 (0.31 mL). Sodium chlorite (434 mg, 4.8 mmol) in water (3.5 mL) was added dropwise to this reaction mixture at 0° C. The mixture was stirred at room temperature for 1 h, quenched with aqueous sodium sulfite solution at 0° C. and then acidified with 1.5N HCl solution. The aqueous solution was extracted with EtOAc and the combined extracts were dried over anhydrous sodium sulfate, and concentrated under reduced pressure to afford 5-cyano-2-fluorobenzoic acid (500 mg, yield 90%). 1H NMR (300 MHz, DMSO-d6) δ 13.79 (br s, 1H), 8.30-8.27 (dd, J=6.6 Hz, 2.2 Hz, 1H), 8.17-8.12 (ddd, J=8.6 Hz, 4.4 Hz, 2.3 Hz, 1H), 7.60-7.53 (dd, J=10.5 Hz, 8.8 Hz, 1H). MS (ESI) m/z: Calculated for C8H4FNO2: 165.02. found: 163.6 (M−H)−.

Workup

  1. customquenched with aqueous sodium sulfite solution at 0° C.
  2. extractionThe aqueous solution was extracted with EtOAc
  3. dry with materialthe combined extracts were dried over anhydrous sodium sulfate
  4. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-18836b46f9df4cca820677d9aaa0cbbf
Source dataset
uspto-grants-2014_12
Patent number
US08901156B2

Reaction notes

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