Benzoic Acid → Benzoyl fluoride

HRID 1193005Notes

Reaction equation

HRID 1193005 reaction equation
[F:1][B-](F)(F)F.[C:6]([OH:14])(=O)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C1CCN2C(=NCCC2)CC1.Cl>ClCCl>[C:6]([F:1])(=[O:14])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

6

Reactant 4

HCID 243Benzoic AcidHCID 313Hydrochloric AcidHCID 26255TetrafluoroborateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene

Product 1

HCID 67999Benzoyl fluorideYield 74%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of diethylaminosulfinium tetrafluoroborate (344 mg, 1.5 mmol) in dichloromethane (3.0 mL) at room temperature is added benzoic acid (122 mg, 1.0 mmol) and DBU (224 μl, 1.5 mmol). The reaction mixture is stirred for 4 hours, then an 10% aqueous solution of HCl is added and stirring is continued for 15 minutes. The resulting mixture is extracted twice using dichloromethane. The organic phases are combined, dried over magnesium sulphate, filtered and concentrated. The crude material is diluted with pentane and the solution is passed through a pad of silica gel with pentane elution. Solvent are evaporated in vacuum to provide benzoyl fluoride (90 mg, 74%) as a clear liquid. 1H NMR (CDCl3, 300 MHz) δ 7.94 (d, J=7.8, 2H), 7.62 (t, J=7.3 Hz, 1H), 7.43 (t, J=8.2 Hz, 2H); 19F NMR (CDCl3, 282 MHz) δ 17.5 (s, 1F); 13C NMR (CDCl3, 75 MHz) δ 157.3 (d, 1JC-F=344.3 Hz), 135.5, 131.5 (d, 3JC-F=4.0 Hz), 129.2, 125.0 (d, 2JC-F=60.4 Hz).

Workup

  1. stirringstirring
  2. waitis continued for 15 minutes
  3. extractionThe resulting mixture is extracted twice using dichloromethane
  4. dry with materialdried over magnesium sulphate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. additionThe crude material is diluted with pentane
  8. washthe solution is passed through a pad of silica gel with pentane elution
  9. customSolvent are evaporated in vacuum

Sources & evidence

ORD record
ord-9e9ffaaaf898447589200c08322ecb92
Source dataset
uspto-grants-2014_03
Patent number
US08680332B2

Reaction notes

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