Sulfuric Acid → 3-Cyano-4-fluorobenzoic acid

HRID 1953762Notes

Reaction equation

HRID 1953762 reaction equation
[F:1][C:2]1[CH:9]=[CH:8][C:7]([CH3:10])=[CH:6][C:3]=1[C:4]#[N:5].Cl[O-].[Na+].S(=O)(=O)(O)[OH:15].[OH-:19].[Na+]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.ClCCl.O.O.O.[Ru](Cl)(Cl)Cl>[F:1][C:2]1[CH:9]=[CH:8][C:7]([C:10]([OH:15])=[O:19])=[CH:6][C:3]=1[C:4]#[N:5]

Participants

8

Reactant 4

HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 27745842-Fluoro-5-methylbenzonitrileHCID 23665760Sodium Hypochlorite

Product 1

HCID 27739323-Cyano-4-fluorobenzoic acidYield 20%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 12090026Ruthenium chloride trihydrateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a mixture of 2-fluoro-5-methylbenzonitrile (13.5 g, 0.1 mol), tetrabutylammonium bromide (1.61 g, 5 mmol), and ruthenium(III)chloride trihydrate (0.261 g, 1 mmol) in dichloromethane (150 mL) was added a solution of sodium hypochlorite (645 mL, 0.45 mol) which had been neutralized to pH 9 with 20% sulfuric acid. The reaction mixture was stirred and maintained at pH 9 by adding 20% sodium hydroxide solution at RT. After 3 h, the aqueous phase was separated and neutralized to pH 2 with 20% sulfuric acid and the solid which formed was filtered to give the title compound (3.4 g, 20%). mp 177-8° C. 1H NMR (CDCl3) δ 7.35 (t, J=8.70 Hz, 1H), 8.38 (m, 1H), 8.42 (m, 1H).

Workup

  1. temperaturemaintained at pH 9
  2. customthe aqueous phase was separated
  3. customthe solid which formed
  4. filtrationwas filtered

Sources & evidence

ORD record
ord-7905b623a3e14703a73b1da9ade36f3e
Source dataset
uspto-grants-2000_09
Patent number
US06117866

Reaction notes

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