Sulfuric Acid → 2-Chloro-5-Fluorobenzaldehyde

HRID 49195Notes

Reaction equation

HRID 49195 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[CH3:9].S(=O)(=O)(O)[OH:11]>C(OC(=O)C)(=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[CH:9]=[O:11]

Participants

4

Reactant 2

HCID 1118Sulfuric AcidHCID 1184752-Chloro-5-fluorotoluene

Product 1

HCID 27791842-Chloro-5-Fluorobenzaldehyde

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent2×

Procedure

A solution of 2-chloro-5-fluorotoluene (5.0 g) in acetic anhydride (40 ml) was treated dropwise with concentrated sulfuric acid (40 ml) with cooling on ice. Subsequently, a solution of chromic anhydride (9.3 g) in acetic anhydride (40 ml) was added dropwise over a period of 2 hours. At the same temperature, the mixture was stirred for 1 hour, and added to an ice-water. The mixture was extracted with diethyl ether and the organic layer was washed successively with aqueous sodium carbonate, water and saturated brine, and then dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was dissolved in tetrahydrofuran (10 ml), combined with water (4 ml) and concentrated sulfuric acid (4 ml), and heated with stirring at 100° C. for 30 minutes. After allowed to stand to cool, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed successively with aqueous sodium carbonate, water and saturated brine, and dried over magnesium sulfate. The solvent was distilled off and the residue was subjected to a column chromatography on a silica gel to obtain 2-chloro-5-fluorobenzaldehyde (1.6 g).

Workup

  1. temperaturewith cooling on ice
  2. extractionThe mixture was extracted with diethyl ether
  3. washthe organic layer was washed successively with aqueous sodium carbonate, water and saturated brine
  4. dry with materialdried over magnesium sulfate
  5. distillationThe solvent was distilled off under reduced pressure
  6. dissolutionthe residue was dissolved in tetrahydrofuran (10 ml)
  7. temperatureheated
  8. stirringwith stirring at 100° C. for 30 minutes
  9. temperatureto cool
  10. extractionthe reaction mixture was extracted with ethyl acetate
  11. washthe organic layer was washed successively with aqueous sodium carbonate, water and saturated brine
  12. dry with materialdried over magnesium sulfate
  13. distillationThe solvent was distilled off

Sources & evidence

ORD record
ord-68a37d73731c4dc9b70bfce304b4484d
Source dataset
uspto-grants-2004_03
Patent number
US06706732B1

Reaction notes

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