Hydrogen Peroxide → 2-Chloro-6-ethylbenzoic acid

HRID 844856Notes

Reaction equation

HRID 844856 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([CH2:10][CH3:11])[C:3]=1[CH:4]=[O:5].P([O-])([O-])([O-])=[O:13].[Na+].[Na+].[Na+].OO.Cl([O-])=O.[Na+].S(=O)(O)[O-].[Na+]>C(#N)C.O>[Cl:1][C:2]1[CH:9]=[CH:8][CH:7]=[C:6]([CH2:10][CH3:11])[C:3]=1[C:4]([OH:13])=[O:5]

Participants

8

Reactant 5

HCID 784Hydrogen PeroxideHCID 24243Trisodium PhosphateHCID 226137462-Chloro-6-ethylbenzaldehydeHCID 23665763Sodium BisulfiteHCID 23668197Sodium Chlorite

Product 1

HCID 226137692-Chloro-6-ethylbenzoic acidYield 384.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 6342AcetonitrileSolvent

Procedure

To a room temperature suspension of 2-chloro-6-ethylbenzaldehyde (13.5 mmol, 2.27 g) in acetonitrile (25 mL) was added a solution of monobasic sodium phosphate (3.4 mmol, 0.465 g) in water (7.5 mL) followed by hydrogen peroxide (1.8 mL, 30%). Then, a solution of sodium chlorite (23.7 mmol, 2.15 g) in water (20 mL) was added dropwise at 0° C. while maintaining the temperature below 3° C. After addition, the yellow suspension was stirred for 15 h at 0° C. to room temperature. At this time TLC analysis of the mixture indicated the absence of starting material. Then, a solution of sodium bisulfite (20.5 mmol, 2.8 g) in water (10 mL) was added dropwise at 0° C. until the yellow color disappeared (KI-paper positive). Cooling is essential to control the exothermic reaction. After 1 h, the solvent was removed under vacuum. The neutral impurities were extracted with diethyl ether (200 mL). Then, the basic aqueous solution was neutralized with 10% HCl to pH ˜1. The precipitated white solid was collected by filtration and dried at in air to afford 2.415 g (97% yield) of 2-chloro-6-ethylbenzoic acid as an amorphous white solid. EI-HRMS m/e calcd for C9H9ClO2 (M+) 184.0291, found 184.0295.

Workup

  1. temperaturewhile maintaining the temperature below 3° C
  2. additionAfter addition
  3. temperatureCooling
  4. customthe exothermic reaction
  5. waitAfter 1 h
  6. customthe solvent was removed under vacuum
  7. extractionThe neutral impurities were extracted with diethyl ether (200 mL)
  8. filtrationThe precipitated white solid was collected by filtration
  9. customdried at in air

Sources & evidence

ORD record
ord-885d5a7070814e72bbd1fe6c6b607137
Source dataset
uspto-grants-2002_04
Patent number
US06380387B1

Reaction notes

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