Hydrochloric Acid → 2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorobenzoic acid

HRID 1738366Notes

Reaction equation

HRID 1738366 reaction equation
O.O.P([O-])(O)(O)=O.[Na+].[Cl:9][C:10]1[CH:17]=[C:16]([F:18])[C:15]([C:19]2[C:23]([Cl:24])=[C:22]([O:25][CH:26]([F:28])[F:27])[N:21]([CH3:29])[N:20]=2)=[CH:14][C:11]=1[CH:12]=[O:13].OO.Cl([O-])=[O:33].[Na+].Cl>O.C(#N)C>[Cl:9][C:10]1[CH:17]=[C:16]([F:18])[C:15]([C:19]2[C:23]([Cl:24])=[C:22]([O:25][CH:26]([F:27])[F:28])[N:21]([CH3:29])[N:20]=2)=[CH:14][C:11]=1[C:12]([OH:33])=[O:13]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 118099222-Chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorobenzaldehydeHCID 23668197Sodium ChloriteHCID 23673460Sodium Phosphate, Monobasic, Dihydrate

Product 1

HCID 156719592-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorobenzoic acid

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

A solution of 2.8 g (18 mmol) of sodium dihydrogen phosphate dihydrate in 28 ml of water was added at 10-15° C. to a solution of 24 g (71 mmol) of 2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorobenzaldehyde in 130 ml of acetonitrile. Then, 6.8 ml of 30% strength aqueous hydrogen peroxide solution and (in the course of one hour) 9.8 g (108 mmol) of sodium chlorite were added in succession. After the mixture had been stirred for a further hour, it was heated to room temperature. After it had been stirred for a further 16 hours, it was acidified using dilute hydrochloric acid. The aqueous solution was then extracted twice using ethyl acetate, whereupon the combined organic phases were washed in succession with concentrated aqueous thiosulfate solution, water and saturated sodium chloride solution, dried over magnesium sulfate and finally concentrated. Yield: 23 g; m.p.: 137-140° C.

Workup

  1. stirringAfter it had been stirred for a further 16 hours
  2. extractionThe aqueous solution was then extracted twice using ethyl acetate
  3. washwhereupon the combined organic phases were washed in succession with concentrated aqueous thiosulfate solution, water and saturated sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. concentrationfinally concentrated

Sources & evidence

ORD record
ord-7b832928780c4aa4812d0e862d3871fa
Source dataset
uspto-grants-1999_10
Patent number
US05962694

Reaction notes

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