Sodium Thiosulfate → 2-Chloro-6-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoic acid

HRID 1885960Notes

Reaction equation

HRID 1885960 reaction equation
[Cl:1][C:2]1[C:7]([CH:8]=[O:9])=[C:6]([O:10][C:11]2[N:16]=[C:15]([O:17][CH3:18])[CH:14]=[C:13]([O:19][CH3:20])[N:12]=2)[CH:5]=[CH:4][CH:3]=1.[Mn]([O-])(=O)(=O)=[O:22].[K+].O.O.O.O.O.O.O.OP([O-])([O-])=O.[Na+].[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>CC(C)=O.O>[Cl:1][C:2]1[C:7]([C:8]([OH:22])=[O:9])=[C:6]([O:10][C:11]2[N:12]=[C:13]([O:19][CH3:20])[CH:14]=[C:15]([O:17][CH3:18])[N:16]=2)[CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 24477Sodium ThiosulfateHCID 516875Potassium PermanganateHCID 6096963Phosphoric acid, disodium salt, heptahydrateHCID 156120076-Chloro-2-(4,6-dimethoxypyrimidin-2-yloxy)benzaldehyde

Product 1

HCID 156119442-Chloro-6-((4,6-dimethoxypyrimidin-2-yl)oxy)benzoic acidYield 97.5%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

To stirred solution of 9.6 grams (0.033 mole) of 6-chloro-2-(4,6-dimethoxypyrimidin-2-yloxy)benzaldehyde in 260 mL of acetone was added dropwise a solution of 7.7 grams (0.049 mole) of potassium permanganate and 6.6 grams (0.024 mole) of sodium phosphate dibasic heptahydrate in 105 mL of water while maintaining the reaction mixture temperature at 20°-25° C. Upon completion of addition, the reaction mixture was stirred at ambient temperature for 18 hours. After this time sodium thiosulfate was added to the reaction mixture to destroy excess permanganate. The reaction mixture was then filtered through diatomaceous earth. The filtrate was cooled and acidified to a pH of 3-4 with aqueous 10% hydrochloric acid. The mixture was extracted with two 50 mL portions of methylene chloride. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was crystallized from methylene chloride and carbon tetrachloride to yield 10.0 grams of 6-chloro-2 -(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid. The nmr spectrum was consistent with the proposed structure.

Workup

  1. temperaturewhile maintaining the reaction mixture temperature at 20°-25° C
  2. additionUpon completion of addition
  3. customto destroy excess permanganate
  4. filtrationThe reaction mixture was then filtered through diatomaceous earth
  5. temperatureThe filtrate was cooled
  6. extractionThe mixture was extracted with two 50 mL portions of methylene chloride
  7. dry with materialThe combined extracts were dried with magnesium sulfate
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated under reduced pressure to a residue
  10. customThe residue was crystallized from methylene chloride and carbon tetrachloride

Sources & evidence

ORD record
ord-45aacbdfd22047c3964bf0e8ed3d117d
Source dataset
uspto-grants-1992_09
Patent number
US05149357

Reaction notes

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