Water → 6-[(2-chloro-alpha,alpha,alpha,6-tetrafluoro-p-tolyl)oxy]-alpha-methyl-1H-benzotriazole-1-acetic acid

HRID 2293729Notes

Reaction equation

HRID 2293729 reaction equation
C[O:2][CH:3]([O:28]C)[CH:4]([CH3:27])[N:5]1[C:9]2[CH:10]=[C:11]([O:14][C:15]3[CH:20]=[C:19]([F:21])[C:18]([C:22]([F:25])([F:24])[F:23])=[C:17]([Cl:26])[CH:16]=3)[CH:12]=[CH:13][C:8]=2[N:7]=[N:6]1.OS(O)(=O)=O.[O-][Mn](=O)(=O)=O.[K+].O>C(O)(=O)C>[Cl:26][C:17]1[CH:16]=[C:15]([O:14][C:11]2[CH:12]=[CH:13][C:8]3[N:7]=[N:6][N:5]([CH:4]([CH3:27])[C:3]([OH:28])=[O:2])[C:9]=3[CH:10]=2)[CH:20]=[C:19]([F:21])[C:18]=1[C:22]([F:25])([F:24])[F:23]

Participants

6

Reactant 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 516875Potassium PermanganateHCID 86747944HCID 86747944, compound

Product 1

HCID 867479436-[(2-chloro-alpha,alpha,alpha,6-tetrafluoro-p-tolyl)oxy]-alpha-methyl-1H-benzotriazole-1-acetic acid

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
70 °C

Procedure

A solution of 6-[(2-chloro-α,α,α,6-tetrafluoro-p-tolyl)oxy]-α-methyl-1H-benzotriazole-1-acetaldehyde dimethyl acetal (23.0 g, 0.053 mole) in acetic acid is treated with 54 ml of 2.5N H2SO4 and heated at 70° C. for 12 hours. A portion of the reaction solution is concentrated, diluted with acetone and treated portionwise, at 25°-38° C., with an aqueous solution of KMnO4 (23.7 g, 0.15 mole). Addition is continued until a persistent pink color is obtained at 27° C. The reaction mixture is filtered to remove MnO2 and the filtrate is concentrated in vacuo to give a residue. Addition of water to the thus-obtained residue precipitates the title compound as a pale yellow solid, 16.6 g. A sample is recrystallized twice from 75% aqueous ethanol to afford a crystalline solid, mp 174°-175.5° C., identified by elemental and NMR analyses.

Workup

  1. concentrationA portion of the reaction solution is concentrated
  2. additiondiluted with acetone
  3. additionAddition
  4. customis obtained at 27° C
  5. filtrationThe reaction mixture is filtered
  6. customto remove MnO2
  7. concentrationthe filtrate is concentrated in vacuo
  8. customto give a residue
  9. customprecipitates the title compound as a pale yellow solid, 16.6 g
  10. customA sample is recrystallized twice from 75% aqueous ethanol
  11. customto afford a crystalline solid, mp 174°-175.5° C.

Sources & evidence

ORD record
ord-efb1d72de6194d2c863d1301fb232204
Source dataset
uspto-grants-1997_11
Patent number
US05686617

Reaction notes

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