Hydrochloric Acid → 2,4-Dichloro-5-(2,2,2-trifluoroethylthio)phenol

HRID 522445Notes

Reaction equation

HRID 522445 reaction equation
C1(C)C=CC=CC=1.C[N+]1([O-])[CH2:14][CH2:13][O:12]CC1.[Cl:16][C:17]1[CH:22]=[C:21]([Cl:23])[C:20]([S:24][CH2:25][C:26]([F:29])([F:28])[F:27])=CC=1B(O)O.Cl>C(OCC)(=O)C.CCCCCC>[Cl:16][C:17]1[CH:22]=[C:21]([Cl:23])[C:20]([S:24][CH2:25][C:26]([F:27])([F:28])[F:29])=[CH:14][C:13]=1[OH:12]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 1140TolueneHCID 82029Methyl morpholine oxideHCID 1235458932,4-Dichloro-5-(2,2,2-trifluoroethylthio)phenylboronic acid

Product 1

HCID 1178997482,4-Dichloro-5-(2,2,2-trifluoroethylthio)phenolYield 95.3%

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

To 150 ml of toluene was added 29.0 g (50% aqueous solution, 124 mmol) of N-methylmorpholine-N-oxide, and dehydration was conducted by heating under reflux for 1 hour. To the reaction mixture was dropwise added 31.5 g (103 mmol) of 2,4-dichloro-5-(2,2,2-trifluoroethylthio)phenylboronic acid dissolved in ethyl acetate, and the mixture was refluxed for 3 hours under heating. Then, the mixture was allowed to cool to room temperature, and 10% aqueous hydrochloric acid was added, followed by extraction with ethyl acetate. The organic phase obtained was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: a mixed solvent of n-hexane:ethyl acetate=10:1), to obtain 27.2 g (yield: 95%) of an intended product.

Workup

  1. temperatureby heating
  2. temperatureunder reflux for 1 hour
  3. temperaturethe mixture was refluxed for 3 hours
  4. temperatureunder heating
  5. extractionfollowed by extraction with ethyl acetate
  6. customThe organic phase obtained
  7. washwas washed with saturated sodium chloride solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationthe solvent was distilled off under reduced pressure
  10. customThe residue was purified by silica gel column chromatography (

Sources & evidence

ORD record
ord-35d28b722e7b47389fa4f8ededa70891
Source dataset
uspto-grants-2016_05
Patent number
US09332754B2

Reaction notes

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