Hydrochloric Acid → 4-[(2,2,2-Trifluoroethyl)sulfanyl]phenol

HRID 484996Notes

Reaction equation

HRID 484996 reaction equation
C(=O)([O-])[O-].[K+].[K+].[OH:7][C:8]1[CH:13]=[CH:12][C:11]([SH:14])=[CH:10][CH:9]=1.C1(C)C=CC(S(O[CH2:25][C:26]([F:29])([F:28])[F:27])(=O)=O)=CC=1.Cl>O.CN(C)C=O>[F:27][C:26]([F:29])([F:28])[CH2:25][S:14][C:11]1[CH:12]=[CH:13][C:8]([OH:7])=[CH:9][CH:10]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 67942Ethanol, 2,2,2-trifluoro-, 1-(4-methylbenzenesulfonate)HCID 2401474-Mercaptophenol

Product 1

HCID 132720764-[(2,2,2-Trifluoroethyl)sulfanyl]phenolYield 80.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

With stirring in an atmosphere of nitrogen, 110 g of anhydrous potassium carbonate was added to a solution composed of 51 g of 4-hydroxybenzenethiol and 250 ml of dimethylformamide. Furthermore, 112 g of 2,2,2-trifluoroethyl p-toluenesulfonate was added at a temperature of 25° to 30° C. The mixture was stirred at the same temperature for 3 hours, then at 30° to 40° C. for 4 hours, and finally at 50° C. for 6 hours. After cooling, the solution was poured into 2 liters of water, and concentrated hydrochloric acid was added at a temperature lower than 20° C. to adjust the pH of the solution to 3. The resulting oily product was extracted with toluene. The toluene layer was washed with water, and stirred together with 600 ml of a 10% aqueous solution of potassium hydroxide. The aqueous layer was separated, and hydrochloric acid was added at a temperature lower than 20° C. to adjust the pH of the aqueous layer to 2. The resulting oily product was extracted with toluene. The toluene layer was separated, washed with water, and then dried over anhydrous sodium sulfate. The toluene was evaporated, and the residue was distilled under reduced pressure to give 68 g of the desired 4-(2,2,2-trifluoroethylthio)phenol. b.p. 102°-105° C./0.8 mmHg.

Workup

  1. additionwas added to a solution
  2. waitat 30° to 40° C. for 4 hours
  3. waitfinally at 50° C. for 6 hours
  4. temperatureAfter cooling
  5. additionwas added at a temperature lower than 20° C.
  6. extractionThe resulting oily product was extracted with toluene
  7. washThe toluene layer was washed with water
  8. stirringstirred together with 600 ml of a 10% aqueous solution of potassium hydroxide
  9. customThe aqueous layer was separated
  10. additionhydrochloric acid was added at a temperature lower than 20° C.
  11. extractionThe resulting oily product was extracted with toluene
  12. customThe toluene layer was separated
  13. washwashed with water
  14. dry with materialdried over anhydrous sodium sulfate
  15. customThe toluene was evaporated
  16. distillationthe residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-07d9e603616442569c047915fe070805
Source dataset
uspto-grants-1985_08
Patent number
US04535076

Reaction notes

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