Hydrochloric Acid → HCID 19024387, compound

HRID 1033736Notes

Reaction equation

HRID 1033736 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C:9](O)([C:12]([S:15][CH2:16][C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=1)([CH3:14])[CH3:13])[CH2:10][OH:11].CS(Cl)(=O)=O.[OH-].[K+].Cl>N1C=CC=CC=1.O.CO>[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C:9]1([C:12]([S:15][CH2:16][C:17]2[CH:18]=[CH:19][C:20]([O:23][CH3:24])=[CH:21][CH:22]=2)([CH3:14])[CH3:13])[CH2:10][O:11]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 31297Methanesulfonyl chlorideHCID 15190126HCID 15190126, compound

Product 1

HCID 19024387HCID 19024387, compoundYield 96.1%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 1049PyridineSolvent

Procedure

In 580 ml of pyridine was dissolved 70.0 g (0.19 mol) of (+)-2-(2,4-difluorophenyl)-3-((4-methoxy-phenyl)methylthio)-3-methylbutane-1,2-diol, and 25.2 g (0.22 mol) of methanesulfonyl chloride was added dropwise thereto with stirring under ice-cooling. After being stirred for 3 hours, a solution of 32.0 g (0.57 mol) of potassium hydroxide in a mixed solvent of 340 ml of methanol and 340 ml of water was added dropwise to the mixture. After being warmed to room temperature, the mixture was stirred for 12 hours. The mixture was then acidified by slow addition of 850 ml of 4N hydrochloric acid with stirring under ice-cooling, followed by extraction with diethyl ether. The organic layer was washed successively with IN hydrochloric acid, a saturated sodium hydrogencarbonate aqueous solution, and a saturated sodium chloride aqueous solution, and dried. The solvent was removed by distillation under reduced pressure, and the residue was purified by column chromatography using a mixed solvent of hexane and ethyl acetate (100:1). The solvent was removed by distillation under reduced pressure, and the residue was recrystallized from a mixed solvent of hexane and diethyl ether to obtain 64.0 g (96%) of (-)-2-(2,4-difluorophenyl)-2-(1-((4-methoxyphenyl)methylthio)-1-methylethyl)oxirane as a colorless crystal.

Workup

  1. additionwas added dropwise
  2. temperaturecooling
  3. stirringAfter being stirred for 3 hours
  4. stirringthe mixture was stirred for 12 hours
  5. stirringwith stirring under ice-
  6. temperaturecooling
  7. extractionfollowed by extraction with diethyl ether
  8. washThe organic layer was washed successively with IN hydrochloric acid
  9. dry with materiala saturated sodium hydrogencarbonate aqueous solution, and a saturated sodium chloride aqueous solution, and dried
  10. customThe solvent was removed by distillation under reduced pressure
  11. customthe residue was purified by column chromatography
  12. customThe solvent was removed by distillation under reduced pressure
  13. customthe residue was recrystallized from a mixed solvent of hexane and diethyl ether

Sources & evidence

ORD record
ord-d1decb6cdf304a28a308cc1cc367b3ea
Source dataset
uspto-grants-1994_05
Patent number
US05312815

Reaction notes

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