Potassium Carbonate → 1-Methyl-2-(methylsulfanyl)benzene

HRID 2387302Notes

Reaction equation

HRID 2387302 reaction equation
[F:1][C:2]([F:27])([F:26])[C@@:3]([CH2:17][S:18][C:19]1[CH:24]=[CH:23][C:22](C)=[CH:21][CH:20]=1)([OH:16])[CH2:4][C:5]([C:8]1[CH:13]=[C:12]([F:14])[CH:11]=[CH:10][C:9]=1[CH3:15])([CH3:7])[CH3:6].F[B-](F)(F)F.[CH3:33][O+](C)C.C(=O)([O-])[O-].[K+].[K+].C(=O)(O)[O-].[Na+]>ClCCl.O>[F:14][C:12]1[CH:11]=[CH:10][C:9]([CH3:15])=[C:8]([C:5]([CH3:7])([CH3:6])[CH2:4][C@:3]2([C:2]([F:27])([F:26])[F:1])[CH2:17][O:16]2)[CH:13]=1.[C:24]1([CH3:33])[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[S:18][CH3:17]

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 516892Sodium BicarbonateHCID 2735153Oxonium, trimethyl-, tetrafluoroborate(1-) (1:1)HCID 58933188(S)-1,1,1-trifluoro-4-(5-fluoro-2-methylphenyl)-4-methyl-2-p-tolylsulfanylmethylpentan-2-ol

Product 2

HCID 2597431-Methyl-2-(methylsulfanyl)benzeneYield 20%HCID 11701812(R)-2-[2-(5-Fluoro-2-methylphenyl)-2-methylpropyl]-2-trifluoromethyloxirane

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of (S)-1,1,1-trifluoro-4-(5-fluoro-2-methylphenyl)-4-methyl-2-p-tolylsulfanylmethylpentan-2-ol (31.0 g, 77.0 mmol) in 200 mL of anhydrous dichloromethane was added trimethyloxonium tetrafluoroborate (17.2 g, 116 mmol). The resulting suspension was stirred at room temperature for 4.5 hours. A solution of potassium carbonate (K2CO3, 32.1 g, 232 mmol) in 200 mL of water was then added. After 19 hours, the reaction mixture was poured into 400 mL of saturated aqueous sodium bicarbonate solution and extracted with three 400 mL portions of dichloromethane. The combined organic phases were washed with brine, dried over magnesium sulfate, filtered, and concentrated in vacuo. The crude mixture can be used in the next step without reducing the yield or can be purified by column chromatography with silica gel (eluted with 0%-2% EtOAc/hexanes) to afford (R)-2-[2-(5-fluoro-2-methylphenyl)-2-methylpropyl]-2-trifluoromethyloxirane as a clear oil (23.2 g, contains 20% methyl tolyl thioether, 87%) which was used without further purification.

Workup

  1. waitAfter 19 hours
  2. extractionextracted with three 400 mL portions of dichloromethane
  3. washThe combined organic phases were washed with brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customyield
  8. customcan be purified by column chromatography with silica gel (eluted with 0%-2% EtOAc/hexanes)

Sources & evidence

ORD record
ord-5c8a86299e4c466ba8168cf9827cf0aa
Source dataset
uspto-grants-2012_09
Patent number
US08268859B2

Reaction notes

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