tert-Butyl hydroperoxide → Rac-2-benzenesulfonyl-2-methyl-3-trifluoromethyl-oxirane

HRID 1352387Notes

Reaction equation

HRID 1352387 reaction equation
C([Li])CCC.C([O:10]O)(C)(C)C.[F:12][C:13]([F:27])([F:26])/[CH:14]=[C:15](/[S:17]([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)(=[O:19])=[O:18])\[CH3:16]>O1CCCC1.C(OCC)(=O)C>[C:20]1([S:17]([C:15]2([CH3:16])[CH:14]([C:13]([F:12])([F:26])[F:27])[O:10]2)(=[O:18])=[O:19])[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

6

Reactant 3

HCID 6410tert-Butyl hydroperoxideHCID 67549587((e)-4,4,4-Trifluoro-but-2-ene-2-sulfonyl)-benzeneHCID 178418339Butyllithium

Product 1

HCID 21100322Rac-2-benzenesulfonyl-2-methyl-3-trifluoromethyl-oxiraneYield 49%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 15.2 mmol n-butyllithium solution (1.6 M in hexane) in 20 ml tetrahydrofuran at −78° C. was added dropwise 15.2 mmol tert-butyl hydroperoxide solution (5.5 M in nonane) and the mixture was stirred at −78° C. for 10 min, then warmed to −50° C. and re-cooled to −78° C. A solution of 10.1 mmol ((E)-4,4,4-trifluoro-but-2-ene-2-sulfonyl)-benzene in 6 ml tetrahydrofuran was then added dropwise and stirring continued for a further 30 min at −78° C. and then the reaction mixture was allowed to warm to room temperature. The reaction mixture was diluted with ethyl acetate and washed sequentially with 1 M hydrochloric acid and with brine. The organic phase was then dried over sodium sulphate and concentrated in vacuo. The residue was purified by chromatography (SiO2, ethyl acetate/heptane) to afford the title compound as a colourless oil (yield 49%). EI-MS (m/e): 251.1 ([M−CH3]+, 6%), 250.1 ([M−O]+, 20%), 126.1 (PhSOH+, 61%), 125.0 ([M−PhSO2]+, 100%), 78.2 (PhH+, 21%), 77.2 (Ph+, 44%), 43.3 (CH3CHCH3+, 73%).

Workup

  1. temperaturewarmed to −50° C.
  2. temperaturere-cooled to −78° C
  3. stirringstirring
  4. waitcontinued for a further 30 min at −78° C.
  5. temperatureto warm to room temperature
  6. washwashed sequentially with 1 M hydrochloric acid and with brine
  7. dry with materialThe organic phase was then dried over sodium sulphate
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by chromatography (SiO2, ethyl acetate/heptane)

Sources & evidence

ORD record
ord-4e43196d4ef8492cab4b246760b0c6aa
Source dataset
uspto-grants-2007_05
Patent number
US07220744B2

Reaction notes

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