Hydrogen Peroxide → 2-(5-Bromo-2-trifluoromethoxyphenyl)-4,4,6,6-tetramethyl-1,5-dioxaspiro[2.4]heptan-7-one

HRID 537690Notes

Reaction equation

HRID 537690 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:19][C:20]([F:23])([F:22])[F:21])=[C:6]([CH:8]=[C:9]2[C:13]([CH3:15])([CH3:14])[O:12][C:11]([CH3:17])([CH3:16])[C:10]2=[O:18])[CH:7]=1.[OH:24]O.[OH-].[Li+]>CO>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:19][C:20]([F:23])([F:21])[F:22])=[C:6]([CH:8]2[C:9]3([C:10](=[O:18])[C:11]([CH3:17])([CH3:16])[O:12][C:13]3([CH3:14])[CH3:15])[O:24]2)[CH:7]=1

Participants

5

Reactant 3

HCID 784Hydrogen PeroxideHCID 3939Lithium HydroxideHCID 666794284-[1-(5-Bromo-2-trifluoromethoxyphenyl)-methylidene]-2,2,5,5-tetramethyl-dihydrofuran-3-one

Product 1

HCID 580612462-(5-Bromo-2-trifluoromethoxyphenyl)-4,4,6,6-tetramethyl-1,5-dioxaspiro[2.4]heptan-7-oneYield 86.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 4-[1-(5-bromo-2-trifluoromethoxyphenyl)-methylidene]-2,2,5,5-tetramethyldihydrofuran-3-one (7.06 g, 18.00 mmol) in methanol (300 ml) at 35° C. is added 50% aqueous hydrogen peroxide (1.80 ml, 27.00 mmol), immediately followed by 2M aqueous lithium hydroxide (1.80 ml, 3.60 mmol). After stirring at this temperature for 1 hour the reaction mixture is allowed to cool, then quenched with 10% sodium metabisulfite solution (negative KI-starch indicator test). The reaction mixture is extracted with diethyl ether (×3), then the organic phase is further washed with saturated aqueous sodium bicarbonate (×2) then brine. All organics are combined, dried over magnesium sulfate, filtered and the filtrate concentrated in vacuo to afford 2-(5-bromo-2-trifluoromethoxyphenyl)-4,4,6,6-tetramethyl-1,5-dioxaspiro[2.4]heptan-7-one (6.34 g, 86%) as a yellow oil.

Workup

  1. temperatureto cool
  2. customquenched with 10% sodium metabisulfite solution (negative KI-starch indicator test)
  3. extractionThe reaction mixture is extracted with diethyl ether (×3)
  4. washthe organic phase is further washed with saturated aqueous sodium bicarbonate (×2)
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationthe filtrate concentrated in vacuo

Sources & evidence

ORD record
ord-bcac3b9979ae42b2b2d430c26ae51830
Source dataset
uspto-grants-2014_10
Patent number
US08865623B2

Reaction notes

Loading…