Ethyl Acetate → 1-(4-Bromophenyl)-6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione

HRID 600307Notes

Reaction equation

HRID 600307 reaction equation
[Br:1][C:2]1[CH:18]=[CH:17][C:5]([CH:6]=[C:7]2[C:12](=[O:13])[O:11][C:10]([CH3:15])([CH3:14])[O:9][C:8]2=[O:16])=[CH:4][CH:3]=1.[H-].[Na+].[I-].[CH3:22][S+](C)(C)=O.C(OCC)(=O)C>CN(C=O)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH:6]2[C:7]3([C:8](=[O:16])[O:9][C:10]([CH3:15])([CH3:14])[O:11][C:12]3=[O:13])[CH2:22]2)=[CH:17][CH:18]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 3671611,3-Dioxane-4,6-dione, 5-((4-bromophenyl)methylene)-2,2-dimethyl-

Product 1

HCID 579996301-(4-Bromophenyl)-6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dioneYield 43.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a cooled solution of 5-(4-bromobenzylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione (1.48 g) in DMF (20 mL) at 0-5° C. was added by dropwise addition a prepared solution of the dimethylsufoxonium-methylide from sodium hydride (60% in oil) (0.209 g), trimethylsulfoxonium iodide (1.152 g) in DMF (20 mL) at room temperature. Upon completion of addition the mixture was stirred at this temperature for a further 20 min. The mixture was then carefully poured onto a stirred mixture of ice/water and ethyl acetate. The crude product was extracted into ethyl acetate, washed well with saturated brine and dried over sodium sulfate. Filtration and evaporation gave the crude product. This sample was then recrystallised from a mixture of ethyl acetate:isohexane (3:1) to give the subtitle compound (0.670 g) as a colourless solid.

Workup

  1. additionUpon completion of addition the mixture
  2. extractionThe crude product was extracted into ethyl acetate
  3. washwashed well with saturated brine
  4. dry with materialdried over sodium sulfate
  5. filtrationFiltration and evaporation
  6. customgave the crude product
  7. customThis sample was then recrystallised from a mixture of ethyl acetate:isohexane (3:1)

Sources & evidence

ORD record
ord-89fa8698d89f4b0b8b358418b21189d7
Source dataset
uspto-grants-2011_03
Patent number
US07902181B2

Reaction notes

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