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

HRID 1193211Notes

Reaction equation

HRID 1193211 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:19][CH3:20])=[C:6]([CH:18]=1)[CH:7]=[C:8]1[C:12]([CH3:14])([CH3:13])[O:11][C:10]([CH3:16])([CH3:15])[C:9]1=[O:17].[OH:21]O.[OH-].[Li+]>CO>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:19][CH3:20])=[C:6]([CH:7]2[C:8]3([C:9](=[O:17])[C:10]([CH3:15])([CH3:16])[O:11][C:12]3([CH3:13])[CH3:14])[O:21]2)[CH:18]=1

Participants

5

Reactant 3

HCID 784Hydrogen PeroxideHCID 3939Lithium HydroxideHCID 668231984-(5-Bromo-2-ethylbenzylidene)-2,2,5,5-tetramethyldihydrofuran-3-one

Product 1

HCID 866636592-(5-Bromo-2-ethylphenyl)-4,4,6,6-tetramethyl-1,5-dioxaspiro[2.4]heptan-7-oneYield 87.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
35 °C

Procedure

To a solution of 4-(5-bromo-2-ethylbenzylidene)-2,2,5,5-tetramethyldihydrofuran-3-one (32.07 g, 95.15 mmol) in methanol (1570 ml) at 35° C. is added 50% aqueous hydrogen peroxide (8.10 ml, 142.73 mmol), followed immediately by a solution of 2M aqueous lithium hydroxide (9.51 ml, 19.03 mmol). This reaction mixture is stirred at 35° C. for exactly 1 hour, then quenched with saturated sodium metabisulfite (340 ml) and distilled water (340 ml). After stirring at room temperature for 15 minutes solvents are then concentrated in vacuo (to approximately 500 ml), over which time the product precipitates as a yellow solid. To this suspension is added distilled water (500 ml), and the product is isolated by filtration. After additional washing with distilled water the solid is dried under vacuum overnight to afford 2-(5-bromo-2-ethylphenyl)-4,4,6,6-tetramethyl-1,5-dioxaspiro[2.4]heptan-7-one (29.30 g) as a yellow solid which is used without purification in the next step.

Workup

  1. customquenched with saturated sodium metabisulfite (340 ml)
  2. distillationdistilled water (340 ml)
  3. stirringAfter stirring at room temperature for 15 minutes solvents
  4. concentrationare then concentrated in vacuo (to approximately 500 ml), over which time the product
  5. customprecipitates as a yellow solid
  6. additionTo this suspension is added
  7. distillationdistilled water (500 ml)
  8. customthe product is isolated by filtration
  9. washAfter additional washing with distilled water the solid
  10. customis dried under vacuum overnight

Sources & evidence

ORD record
ord-ac607ce88a714e5f823ba3b4175e6b62
Source dataset
uspto-grants-2014_03
Patent number
US08680299B2

Reaction notes

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