Water → 8-Methylidene-1,4-dioxaspiro[4.5]decane

HRID 1816328Notes

Reaction equation

HRID 1816328 reaction equation
[CH3:1]C(C)([O-])C.[K+].[O:7]1[C:11]2([CH2:16][CH2:15][C:14](=O)[CH2:13][CH2:12]2)[O:10][CH2:9][CH2:8]1.O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CS(C)=O>[CH2:1]=[C:14]1[CH2:15][CH2:16][C:11]2([O:10][CH2:9][CH2:8][O:7]2)[CH2:12][CH2:13]1

Participants

6

Reactant 3

HCID 962WaterHCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 23665647Potassium tert-butoxide

Product 1

HCID 109537438-Methylidene-1,4-dioxaspiro[4.5]decaneYield 112.6%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

To a solution of methyl triphenylphosphonium bromide (13.7 g) in DMSO (140 ml) was added potassium tert-butoxide (4.31 g) under ice-cooling and the mixture was stirred for 1.5 hours at ambient temperature. After cooling, 1,4-dioxaspiro[4,5]decan-8-one (5.0 g) was dropwise added to the solution under ice-cooling and then stirred for 1 hour at room temperature. The reaction mixture was poured into water (300 ml) and extracted twice with ethyl acetate (150 ml). The extracts were washed with saturated aqueous sodium chloride, dried over magnesium sulfate and evaporated in vacuo to give a residue. The residue was washed with a mixture of hexane and ethyl acetate (5:1 v/v) (300 ml). The resulting precipitates were collected and were chromatographed on silica gel (500 ml) eluting with a mixture of n-hexane and ethyl acetate (5:1 v/v). The fractions containing the desired compound were collected and evaporated under reduced pressure to give 8-methylene 1,4-dioxaspiro[4,5]decane (5.56 g).

Workup

  1. temperaturecooling
  2. temperatureAfter cooling
  3. temperaturecooling
  4. stirringstirred for 1 hour at room temperature
  5. extractionextracted twice with ethyl acetate (150 ml)
  6. washThe extracts were washed with saturated aqueous sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. customevaporated in vacuo
  9. customto give a residue
  10. washThe residue was washed with a mixture of hexane and ethyl acetate (5:1 v/v) (300 ml)
  11. customThe resulting precipitates
  12. customwere collected
  13. customwere chromatographed on silica gel (500 ml)
  14. washeluting with a mixture of n-hexane and ethyl acetate (5:1 v/v)
  15. additionThe fractions containing the desired compound
  16. customwere collected
  17. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-702b9dbffb634efba9b37a432d484323
Source dataset
uspto-grants-2005_04
Patent number
US06884774B2

Reaction notes

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