1,4-Dioxaspiro[4.5]decan-8-one → 8-Methylidene-1,4-dioxaspiro[4.5]decane

HRID 252027Notes

Reaction equation

HRID 252027 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[O:6]1[C:10]2(CCC(=O)[CH2:12][CH2:11]2)[O:9][CH2:8][CH2:7]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH2:4]=[C:3]1[CH2:12][CH2:11][C:10]2([O:9][CH2:8][CH2:7][O:6]2)[CH2:1][CH2:2]1

Participants

5

Reactant 2

HCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 178418339Butyllithium

Product 1

HCID 109537438-Methylidene-1,4-dioxaspiro[4.5]decaneYield 79%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To solution of methyltriphenylphosphonium bromide (17 g, 1.5 eq.) in THF (100 mL) at 0° C. was added dropwise n-butyllithium (2.5 M in hexanes, 18 mL, 1.4 eq.) and the resulting mixture was stirred for 1 h. A solution of 1,4-dioxa-spiro[4.5]decan-8-one (5.0 g, 32 mmol, 1.0 eq.) in THF (10 mL) was then introduced dropwise and the resulting mixture was warmed to room temperature and stirred overnight. The reaction was quenched by addition of sat. NaHCO3 and the separated aqueous layer was extracted with 4×EtOAc. The combined organic phase was dried over Na2SO4, filtered and concentrated. The residue was purified by chromatography (5% to 10% EtOAc/hexanes) to give 8-methyene-1,4-dioxa-spiro[4.5]decane (3.92 g, 79%).

Workup

  1. stirringstirred overnight
  2. customThe reaction was quenched by addition of sat. NaHCO3
  3. extractionthe separated aqueous layer was extracted with 4×EtOAc
  4. dry with materialThe combined organic phase was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by chromatography (5% to 10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-058feca66c504484af53b584355b3362
Source dataset
uspto-grants-2011_01
Patent number
US07868002B2

Reaction notes

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