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

HRID 2361869Notes

Reaction equation

HRID 2361869 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-005b6695b5dd40c193eca41426474c7c
Source dataset
uspto-grants-2014_04
Patent number
US08691814B2

Reaction notes

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