Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)- → 8-[2,4-Bis(methoxymethoxy)phenyl]-1,4-dioxaspiro[4.5]dec-7-ene

HRID 585633Notes

Reaction equation

HRID 585633 reaction equation
[CH3:1][O:2][CH2:3][O:4][C:5]1[CH:10]=[C:9]([O:11][CH2:12][O:13][CH3:14])[CH:8]=[CH:7][C:6]=1[C:15]1(O)[CH2:24][CH2:23][C:18]2([O:22][CH2:21][CH2:20][O:19]2)[CH2:17][CH2:16]1.C12(CS(O)(=O)=O)C(C)(C)C(CC1)CC2=O.C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1>[CH3:1][O:2][CH2:3][O:4][C:5]1[CH:10]=[C:9]([O:11][CH2:12][O:13][CH3:14])[CH:8]=[CH:7][C:6]=1[C:15]1[CH2:24][CH2:23][C:18]2([O:19][CH2:20][CH2:21][O:22]2)[CH2:17][CH:16]=1

Participants

5

Reactant 3

HCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 516892Sodium BicarbonateHCID 121351678-[2,4-Bis(methoxymethoxy)phenyl]-1,4-dioxaspiro[4.5]decan-8-ol

Product 1

HCID 121351688-[2,4-Bis(methoxymethoxy)phenyl]-1,4-dioxaspiro[4.5]dec-7-eneYield 70.7%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

8-[2,4-Bis(methoxymethoxy)phenyl]-1,4-dioxaspiro[4.5]decan-8-ol (1.40 g, 3.95 mmol) was placed in a 50 ml round bottomed flask equipped with magnetic stirrer and Dean-Stark apparatus. Toluene (30 ml) was added, followed by camphor sulphonic acid (10 mg). The stirred solution was then heated under reflux for 1 hr, cooled and saturated aqueous sodium bicarbonate solution (10 ml) added. The mixture was poured into a separating funnel and the phases separated. The aqueous phase was extracted with ethyl acetate (2×15 ml) and the combined organics were washed with brine (15 ml), dried over anhydrous magnesium sulphate, filtered and then concentrated in vacuo yielding an orange oil which was purified by flash column chromatography (SiO2, ethyl acetate/petroleum ether, 45:55, v/v) to afford the title product (0.94 g) as a colourless oil. δH (CDCl3) 1.84 (2H, t), 2.41-2.43 (2H, m), 2.56-2.62 (2H, m), 3.47 (6H, s), 3.98-4.02 (4H, m), 5.13 (4H, s), 5.58-5.63 (1H, m), 6.64 (1H, dd), 6.78 (1H, d), 7.08 (1H, d).

Workup

  1. customequipped with magnetic stirrer
  2. temperatureThe stirred solution was then heated
  3. temperatureunder reflux for 1 hr
  4. temperaturecooled
  5. additionThe mixture was poured into a separating funnel
  6. customthe phases separated
  7. extractionThe aqueous phase was extracted with ethyl acetate (2×15 ml)
  8. washthe combined organics were washed with brine (15 ml)
  9. dry with materialdried over anhydrous magnesium sulphate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customyielding an orange oil which
  13. customwas purified by flash column chromatography (SiO2, ethyl acetate/petroleum ether, 45:55

Sources & evidence

ORD record
ord-12f6201280f34aaa8308d2e9b2c4568a
Source dataset
uspto-grants-2005_08
Patent number
US06933319B2

Reaction notes

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