Water → Ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate

HRID 1455456Notes

Reaction equation

HRID 1455456 reaction equation
[H-].[Na+].[CH2:3]([O:5][C:6](=O)[O:7]CC)[CH3:4].[CH2:11]1[O:21][C:14]2([CH2:19][CH2:18][C:17](=[O:20])[CH2:16][CH2:15]2)[O:13][CH2:12]1.O>CCCCCC.C1COCC1.C(O)(=O)C>[CH2:3]([O:5][C:6]([CH:18]1[C:17](=[O:20])[CH2:16][CH2:15][C:14]2([O:13][CH2:12][CH2:11][O:21]2)[CH2:19]1)=[O:7])[CH3:4]

Participants

8

Reactant 4

HCID 962WaterHCID 7766Diethyl CarbonateHCID 24758Sodium hydrideHCID 5674151,4-Dioxaspiro[4.5]decan-8-one

Product 1

HCID 559688Ethyl 8-oxo-1,4-dioxaspiro[4.5]decane-7-carboxylate

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

Sodium hydride (60% dispersion; 45 g, 1.17 mol) was washed with 500 ml of hexane (2×), suspended in 750 mL of THF and treated with diethylcarbonate (112.5 g, 0.94 mol). The suspension was heated to reflux and treated drop-wise with a solution of 1,4-cyclohexanedione mono-ethylene ketal (60.0 g , 0.384 mol) in THF (250 mL). After the addition was complete the suspension was heated to reflux for an additional 4 hours. The mixture was cooled in an ice bath to 0° C. and then poured, while vigorously stirring, into a mixture of ice (1 L), water (100 mL) and acetic acid (100 mL). The resulting mixture was extracted with hexane (2 L total) and the extracts washed with water and brine. The hexane extract was dried over Na2SO4, filtered and concentrated to give 8-Oxo-1,4-dioxa-spiro[4.5]decane-7-carboxylic acid ethyl ester as a pale yellow oil. This was used without further purification.

Workup

  1. temperatureThe suspension was heated
  2. temperatureto reflux
  3. additionAfter the addition
  4. temperaturewas heated
  5. temperatureto reflux for an additional 4 hours
  6. additionpoured
  7. extractionThe resulting mixture was extracted with hexane (2 L total)
  8. washthe extracts washed with water and brine
  9. extractionThe hexane extract
  10. dry with materialwas dried over Na2SO4
  11. filtrationfiltered
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-02c38b410631405c8ee07df342044375
Source dataset
uspto-grants-2009_01
Patent number
US07482335B2

Reaction notes

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