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

HRID 1171587

Reaktionsgleichung

Reaktionsgleichung von HRID 1171587
[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]

Komponenten

8

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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. 1H NMR (300 MHz, CDCl3) 6 (TMS): 12.25 (s, 1H), 4.20 (q, J=7 Hz, 2H), 4.06-3.96 (m, 4H), 2.53-2.48 (m, 4H), 1.84 (t, J=6.6 Hz, 2H), 1.29 (t, J=7 Hz, 3H).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-a0b1e02a97f34ac3b6b66d51a692f7bf
Quelldatensatz
uspto-grants-2010_11
Patentnummer
US07829571B2

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