Dimethyl (2-oxopropyl)phosphonate → methyl(3E)-2,2-dimethyl-5-oxohex-3-enoate

HRID 1039976

Reaktionsgleichung

Reaktionsgleichung von HRID 1039976
COP([CH2:7][C:8](=[O:10])[CH3:9])(=O)OC.CC(C)([O-])C.[K+].[CH3:17][C:18]([CH3:25])([CH:23]=O)[C:19]([O:21][CH3:22])=[O:20]>O1CCCC1>[CH3:17][C:18]([CH3:25])(/[CH:23]=[CH:7]/[C:8](=[O:10])[CH3:9])[C:19]([O:21][CH3:22])=[O:20]

Komponenten

5

Edukt 3

HCID 77872Dimethyl (2-oxopropyl)phosphonateHCID 11137194Methyl 2,2-dimethyl-3-oxopropanoateHCID 23665647Potassium tert-butoxide

Produkt 1

HCID 86658242methyl(3E)-2,2-dimethyl-5-oxohex-3-enoateAusbeute 47 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To a solution of dimethyl(2-oxopropyl)phosphonate (4.09 mL, 30 mmol) in tetrahydrofuran (200 mL) at 0° C. was added potassium tert-butoxide (3.22 g, 28.7 mmol). After 15 minutes, the reaction flask was moved to a 20° C. water bath and then a solution of methyl 2,2-dimethyl-3-oxopropanoate (3.39 g, 26 mmol) in tetrahydrofuran (10 mL) was added. After 20 hours, the opaque reaction mixture was partitioned between diethyl ether (100 mL) and water (100 mL). The layers were separated and the aqueous layer was extracted with diethyl ether (1×100 mL, 1×50 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate solution and brine, dried over sodium sulfate, filtered, and concentrated. The residue was purified by silica gel flash column chromatography (0-4% methanol/dichloromethane gradient) to afford methyl(3E)-2,2-dimethyl-5-oxohex-3-enoate (2.21 g, 12.21 mmol, 47% yield) as a light yellow oil. 1H NMR (500 MHz, CDCl3) δ 6.95 (d, J=16.3, 1H), 6.09 (d, J=16.3, 1H), 3.71 (s, 3H), 2.29 (s, 3H), 1.37 (d, J=2.3, 6H).

Aufarbeitung

  1. customwas moved to a 20° C.
  2. waitAfter 20 hours
  3. customthe opaque reaction mixture
  4. customwas partitioned between diethyl ether (100 mL) and water (100 mL)
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with diethyl ether (1×100 mL, 1×50 mL)
  7. washThe combined organic layers were washed with saturated aqueous sodium bicarbonate solution and brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by silica gel flash column chromatography (0-4% methanol/dichloromethane gradient)

Quellen und Nachweise

ORD-Eintrag
ord-f140cb066a19433bb2889867e24e23f1
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08551984B2

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