Methanol → 4-(3-Oxo-propyl)tetrahydro-pyran-4-carboxylic acid methyl ester

HRID 391185Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 391185
[CH3:1][O:2][C:3]([C:5]1([CH2:11][CH2:12][CH:13]=C)[CH2:10][CH2:9][O:8][CH2:7][CH2:6]1)=[O:4].CO.CC[O:19]C(C)=O>CC(O)C.O.C(Cl)Cl.O=[Os](=O)(=O)=O>[CH3:1][O:2][C:3]([C:5]1([CH2:11][CH2:12][CH:13]=[O:19])[CH2:6][CH2:7][O:8][CH2:9][CH2:10]1)=[O:4]

Komponenten

8

Edukt 3

HCID 887Methanol2×HCID 8857Ethyl AcetateHCID 584680534-But-3-enyl-tetrahydro-pyran-4-carboxylic acid methyl ester

Produkt 1

HCID 584680574-(3-Oxo-propyl)tetrahydro-pyran-4-carboxylic acid methyl esterAusbeute 94 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 30318Osmium TetroxideKatalysatorHCID 962WaterLösungsmittel2×HCID 3776IsopropanolLösungsmittelHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

4-But-3-enyl-tetrahydro-pyran-4-carboxylic acid methyl ester (6 g, 30 mmol) was dissolved in iPrOH (150 mL). To this was added a aqueous solution of NaIO4 (14 g, 65.2 mmol, 2.18 equiv.) in water (150 mL), followed by addition of OsO4 (25 mg, crystals, in one portion) at rt. The solution was stirred with a mechanical stirrer at rt (water bath). After 30 min, milky cloudy product was formed. Stirring was continued for 4 h. TLC (1% MeOH in DCM, and 5% MeOH in DCM) did not detect the SM. An aliquot was taken and dissolved in CDCl3 to run NMR, there was no alkene peak in the sample. The reaction was judged to be complete. The reaction mixture was poured into ice water (200 mL) and EtOAc (200 mL). The two layers were separated and the aqueous layer was extracted with EtOAc (5×50 mL). More water was added to dissolve the solid resulting in a clear solution. The combined extracts were washed with brine, and concentrated to dryness to get a liquid. The liquid was subject a reduced distillation to remove isopropanol. The remaining liquid was purified on a 50-g silica gel column, eluted with 50% EtOAc in Heptane. Note: the product is not UV active. Anisaldehyde visualization was used. The product fractions were collected and concentrated to yield 5.62 g (94% yield) of the title compound as a liquid.

Aufarbeitung

  1. custommilky cloudy product was formed
  2. waitwas continued for 4 h
  3. dissolutiondissolved in CDCl3
  4. customThe two layers were separated
  5. extractionthe aqueous layer was extracted with EtOAc (5×50 mL)
  6. additionMore water was added
  7. dissolutionto dissolve the solid
  8. customresulting in a clear solution
  9. washThe combined extracts were washed with brine
  10. concentrationconcentrated to dryness
  11. customto get a liquid
  12. distillationa reduced distillation
  13. customto remove isopropanol
  14. customThe remaining liquid was purified on a 50-g silica gel column
  15. washeluted with 50% EtOAc in Heptane
  16. customThe product fractions were collected
  17. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-d3a63f60f5ae4fba84fc45e6a974bf08
Quelldatensatz
uspto-grants-2013_02
Patentnummer
US08383814B2

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