Sulfuric Acid → 3-Methoxy-2,8-dimethyl-1-oxa-8-azaspiro[4.5]decane

HRID 36013

Reaktionsgleichung

Reaktionsgleichung von HRID 36013
[H-].[Al+3].[Li+].[H-].[H-].[H-].S(=O)(=O)(O)O.C(O[C:15]([N:17]1[CH2:29][CH2:28][C:20]2([O:24][CH:23]([CH3:25])[CH:22]([O:26][CH3:27])[CH2:21]2)[CH2:19][CH2:18]1)=O)C.O.O.O.O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Na+].[Na+]>O1CCCC1.CCOCC>[NH3:17].[CH3:27][O:26][CH:22]1[CH2:21][C:20]2([CH2:28][CH2:29][N:17]([CH3:15])[CH2:18][CH2:19]2)[O:24][CH:23]1[CH3:25]

Komponenten

8

Edukt 4

HCID 1118Sulfuric AcidHCID 62649Sodium sulfate decahydrateHCID 148520668-Ethoxycarbonyl-3-methoxy-2-methyl-1-oxa-8-azaspiro[4,5]decaneHCID 21226445Aluminium lithium hydride

Produkt 2

HCID 222AmmoniaHCID 103303903-Methoxy-2,8-dimethyl-1-oxa-8-azaspiro[4.5]decaneAusbeute 145,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A suspension of 1.05 g lithium aluminum hydride in 35 ml anhydrous tetrahydrofuran was cooled to 0° C., 0.92 ml of 100% sulfuric acid was added dropwise while maintaining the temperature in the range from 0° to 7° C., and the mixture was stirred for 30 minutes in the above temperature range. A tetrahydrofuran solution (7 ml) containing 711 mg 8-ethoxycarbonyl-3-methoxy-2-methyl-1-oxa-8-azaspiro[4,5]-decane was then added, and stirring was continued at that temperature for one hour. Ether (35 ml) was then added, sodium sulfate decahydrate (2.6 g) was further added in small portions, and stirring was continued for an additional one hour. The white suspension thus obtained was filtered using perlite as filter aid, and the filter cake was washed with a mixed solvent of ethanol/chloroform (1:5). The washings were joined to the filtrate, the combined solution was concentrated under reduced pressure, and the residue was dissolved in chloroform. This solution was dried over anhydrous magnesium sulfate, chloroform was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using, as eluent, a mixed solvent of chloroform/methanol/conc. ammonia (10:1:0.1 by volume), giving 400 mg 3-methoxy-2,8-dimethyl-1-oxa-8-azaspiro[4,5]decane as oil. It was converted to hydrochloride by addition of ethanolic hydrogen chloride to its ethereal solution.

Aufarbeitung

  1. temperaturewhile maintaining the temperature in the range from 0° to 7° C.
  2. additionwas then added
  3. stirringstirring
  4. waitwas continued at that temperature for one hour
  5. stirringstirring
  6. waitwas continued for an additional one hour
  7. customThe white suspension thus obtained
  8. filtrationwas filtered
  9. filtrationas filter aid
  10. washthe filter cake was washed with a mixed solvent of ethanol/chloroform (1:5)
  11. concentrationthe combined solution was concentrated under reduced pressure
  12. dissolutionthe residue was dissolved in chloroform
  13. dry with materialThis solution was dried over anhydrous magnesium sulfate, chloroform
  14. distillationwas distilled off under reduced pressure
  15. customthe residue was purified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-9c8e49a27a364f379c2d7593f334697a
Quelldatensatz
uspto-grants-1995_05
Patentnummer
US05412096

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