Sodium Phosphate, Dibasic → Methyl cis-3-t-butoxycarbonylamino-4-oxoazetidine-2-carboxylate

HRID 616157

Reaktionsgleichung

Reaktionsgleichung von HRID 616157
[C:1]([O:5][C:6]([NH:8][CH:9]1[C:12](=[O:13])[N:11](CC2C=CC(OC)=CC=2OC)[CH:10]1[C:25]([O:27][CH3:28])=[O:26])=[O:7])([CH3:4])([CH3:3])[CH3:2].S(OOS([O-])(=O)=O)([O-])(=O)=O.[K+].[K+].P([O-])([O-])(O)=O.[Na+].[Na+]>C(#N)C.O>[C:1]([O:5][C:6]([NH:8][C@H:9]1[C:12](=[O:13])[NH:11][C@H:10]1[C:25]([O:27][CH3:28])=[O:26])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Komponenten

6

Edukt 3

HCID 24203Sodium Phosphate, DibasicHCID 24412Potassium PersulfateHCID 23470103Methyl 3-t-butoxycarbonylamino-1-(2,4-dimethoxybenzyl)-4-oxoazetidine-2-carboxylate

Produkt 1

HCID 70428372Methyl cis-3-t-butoxycarbonylamino-4-oxoazetidine-2-carboxylateAusbeute 31 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

A solution of 10.5 g (26.7 mmole) of methyl 3-t-butoxycarbonylamino-1-(2,4-dimethoxybenzyl)-4-oxoazetidine-2-carboxylate in 500 ml of acetonitrile is degassed with argon and warmed to 80°. A degassed solution of 15 g (55.5 mmole) of potassium persulfate and 7.5 g (28 mmole) of sodium monohydrogen phosphate in 150 ml of water is added in five portions over 1 hr. The reaction is stirred at 80°-85° under argon for 2-3 hrs until all starting material is consumed (tlc). The reaction mixture is cooled, concentrated in vacuum, shaken with ethyl acetatewater. The organic phase is washed with dilute HCl, NaHCO3 solution and brine; dried over magnesium sulfate and evaporated to dryness. The residue is chromatographed over silica gel with 1:1 benzene-ethyl acetate to afford pure product which crystallized from ethyl acetate-hexane to yield 2.0 g (31%) of the title compound. A less pure fraction from the column, is crystallized from ethyl acetate-hexane to give an additional 0.5 g of product, overall yield, 38%.

Aufarbeitung

  1. temperaturewarmed to 80°
  2. customis consumed (tlc)
  3. temperatureThe reaction mixture is cooled
  4. concentrationconcentrated in vacuum
  5. stirringshaken with ethyl acetatewater
  6. washThe organic phase is washed with dilute HCl, NaHCO3 solution and brine
  7. dry with materialdried over magnesium sulfate
  8. customevaporated to dryness
  9. customThe residue is chromatographed over silica gel with 1:1 benzene-ethyl acetate
  10. customto afford pure product which
  11. customcrystallized from ethyl acetate-hexane

Quellen und Nachweise

ORD-Eintrag
ord-d504fd3780a844abb0c2b5ea5e1cea0d
Quelldatensatz
uspto-grants-1978_02
Patentnummer
US04072674

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