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

HRID 127894

Reaction equation

HRID 127894 reaction equation
[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]

Participants

6

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

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 acetate-water. 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%.

Workup

  1. temperaturewarmed to 80°
  2. customis consumed (tlc)
  3. temperatureThe reaction mixture is cooled
  4. concentrationconcentrated in vacuum
  5. stirringshaken with ethyl acetate-water
  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

Sources & evidence

ORD record
ord-ff5dfa54c89b4e1b8c5e40f56d662fab
Source dataset
uspto-grants-1981_03
Patent number
US04257947

Linked notes

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