Ethyl Acetate → dibutyl 3-(N-benzyloxy-N-ethoxycarbonylamino)propylphosphonate

HRID 2051969Notes

Reaction equation

HRID 2051969 reaction equation
[CH2:1]([O:8][NH:9][C:10](=[O:14])[O:11][CH2:12][CH3:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[O-]CC.[Na+].Cl[CH2:20][CH2:21][CH2:22][P:23](=[O:34])([O:29][CH2:30][CH2:31][CH2:32][CH3:33])[O:24][CH2:25][CH2:26][CH2:27][CH3:28].C(OCC)(=O)C>C(O)C.C(Cl)(Cl)Cl.O>[CH2:1]([O:8][N:9]([CH2:20][CH2:21][CH2:22][P:23](=[O:34])([O:29][CH2:30][CH2:31][CH2:32][CH3:33])[O:24][CH2:25][CH2:26][CH2:27][CH3:28])[C:10]([O:11][CH2:12][CH3:13])=[O:14])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 255288ethyl N-phenylmethoxycarbamateHCID 2723922Sodium ethoxideHCID 20337237Dibutyl 3-chloropropylphosphonate

Product 1

HCID 20337230dibutyl 3-(N-benzyloxy-N-ethoxycarbonylamino)propylphosphonateYield 42.8%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

A solution of ethyl N-benzyloxycarbamate (7.80 g.) in absolute ethanol (5 ml.) was added dropwise to a solution of sodium ethoxide in absolute ethanol [Na: 920 mg., absolute C2H5OH: 100 ml.] at 70° C. and the mixture was stirred at the same temperature for 30 minutes. To the mixture was added dropwise dibutyl 3-chloropropylphosphonate (10.8 g.), whereafter the reaction mixture was refluxed with stirring for 22 hours. The resultant mixture was cooled to give precipitates, which were filtered off. The filtrate was concentrated under reduced pressure to give a residue. To the residue was added ethyl acetate (100 ml.) and water (50 ml.). The ethyl acetate layer was separated, dried over magnesium sulfate and then concentrated under reduced pressure to give an oily residue (16.6 g.). The residue was subjected to column chromatography on silica gel with an eluent (chloroform). Fractions containing the object compound were collected and concentrated under reduced pressure to give oily dibutyl 3 -(N-benzyloxy-N-ethoxycarbonylamino)propylphosphonate (7.33 g.)

Workup

  1. temperaturewhereafter the reaction mixture was refluxed
  2. stirringwith stirring for 22 hours
  3. customto give
  4. customprecipitates
  5. filtrationwhich were filtered off
  6. concentrationThe filtrate was concentrated under reduced pressure
  7. customto give a residue
  8. customThe ethyl acetate layer was separated
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customto give an oily residue (16.6 g.)
  12. additionFractions containing the object compound
  13. customwere collected
  14. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-0e95dd514f3246018aadbc46dab0855e
Source dataset
uspto-grants-1980_01
Patent number
US04182758

Reaction notes

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