Carbon Dioxide → trichloroethyl N-benzylidene-alpha-amino-diethylphosphonoacetate

HRID 1657993Notes

Reaction equation

HRID 1657993 reaction equation
C1([Li])C=CC=CC=1.C(=O)=O.[CH:11](=[N:18][CH2:19][P:20](=[O:27])([O:24][CH2:25][CH3:26])[O:21][CH2:22][CH3:23])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.Cl[C:29]([O:31][CH2:32][C:33]([Cl:36])([Cl:35])[Cl:34])=[O:30]>O1CCCC1.C(OCC)(=O)C.CC(C)=O.C1C=CC=CC=1.C(OCC)C>[CH:11](=[N:18][CH:19]([P:20]([O:24][CH2:25][CH3:26])([O:21][CH2:22][CH3:23])=[O:27])[C:29]([O:31][CH2:32][C:33]([Cl:36])([Cl:35])[Cl:34])=[O:30])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

8

Reactant 4

HCID 280Carbon DioxideHCID 870632,2,2-Trichloroethyl chloroformateHCID 2773681N-(diethoxyphosphorylmethyl)-1-phenylmethanimineHCID 178506676HCID 178506676, compound

Product 1

HCID 54407468trichloroethyl N-benzylidene-alpha-amino-diethylphosphonoacetate

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 21584569Ethylacetate acetoneSolventHCID 22174802Benzene etherSolvent

Conditions

Temperature
-78 °C

Procedure

Phenyllithium (12.5 ml. of a 2.0M solution in 7:3 benzene-ethyl ether) is added to a dry-ice cooled, stirring solution of diethyl N-benzylidene-aminomethylphosphonate (6.073 g., 23.8 mMol) in dry tetrahydrofuran (130 ml.). After having been stirred for 30 minutes at -78°C. under a N2 atmosphere, the solution is treated dropwise over 25 minutes with a solution of trichloroethyl chloroformate (5.04 g., 23.8 mMol) in dry tetrahydrofuran (25 ml.). The resulting solution is stirred an additional 2 hours at -78°C., then allowed to warm to 3°C. over a period of 30 minutes. Evaporation of the solvent in vacuo yields a yellow foam which is partitioned between ethyl ether (150 ml.) and 0.5M pH3 phosphate buffer (50 ml.). The aqueous phase is separated and extracted with two additional portions of ether (25 ml.). The combined ethereal solution is washed with saturated brine (100 ml.), dried over MgSO4, and evaporated under reduced pressure to give a cloudy, yellow oil. Chromatography of the crude product on silica gel (200 g.) using 9:1 ethyl acetate-acetone as eluting solvent gives trichloroethyl N-benzylidene-α-amino-diethylphosphonoacetate as a pale yellow oil.

Workup

  1. temperaturecooled
  2. stirringThe resulting solution is stirred an additional 2 hours at -78°C.
  3. temperatureto warm to 3°C. over a period of 30 minutes
  4. customEvaporation of the solvent in vacuo
  5. customyields a yellow foam which
  6. customis partitioned between ethyl ether (150 ml.) and 0.5M pH3 phosphate buffer (50 ml.)
  7. customThe aqueous phase is separated
  8. extractionextracted with two additional portions of ether (25 ml.)
  9. washThe combined ethereal solution is washed with saturated brine (100 ml.)
  10. dry with materialdried over MgSO4
  11. customevaporated under reduced pressure
  12. customto give a cloudy, yellow oil
  13. washas eluting solvent

Sources & evidence

ORD record
ord-3e60c1bb5b624fbeaaf1cde4f766e5ff
Source dataset
uspto-grants-1976_06
Patent number
US03962224

Reaction notes

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