Carbonochloridic acid, (4-methoxyphenyl)methyl ester → p-methoxybenzyl N-benzylidene-alpha-amino-dimethylphosphonoacetate

HRID 1658027Notes

Reaction equation

HRID 1658027 reaction equation
[CH:1](=[N:8][CH2:9][P:10](=[O:15])([O:13][CH3:14])[O:11][CH3:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1([Li])C=CC=CC=1.Cl[C:24]([O:26][CH2:27][C:28]1[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=1)=[O:25]>O1CCCC1>[CH:1](=[N:8][CH:9]([P:10]([O:13][CH3:14])([O:11][CH3:12])=[O:15])[C:24]([O:26][CH2:27][C:28]1[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=1)=[O:25])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 13305526Carbonochloridic acid, (4-methoxyphenyl)methyl esterHCID 54511350Dimethyl N-benzylidene-aminomethylphosphonateHCID 178506676HCID 178506676, compound

Product 1

HCID 54064440p-methoxybenzyl N-benzylidene-alpha-amino-dimethylphosphonoacetate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Dimethyl N-benzylidene-aminomethylphosphonate (22.72 g) is dissolved in anhydrous tetrahydrofuran (500 ml) under nitrogen. The solution is cooled to -78°, and phenyllithium (45 ml of a 2.3 M solution in benzene-ether) is added with stirring. The solution is stirred an additional 15 minutes at -78°. and then treated dropwise over 45 minutes with p-methoxybenzyl chloroformate (10.03 g) in tetrahydrofuran (100 ml). After stirring for 2 hours at -78°, the reaction mixture is allowed to warm to 0° over 30 minutes. The solvent is evaporated in vacuo and the residue is partitioned between ether (500 ml) and 0.5 M pH 3 phosphate buffer (100 ml). The ether portion is washed with water and saturated brine, dried over magnesium sulfate, filtered, and evaporated in vacuo to dryness. Chromatography of the residue on silica gel affords p-methoxybenzyl N-benzylidene-α-amino-dimethylphosphonoacetate.

Workup

  1. temperatureThe solution is cooled to -78°
  2. stirringThe solution is stirred an additional 15 minutes at -78°
  3. stirringAfter stirring for 2 hours at -78°
  4. temperatureto warm to 0° over 30 minutes
  5. customThe solvent is evaporated in vacuo
  6. customthe residue is partitioned between ether (500 ml) and 0.5 M pH 3 phosphate buffer (100 ml)
  7. washThe ether portion is washed with water and saturated brine
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated in vacuo to dryness

Sources & evidence

ORD record
ord-923c94e8f89f4a0d924f607d0ae367b9
Source dataset
uspto-grants-1976_06
Patent number
US03962224

Reaction notes

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