HCID 21529912, compound → HCID 54200967, compound

HRID 1658016Notes

Reaction equation

HRID 1658016 reaction equation
[CH:1](=[N:8][CH2:9][P:10](=[O:21])([O:16][CH2:17][CH2:18][CH2:19][CH3:20])[O:11][CH2:12][CH2:13][CH2:14][CH3:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Li])CCC.Cl[C:28]([O:30][CH2:31][C:32]([C:34]1[CH:39]=[CH:38][C:37]([Br:40])=[CH:36][CH:35]=1)=[O:33])=[O:29]>O1CCCC1.CCCCCC>[CH:1](=[N:8][CH:9]([P:10]([O:16][CH2:17][CH2:18][CH2:19][CH3:20])([O:11][CH2:12][CH2:13][CH2:14][CH3:15])=[O:21])[C:28]([O:30][CH2:31][C:32]([C:34]1[CH:35]=[CH:36][C:37]([Br:40])=[CH:38][CH:39]=1)=[O:33])=[O:29])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 21529912HCID 21529912, compoundHCID 54295138HCID 54295138, compoundHCID 178418339Butyllithium

Product 1

HCID 54200967HCID 54200967, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

Dibutyl N-benzylidene-aminomethylphosphonate (31.1 g) is dissolved in anhydrous tetrahydrofuran (500 ml) and the solution is cooled to -78° under a nitrogen atmosphere. Butyllithium (46 ml of a 2.2 M solution in hexane) is added over a period of 5 minutes. The resulting solution is stirred an additional 30 minutes at -78°, then treated dropwise over a period of 45 minutes with p-bromophenacyl chloroformate (13.9 g) in tetrahydrofuran (100 ml). The reaction mixture is stirred an additiona 2 hours at -78° followed by gradual warming to 3° over a period of 30 minutes. Evaporation of the solvent in vacuo leaves a gum which is partitioned between ether (500 ml) and 0.5 M pH 3 phosphate buffer (100 ml). The ethereal phase is separated, washed with water and saturated brine, dried over magnesium sulfate filtered, and evaporated in vacuo to an oil. Chromatographic purification of this material on silica gel gives p-bromophenacyl N-benzylidene-α-amino-dibutylphosphonoacetate.

Workup

  1. temperaturethe solution is cooled to -78° under a nitrogen atmosphere
  2. stirringThe reaction mixture is stirred an additiona 2 hours at -78°
  3. temperatureby gradual warming to 3° over a period of 30 minutes
  4. customEvaporation of the solvent in vacuo
  5. customleaves a gum which
  6. customis partitioned between ether (500 ml) and 0.5 M pH 3 phosphate buffer (100 ml)
  7. customThe ethereal phase is separated
  8. washwashed with water and saturated brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationfiltered
  11. customevaporated in vacuo to an oil
  12. customChromatographic purification of this material on silica gel

Sources & evidence

ORD record
ord-d92cf796af8143b382ad3e6616232aef
Source dataset
uspto-grants-1976_06
Patent number
US03962224

Reaction notes

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