Tetraethyl methylenediphosphonate → HCID 14850767, compound

HRID 1587315Notes

Reaction equation

HRID 1587315 reaction equation
C(OP([CH2:9][P:10]([O:15][CH2:16][CH3:17])([O:12][CH2:13][CH3:14])=[O:11])(OCC)=O)C.C([Li])CCC.[CH2:23]([O:25][C:26]([N:28]1[CH2:32][CH2:31][C:30](=O)[CH:29]1[C:34]([O:36][CH2:37][CH3:38])=[O:35])=[O:27])[CH3:24]>O1CCCC1>[CH2:23]([O:25][C:26]([N:28]1[CH2:32][CH:31]=[C:30]([CH2:9][P:10]([O:12][CH2:13][CH3:14])([O:15][CH2:16][CH3:17])=[O:11])[CH:29]1[C:34]([O:36][CH2:37][CH3:38])=[O:35])=[O:27])[CH3:24]

Participants

5

Reactant 3

HCID 15455Tetraethyl methylenediphosphonateHCID 15618374HCID 15618374, compoundHCID 178418339Butyllithium

Product 1

HCID 14850767HCID 14850767, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A stirred solution of 5.3 ml of bis-(diethylphosphono)methane in 30 ml of anhydrous tetrahydrofuran (THF) under nitrogen is cooled to -78° and 8.5 ml of 2.5M butyl lithium is added dropwise. After stirring 5 minutes a solution of 4.64 g of ethyl 1-ethoxycarbonyl-3-oxopyrrolidine-2-carboxylate [J. Am. Chem. Soc. 86, 5297 (1964)] in 30 ml dry THF is added dropwise rapidly. The solution is heated at reflux for 18 hours, cooled to room temperature and concentrated; 40 ml of 1N hydrochloric acid is added and the mixture is extracted with 100 ml of methylene chloride. The organic fraction is washed with 25 ml water, dried over Na2SO4 filtered and concentrated. Purification by flash chromatography using ethyl acetate as solvent yields ethyl 1-ethoxycarbonyl-3-(diethylphosphonomethyl)-2,5-dihydropyrrole-2-carboxylate.

Workup

  1. additionis added dropwise rapidly
  2. temperatureThe solution is heated
  3. temperatureat reflux for 18 hours
  4. concentrationconcentrated
  5. addition40 ml of 1N hydrochloric acid is added
  6. extractionthe mixture is extracted with 100 ml of methylene chloride
  7. washThe organic fraction is washed with 25 ml water
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customPurification by flash chromatography

Sources & evidence

ORD record
ord-6afff826165f492fb8aa6344379dd36e
Source dataset
uspto-grants-1993_06
Patent number
US05217963

Reaction notes

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