Triethyl 2-phosphonopropionate → Diethyl 1-ethoxycarbonyl-4-methyl-pent-3-ene-1-phosphonate

HRID 1200280Notes

Reaction equation

HRID 1200280 reaction equation
[Na].[CH2:2]([O:4][C:5]([CH:7]([P:9](=[O:16])([O:13][CH2:14][CH3:15])[O:10][CH2:11][CH3:12])[CH3:8])=[O:6])[CH3:3].Br[C:18]([CH3:22])([CH:20]=C)[CH3:19]>C(O)C>[CH2:2]([O:4][C:5]([CH:7]([P:9]([O:10][CH2:11][CH3:12])(=[O:16])[O:13][CH2:14][CH3:15])[CH2:8][CH:19]=[C:18]([CH3:22])[CH3:20])=[O:6])[CH3:3]

Participants

5

Reactant 3

HCID 107155Triethyl 2-phosphonopropionateHCID 5360545SodiumHCID 109536793-Bromo-3-methyl-1-butene

Product 1

HCID 14714201Diethyl 1-ethoxycarbonyl-4-methyl-pent-3-ene-1-phosphonate

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

The diethyl 2-ethoxycarbonly-5-methyl-hex-4-ene-2-phosphonate used in this reaction was prepared by the following procedure. 4.8 Parts of sodium metal were dissolved in 200 parts of absolute ethanol and to this solution was added 50 parts of diethyl 1-ethoxycarbonyl-ethylphosphonate. To this stirred reaction mixture at room temperature was added 31.3 parts of 2-bromo-2-methyl-but-3-ene dropwise over 1 hour. On completion of the addition stirring was continued for 1 hour at room temperature and then for 2 hours at 60° C. After cooling, the reaction mixture was filtered free of sodium bromide and the filtrate concentrated under reduced pressure to remove ethanol. The residual oil was taken up in ether, and the ether solution washed with water and evaporated. Fractional distillation of the residue gave diethyl 1-ethoxycarbonyl-4-methyl-pent-3-ene-1-phosphonate b0.3 126°-34° C. with the following percentage composition by weight.

Workup

  1. customwas prepared by the following procedure
  2. customTo this stirred reaction mixture at room temperature
  3. additionOn completion of the addition
  4. waitfor 2 hours at 60° C
  5. temperatureAfter cooling
  6. filtrationthe reaction mixture was filtered free of sodium bromide
  7. concentrationthe filtrate concentrated under reduced pressure
  8. customto remove ethanol
  9. washthe ether solution washed with water
  10. customevaporated
  11. distillationFractional distillation of the residue

Sources & evidence

ORD record
ord-c5e625e90f6749c597ec36ca3ff4e898
Source dataset
uspto-grants-1990_02
Patent number
US04904815

Reaction notes

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