Tetrahydrofuran → Diphenyl chlorophosphate

HRID 2289829Notes

Reaction equation

HRID 2289829 reaction equation
O1CCOCC1.[CH2:7]([Li])[CH2:8][CH2:9][CH3:10].[P:12]([Cl:20])([O:17][CH2:18][CH3:19])([O:14][CH2:15][CH3:16])=[O:13].[CH2:21]1[CH2:25]O[CH2:23][CH2:22]1>>[P:12]([Cl:20])([O:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:25][CH:19]=1)([O:14][C:15]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:16]=1)=[O:13]

Participants

5

Reactant 4

HCID 8028TetrahydrofuranHCID 13139Diethyl chlorophosphateHCID 312751,4-DioxaneHCID 178418339Butyllithium

Product 1

HCID 75654Diphenyl chlorophosphate

Conditions

Temperature
-78 °C

Procedure

Compound 6 (0.75 g) is first dissolved in refluxing dioxane, evaporated to dryness under reduced pressure, and then dissolved in 600 mL THF. The solution is cooled to -78° C. To this solution is slowly added 4.8 mL (2 eq) butyllithium solution, and the resultant cloudy mixture is stirred at 78° C. for 1 hour. A solution of 2.61 g (2.6 eq) diethyl chlorophosphate in 10 mL THF is then added dropwise. The mixture is maintained at -78° C. for three hours and then quenched by the dropwise addition of 10 mL distilled water, at which point the product precipitated from solution. The mixture is warmed to room temperature and filtered to give a white solid. The product is washed with distilled water, hot THF, toluene, ethanol, and DMF and dried under vacuum. Yield: 0.2 g. IR (cm-1): 3300-3150, 2966, 1601, 1492, 1389, 1280, 1216, 1120, 1030, 934, 844, 767.

Workup

  1. customevaporated to dryness under reduced pressure
  2. dissolutiondissolved in 600 mL THF
  3. temperatureThe mixture is maintained at -78° C. for three hours
  4. customquenched by the dropwise addition of 10 mL
  5. distillationdistilled water
  6. customat which point the product precipitated from solution
  7. temperatureThe mixture is warmed to room temperature
  8. filtrationfiltered
  9. customto give a white solid
  10. washThe product is washed with distilled water, hot THF, toluene, ethanol, and DMF
  11. customdried under vacuum

Sources & evidence

ORD record
ord-5f16304914d04ad991a4e31ee9ab3aea
Source dataset
uspto-grants-2000_07
Patent number
US06093758

Reaction notes

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