Diethyl chlorophosphate → HCID 15725975, Verbindung

HRID 129788

Reaktionsgleichung

Reaktionsgleichung von HRID 129788
[CH3:1][S:2]([O:5][CH:6]([CH3:8])[CH3:7])(=[O:4])=[O:3].C([Li])CCC.[P:14](Cl)([O:19][CH2:20][CH3:21])([O:16][CH2:17][CH3:18])=[O:15]>C1COCC1>[CH2:17]([O:16][P:14]([CH2:1][S:2]([O:5][CH:6]([CH3:8])[CH3:7])(=[O:4])=[O:3])([O:19][CH2:20][CH3:21])=[O:15])[CH3:18]

Komponenten

5

Edukt 3

HCID 13139Diethyl chlorophosphateHCID 13551Isopropyl methanesulfonateHCID 178418339Butyllithium

Produkt 1

HCID 15725975HCID 15725975, VerbindungAusbeute 67 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
-40 °C

Versuchsvorschrift

To a rapidly stirred solution of 8.28 g (60 mmol) of isopropyl methanesulfonate in 150 mL of THF at -73° C. (internal temp.) was added 25 mL (60 mmol) of 2.4M n-butyllithium dropwise over 20 min. The internal temperature was not allowed to rise above -69° C. throughout the course of the addition. After an additional 15 min., 5.17 g (30 mmol) of freshly distilled diethyl chlorophosphate was added at a rate to keep the solution temperature below -69° C. The reaction mixture was stirred for 0.3 h at -73° C. and for 0.5 h at -40° C. when it was quenched with 125 mL of saturated NH4Cl solution. The reaction mass was warmed to room temperature and the THF removed under pressure. The remainder was partitioned between methylene chloride and water (3×75 mL). The extracts were dried (Na2SO4), concentrated, and purified by flash chromatography (350 g silica gel) eluting with 1:1 methylene chloride/ether to provide 5.20 g (67%) of title compound as a colorless oil.

Aufarbeitung

  1. additionto rise above -69° C. throughout the course of the addition
  2. customthe solution temperature below -69° C
  3. customwas quenched with 125 mL of saturated NH4Cl solution
  4. customThe reaction
  5. temperaturemass was warmed to room temperature
  6. customthe THF removed under pressure
  7. customThe remainder was partitioned between methylene chloride and water (3×75 mL)
  8. dry with materialThe extracts were dried (Na2SO4)
  9. concentrationconcentrated
  10. custompurified by flash chromatography (350 g silica gel)
  11. washeluting with 1:1 methylene chloride/ether

Quellen und Nachweise

ORD-Eintrag
ord-9d7c7bb0be384a86b5eab256f0038584
Quelldatensatz
uspto-grants-1995_11
Patentnummer
US05470845

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