Diethyl chlorophosphate → Isopropyl (Diethoxyphosphoryl)methanesulfonate

HRID 865861

반응식

HRID 865861 반응식
[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]

참가 물질

5

반응물 3

HCID 13139Diethyl chlorophosphateHCID 13551Isopropyl methanesulfonateHCID 178418339Butyllithium

생성물 1

HCID 15725975Isopropyl (Diethoxyphosphoryl)methanesulfonate수율 67%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
-40 °C

실험 절차

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 reduced 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.

후처리

  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 reduced 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

출처 및 근거

ORD 기록
ord-5ab54c2848f74290b942047b2972b831
출처 데이터셋
uspto-grants-1996_10
특허 번호
US05567841

연결된 노트

불러오는 중…