Ethyl Methanesulfonate → Ethyl (diethoxyphosphoryl)methanesulfonate

HRID 865856Notes

Reaction equation

HRID 865856 reaction equation
[CH3:1][S:2]([O:5][CH2:6][CH3:7])(=[O:4])=[O:3].[Li]CCCC.[P:13](Cl)([O:18][CH2:19][CH3:20])([O:15][CH2:16][CH3:17])=[O:14].[Cl-].[NH4+]>C1COCC1.CCCCCC>[CH2:16]([O:15][P:13]([CH2:1][S:2]([O:5][CH2:6][CH3:7])(=[O:4])=[O:3])([O:18][CH2:19][CH3:20])=[O:14])[CH3:17]

Participants

7

Reactant 4

HCID 6113Ethyl MethanesulfonateHCID 13139Diethyl chlorophosphateHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 10934205Ethyl (diethoxyphosphoryl)methanesulfonateYield 70%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A solution of ethyl methanesulfonate (4.27 mL, 40.3 mmol) in 100 mL of dry THF was treated at -78° C. with 19.3 mL (44.4 mmol) of n-BuLi in hexane. After 15 min. diethyl chlorophosphate (3.30 ml, 22.2 mmol) was added. The solution was kept at -78° C. for 0.5 h and allowed to stay at -50° C. for 1 h. Saturated ammonium chloride (75 mL) was added to the solution and the mixture warmed to room temperature. The mixture was concentrated (THF removed), diluted with water and extracted with methylene chloride (3×70 mL). The combined organic fractions were dried (MgSO4), concentrated and purified by distillation to yield 3.86 g (70%) of title compound.

Workup

  1. waitto stay at -50° C. for 1 h
  2. concentrationThe mixture was concentrated
  3. custom(THF removed)
  4. additiondiluted with water
  5. extractionextracted with methylene chloride (3×70 mL)
  6. dry with materialThe combined organic fractions were dried (MgSO4)
  7. concentrationconcentrated
  8. distillationpurified by distillation

Sources & evidence

ORD record
ord-2d2302753e824881afee3cda50b14750
Source dataset
uspto-grants-1996_10
Patent number
US05567841

Reaction notes

Loading…