Acetone → Diethyl 3,4-dihydroxybutylphosphonate

HRID 373885Notes

Reaction equation

HRID 373885 reaction equation
[CH2:1]([P:5](=[O:12])([O:9][CH2:10][CH3:11])[O:6][CH2:7][CH3:8])[CH2:2]C=C.C[N+]1([O-])[CH2:19][CH2:18][O:17]CC1.CC(C)=[O:23]>O.[Os](=O)(=O)(=O)=O>[OH:23][CH:19]([CH2:18][OH:17])[CH2:2][CH2:1][P:5](=[O:12])([O:9][CH2:10][CH3:11])[O:6][CH2:7][CH3:8]

Participants

6

Reactant 3

HCID 180AcetoneHCID 82029Methyl morpholine oxideHCID 10997850Diethyl 3-butenylphosphonate

Product 1

HCID 19808663Diethyl 3,4-dihydroxybutylphosphonateYield 71%

Reagents, catalysts & solvents 2

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent

Procedure

To a solution of diethyl but-3-enylphosphonate (10.2 g, 0.053 mol) in acetone (200 ml) and water (40 ml), was added a trace of osmium tetroxide (1 mg). After stirring for 10 minutes at ambient temperature, 4-methylmorpholine-N-oxide (10.75 g, 0.079 mol) was added in one portion. Stirring was continued overnight under an atmosphere of nitrogen. The solution was concentrated under reduced pressure, and final traces of water removed by azeotroping with benzene and ethanol. The residual brown oil was chromatographed on silica gel (dichloromethane-methanol, 95:5 as eluant) to give the title compound as an oil (8.5 g, 71%). IR: υmax (film), 3400, 3000, 2940, 2880, 1450, 1400, 1230, 1170, 1070, 1030, 970, 820, 790 cm-1. 1H NMR: δH ((CD3)2SO) 1.25 (6H, t, J=8Hz, (OCH2CH3)2), 1.3-2.05 (4H, m, CH2CH2P), 3.1-3.5 (3H, m, HOCH2CH(OH)), 4.0 (4H, m, (OCH2CH3)2), 4.6 (2H, m, D2O exchangeable, HOCH2CH(OH)). Found: C, 42.57; H, 8.56%. C8H19O5P requires: C, 42.47; H, 8.46%. m/z:C8H20O5P requires 227.1048; observed: 227.1045 (MH+).

Workup

  1. stirringStirring
  2. waitwas continued overnight under an atmosphere of nitrogen
  3. concentrationThe solution was concentrated under reduced pressure
  4. customfinal traces of water removed
  5. customby azeotroping with benzene and ethanol
  6. customThe residual brown oil was chromatographed on silica gel (dichloromethane-methanol, 95:5 as eluant)

Sources & evidence

ORD record
ord-a6cc4d4ed7a04d11adaf2dfa16fe62e4
Source dataset
uspto-grants-1992_11
Patent number
US05166198

Reaction notes

Loading…