Ethylene Oxide → Ethyl 1-(3-butenyl)cyclopropanecarboxylate

HRID 2377629Notes

Reaction equation

HRID 2377629 reaction equation
[H-].[Na+].C(OP([CH:11]([CH2:17][CH2:18][CH:19]=[CH2:20])[C:12]([O:14][CH2:15][CH3:16])=[O:13])(OCC)=O)C.[CH2:21]1O[CH2:22]1>C1C=CC=CC=1.CCO>[CH2:17]([C:11]1([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:22][CH2:21]1)[CH2:18][CH:19]=[CH2:20]

Participants

6

Reactant 3

HCID 6354Ethylene OxideHCID 24758Sodium hydrideHCID 14217021Ethyl 2-(diethoxyphosphinyl)-5-hexenoate

Product 1

HCID 14217022Ethyl 1-(3-butenyl)cyclopropanecarboxylateYield 48%

Reagents, catalysts & solvents 2

HCID 702EthanolCatalystHCID 241BenzeneSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred suspension of NaH (60% dispersion in mineral oil, 3.02 g, 75.5 mmol) in dry benzene (100 mL), at 22° C. and under nitrogen, was added dropwise ethyl 2-(diethoxyphosphoryl)hex-5-enoate with anhydrous EtOH (0.044 mL, 0.76 mmol) over 30 minutes. Stirred for 30 minutes, this reaction, cooled at 0° C. and attached with a dry ice/acetone condenser, was added via cannula ethylene oxide (12.7 g, 289.3 mmol), then refluxed at 50° C. for 5 hours. Quenched at 22° C. with 1N aqueous NH4Cl (100 mL), the reaction solution was extracted with Et2O (3×200 mL). The combined Et2O layers were washed with aqueous saturated NaHCO3 (100 mL), water (70 mL), brine (70 mL), dried over Na2SO4, filtered and concentrated. The residue was flash chromatographed on 120 g silica gel 60, eluting with 20-100% EtOAc/Hexane, to give the title product (5.07 g, 48%). LRMS (ESI) m/z 169.2 [(M+H)+; calcd for C10H17O2: 169.1].

Workup

  1. customthis reaction
  2. customattached with a dry ice/acetone condenser
  3. temperaturerefluxed at 50° C. for 5 hours
  4. customQuenched at 22° C. with 1N aqueous NH4Cl (100 mL)
  5. extractionthe reaction solution was extracted with Et2O (3×200 mL)
  6. washThe combined Et2O layers were washed with aqueous saturated NaHCO3 (100 mL), water (70 mL), brine (70 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customchromatographed on 120 g silica gel 60
  11. washeluting with 20-100% EtOAc/Hexane

Sources & evidence

ORD record
ord-42a607674f884891912b0a25d7030abb
Source dataset
uspto-grants-2008_12
Patent number
US07470664B2

Reaction notes

Loading…