Diethyl Malonate → Diethyl 3-(benzyloxy)cyclobutane-1,1-dicarboxylate

HRID 2380569Notes

Reaction equation

HRID 2380569 reaction equation
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Cl[CH2:15][CH:16]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH2:17]Br>O1CCOCC1>[C:21]1([CH2:20][O:19][CH:16]2[CH2:17][C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])([C:3]([O:11][CH2:12][CH3:13])=[O:10])[CH2:15]2)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

5

Reactant 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydride2×HCID 3468282{[(1-Bromo-3-chloropropan-2-yl)oxy]methyl}benzene

Product 1

HCID 12815110Diethyl 3-(benzyloxy)cyclobutane-1,1-dicarboxylateYield 44.4%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Procedure

To a stirred suspension of oil-free sodium hydride (10.7 g, 0.446 mol) in 270 ml of dry dioxane under nitrogen at room temperature was added over twenty minutes 69.1 g (0.432 mol) of diethyl malonate. After the addition, 1-chloro-2-benzyloxy-3-bromopropane (115 g, 0.437 mol) was added over 20 minutes, and the reaction was refluxed for 44 hours. The reaction was cooled to room temperature, and then a slurry of 10.7 g (0.446 mol) of oil-free sodium hydride in 100 ml of dioxane was cautiously added in portions. The mixture was refluxed for 120 hours and cooled to room temperature. The inorganics were removed by filtration, and the filtrate was concentrated in vacuo to an oil, which was partitioned between ether and water. The ether layer was dried (Na2SO4) and concentrated to an oil, which was distilled to give 58.8 g of desired product having a b.p. 142°-146°/0.3 mm.

Workup

  1. additionwas added over 20 minutes
  2. temperaturethe reaction was refluxed for 44 hours
  3. temperatureThe mixture was refluxed for 120 hours
  4. temperaturecooled to room temperature
  5. customThe inorganics were removed by filtration
  6. concentrationthe filtrate was concentrated in vacuo to an oil, which
  7. customwas partitioned between ether and water
  8. dry with materialThe ether layer was dried (Na2SO4)
  9. concentrationconcentrated to an oil, which
  10. distillationwas distilled

Sources & evidence

ORD record
ord-635d8599a8274190b5263ef192d991d3
Source dataset
uspto-grants-1994_11
Patent number
US05369098

Reaction notes

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