Diethyl Malonate → 8-Oxabicyclo[3.2.1]octane-3,3-dicarboxylic acid diethyl ester
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].[H][H].S(C1C=CC(C)=CC=1)(O)(=O)=O.S(C1C=CC(C)=CC=1)(O)(=O)=O.O[CH2:39][C@H:40]1[CH2:44][CH2:43][C@@H:42]([CH2:45]O)[O:41]1>CN(C)C=O>[CH2:12]([O:11][C:3]([C:4]1([C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH2:45][CH:42]2[O:41][CH:40]([CH2:44][CH2:43]2)[CH2:39]1)=[O:10])[CH3:13]Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 140 °C
Procedure
Sodium hydride (2.28 grams, 95 mmole) is added in portions to a stirred solution of diethyl malonate (15 mL, 99 mmole) in N,N-dimethylformamide (400 mL). The mixture is stirred for 45 minutes at which time evolution of hydrogen is complete. A solution of cis-2,5-bis(hydroxymethyl)tetrahydrofuran ditosylate (19.0 grams, 43 mmole) in N,N-dimethylformamide (400 mL) is then added dropwise. The mixture is heated in an oil bath at 140° C. overnight. After cooling to room temperature, the mixture was quenched by addition of saturated aqueous ammonium chloride solution and concentrated under vacuum. The residual oil is taken up in water and extracted with diethyl ether. The organic extract is washed with water and brine, dried over magnesium sulfate and concentrated to an oil.
Workup
- temperatureAfter cooling to room temperature
- customthe mixture was quenched by addition of saturated aqueous ammonium chloride solution
- concentrationconcentrated under vacuum
- extractionextracted with diethyl ether
- extractionThe organic extract
- washis washed with water and brine
- dry with materialdried over magnesium sulfate
- concentrationconcentrated to an oil
Sources & evidence
- ORD record
- ord-e26e461067ac4b1ea8671de89f3f983b
- Source dataset
- uspto-grants-2001_09
- Patent number
- US06288246B1
Reaction notes
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