Water → Ethyl 3-(cyanomethylene)cyclobutanecarboxylate
Reaction equation
[H-].[Na+].[C:3]([CH2:5]P(=O)(OCC)OCC)#[N:4].O=[C:15]1[CH2:18][CH:17]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:16]1.O>O1CCCC1.C(OCC)C>[C:3]([CH:5]=[C:15]1[CH2:18][CH:17]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:16]1)#[N:4]Participants
Conditions
- Temperature
- 0 °C
Procedure
To a suspension of sodium hydride (60% dispersion in mineral oil, 0.730 g, 18.3 mmol) in tetrahydrofuran (100 mL) at 0° C. was added diethyl cyanomethylphosphonate (3.22 mL, 19.9 mmol), dropwise. The cooling bath was removed and the reaction was allowed to reach room temperature and was stirred at this temperature for 45 minutes. The solution was re-cooled to 0° C. and a solution of ethyl 3-oxocyclobutanecarboxylate (2.36 g, 16.6 mmol) in tetrahydrofuran (50 mL) was introduced dropwise. After stirring for 2 hours, water and ethyl ether were added into the reaction. The layers were separated and the aqueous portion extracted with two further portions of ether. The combined extracts were washed with brine, dried over sodium sulfate, decanted and concentrated. The residue was azeotroped once with toluene to afford product, used without further purification in Step 5.
Workup
- customThe cooling bath was removed
- customto reach room temperature
- stirringAfter stirring for 2 hours
- customThe layers were separated
- extractionthe aqueous portion extracted with two further portions of ether
- washThe combined extracts were washed with brine
- dry with materialdried over sodium sulfate
- customdecanted
- concentrationconcentrated
- customThe residue was azeotroped once with toluene
- customto afford product
- customused without further purification in Step 5
Sources & evidence
- ORD record
- ord-b878d762a80f49408dd8c3a8e21efbd1
- Source dataset
- uspto-grants-2013_04
- Patent number
- US08420629B2
Reaction notes
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