Malononitrile → Methyl 3,3-dicyano-2,2-dimethylpropanoate
Reaction equation
[C:1](#[N:5])[CH2:2][C:3]#[N:4].[H-].[Na+].Br[C:9]([CH3:15])([CH3:14])[C:10]([O:12][CH3:13])=[O:11].C(=O)(O)[O-].[Na+]>C1COCC1>[C:3]([CH:2]([C:1]#[N:5])[C:9]([CH3:15])([CH3:14])[C:10]([O:12][CH3:13])=[O:11])#[N:4]Participants
Procedure
3 g (45.411 mmol) of malononitrile were added slowly to 1.816 g (45.411 mmol) of sodium hydride (60% in mineral oil) in THF (91 ml). 5.876 ml (45.411 mmol) of methyl 2-bromo-2-methylpropanoate were then added, and the mixture was stirred at RT overnight. Another 5.876 ml (45.411 mmol) of methyl 2-bromo-2-methylpropanoate were then added, and the mixture was heated at 50° C. overnight. Another 1.762 ml (13.623 mmol) of methyl 2-bromo-2-methylpropanoate were then added, and the mixture was heated at 50° C. for another 4 h. Saturated aqueous sodium bicarbonate solution was then added, and the mixture was extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried with sodium sulphate, filtered and concentrated to dryness. This gave 8.9 g of crude product which was purified by chromatography on silica gel (cyclohexane/ethyl acetate 4:1).
Workup
- temperaturethe mixture was heated at 50° C. overnight
- temperaturethe mixture was heated at 50° C. for another 4 h
- extractionthe mixture was extracted three times with ethyl acetate
- washThe combined organic phases were washed with saturated aqueous sodium chloride solution
- dry with materialdried with sodium sulphate
- filtrationfiltered
- concentrationconcentrated to dryness
- customThis gave 8.9 g of crude product which was purified by chromatography on silica gel (cyclohexane/ethyl acetate 4:1)
Sources & evidence
- ORD record
- ord-939b2226c12547898639ed6499ec730b
- Source dataset
- uspto-grants-2015_12
- Patent number
- US09216978B2
Reaction notes
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