Malononitrile → Methyl 3,3-dicyano-2,2-dimethylpropanoate

In THF (91 ml), 1.816 g (45.411 mmol) of sodium hydride (60% in mineral oil) were admixed gradually with 3 g (45.411 mmol) of malononitrile. Subsequently, 5.876 ml (45.411 mmol) of methyl 2-bromo-2-methylpropanoate were added and the reaction mixture was stirred at room temperature overnight. Thereafter, another 5.876 ml (45.411 mmol) of methyl 2-bromo-2-methylpropanoate were added and the reaction mixture was heated to 50° C. overnight. Then yet another 1.762 ml (13.623 mmol) of methyl 2-bromo-2-methylpropanoate were added and the reaction mixture was heated to 50° C. for a further 4 h. The mixture was then admixed with saturated aqueous sodium hydrogencarbonate solution and extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulphate, filtered and concentrated to dryness. This gave 8.9 g of crude product, which was purified by chromatography on silica gel (4:1 cyclohexane-ethyl acetate).

1. temperaturethe reaction mixture was heated to 50° C. overnight
2. temperaturethe reaction mixture was heated to 50° C. for a further 4 h
3. extractionextracted three times with ethyl acetate
4. washThe combined organic phases were washed with saturated aqueous sodium chloride solution
5. dry with materialdried over sodium sulphate
6. filtrationfiltered
7. concentrationconcentrated to dryness
8. customThis gave 8.9 g of crude product, which was purified by chromatography on silica gel (4:1 cyclohexane-ethyl acetate)

ORD-Eintrag

ord-afe7f3ee07c546c69e57f1b6096650e2

Quelldatensatz

uspto-grants-2015_05

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09023849B2