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

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Reaction Steps

In THF (91 ml), 3 g (45.411 mmol) of malonic acid dinitrile was slowly added to 1.816 g (45.411 mmol) of sodium hydride (60% in mineral oil). Then 5.876 ml (45.411 mmol) of methyl-2-bromo-2-methylpropanoate was added and it was stirred overnight at RT. Then a further 5.876 ml (45.411 mmol) of methyl-2-bromo-2-methylpropanoate was added and it was heated overnight to 50° C. Then once again, 1.762 ml (13.623 mmol) of methyl-2-bromo-2-methylpropanoate was added and it was heated for a further 4 h to 50° C. Saturated aqueous sodium hydrogen carbonate solution was then added to the mixture and it was extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulphate, filtered and evaporated to dryness. 8.9 g of raw product was obtained, and was purified by silica gel chromatography (cyclohexane-ethyl acetate 4:1).

Provenance & Evidence