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

HRID 400550Notes

Reaction equation

HRID 400550 reaction equation
[C:1](#[N:5])[CH2:2][C:3]#[N:4].CC(C)([O-])C.[K+].Br[C:13]([CH3:19])([CH3:18])[C:14]([O:16][CH3:17])=[O:15]>C1COCC1>[C:3]([CH:2]([C:1]#[N:5])[C:13]([CH3:19])([CH3:18])[C:14]([O:16][CH3:17])=[O:15])#[N:4]

Participants

5

Reactant 3

HCID 8010MalononitrileHCID 90097Methyl 2-bromo-2-methylpropionateHCID 23665647Potassium tert-butoxide

Product 1

HCID 86657403Methyl 3,3-dicyano-2,2-dimethylpropanoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

A 12 liter 3 neck round bottom flask equipped with a mechanical stirrer, thermometer, condenser and nitrogen bubbler, was charged with malononitrile (251 g, 3.802 moles) and THF (2 liters). Potassium t-butoxide (1M THF, 3.802 L, 3.802 moles) was then added. The mixture was stirred at 50° C. for 30 min. Methyl 2-bromoisobutyrate (688 g, 3.80 moles) was added and the reaction mixture was stirred overnight at 50° C. The reaction was partitioned between aqueous 1N HCl and EtOAc. The organic phase was washed with brine, dried over MgSO4, filtered and concentrated to give the indicated product. 1H NMR (400 MHz, CD3CN): δ 4.35 (s, 1H); 3.73 (s, 3H); 1.43 (s, 6H).

Workup

  1. stirringthe reaction mixture was stirred overnight at 50° C
  2. customThe reaction was partitioned between aqueous 1N HCl and EtOAc
  3. washThe organic phase was washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give the indicated product

Sources & evidence

ORD record
ord-4c3d11e499284575b969bb24664310e1
Source dataset
uspto-grants-2014_06
Patent number
US08741910B2

Reaction notes

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