Water → tert-Butyl 3,3-dicyanopropanoate

HRID 2116669Notes

Reaction equation

HRID 2116669 reaction equation
[C:1](#[N:5])[CH2:2][C:3]#[N:4].C(=O)([O-])[O-].[K+].[K+].Br[CH2:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15].O>CN(C)C=O.C(OCC)(=O)C.CCCCCC>[C:17]([O:16][C:14]([CH2:13][CH:2]([C:1]#[N:5])[C:3]#[N:4])=[O:15])([CH3:20])([CH3:19])[CH3:18]

Participants

8

Reactant 4

HCID 962WaterHCID 8010MalononitrileHCID 11430Potassium CarbonateHCID 79177tert-Butyl bromoacetate

Product 1

HCID 58586409tert-Butyl 3,3-dicyanopropanoateYield 33.9%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

13.2 g of malononitrile was dissolved in 50 ml of N,N-dimethylformamide and 28 g of potassium carbonate was added thereto, followed by stirring for 1 hour at room temperature. To the solution was added 19.6 g of tert-butyl bromoacetate at about 0° C. and stirred for 15 minutes at the same temperature and for additional 4 hours at room temperature. Then, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed successively with water and saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To the residue obtained was added about 50 ml of mixed solution of hexane and ethyl acetate (hexane/ethyl acetate=3/1) and filtered. The residue obtained by concentrating the filtrate under reduced pressure was subjected to silica gel column chromatography to give 6.13 g of 2-(tert-butoxycarbonylmethyl)malononitrile.

Workup

  1. stirringstirred for 15 minutes at the same temperature and for additional 4 hours at room temperature
  2. extractionextracted with ethyl acetate
  3. washThe organic layer was washed successively with water and saturated brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customTo the residue obtained
  7. filtrationfiltered
  8. customThe residue obtained
  9. concentrationby concentrating the filtrate under reduced pressure

Sources & evidence

ORD record
ord-dd9ca469ec6c49d5a10c2605107d8f78
Source dataset
uspto-grants-2008_10
Patent number
US07439266B2

Reaction notes

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