Methyl cyanoacetate → HCID 14093058, compound

HRID 1381677Notes

Reaction equation

HRID 1381677 reaction equation
[H-].[Na+].[C:3]([CH2:5][C:6]([O:8][CH3:9])=[O:7])#[N:4].[CH3:10][O:11][CH:12]([O:15][CH3:16])[CH2:13]Br.[Na+].[Br-]>CN(C)C=O.C1C=CC=CC=1>[C:3]([CH:5]([CH2:13][CH:12]([O:15][CH3:16])[O:11][CH3:10])[C:6]([O:8][CH3:9])=[O:7])#[N:4]

Participants

7

Reactant 4

HCID 7747Methyl cyanoacetateHCID 24758Sodium hydride2×HCID 816722-Bromo-1,1-dimethoxyethaneHCID 253881Sodium Bromide

Product 1

HCID 14093058HCID 14093058, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent2×HCID 6228DimethylformamideSolvent

Conditions

Temperature
-10 °C

Procedure

A vigorously stirred suspension of sodium hydride (36 g, 1.5 mole) in a mixture of 1400 ml of anhydrous N,N-dimethylformamide and 450 ml of anhydrous benzene was cooled to -10° C. under an argon atmosphere and methyl cyanoacetate (163.5 g, 1.65 mole) dissolved in 150 ml of anhydrous benzene was added dropwise over a period of 60 minutes. The temperature of this solution was allowed to slowly reach the room temperature and further stirred for 60 minutes until all the sodium hydride dissolved. A solution of bromoacetaldehyde dimethyl acetal (228.2 g, 1.35 mole) was added at once and the temperature of the reaction mixture was slowly rised to about 100° C. over a period of 60 minutes and further maintained for additional 120 minutes until the precipitation of all NaBr occurred. The solution was filtered, and the filtrate was concentrated to a small volume by evaporation under vacuum and then partitioned between ether and water. The ether portion was washed with water, dried over anhydrous Na2SO4 which was then removed by filtration, and evaporated to leave a liquid residue. This liquid was distilled at reduced pressure. The fraction distilling at 65°-68° C. and 0.15 Torr was collected yielding 83.2 g (32.9% theory).

Workup

  1. additionwas added dropwise over a period of 60 minutes
  2. customthe room temperature
  3. dissolutiondissolved
  4. filtrationThe solution was filtered
  5. concentrationthe filtrate was concentrated to a small volume by evaporation under vacuum
  6. custompartitioned between ether and water
  7. washThe ether portion was washed with water
  8. dry with materialdried over anhydrous Na2SO4 which
  9. customwas then removed by filtration
  10. customevaporated
  11. customto leave a liquid residue
  12. distillationThis liquid was distilled at reduced pressure
  13. distillationThe fraction distilling at 65°-68° C.
  14. custom0.15 Torr was collected
  15. customyielding 83.2 g (32.9% theory)

Sources & evidence

ORD record
ord-b6fab79c0e16486ca556e346050ec28d
Source dataset
uspto-grants-1989_02
Patent number
US04803284

Reaction notes

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