Methyl cyanoacetate → methyl 2-cyano-2-(2-nitrophenyl)acetate

HRID 1710052Notes

Reaction equation

HRID 1710052 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH3:7])=[O:5])#[N:2].[H-].[Na+].F[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[N+:17]([O-:19])=[O:18]>CN(C)C=O.[Cl-].[Na+].O>[N+:17]([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=1[CH:3]([C:1]#[N:2])[C:4]([O:6][CH3:7])=[O:5])([O-:19])=[O:18]

Participants

6

Reactant 3

HCID 7747Methyl cyanoacetateHCID 24758Sodium hydrideHCID 738951-Fluoro-2-nitrobenzene

Product 1

HCID 2779220methyl 2-cyano-2-(2-nitrophenyl)acetateYield 97%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent3×HCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of methyl cyanoacetate (24.75 g; 0.25M) in dimethylformamide (70 ml) was added dropwise over 40 minutes to a stirred suspension of sodium hydride (8.25 g; 0.275M) in dimethylformamide (250 ml) at 0° under nitrogen atmosphere. The solution was stirred for 0.5 h, then a solution of 2-fluoronitrobenzene (17.65 g; 0.125M) in dimethylformamide (70 ml) added. After stirring for 16 h at room temperature, the red solution was poured onto excess brine, and extracted with ether (×6). The aqueous layer was then acidified with hydrochloric acid (5M) until the red colour was discharged. The resultant solution was extracted with ether (×4) and the combined organic extracts washed with brine, dried and evaporated to afford the title compound as a yellow oil (26.7 g; 97%) which slowly solidified.

Workup

  1. stirringAfter stirring for 16 h at room temperature
  2. extractionextracted with ether (×6)
  3. extractionThe resultant solution was extracted with ether (×4)
  4. washthe combined organic extracts washed with brine
  5. customdried
  6. customevaporated

Sources & evidence

ORD record
ord-b0b9b4a8aac74804aa5fea95182af6e3
Source dataset
uspto-grants-1990_08
Patent number
US04952584

Reaction notes

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