Acetic Acid → Dimethyl 3-(cyanomethylidene)pentanedioate

HRID 552323Notes

Reaction equation

HRID 552323 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5](=O)[CH2:6][C:7]([O:9][CH3:10])=[O:8].[C:13]([CH2:15]C(O)=O)#[N:14].C(O)(=O)C>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5](=[CH:15][C:13]#[N:14])[CH2:6][C:7]([O:9][CH3:10])=[O:8]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 9740Cyanoacetic acidHCID 74591Dimethyl 3-oxoglutarate

Product 1

HCID 254955Dimethyl 3-(cyanomethylidene)pentanedioateYield 68.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 3-oxo-pentanedioic acid dimethyl ester (523 g) in toluene (750 mL), cyanoacetic acid (511 g), NH4OAc (46.3 g) and acetic acid (90.1 g) were added and heated at reflux with dehydrating by Dean-Stark apparatus for 8 h. After cooling to room temperature, the reaction mixture was washed with water, saturated aqueous NaHCO3 solution and brine. The organic phase was dried over MgSO4, filtered, and concentrated under reduced pressure to give crude 3-cyanomethylene-pentanedioic acid dimethyl ester (403 g) as an oil. 1H NMR (200 MHz, CDCl3) δ ppm 3.39 (d, J=0.88 Hz, 2 H), 3.62 (s, 2 H), 3.72 (s, 3 H), 3.74 (s, 3 H), 5.51 (s, 1 H).

Workup

  1. temperatureheated
  2. temperatureat reflux with dehydrating by Dean-Stark apparatus for 8 h
  3. washthe reaction mixture was washed with water, saturated aqueous NaHCO3 solution and brine
  4. dry with materialThe organic phase was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-8707aa4769d24718a1ef1f2b54279d00
Source dataset
uspto-grants-2011_05
Patent number
US07951811B2

Reaction notes

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