Diethyl (ethoxymethylene)malonate → Diethyl [(4-cyanoanilino)methylidene]propanedioate

HRID 131538Notes

Reaction equation

HRID 131538 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[CH2:10]([O:12][C:13](=[O:24])[C:14](=[CH:20]OCC)[C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH3:11].CCCCCC>C1(C)C=CC=CC=1>[C:6]([C:5]1[CH:8]=[CH:9][C:2]([NH:1][CH:20]=[C:14]([C:13]([O:12][CH2:10][CH3:11])=[O:24])[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:3][CH:4]=1)#[N:7]

Participants

5

Reactant 3

HCID 6871Diethyl (ethoxymethylene)malonateHCID 8058HexaneHCID 133964-Aminobenzonitrile

Product 1

HCID 1989756Diethyl [(4-cyanoanilino)methylidene]propanedioateYield 87.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To 5.00 g (42.3 mmol) 4-aminobenzonitrile (Aldrich, 98%) was added 10.1 g (9.41 mL, 46.6 mmol, 1.1 eq) diethylethoxymethylenemalonate (Aldrich, 99%), and the mixture was dissolved in 50 mL toluene (HPLC grade). The solution was refluxed for four hours with a condenser open to the air. The solution was then poured into 200 mL hexane, and the resulting white precipitate was filtered and washed well with more hexane to yield 10.62 g (37.0 mmol, 85% yield) of the title compound as a slightly off-white solid (per LC/MS and 1H NMR). LC [MH+] 289, 97% purity.

Workup

  1. temperatureThe solution was refluxed for four hours with a condenser open to the air
  2. filtrationthe resulting white precipitate was filtered
  3. washwashed well with more hexane

Sources & evidence

ORD record
ord-a01912361e5f4606bd51e7ec1b3163bc
Source dataset
uspto-grants-2008_06
Patent number
US07384958B2

Reaction notes

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