Methyl acetoacetate → 4-[1-(4-Cyano-benzylamino)-ethylidene]-pent-2-enedioic acid dimethyl ester

HRID 1410904Notes

Reaction equation

HRID 1410904 reaction equation
[C:1]([C:3]1[CH:10]=[CH:9][C:6]([CH2:7][NH2:8])=[CH:5][CH:4]=1)#[N:2].[CH3:11][O:12][C:13](=[O:18])[CH2:14][C:15](=O)[CH3:16].[CH3:19][O:20][C:21](=[O:24])[C:22]#[CH:23]>CO>[CH3:19][O:20][C:21](=[O:24])[CH:22]=[CH:23][C:14](=[C:15]([NH:2][CH2:1][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][CH:4]=1)[CH3:16])[C:13]([O:12][CH3:11])=[O:18]

Participants

5

Reactant 3

HCID 7757Methyl acetoacetateHCID 13536Methyl propiolateHCID 826084-(Aminomethyl)benzonitrile

Product 1

HCID 867141454-[1-(4-Cyano-benzylamino)-ethylidene]-pent-2-enedioic acid dimethyl esterYield 46.9%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of 4-cyanobenzyl amine (3 g, 22.7 mmol) and 3-oxo-butyric acid methyl ester (2.94 mL, 27.2 mmol) in MeOH (80 mL) was refluxed for 2 h. Propynoic acid methyl ester (3.03 mL, 34 mmol) was added, and the resulting mixture was refluxed for 48 h. After cooling to r.t., the solvent was evaporated, and the crude residue was recrystallized from MeOH to give 3.35 g of the title compound as a light yellow solid. 1H NMR (CDCl3, 200 MHz): δ=10.97 (br s, 1H), 7.72 (d, 1H, J=15.4 Hz), 7.67 (d, 2H, J=8.8 Hz), 7.37 (d, 2H, J=8.4 Hz), 6.11 (d, 1H, J=15.8 Hz), 4.63 (d, 2H, J=6.0 Hz), 3.79 (s, 3H), 3.73 (s, 3H), 2.21 (s, 3H).

Workup

  1. temperaturewas refluxed for 2 h
  2. temperaturethe resulting mixture was refluxed for 48 h
  3. customthe solvent was evaporated
  4. customthe crude residue was recrystallized from MeOH

Sources & evidence

ORD record
ord-456fe93080944365a757c9c782ff1d32
Source dataset
uspto-grants-2014_12
Patent number
US08921389B2

Reaction notes

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