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

HRID 1410904Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1410904
[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]

Komponenten

5

Edukt 3

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

Produkt 1

HCID 867141454-[1-(4-Cyano-benzylamino)-ethylidene]-pent-2-enedioic acid dimethyl esterAusbeute 46,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-456fe93080944365a757c9c782ff1d32
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08921389B2

Notizen zur Reaktion

Wird geladen…