Hydrochloric Acid → (E)-N,N-diisopropyl-3-(2-methoxy-5-methoxycarbonylphenyl)acrylamide

HRID 1015581

Reaktionsgleichung

Reaktionsgleichung von HRID 1015581
CN(C)CC(O)=O.C([O-])(=O)C.[Na+].Br[C:14]1[CH:15]=[C:16]([CH:21]=[CH:22][C:23]=1[O:24][CH3:25])[C:17]([O:19][CH3:20])=[O:18].[CH:26]([N:29]([CH:34]([CH3:36])[CH3:35])[C:30](=[O:33])[CH:31]=[CH2:32])([CH3:28])[CH3:27].Cl>ClCCl.CN1CCCC1=O>[CH:34]([N:29]([CH:26]([CH3:28])[CH3:27])[C:30](=[O:33])/[CH:31]=[CH:32]/[C:14]1[CH:15]=[C:16]([C:17]([O:19][CH3:20])=[O:18])[CH:21]=[CH:22][C:23]=1[O:24][CH3:25])([CH3:36])[CH3:35]

Komponenten

8

Edukt 5

HCID 313Hydrochloric AcidHCID 673N,N-DimethylglycineHCID 517045Sodium AcetateHCID 559397N,N-Diisopropylacrylamide2×HCID 611662Methyl 3-bromo-4-methoxybenzoate2×

Produkt 1

HCID 22735209(E)-N,N-diisopropyl-3-(2-methoxy-5-methoxycarbonylphenyl)acrylamideAusbeute 69 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6344DichloromethaneLösungsmittelHCID 13387N-methyl-2-pyrrolidoneLösungsmittel

Reaktionsbedingungen

Temperatur
130 °C

Versuchsvorschrift

A stirred suspension consisting of N,N-dimethylglycine (6.0 mmol), anhydrous sodium acetate (40 mmol), methyl 3-bromo-4-methoxybenzoate (20 mmol, 4.90 g), N,N-diisopropylacrylamide (24 mmol, 3.72 g), bis-(benzonitrile)-palladium-II chloride (1.5 mol %), and 20 ml of N-methyl-2-pyrrolidinone was heated at 130° C. until no starting material could be detected by tlc (starting material methyl 3-bromo-4-methoxybenzoate: Rf 0.73; N,N-diisopropylacrylamide: Rf 0.46; solvent system (1)). After cooling to room temperature 50 ml of an aqueous 2N HCl solution was added. The reaction was diluted with dichloromethane (50 ml) and the precipitated grey palladium metal was filtered off. The organic phase was washed with five portions (50 ml each) of 2N aqueous hydrochloric acid, dried (MgSO4) and evaporated to dryness. The remaining off-white solid was recrystallized from ethyl acetate/n-hexane to give 4.40 g (E)-N,N-diisopropyl-3-(2-methoxy-5-methoxycarbonylphenyl)-acrylamide in 69% yield, m.p. 139-140° C., tlc: (1) Rf 0.40. NMR (CD2Cl2): 21.22, 22.10, 46.39, 48.87, 52.59, 56.61, 111.42, 123.39, 123.78, 125.54, 130.32, 132.53, 135.07.

Aufarbeitung

  1. additionwas added
  2. filtrationthe precipitated grey palladium metal was filtered off
  3. washThe organic phase was washed with five portions (50 ml each) of 2N aqueous hydrochloric acid
  4. dry with materialdried (MgSO4)
  5. customevaporated to dryness
  6. customThe remaining off-white solid was recrystallized from ethyl acetate/n-hexane

Quellen und Nachweise

ORD-Eintrag
ord-528457fe00d246eb82c96992a39f7a79
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07985772B2

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