Triethylamine → Tert-butyl 3-(3-amino-2-methylphenyl)propanoate

HRID 877168Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 877168
[C:1]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])(=[O:4])[CH:2]=[CH2:3].Br[C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([N+:17]([O-])=O)[C:12]=1[CH3:20].C(N(CC)CC)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[Cl-].[NH4+]>CN(C=O)C.C(O)C.[Pd].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:17][C:13]1[C:12]([CH3:20])=[C:11]([CH2:3][CH2:2][C:1]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4])[CH:16]=[CH:15][CH:14]=1

Komponenten

10

Edukt 5

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 25517Ammonium ChlorideHCID 80271Tri-o-tolylphosphineHCID 1235372-Bromo-6-nitrotoluene

Produkt 1

HCID 58136633Tert-butyl 3-(3-amino-2-methylphenyl)propanoate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 23938PalladiumKatalysatorHCID 167845palladium(II) acetateKatalysatorHCID 702EthanolLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
125 °C

Versuchsvorschrift

Under argon, 201 ml (1.39 mol) of tert-butyl prop-2-enoate were added dropwise to a solution of 100 g (463 mmol) of 1-bromo-2-methyl-3-nitrobenzene, 322 ml (2.31 mol) of triethylamine, 28.18 g (92.58 mmol) of tri-2-tolylphosphine and 10.39 g (46.29 mmol) of palladium(II) acetate in 2 liters of DMF, and the mixture was then stirred at 125° C. for 36 h. After cooling to room temperature, the reaction mixture was stirred with saturated aqueous ammonium chloride solution and the organic phase was separated off. The aqueous phase was extracted three times with tert-butyl methyl ether, and the combined organic phases were washed with saturated sodium chloride solution and dried over sodium sulfate. After filtration, the solvent was removed to dryness under reduced pressure. The residue obtained was purified by flash chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 9:1). This gave 89 g (338 mmol, 73% of theory) of the intermediate tert-butyl(2E)-3-(2-methyl-3-nitrophenyl)prop-2-enoate as a colorless solid. 88 g (334 mmol) of this solid were dissolved in 2 liters of ethanol, 7 g of palladium on carbon (10%) were added at room temperature and the mixture was hydrogenated at atmosperic pressure for 18 h. After the reaction had gone to completion, the reaction solution was filtered through kieselguhr and the filtrate obtained was concentrated under reduced pressure. This gave 61.3 g (260.5 mmol, 78% of theory) of the title compound as a colorless solid.

Aufarbeitung

  1. temperatureAfter cooling to room temperature
  2. customthe organic phase was separated off
  3. extractionThe aqueous phase was extracted three times with tert-butyl methyl ether
  4. washthe combined organic phases were washed with saturated sodium chloride solution
  5. dry with materialdried over sodium sulfate
  6. filtrationAfter filtration
  7. customthe solvent was removed to dryness under reduced pressure
  8. customThe residue obtained
  9. customwas purified by flash chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 9:1)
  10. waitthe mixture was hydrogenated at atmosperic pressure for 18 h
  11. filtrationthe reaction solution was filtered through kieselguhr
  12. customthe filtrate obtained
  13. concentrationwas concentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-6c15cb623fa54d7b9f2a18e94aa93033
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08987256B2

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