Triphenylphosphine → N-Trifluoroacetyl-7-methoxy-1-methylene 2,3,4,5-tetrahydro-1H-3-benzazepine

HRID 881913Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 881913
[F:1][C:2]([F:18])([F:17])[C:3]([NH:5][CH2:6][CH2:7][C:8]1[CH:13]=[C:12]([O:14][CH3:15])[CH:11]=[CH:10][C:9]=1I)=[O:4].CC([O-])=O.[K+].[CH:24]1[CH:29]=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=C[CH:25]=1>CN(C)C=O.[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].CC([O-])=O.CC([O-])=O.[Pd+2]>[F:1][C:2]([F:18])([F:17])[C:3]([N:5]1[CH2:29][C:24](=[CH2:25])[C:9]2[CH:10]=[CH:11][C:12]([O:14][CH3:15])=[CH:13][C:8]=2[CH2:7][CH2:6]1)=[O:4]

Komponenten

7

Edukt 3

HCID 11776TriphenylphosphineHCID 517044Potassium AcetateHCID 222927722,2,2-Trifluoro-N-[2-(2-iodo-5-methoxyphenyl)ethyl]acetamide

Produkt 1

HCID 22292788N-Trifluoroacetyl-7-methoxy-1-methylene 2,3,4,5-tetrahydro-1H-3-benzazepineAusbeute 462,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

A solution of N-allyl, N-trifluoroacetyl-2-iodo-5-methoxyphenethylamine (20.5 g, 50 mmol) in dimethylformamide (250 mL) is treated with KOAc (14.6 g, 149 mmol), n-Bu4NBr (16.0 g, 50 mmol), PPh3 (1.3 g, 5.0 mmol), Pd(OAc)2 (0.56 g, 2.5 mmol) and stirred overnight at 90 C. The product mixture was cooled to 20 C, filtered, diluted with water (500 mL) and extracted with ether (3×500 mL). The combined organic phases were washed with water (100 mL), brine (100 mL), dried with Na2SO4 and concentrated. Flash chromatography (10% EtOAc in hexane, silica) resulted in 6.6 g of a yellow oil. 1H NMR (400 MHz, CDCl3) d 7.26 (d, J=8 Hz, 1H), 6.77 (d, J=8 Hz, 1H), 6.66 (s, 1H), 5.34-5.19 (m, 2H), 4.40 (m, 2H), 3.83 (m, 2H), 3.80 (s, 3H), 3.00 (m, 2H). MS calculated for C14H14F3NO2+H: 285, observed: 285.

Aufarbeitung

  1. temperatureThe product mixture was cooled to 20 C
  2. filtrationfiltered
  3. additiondiluted with water (500 mL)
  4. extractionextracted with ether (3×500 mL)
  5. washThe combined organic phases were washed with water (100 mL), brine (100 mL)
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-81dbbd664e934fada42ba81be2709c6f
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08993750B2

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