Binap, (A+-)- → 8-Bromo-3,4-dihydro-2H-1,4-benzoxazine

HRID 388289Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 388289
C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+].[Br:53][C:54]1[CH:63]=[CH:62][CH:61]=[C:60](Br)[C:55]=1[O:56][CH2:57][CH2:58][NH2:59]>C1(C)C=CC=CC=1.C(OCC)(=O)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Br:53][C:54]1[C:55]2[O:56][CH2:57][CH2:58][NH:59][C:60]=2[CH:61]=[CH:62][CH:63]=1

Komponenten

7

Edukt 3

HCID 634876Binap, (A+-)-HCID 225572812-(2,6-Dibromo-phenoxy)ethylamineHCID 23676156Sodium t-butoxide

Produkt 1

HCID 162444528-Bromo-3,4-dihydro-2H-1,4-benzoxazineAusbeute 48 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
95 °C

Versuchsvorschrift

A three neck flask was charge with tris(dibenzylideneacetone)dipalladium(0) (0.37 g, 0.0004 mol, 2 mol % Pd), (±) racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.64 g, 0.001 mol, 5 mol % Pd), and sodium tert-butoxide (2.7 g, 0.028 mol) and flushed with nitrogen. A solution of 2-(2,6-dibromo-phenoxy)ethylamine (6 g, 0.02 mol) in toluene (50 mL) was added. The mixture was heated to 95° C. and was stirred for 12 h. The mixture was cooled to room temperature, taken up in ethyl acetate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (eluting with hexane-ethyl acetate; 7:3, v/v) to give 8-bromo-3,4-dihydro-2H-benzo[1,4]oxazine as an oil (275 mg, 48%). The hydrochloride salt was prepared from ethanol-hydrogen chloride. MS: MH+=214. M.p. 184.1-195.4° C.

Aufarbeitung

  1. customflushed with nitrogen
  2. temperatureThe mixture was cooled to room temperature
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe crude material was purified by flash chromatography on silica gel (
  6. washeluting with hexane-ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-ac46deb7121a448ba19a56a280184319
Quelldatensatz
uspto-grants-2013_02
Patentnummer
US08377931B2

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