Pivalic acid → 3-Chloro-10,11-dihydro-5H-benzo(d)naphtho(2,3-b)pyran-8(9H)-one

HRID 590647

Reaktionsgleichung

Reaktionsgleichung von HRID 590647
C(O)(=O)C(C)(C)C.C(=O)([O-])[O-].[K+].[K+].Br[C:15]1[CH:33]=[CH:32][C:31]([Cl:34])=[CH:30][C:16]=1[CH2:17][O:18][C:19]1[CH:28]=[C:27]2[C:22]([CH2:23][CH2:24][CH2:25][C:26]2=[O:29])=[CH:21][CH:20]=1>CC(N(C)C)=O.C([O-])(=O)C(C)(C)C.[Pd+2].C([O-])(=O)C(C)(C)C.FC1C=CC(P(C2C=CC(F)=CC=2)C2C=CC(F)=CC=2)=CC=1>[Cl:34][C:31]1[CH:32]=[CH:33][C:15]2[C:20]3[CH:21]=[C:22]4[CH2:23][CH2:24][CH2:25][C:26](=[O:29])[C:27]4=[CH:28][C:19]=3[O:18][CH2:17][C:16]=2[CH:30]=1

Komponenten

7

Edukt 3

HCID 6417Pivalic acidHCID 11430Potassium CarbonateHCID 696728137-((2-Bromo-5-chlorophenyl)methoxy)-1,2,3,4-tetrahydronaphthalen-1-one

Produkt 1

HCID 696733663-Chloro-10,11-dihydro-5H-benzo(d)naphtho(2,3-b)pyran-8(9H)-oneAusbeute 67 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 140387Tris(4-fluorophenyl)phosphineKatalysatorHCID 24905427palladium(II) pivalateKatalysatorHCID 31374DimethylacetamideLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

To a 1 L flask containing palladium(II) pivalate (1.18 g, 3.8 mmol), tri(4-fluorophenyl)phosphine (1.20 g, 3.8 mmol), pivalic acid (2.33 g, 22.8 mmol) and potassium carbonate (31.8 g, 228 mmol) was added a solution of 7-(2-bromo-5-chlorobenzyloxy)-3,4-dihydronaphthalen-1(2H)-one (27.8 g, 76.2 mmol) in dimethyacetamide (380 mL). The flask was evacuated and backfilled with argon 5 times and then stirred under argon at 60° C. for 24 hours. The reaction was cooled to room temperature and diluted with MTBE and water. The resulting biphasic mixture was stirred for 3 hours and filtered through Celite, rinsing with MTBE. The organic layer of the filtrate was separated and then washed twice with water and once with brine. The organics were then dried with magnesium sulfate, filtered, concentrated and purified by flash column chromatography (Hexanes/DCM) to yield 3-chloro-10,11-dihydro-5H-dibenzo[c,g]chromen-8(9H)-one (14.4 g, 67% yield) as an off-white solid.

Aufarbeitung

  1. customThe flask was evacuated
  2. temperatureThe reaction was cooled to room temperature
  3. additiondiluted with MTBE and water
  4. stirringThe resulting biphasic mixture was stirred for 3 hours
  5. filtrationfiltered through Celite
  6. washrinsing with MTBE
  7. customThe organic layer of the filtrate was separated
  8. washwashed twice with water and once with brine
  9. dry with materialThe organics were then dried with magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. custompurified by flash column chromatography (Hexanes/DCM)

Quellen und Nachweise

ORD-Eintrag
ord-378a72ed2f4340af935a90e193ae548a
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09233974B2

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