Ethyl Acetate → 2,3-Dihydro-5-(5-methylthiazol-2-yl)inden-1-one

HRID 1913408Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1913408
Cl[C:2]1[S:3][C:4]([CH3:7])=[CH:5][N:6]=1.CC1(C)C(C)(C)OB([C:16]2[CH:17]=[C:18]3[C:22](=[CH:23][CH:24]=2)[C:21](=[O:25])[CH2:20][CH2:19]3)O1.C(=O)([O-])[O-].[Na+].[Na+].C(OCC)(=O)C>O1CCOCC1.O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[CH3:7][C:4]1[S:3][C:2]([C:16]2[CH:17]=[C:18]3[C:22](=[CH:23][CH:24]=2)[C:21](=[O:25])[CH2:20][CH2:19]3)=[N:6][CH:5]=1

Komponenten

8

Edukt 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 109970832-Chloro-5-methyl-1,3-thiazoleHCID 185417105-(tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3-dihydro-1H-inden-1-one

Produkt 1

HCID 584385052,3-Dihydro-5-(5-methylthiazol-2-yl)inden-1-oneAusbeute 35,5 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

In a 200 mL flask, a mixture of 2-chloro-5-methylthiazole (1.00 g, 7.48 mmol), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)indan-1-one (SM-1a, 1.93 g, 7.48 mmol) and sodium carbonate (3.18 g, 30 mmol) was dissolved in 68 mL dioxane and 6.8 mL water. The solution was degassed for 15 minutes with nitrogen. Palladium tetrakis(triphenylphosphine) (174 mg, 0.15 mmol) was added and the solution was degassed for an additional 15 minutes. The reaction was heated under reflux for 16 hours. After cooling, the mixture was concentrated to dryness and the residue partitioned between ethyl acetate and water. The water layer was extracted once with ethyl acetate. The combined organic layers were washed twice with water, once with brine, and were dried over anhydrous sodium sulfate. Evaporation afforded the crude product as an orange solid (1.96 g). The material was suspended in a minimal amount of ethyl acetate and was stirred at room temperature for 16 hours. The resulting solid was filtered off and dried to afford the title compound as a brown solid (609 mg, 35%). MS (ES+) 230.2 (M+H+). 1H NMR (CDCl3) δ 2.53 (s, 3H), 2.71-2.75 (m, 2H), 3.18 (t, 2H), 7.56-7.57 (m, 1H), 7.76-7.79 (m, 1H), 7.85-7.89 (m, 1H), 8.02 (br S, 1H).

Aufarbeitung

  1. customThe solution was degassed for 15 minutes with nitrogen
  2. customthe solution was degassed for an additional 15 minutes
  3. temperatureThe reaction was heated
  4. temperatureunder reflux for 16 hours
  5. temperatureAfter cooling
  6. concentrationthe mixture was concentrated to dryness
  7. customthe residue partitioned between ethyl acetate and water
  8. extractionThe water layer was extracted once with ethyl acetate
  9. washThe combined organic layers were washed twice with water, once with brine
  10. dry with materialwere dried over anhydrous sodium sulfate
  11. customEvaporation
  12. customafforded the crude product as an orange solid (1.96 g)
  13. filtrationThe resulting solid was filtered off
  14. customdried

Quellen und Nachweise

ORD-Eintrag
ord-15c0fa32b0d14a639f3af9f0472c6d87
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08609680B2

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