Potassium Carbonate → 4-Chloro-2-{6-oxo-8-thia-5-azatricyclo[7.4.0.02,7]trideca-1(9),2(7)-dien-5-yl}pyridine-3-carbaldehyde

HRID 1021803

Reaktionsgleichung

Reaktionsgleichung von HRID 1021803
Br[C:2]1[N:9]=[CH:8][CH:7]=[C:6]([Cl:10])[C:3]=1[CH:4]=[O:5].[C:11]1(=[O:24])[C:16]2[S:17][C:18]3[CH2:23][CH2:22][CH2:21][CH2:20][C:19]=3[C:15]=2[CH2:14][CH2:13][NH:12]1.C([O-])([O-])=O.[K+].[K+].COC1C2C(=C3C(=CC=2)C(OC)=CC=N3)N=CC=1>[Cu]I.O1CCOCC1>[Cl:10][C:6]1[CH:7]=[CH:8][N:9]=[C:2]([N:12]2[C:11](=[O:24])[C:16]3[S:17][C:18]4[CH2:23][CH2:22][CH2:21][CH2:20][C:19]=4[C:15]=3[CH2:14][CH2:13]2)[C:3]=1[CH:4]=[O:5]

Komponenten

7

Edukt 4

HCID 11430Potassium CarbonateHCID 104622984,7-Dimethoxy-1,10-phenanthrolineHCID 208997543,4,5,6,7,8-Hexahydrobenzo[4,5]thieno[2,3-c]pyridin-1(2H)-oneHCID 866839142-Bromo-4-chloropyridine-3-carbaldehyde

Produkt 1

HCID 866842984-Chloro-2-{6-oxo-8-thia-5-azatricyclo[7.4.0.02,7]trideca-1(9),2(7)-dien-5-yl}pyridine-3-carbaldehydeAusbeute 17 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
95 °C

Versuchsvorschrift

A 100-mL single-neck round-bottomed flask equipped with a reflux condenser was charged with 2-bromo-4-chloronicotinaldehyde 103a (1276 mg, 5.80 mmol), 8-thia-5-azatricyclo[7.4.0.02,7}]trideca-1(9),2(7)-dien-6-one 105e (600 mg, 2.90 mmol), CuI (551 mg, 2.90 mmol), K2CO3 (800 mg, 5.80 mmol), 4,7-dimethoxy-1,10-phenanthroline (696 mg, 2.90 mmol), and dioxane (20 mL). After bubbling nitrogen through the resulting solution for 10 min, the mixture was stirred at 95° C. for 16 h. It was then cooled to room temperature and filtered. To the residue was added water (20 mL). The aqueous layer was separated and extracted with ethyl acetate (3×20 mL). The combined organic layer was washed with brine (50 mL) and dried over sodium sulfate. The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by silica-gel column chromatography eluting with 10:1 petroleum ether/ethyl acetate to afford 169a (171 mg, 17%). LCMS-ESI: [M+H]+ 347

Aufarbeitung

  1. customA 100-mL single-neck round-bottomed flask equipped with a reflux condenser
  2. customAfter bubbling nitrogen through the resulting solution for 10 min
  3. temperatureIt was then cooled to room temperature
  4. filtrationfiltered
  5. additionTo the residue was added water (20 mL)
  6. customThe aqueous layer was separated
  7. extractionextracted with ethyl acetate (3×20 mL)
  8. washThe combined organic layer was washed with brine (50 mL)
  9. dry with materialdried over sodium sulfate
  10. customThe drying agent was removed by filtration
  11. concentrationthe filtrate was concentrated under reduced pressure
  12. customThe residue was purified by silica-gel column chromatography
  13. washeluting with 10:1 petroleum ether/ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-92493339f0274bcbbf7f570c7a0f7ee5
Quelldatensatz
uspto-grants-2014_05
Patentnummer
US08716274B2

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