3-Fluoro-4-(tributylstannyl)pyridine → 3''-Fluoro-5'-nitro-3,2':3',4''-terpyridin-6'-amine

HRID 2264178

Reaktionsgleichung

Reaktionsgleichung von HRID 2264178
Br[C:2]1[C:3]([C:12]2[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=2)=[N:4][C:5]([NH2:11])=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.[F:18][C:19]1[CH:20]=[N:21][CH:22]=[CH:23][C:24]=1[Sn](CCCC)(CCCC)CCCC>C1(P([Pd-](Cl)P(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I.CN(C)C=O>[F:18][C:19]1[CH:20]=[N:21][CH:22]=[CH:23][C:24]=1[C:2]1[C:3]([C:12]2[CH:13]=[N:14][CH:15]=[CH:16][CH:17]=2)=[N:4][C:5]([NH2:11])=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1

Komponenten

6

Edukt 2

HCID 222736013-Fluoro-4-(tributylstannyl)pyridineHCID 595960023-Bromo-5-nitro-2,3'-bipyridin-6-amine

Produkt 1

HCID 595960063''-Fluoro-5'-nitro-3,2':3',4''-terpyridin-6'-amineAusbeute 51 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178479804HCID 178479804, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

An oven dried resealable Schlenk tube was charged with 3-bromo-5-nitro-2,3′-bipyridin-6-amine (4.51 g, 15.3 mmol), 3-fluoro-4-(tributylstannyl)pyridine (11.8 g, 30.6 mmol) and dimethylformamide (150 mL). The Schienk tube was subjected to three cycles of evacuation-backfilling with argon, and bis(triphenylphosphino)-palladium (II) chloride (1.1 g, 1.53 mmol) and copper (I) iodide (291 mg, 1.53 mmol) were added. After three new cycles of evacuation-backfilling with argon, the Schlenk tube was capped and placed in a 160° C. oil bath. After 3 h, the solvent was evaporated and the crude residue was treated with 2N hydrogen chloride (130 mL) aqueous solution for 45 minutes. The aqueous solution was washed with ethyl acetate and then neutralised with 6N sodium hydroxide aqueous solution. The solution was extracted with ethyl acetate, dried (MgSO4) and evaporated. The residue was purified by silica gel flash chromatography (95:5 dichloromethane/methanol) to give the title compound (2.39 g, 51%) as a solid.

Aufarbeitung

  1. customAn oven dried resealable Schlenk tube
  2. additionwere added
  3. customAfter three new cycles of evacuation-backfilling with argon, the Schlenk tube was capped
  4. customplaced in a 160° C.
  5. customthe solvent was evaporated
  6. additionthe crude residue was treated with 2N hydrogen chloride (130 mL) aqueous solution for 45 minutes
  7. washThe aqueous solution was washed with ethyl acetate
  8. extractionThe solution was extracted with ethyl acetate
  9. dry with materialdried (MgSO4)
  10. customevaporated
  11. customThe residue was purified by silica gel flash chromatography (95:5 dichloromethane/methanol)

Quellen und Nachweise

ORD-Eintrag
ord-da3ea45afe0640649b9e02357679094a
Quelldatensatz
uspto-grants-2010_12
Patentnummer
US07855202B2

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