2-Amino-4-(trifluoromethyl)pyridine → 6-bromo-4-methyl-N-[4-(trifluoromethyl)pyridine-2-yl]pyridine-2-amine

HRID 595172Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 595172
CC(C)([O-])C.[Na+].Br[C:8]1[CH:13]=[C:12]([CH3:14])[CH:11]=[C:10]([Br:15])[N:9]=1.[NH2:16][C:17]1[CH:22]=[C:21]([C:23]([F:26])([F:25])[F:24])[CH:20]=[CH:19][N:18]=1>>[Br:15][C:10]1[N:9]=[C:8]([NH:16][C:17]2[CH:22]=[C:21]([C:23]([F:25])([F:24])[F:26])[CH:20]=[CH:19][N:18]=2)[CH:13]=[C:12]([CH3:14])[CH:11]=1

Komponenten

4

Edukt 3

HCID 27783152-Amino-4-(trifluoromethyl)pyridineHCID 112881742,6-Dibromo-4-methylpyridineHCID 23676156Sodium t-butoxide

Produkt 1

HCID 866807956-bromo-4-methyl-N-[4-(trifluoromethyl)pyridine-2-yl]pyridine-2-amine

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

Sodium tert-butoxide (5.87 g, 61.1 mmol) and 1,1′-bis(di-tert-butylphsophino)ferrocene palladium dichloride (0.91 g, 1.4 mmol) were added to a solution of 2,6-dibromo-4-methyl pyridine (13.9 g, 55.5 mmol) and 2-amino-4-trifluoromethyl pyridine (9.0 g, 55.5 mmol) in nitrogen sparged dioxane (180 mL). The slurry was evacuated and refilled with nitrogen. The mixture was stirred at 25° C. for 15 minutes and then heated to 75° C. for 12 hours. The reaction mixture was cooled to 25° C., water (20 mL) was added, and the mixture was extracted with EtOAc (2×200 mL). The combined extracts were dried over sodium sulfate, filtered, concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to afford 6-bromo-4-methyl-N-[4-(trifluoromethyl)pyridine-2-yl]pyridine-2-amine as a white solid. MS ESI calc'd. for C12H10BrF3N3 [M+H]+ 332 and 334. found 332 and 334. 1H NMR (600 MHz, DMSO-d6) δ 10.40 (s, 1H), 8.46 (d, J=6.0 Hz, 1H), 7.90 (s, 1H), 7.60 (s, 1H), 7.18 (d, J=6.0 Hz, 1H), 7.00 (s, 1H), 2.25 (s, 3H).

Aufarbeitung

  1. customsparged dioxane (180 mL)
  2. customThe slurry was evacuated
  3. additionrefilled with nitrogen
  4. temperatureheated to 75° C. for 12 hours
  5. temperatureThe reaction mixture was cooled to 25° C.
  6. additionwater (20 mL) was added
  7. extractionthe mixture was extracted with EtOAc (2×200 mL)
  8. dry with materialThe combined extracts were dried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was purified by column chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-092a7482ce334b2f9c4d618472d06695
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09242984B2

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