Nitrogen → 1-(5-bromopyridin-2-yl)-N,N-dimethylpiperidin-4-amine

HRID 875954

Reaktionsgleichung

Reaktionsgleichung von HRID 875954
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1.[CH3:9][N:10]([CH3:17])[CH:11]1[CH2:16][CH2:15][NH:14][CH2:13][CH2:12]1.CC(C)([O-])C.[Na+].N#N.[OH-].[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.C1(C)C=CC=CC=1>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([N:14]2[CH2:15][CH2:16][CH:11]([N:10]([CH3:17])[CH3:9])[CH2:12][CH2:13]2)=[N:3][CH:4]=1

Komponenten

9

Edukt 5

HCID 947NitrogenHCID 14798Sodium HydroxideHCID 693532,5-DibromopyridineHCID 417391N,N-Dimethylpiperidin-4-amineHCID 23676156Sodium t-butoxide

Produkt 1

HCID 582995761-(5-bromopyridin-2-yl)-N,N-dimethylpiperidin-4-amineAusbeute 95 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)KatalysatorHCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To a 100 mL single-necked round-bottom flask were placed 2,5-dibromopyridine (2 g, 8 mmol), 4-(dimethylamino)piperidine (1 ml, 8 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.07 g, 0.08 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (0.1 g, 0.2 mmol), and sodium t-butoxide (1 g, 12 mmol). The flask was subjected to 3 cycles of evacuation and back-filling with N2 before toluene (40 mL) was introduced under N2. The resulting mixture was stirred at a preheated oil bath at 100° C. for 40 min. The crude mixture was poured into ice and 4 N NaOH aqueous solution and extracted with ethyl acetate (2×). The combine organics were dried over sodium sulfate and concentrated in vacuo to give 2.7 g crude product. Trituration with ethyl acetate/hexanes gave highly pure 1-(5-bromopyridin-2-yl)-N,N-dimethylpiperidin-4-amine (91) (1.9 g, 95%) 1H NMR (400 MHz, CDCl3) δ 8.18 (1 H, d, J=2.3 Hz), 7.52 (1 H, dd, J=9.0, 2.7 Hz), 6.58 (1 H, d, J=9.0 Hz), 4.30 (2 H, d, J=12.9 Hz), 2.79-2.91 (2 H, m), 2.49 (1 H, br. s.), 2.37 (6 H, s), 1.97 (2 H, d, J=12.5 Hz), 1.45-1.60 (2 H, m) ppm.

Aufarbeitung

  1. customTo a 100 mL single-necked round-bottom flask were placed
  2. additionwas introduced under N2
  3. extractionextracted with ethyl acetate (2×)
  4. dry with materialThe combine organics were dried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customto give 2.7 g crude product

Quellen und Nachweise

ORD-Eintrag
ord-1ac13ee5ba4b463dbe46bd8998cb60ac
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08980903B2

Verknüpfte Notizen

Wird geladen…