Di(pyridin-3-yl)methanamine → 2-(2,3-dihydro-4H-1,4-benzoxazin-4-yl)-N-(dipyridin-3-ylmethyl)pyridine-3-amine

HRID 1661132

Reaktionsgleichung

Reaktionsgleichung von HRID 1661132
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH:7]([NH2:14])[C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[CH:2]=1.Cl[C:16]1[C:17]([N:22]2[C:27]3[CH:28]=[CH:29][CH:30]=[CH:31][C:26]=3[O:25][CH2:24][CH2:23]2)=[N:18][CH:19]=[CH:20][CH:21]=1.CC(C)([O-])C.[Na+]>O1CCOCC1.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[O:25]1[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=2[N:22]([C:17]2[C:16]([NH:14][CH:7]([C:8]3[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=3)[C:3]3[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=3)=[CH:21][CH:20]=[CH:19][N:18]=2)[CH2:23][CH2:24]1

Komponenten

6

Edukt 3

HCID 12294459Di(pyridin-3-yl)methanamineHCID 23676156Sodium t-butoxideHCID 576132544-(3-chloropyridin-2-yl)-3,4-dihydro-2H-1,4-benzoxazine

Produkt 1

HCID 166780742-(2,3-dihydro-4H-1,4-benzoxazin-4-yl)-N-(dipyridin-3-ylmethyl)pyridine-3-amine

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418851HCID 178418851, VerbindungKatalysatorHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a solution of (dipyridin-3-ylmethyl)amine (139 mg, 0.75 mmol) (prepared according to the procedure in German patent DE 2447258 (1976)) and 4-(3-chloropyridin-2-yl)-3,4-dihydro-2H-1,4-benzoxazine (183 mg, 0.75 mmol) in dry dioxane (1.5 mL) was added sodium t-butoxide (91 mg, 0.95 mmol), bis(tri-t-butylphosphine)palladium(0) (30 mg, 0.058 mmol). The vessel was sealed with a septum cap, degassed (3×), and heated at 100 C for 8 hours. The reaction was cooled and diluted with methylene chloride and washed with NaHCO3 solution. The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent evaporated. The residue was purified by chromatography on silica gel eluting with a 20-90% acetone/hexane gradient to the title compound as a clear glass. 1H-NMR (500 MHz, CDCl3): δ 8.60 (2H, s), 8.56 (2H, d, J=4.4 Hz), 7.91 (1H, d, J=4.6 Hz), 7.54 (1H, d, J=7.8 Hz), 7.26 (1H, t, J=7.5 Hz), 6.97 (1H, dd, J=4.6, 7.8 Hz), 6.87 (1H, d, J=7.8 Hz), 6.77-6.81 (3H, m), 6.37 (1H, d, J=7.6 Hz); 5.57 (1H, d, J=4.4 Hz), 4.77 (1H, d, J=4.1 Hz), 4.40 (2H, t, J=4.4 Hz), 3.76 (2H, br s). m/e (m+1): 396.2

Aufarbeitung

  1. customThe vessel was sealed with a septum
  2. customcap
  3. customdegassed (3×)
  4. temperatureheated at 100 C for 8 hours
  5. temperatureThe reaction was cooled
  6. additiondiluted with methylene chloride
  7. washwashed with NaHCO3 solution
  8. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. customthe solvent evaporated
  11. customThe residue was purified by chromatography on silica gel eluting with a 20-90% acetone/hexane gradient to the title compound as a clear glass

Quellen und Nachweise

ORD-Eintrag
ord-915157c76ee44502a2b465a651cd249c
Quelldatensatz
uspto-grants-2011_10
Patentnummer
US08030332B2

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