Potassium Carbonate → 1-[3-(6-tert-Butyl-1-oxo-1H-phthalazin-2-yl)-2-formyl-phenyl]-3-(trityl-amino)-1H-pyrazole-4-carbonitril

HRID 1025649

Reaktionsgleichung

Reaktionsgleichung von HRID 1025649
[C:1]([NH:20][C:21]1[NH:25][N:24]=[CH:23][C:22]=1[C:26]#[N:27])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[C:29]1[CH:36]=[CH:35][CH:34]=[C:33]([N:37]2[N:46]=[CH:45][C:44]3[C:39](=[CH:40][CH:41]=[C:42]([C:47]([CH3:50])([CH3:49])[CH3:48])[CH:43]=3)[C:38]2=[O:51])[C:30]=1[CH:31]=[O:32].C(=O)([O-])[O-].[K+].[K+]>[Cu]I>[C:47]([C:42]1[CH:43]=[C:44]2[C:39](=[CH:40][CH:41]=1)[C:38](=[O:51])[N:37]([C:33]1[C:30]([CH:31]=[O:32])=[C:29]([N:24]3[CH:23]=[C:22]([C:26]#[N:27])[C:21]([NH:20][C:1]([C:2]4[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=4)([C:14]4[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=4)[C:8]4[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=4)=[N:25]3)[CH:36]=[CH:35][CH:34]=1)[N:46]=[CH:45]2)([CH3:50])([CH3:48])[CH3:49]

Komponenten

5

Edukt 3

HCID 11430Potassium CarbonateHCID 580161852-bromo-6-(6-tert-butyl-1-oxophthalazin-2(1H)-yl)benzaldehydeHCID 71008230HCID 71008230, Verbindung

Produkt 1

HCID 866737261-[3-(6-tert-Butyl-1-oxo-1H-phthalazin-2-yl)-2-formyl-phenyl]-3-(trityl-amino)-1H-pyrazole-4-carbonitrilAusbeute 37,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Katalysator

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To degassed DMF (1.5 mL) were added 5-(tritylamino)-1H-pyrazole-4-carbonitrile (1.36 g, 3.89 mmol), 2-bromo-6-(6-tert-butyl-1-oxophthalazin-2(1H)-yl)benzaldehyde (1.0 g, 2.6 mmol), copper (I) iodide (494 mg, 2.6 mmol) and potassium carbonate (717 mg, 5.19 mmol). The reaction was inerted five times by alternating vacuum and a nitrogen purge and then heat to 100° C. (external); for 8 hr. TLC the following morning showed trace amounts of starting materials. The reaction was diluted with EtOAc (50 mL) and through a pad of diatomaceous earth. The pad was rinsed with additional EtOAc (50 mL) and concentrated in vacuo. The crude material was bound to silica column and purified over a 40 g silica gel cartridge, eluting the column with a 20-40% EtOAc/hexanes, isocratic hold for 5 minutes, then 40-100% EtOAc/hexanes gradient over 20 minutes. The product containing fractions were combined and concentrated to give 1-[3-(6-tert-Butyl-1-oxo-1H-phthalazin-2-yl)-2-formyl-phenyl]-3-(trityl-amino)-1H-pyrazole-4-carbonitril (632 mg, 37%).

Aufarbeitung

  1. customTo degassed DMF (1.5 mL)
  2. customa nitrogen purge
  3. additionThe reaction was diluted with EtOAc (50 mL) and through a pad of diatomaceous earth
  4. washThe pad was rinsed with additional EtOAc (50 mL)
  5. concentrationconcentrated in vacuo
  6. custompurified over a 40 g silica gel cartridge
  7. washeluting the column with a 20-40% EtOAc/hexanes, isocratic hold for 5 minutes
  8. wait40-100% EtOAc/hexanes gradient over 20 minutes
  9. additionThe product containing fractions
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-864d8dbd2beb44888627c26337e3c091
Quelldatensatz
uspto-grants-2014_05
Patentnummer
US08729078B2

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