Benzaldehyde → HCID 58072522, Verbindung

HRID 1895309Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1895309
[NH2:1][C:2]1[C:7](=[O:8])[CH:6]=[CH:5][N:4]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:18])([F:17])[F:16])[CH:10]=2)[N:3]=1.[CH:19]([CH:21]=O)=O.[CH:23](=O)[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.[NH4+:31].[Cl-].OP(O)(O)=O>CO.O>[C:24]1([C:23]2[N:1]([C:2]3[C:7](=[O:8])[CH:6]=[CH:5][N:4]([C:9]4[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:16])([F:18])[F:17])[CH:10]=4)[N:3]=3)[CH:19]=[CH:21][N:31]=2)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Komponenten

8

Edukt 5

HCID 240BenzaldehydeHCID 1004Phosphoric AcidHCID 7860GlyoxalHCID 25517Ammonium ChlorideHCID 14820794HCID 14820794, Verbindung

Produkt 1

HCID 58072522HCID 58072522, VerbindungAusbeute 3,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

A solution of 3-amino-1-[3-(trifluoromethyl)phenyl]pyridazin-4(1H)-one (200 mg, 0.783 mmol) and glyoxal (40% solution, 0.0895 mL, 0.783 mmol) in MeOH (2 mL) was stirred at room temperature for 20 h. To the solution were added benzaldehyde (0.159 mL, 1.57 mmol) and NH4Cl (84 mg, 1.57 mmol). The mixture was heated to reflux for 90 min. To the mixture was added H3PO4 (0.106 mL). The mixture was heated to reflux for 24 h. The mixture was diluted with water, extracted with AcOEt, washed with NaHCO3 aqueous solution, dried over Na2SO4, filtered, concentrated in vacuo, purified by column chromatography on silica gel (hexane/AcOEt=50/50 to 0/100) and on basic silica gel (hexane/AcOEt=50/50 to 0/100) and recrystallized with AcOEt/heptane to yield the title compound (9.3 mg, 3% yield) as a white solid: mp 204-205° C. 1H NMR (DMSO-d6, 300 MHz): δ ppm 6.82 (1H, d, J=8.0 Hz), 7.20 (1H, d, J=1.6 Hz), 7.33-7.41 (3H, m), 7.44-7.50 (2H, m), 7.62 (1H, s), 7.64-7.81 (4H, m), 9.06 (1H, d, J=8.0 Hz). Anal. Calcd for C20H13F3N4O: C, 62.83; H, 3.43; N, 14.65. Found: C, 62.50; H, 3.64; N, 14.56.

Aufarbeitung

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 90 min
  3. temperatureThe mixture was heated
  4. temperatureto reflux for 24 h
  5. extractionextracted with AcOEt
  6. washwashed with NaHCO3 aqueous solution
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. custompurified by column chromatography on silica gel (hexane/AcOEt=50/50 to 0/100) and on basic silica gel (hexane/AcOEt=50/50 to 0/100)
  11. customrecrystallized with AcOEt/heptane

Quellen und Nachweise

ORD-Eintrag
ord-f0ea20e06ba4402f8a032e80b3412c73
Quelldatensatz
uspto-grants-2013_08
Patentnummer
US08513251B2

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