Benzaldehyde → HCID 58072522, compound

HRID 1624776Notes

Reaction equation

HRID 1624776 reaction equation
[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

Participants

8

Reactant 5

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

Product 1

HCID 58072522HCID 58072522, compoundYield 3.1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-d12003282de342a4852784ee9ee5d603
Source dataset
uspto-grants-2014_07
Patent number
US08778944B2

Reaction notes

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