Potassium Carbonate → HCID 58072330, compound

HRID 2089974Notes

Reaction equation

HRID 2089974 reaction equation
Br[C:2]1[C:7](=[O:8])[C:6]([O:9][CH3:10])=[CH:5][N:4]([C:11]2[C:21]([F:22])=[CH:20][C:14]3[O:15][C:16]([F:19])([F:18])[O:17][C:13]=3[CH:12]=2)[N:3]=1.[C:23]1([N:29]2[C:33](B3OC(C)(C)C(C)(C)O3)=[CH:32][CH:31]=[N:30]2)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.C([O-])([O-])=O.[K+].[K+]>C1(C)C=CC=CC=1.O.C([O-])(O)=O.[Na+]>[CH3:10][O:9][C:6]1[C:7](=[O:8])[C:2]([C:33]2[N:29]([C:23]3[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=3)[N:30]=[CH:31][CH:32]=2)=[N:3][N:4]([C:11]2[C:21]([F:22])=[CH:20][C:14]3[O:15][C:16]([F:19])([F:18])[O:17][C:13]=3[CH:12]=2)[CH:5]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 580723671-Phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 594362543-bromo-5-methoxy-1-(2,2,6-trifluoro-1,3-benzodioxol-5-yl)pyridazin-4(1H)-one

Product 1

HCID 58072330HCID 58072330, compoundYield 60.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

A mixture of 3-bromo-5-methoxy-1-(2,2,6-trifluoro-1,3-benzodioxol-5-yl)pyridazin-4(1H)-one (145 mg, 0.383 mmol), 1-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (155 mg, 0.575 mmol), K2CO3 (106 mg, 0.766 mmol) and PdCl2{P(t-Bu)2(Ph-p-NMe2)}2 (13.6 mg, 0.0192 mmol) in toluene (1.9 mL) and water (0.19 mL) was heated to reflux for 18 h under Ar. The mixture was diluted with NaHCO3 aqueous solution, extracted with AcOEt, dried over Na2SO4, filtered, concentrated in vacuo and purified by column chromatography on basic silica gel (hexane/AcOEt=50/50 to 0/100) and recrystallized with AcOEt/hexane to yield the title compound (102 mg, 60% yield) as a pale yellow solid: mp 200-202° C. 1H NMR (DMSO-d6, 300 MHz): δ ppm 3.76 (3H, s), 6.97 (1H, d, J=1.9 Hz), 7.27-7.47 (6H, m), 7.79 (1H, d, J=1.9 Hz), 7.86 (1H, d, J=9.4 Hz), 8.48 (1H, d, J=1.9 Hz). Anal. Calcd for C21H13F3N4O4: C, 57.02; H, 2.96; N, 12.67. Found: C, 56.94; H, 3.01; N, 12.59.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 18 h under Ar
  3. extractionextracted with AcOEt
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. custompurified by column chromatography on basic silica gel (hexane/AcOEt=50/50 to 0/100)
  8. customrecrystallized with AcOEt/hexane

Sources & evidence

ORD record
ord-63dcf94899b6493d8c6d3948edbd5762
Source dataset
uspto-grants-2013_05
Patent number
US08435995B2

Reaction notes

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