Triethylamine → HCID 178422384, compound

HRID 1645471Notes

Reaction equation

HRID 1645471 reaction equation
BrC1C(C)=[C:4]([C:12]2[CH2:16][CH2:15]ON=2)[C:5]([S:8](C)(=[O:10])=[O:9])=[CH:6][CH:7]=1.[CH3:18][N:19]1[C:23]([OH:24])=[CH:22][CH:21]=[N:20]1.[C:25](=[O:28])([O-])[O-].[K+].[K+].C([N:33]([CH2:36][CH3:37])CC)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[O:57]1[CH2:62][CH2:61]OCC1>[Pd](Cl)Cl>[CH3:18][N:19]1[C:23]([OH:24])=[C:22]([C:25](=[O:28])[C:12]2[C:16]([CH3:15])=[C:37]([C:36]3[CH2:61][CH2:62][O:57][N:33]=3)[CH:6]([CH3:7])[C:5](=[S:8](=[O:10])=[O:9])[CH:4]=2)[CH:21]=[N:20]1

Participants

8

Reactant 6

HCID 8471TriethylamineHCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 312751,4-DioxaneHCID 109470753-(3-Bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazoleHCID 178481816HCID 178481816, compound

Product 1

HCID 178422384HCID 178422384, compound

Reagents, catalysts & solvents 1

HCID 24290Palladium ChlorideCatalyst

Conditions

Temperature
130 °C

Procedure

2 l of 1,4-dioxane, 250 g (0.77 mol) of 3-(3-bromo-2-methyl-6-methylsulfonylphenyl)-4,5-dihydroisoxazole, 77 g (0.77 mol) of 1-methyl-5-hydroxypyrazole, 269 g (1.93 mol) of potassium carbonate, 197 g (1.93 mol) of triethylamine, 1.39 g (0.0077 mol) of palladium(II) chloride and 4.12 g (0.0154 mol) of triphenylphosphine were added to a 3.5 l autoclave. The autoclave was washed twice with nitrogen, the mixture was heated with stirring to 130° C. and a carbon monoxide pressure of 6 kg/cm2 was applied. By continuous addition of carbon monoxide, the carbon monoxide pressure was kept constant at 6 kg/cm2 and the mixture was stirred at 130° C. for 36 h. The mixture was then admixed with 1 l of demineralized water and the precipitated palladium was filtered off over a blue-band filter (pore size 2 to 3 g) and washed with water. Dioxane, triethylamine and some of the water were then distilled off in one step (150 mbar or atmospheric pressure). The aqueous phase was adjusted to pH 2.5 using 20% strength sulfuric acid and stirred at 5° C. for 12 h, while the pH was being readjusted. The precipitate was filtered off, washed three times with water and dried at 70° C. under reduced pressure. This gave 227 g of product (calc. 100%).

Workup

  1. washThe autoclave was washed twice with nitrogen
  2. temperaturethe mixture was heated
  3. additionBy continuous addition of carbon monoxide
  4. stirringthe mixture was stirred at 130° C. for 36 h
  5. filtrationthe precipitated palladium was filtered off over a blue-band filter (pore size 2 to 3 g)
  6. washwashed with water
  7. distillationDioxane, triethylamine and some of the water were then distilled off in one step (150 mbar or atmospheric pressure)
  8. stirringstirred at 5° C. for 12 h, while the pH
  9. filtrationThe precipitate was filtered off
  10. washwashed three times with water
  11. customdried at 70° C. under reduced pressure

Sources & evidence

ORD record
ord-08b01aead3a44c97a25ca6802f4e9774
Source dataset
uspto-grants-2012_02
Patent number
US08124810B2

Reaction notes

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