Sodium Carbonate → 3-bromo-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyrimidine

HRID 1255867Notes

Reaction equation

HRID 1255867 reaction equation
[Br:1][C:2]1[CH:3]=[N:4][N:5]2[CH:10]=[C:9](Br)[CH:8]=[N:7][C:6]=12.[CH3:12][N:13]1[CH:17]=[C:16](B2OC(C)(C)C(C)(C)O2)[CH:15]=[N:14]1.O1CCOCC1.C([O-])([O-])=O.[Na+].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[Br:1][C:2]1[CH:3]=[N:4][N:5]2[CH:10]=[C:9]([C:16]3[CH:15]=[N:14][N:13]([CH3:12])[CH:17]=3)[CH:8]=[N:7][C:6]=12

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 27739871-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 122032093,6-Dibromopyrazolo(1,5-a)pyrimidine

Product 1

HCID 687776973-bromo-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyrimidine

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
85 °C

Procedure

3,6-Dibromopyrazolo[1,5-a]pyrimidine (2.0 g, 7.22 mmol) was mixed with 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (1.51 g, 7.22 mmol). Dioxane (36 mL) and 1M Na2CO3 (10.8 mL) were added. The mixture was evacuated and flushed with nitrogen under stirring, then Pd(Ph3P)4 (0.42 g, 0.36 mmol) was added in a counter flow of nitrogen. The reaction mixture was heated to 85° C. under stirring for 16 h, cooled, and poured into a 5-fold excess of water. The product was extracted thrice with CH2Cl2. The organic layer was washed with brine, dried with MgSO4, filtered, and evaporated. The residue was purified by column chromatography (1-5% methanol/DCM) to give 3-bromo-6-(1-methyl-1H-pyrazol-4-yl)pyrazolo[1,5-a]pyrimidine as a yellow solid: LC/MS [M+H]=277.9.

Workup

  1. customThe mixture was evacuated
  2. customflushed with nitrogen
  3. stirringunder stirring for 16 h
  4. temperaturecooled
  5. extractionThe product was extracted thrice with CH2Cl2
  6. washThe organic layer was washed with brine
  7. dry with materialdried with MgSO4
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by column chromatography (1-5% methanol/DCM)

Sources & evidence

ORD record
ord-15e25948bf3d4d1697fb888c584f19da
Source dataset
uspto-grants-2013_06
Patent number
US08461162B2

Reaction notes

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