Potassium Phosphate, Tribasic → HCID 67167875, compound

HRID 1517599Notes

Reaction equation

HRID 1517599 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:7]([CH3:18])=[N:8][N:9]([C:11]2[C:16](Br)=[CH:15][CH:14]=[CH:13][N:12]=2)[CH:10]=1)=[O:5])[CH3:2].P([O-])([O-])([O-])=O.[K+].[K+].[K+].[CH:27]1(B(O)O)[CH2:29][CH2:28]1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1.O>[CH2:1]([O:3][C:4]([C:6]1[C:7]([CH3:18])=[N:8][N:9]([C:11]2[C:16]([CH:27]3[CH2:29][CH2:28]3)=[CH:15][CH:14]=[CH:13][N:12]=2)[CH:10]=1)=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 2760897Cyclopropylboronic acidHCID 67168187HCID 67168187, compound

Product 1

HCID 67167875HCID 67167875, compoundYield 107.2%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 22272177Toluene waterSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 1-(3-bromo-pyridin-2-yl)-3-methyl-pyrazole-4-carboxylic acid ethyl ester (1.5 g, 5.5 mmol), potassium phosphate (4.0 g, 19.2 mmol), cyclopropyl boronic acid (0.7 g, 8.2 mmol) and toluene/water (2:1, 15 mL) is degassed with nitrogen and tricylohexylphosphene (0.153 g, 0.54 mmol) and palladium acetate (0.061 g, 0.27 mmol) are added. The mixture is degassed again with nitrogen and the reaction vessel is sealed and heated at 100° C. for 16 h. The reaction mixture is concentrated, diluted with water and extracted with ethyl acetate. The organic layer is dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude mixture is purified by chromatography on silica gel eluting with hexane/ethyl acetate (85:15) to yield 1.6 g (93%) of 1-(3-cyclopropyl-pyridin-2-yl)-3-methyl-pyrazole-4-carboxylic acid ethyl ester. MS (m/z): 272 (M+1).

Workup

  1. additionare added
  2. customThe mixture is degassed again with nitrogen
  3. customthe reaction vessel is sealed
  4. concentrationThe reaction mixture is concentrated
  5. additiondiluted with water
  6. extractionextracted with ethyl acetate
  7. dry with materialThe organic layer is dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe crude mixture is purified by chromatography on silica gel eluting with hexane/ethyl acetate (85:15)

Sources & evidence

ORD record
ord-53d61ad3ab2d40fb88d99a578d4a1922
Source dataset
uspto-grants-2012_07
Patent number
US08232289B2

Reaction notes

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