Cesium carbonate → HCID 178493041, compound

HRID 1918905Notes

Reaction equation

HRID 1918905 reaction equation
[CH3:1][O:2][C:3]1[NH:7][N:6]=[C:5]([NH2:8])[CH:4]=1.Br[C:10]1[C:11](=[O:18])[N:12]([CH3:17])[CH:13]=[C:14]([Br:16])[CH:15]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>O1CCOCC1.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.CCOC(C)=O.O>[Br:16][C:14]1[CH:15]=[C:10]([NH:8][C:5]2[CH:4]=[C:3]([O:2][CH3:1])[NH:7][N:6]=2)[C:11](=[O:18])[N:12]([CH3:17])[CH:13]=1

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 36143503,5-Dibromo-1-methylpyridin-2(1H)-oneHCID 178493288HCID 178493288, compound

Product 1

HCID 178493041HCID 178493041, compoundYield 12%

Reagents, catalysts & solvents 4

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A sealed tube was equipped with a magnetic stirrer and charged with 5-methoxy-1H-pyrazol-3-amine (1.9 g, 17 mmol), 3,5-dibromo-1-methylpyridin-2(1H)-one (4.9 g, 18 mmol) and cesium carbonate (12 g, 37 mmol) in 1,4-dioxane (160 mL). After bubbling nitrogen through the solution for 30 min, Xantphos (1.1 g, 2 mmol) and tris(dibenzylideneacetone) dipalladium(0) (1.1 g, 1.2 mmol) were added, and the reaction mixture was heated to 100° C. for 16 hours. After this time, H2O (50 mL) and EtOAc (50 mL) were added. The aqueous layer was separated and extracted with EtOAc (2×50 mL). The combined organic extracts were washed with brine (100 mL) and dried over sodium sulfate. The resulting solution was concentrated under reduced pressure to near dryness and the desired product fell out of solution. Filtering and washing with Et2O (10 mL) afforded 12% yield (590 mg) of crude 157a.

Workup

  1. customA sealed tube was equipped with a magnetic stirrer
  2. customAfter bubbling nitrogen through the solution for 30 min
  3. customThe aqueous layer was separated
  4. extractionextracted with EtOAc (2×50 mL)
  5. washThe combined organic extracts were washed with brine (100 mL)
  6. dry with materialdried over sodium sulfate
  7. concentrationThe resulting solution was concentrated under reduced pressure
  8. filtrationFiltering
  9. washwashing with Et2O (10 mL)

Sources & evidence

ORD record
ord-2cbc9ef400664f0883f759582113863d
Source dataset
uspto-grants-2013_12
Patent number
US08618107B2

Reaction notes

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