Cesium carbonate → HCID 57662819, compound

HRID 1918953Notes

Reaction equation

HRID 1918953 reaction equation
Br[C:2]1[C:3](=[O:10])[N:4]([CH3:9])[CH:5]=[C:6]([Br:8])[CH:7]=1.[NH2:11][C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][N:13]=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>>[Br:8][C:6]1[CH:7]=[C:2]([NH:11][C:12]2[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][N:13]=2)[C:3](=[O:10])[N:4]([CH3:9])[CH:5]=1

Participants

5

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 737487Methyl 6-aminonicotinateHCID 36143503,5-Dibromo-1-methylpyridin-2(1H)-one

Product 1

HCID 57662819HCID 57662819, compound

Conditions

Temperature
120 °C

Procedure

In a 300 mL sealed tube was placed 3,5-dibromo-1-methylpyridin-2(1H)-one (4.0 g, 15.0 mmol), methyl 6-aminonicotinate (2.3 g, 15.0 mmol), cesium carbonate (10.7 g, 33 mmol), and Xantphos (740 mg, 8.5 mol %). The flask was evacuated and filled with nitrogen 3×. Dioxane (100 ml) was added and the mixture degassed for 25 min with bubbling nitrogen. Tris(dibenzylideneacetone)dipalladium(0) (690 mg, 5 mol %) was then added, the vessel sealed and the reaction heated to 120° C. overnight. The reaction was cooled and diluted with Ethyl acetate (500 mL) and saturated aqueous NaHCO3 (150 mL), the layers were separated and extracted ethyl acetate 2×. The organics were washed with brine 3×, dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by chromatography: ISCO 80 g silica, ethyl acetate/hexanes, to give 186a.

Workup

  1. customIn a 300 mL sealed tube
  2. customThe flask was evacuated
  3. additionfilled with nitrogen 3×
  4. additionDioxane (100 ml) was added
  5. customthe mixture degassed for 25 min with bubbling nitrogen
  6. additionTris(dibenzylideneacetone)dipalladium(0) (690 mg, 5 mol %) was then added
  7. customthe vessel sealed
  8. temperatureThe reaction was cooled
  9. additiondiluted with Ethyl acetate (500 mL) and saturated aqueous NaHCO3 (150 mL)
  10. customthe layers were separated
  11. extractionextracted ethyl acetate 2×
  12. washThe organics were washed with brine 3×
  13. dry with materialdried over Na2SO4
  14. filtrationfiltered
  15. concentrationconcentrated under reduced pressure
  16. customThe residue was purified by chromatography

Sources & evidence

ORD record
ord-fed7d28f01314272a8037e17fd537bcf
Source dataset
uspto-grants-2013_12
Patent number
US08618107B2

Reaction notes

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