Potassium Phosphate, Tribasic → HCID 90009177, compound

HRID 531248Notes

Reaction equation

HRID 531248 reaction equation
COC1N=CC([C:9]2[CH:21]=[CH:20][C:12]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])=[CH:11][C:10]=2[CH3:22])=CC=1B1OC(C)(C)C(C)(C)O1.Br[C:33]1[CH:34]=[C:35]([Cl:40])[C:36]([Cl:39])=[N:37][CH:38]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.O>[Cl:40][C:35]1[CH:34]=[C:33]([C:9]2[CH:21]=[CH:20][C:12]([C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])=[CH:11][C:10]=2[CH3:22])[CH:38]=[N:37][C:36]=1[Cl:39]

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 127477605-Bromo-2,3-dichloropyridineHCID 89522254HCID 89522254, compound2×

Product 1

HCID 90009177HCID 90009177, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

A suspension of tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (from INTERMEDIATE 31 Step B, 1.0 g, 3.14 mmol), 5-bromo-2,3-dichloropyridine (0.784 g, 3.46 mmol), potassium phosphate (1.33 g, 6.29 mmol), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (0.077 g, 0.094 mmol) in dioxane (12 mL) and water (1 mL) was flushed with nitrogen and stirred at 70° C. for 4 hours. After cooling down, the mixture was filtered over celite and the filter cake washed with ethyl acetate. The filtrate was diluted with ethyl acetate and water and partitioned. The organic layer was washed with brine, dried over sodium sulfate, filtered and the filtrate concentrated. The crude isolate was purified by silica gel chromatography (0 to 80% ethyl acetate/hexane) to give the titled compound as a white solid. 1H NMR (500 MHz, CDCl3): δ 8.3 (d, J=2.1 Hz, 1H), 7.95 (s, 1H), 7.92 (d, J=7.7 Hz, 1H), 7.78 (d, J=2.0 Hz, 1H), 7.27 (d, J=7.9 Hz, 1H), 2.35 (s, 3H), 1.65 (s, 9H).

Workup

  1. customwas flushed with nitrogen
  2. temperatureAfter cooling down
  3. filtrationthe mixture was filtered over celite
  4. washthe filter cake washed with ethyl acetate
  5. additionThe filtrate was diluted with ethyl acetate and water
  6. custompartitioned
  7. washThe organic layer was washed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationthe filtrate concentrated
  11. customThe crude isolate
  12. customwas purified by silica gel chromatography (0 to 80% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-77dbc3efedd84d509e2df75da047acd5
Source dataset
uspto-grants-2016_05
Patent number
US09353101B2

Reaction notes

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