1,4-Dioxane → HCID 58896802, compound

HRID 522235Notes

Reaction equation

HRID 522235 reaction equation
[CH3:1][NH:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1B1OC(C)(C)C(C)(C)O1.Br[C:19]1[CH:24]=[CH:23][N:22]=[C:21]2[NH:25][CH:26]=[CH:27][C:20]=12.P([O-])([O-])([O-])=O.[K+].[K+].[K+].O1CCOCC1>O>[CH3:1][NH:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:19]1[CH:24]=[CH:23][N:22]=[C:21]2[NH:25][CH:26]=[CH:27][C:20]=12

Participants

6

Reactant 4

HCID 312751,4-DioxaneHCID 62657Potassium Phosphate, TribasicHCID 222736434-Bromo-1H-pyrrolo[2,3-b]pyridineHCID 57362342N-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine

Product 1

HCID 58896802HCID 58896802, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

A 1000 mL round bottom flask containing N-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (18.88 g, 81 mmol) was charged with 4-bromo-1H-pyrrolo[2,3-b]pyridine (11.40 g, 57.9 mmol), potassium phosphate (36.8 g, 174 mmol) and phenylallylchloro[1,3-bis(diisopropylphenyl)-2-imidazol-2-ylidene]palladium (II) (1.873 g, 2.89 mmol) under argon. To this was added a mixture of dioxane (400 mL) and water (100 mL) that had been degassed with argon for 30 minutes. The mixture was purged with nitrogen again, and heated at 80° C. overnight under nitrogen. The reaction mixture was cooled to ambient temperature and partitioned between ethyl acetate (750 mL) and 50% brine (1000 mL). The organic layers were dried over sodium sulfate, filtered and concentrated. The crude residue was dissolved in a minimum of methylene chloride, diluted with an equal volume of heptane and was purified on a Teledyne CombiFlash RF chromatography system on a silica gel Gold Rf cartridge (330 g) eluted with a 5-30% 3:1 ethyl acetate/ethanol in heptane to give the title compound. MS (ESI+) m/z 224 (M+1).

Workup

  1. additionTo this was added
  2. customhad been degassed with argon for 30 minutes
  3. customThe mixture was purged with nitrogen again
  4. temperatureThe reaction mixture was cooled to ambient temperature
  5. custompartitioned between ethyl acetate (750 mL) and 50% brine (1000 mL)
  6. dry with materialThe organic layers were dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. dissolutionThe crude residue was dissolved in a minimum of methylene chloride
  10. additiondiluted with an equal volume of heptane
  11. customwas purified on a Teledyne CombiFlash RF chromatography system on a silica gel Gold Rf cartridge (330 g)
  12. washeluted with a 5-30% 3:1 ethyl acetate/ethanol in heptane

Sources & evidence

ORD record
ord-f5d439d6730f46b292242249b1a57e66
Source dataset
uspto-grants-2016_05
Patent number
US09328112B2

Reaction notes

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