Triphenylphosphine → 7-[2,6-Dimethoxy-4-(methoxymethyl)phenyl]-2-ethyl-3-nitropyrazolo[1,5-a]pyridine

HRID 2253411Notes

Reaction equation

HRID 2253411 reaction equation
Br[C:2]1[N:7]2[N:8]=[C:9]([CH2:14][CH3:15])[C:10]([N+:11]([O-:13])=[O:12])=[C:6]2[CH:5]=[CH:4][CH:3]=1.[CH3:16][O:17][C:18]1[CH:23]=[C:22]([CH2:24][O:25][CH3:26])[CH:21]=[C:20]([O:27][CH3:28])[C:19]=1OB(O)O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C(OCC)(=O)C.COCCOC>[CH3:28][O:27][C:20]1[CH:21]=[C:22]([CH2:24][O:25][CH3:26])[CH:23]=[C:18]([O:17][CH3:16])[C:19]=1[C:2]1[N:7]2[N:8]=[C:9]([CH2:14][CH3:15])[C:10]([N+:11]([O-:13])=[O:12])=[C:6]2[CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 11776TriphenylphosphineHCID 219844817-Bromo-2-ethyl-3-nitropyrazolo[1,5-a]pyridineHCID 22031701Potassium phosphate, tribasic, monohydrateHCID 230809452,6-Dimethoxy-4-methoxymethylphenylboric acid

Product 1

HCID 210841097-[2,6-Dimethoxy-4-(methoxymethyl)phenyl]-2-ethyl-3-nitropyrazolo[1,5-a]pyridineYield 84%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 7-bromo-2-ethyl-3-nitropyrazolo[1,5-a]pyridine (3.0 g, 11.1 mmol), 2,6-dimethoxy-4-(methoxymethyl)phenylboric acid (5.0 g, 22.2 mmol), palladium acetate (125 mg, 0.55 mmol), triphenylphosphine (578 mg, 2.22 mmol), tripotassium phosphate hydrate (5.3 g, 22.2 mmol) and 1,2-dimethoxyethane (30 mL) was heated to reflux for 14 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, ethyl acetate (100 mL) and water (50 mL) were added and the organic layer was separated off. The organic extract was then washed with 10% brine (50 mL), 1N hydrochloric acid (50 mL) and 10% aqueous ammonia (50 mL) in that order. The organic extract was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. The obtained concentrated residue was purified by silica gel column chromatography to afford 3.45 g of the title compound (84% yield).

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 14 hours under a nitrogen atmosphere
  3. customthe organic layer was separated off
  4. extractionThe organic extract
  5. washwas then washed with 10% brine (50 mL), 1N hydrochloric acid (50 mL) and 10% aqueous ammonia (50 mL) in that order
  6. extractionThe organic extract
  7. dry with materialwas dried over anhydrous magnesium sulfate
  8. customthe solvent was evaporated under reduced pressure
  9. customThe obtained concentrated residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-7506f6bf538a45ff853d568baef83c8b
Source dataset
uspto-grants-2008_01
Patent number
US07323569B2

Reaction notes

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