3,5-Dibromopyridine → 3-Bromo-5-(3-methoxyphenylethynyl)-pyridine

HRID 606802Notes

Reaction equation

HRID 606802 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([O:9][CH3:10])[CH:4]=1)#[CH:2].[Br:11][C:12]1[CH:13]=[N:14][CH:15]=[C:16](Br)[CH:17]=1>C(N(CC)CC)C.C(OCC)(=O)C.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[Br:11][C:12]1[CH:13]=[N:14][CH:15]=[C:16]([C:2]#[C:1][C:3]2[CH:8]=[CH:7][CH:6]=[C:5]([O:9][CH3:10])[CH:4]=2)[CH:17]=1

Participants

7

Reactant 2

HCID 693693,5-DibromopyridineHCID 6407531-Ethynyl-3-methoxybenzene

Product 1

HCID 670475133-Bromo-5-(3-methoxyphenylethynyl)-pyridineYield 71%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178419050HCID 178419050, compoundCatalystHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

Add 1-ethynyl-3-methoxybenzene (0.56 g, 4.22 mmol) to a mixture of 3,5-dibromopyridine (1.00 g, 4.22 mmol), bis(triphenylphosphine)palladium (II) dichloride (0.06 g, 0.08 mmol) and copper (I) iodide (0.03 g, 0.17 mmol) in triethylamine (8 mL) and heat at 70° C. for 2 h. Cool to room temperature, dilute with ethyl acetate and an aqueous saturated solution of ammonium chloride, and separate the layers. Wash the organic layer with an aqueous saturated solution of sodium chloride, dry (magnesium sulfate), filter and concentrate. Purify the resulting residue by silica gel chromatography, eluting with 2.5% ethanol in 50:50 chloroform/hexanes, to give the title compound (0.86 g, 71%).

Workup

  1. temperatureCool to room temperature
  2. customan aqueous saturated solution of ammonium chloride, and separate the layers
  3. washWash the organic layer with an aqueous saturated solution of sodium chloride
  4. dry with materialdry (magnesium sulfate)
  5. filtrationfilter
  6. concentrationconcentrate
  7. customPurify the resulting residue by silica gel chromatography
  8. washeluting with 2.5% ethanol in 50:50 chloroform/hexanes

Sources & evidence

ORD record
ord-0e14ac28e0ba4013961877bf11d99a7f
Source dataset
uspto-grants-2011_03
Patent number
US07915424B2

Reaction notes

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