Phenylacetylene → HCID 10679834, compound

HRID 2362426Notes

Reaction equation

HRID 2362426 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([CH:9]=1)[CH:7]=[O:8].[C:10]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)#[CH:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:12]1([C:10]#[C:11][C:2]2[CH:3]=[N:4][CH:5]=[C:6]([CH:9]=2)[CH:7]=[O:8])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

7

Reactant 3

HCID 10821PhenylacetyleneHCID 11776TriphenylphosphineHCID 27847345-Bromo-3-pyridinecarboxaldehyde

Product 1

HCID 10679834HCID 10679834, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A solution of 5-bromonicotinaldehyde (15 g, 81 mmol) and ethynylbenzene (9.74 mL, 89 mmol) in triethylamine (150 mL) was purged with nitrogen for 30 min. The reaction was treated with triphenylphosphine (0.656 g, 2.50 mmol), and purged 10 minutes longer. To this was added bis(triphenylphosphine)palladium dichloride (0.147 g, 0.210 mmol) and copper(I) iodide (0.032 g, 0.169 mmol). After purging 10 min longer, the reaction was warmed to a gentle reflux. The reaction was heated at reflux for 24 h. The reaction was cooled to room temperature, diluted with ethyl acetate, poured into water, and the layers were separated. The organics were washed again with water, then brine, dried over magnesium sulfate, and concentrated. Column chromatography (20% EtOAc/Hex) gave 16.05 g (96%) as faint yellow crystalline solid. 1H NMR (CDCl3) δ: 10.16 (s, 1H), 9.01 (dd, J=17.1, 1.8 Hz, 2H), 8.30 (t, J=2.0 Hz, 1H), 7.54-7.66 (m, 2H), 7.38-7.47 (m, 3H). 13C NMR (CDCl3) δ: 190.2, 156.8, 150.3, 138.2, 131.9, 130.9, 129.4, 128.7, 122.0, 121.5, 94.5, 84.7. Mass spec.: 208.0 (MH)+.

Workup

  1. custompurged 10 minutes longer
  2. customAfter purging 10 min longer
  3. temperaturethe reaction was warmed to a gentle reflux
  4. temperatureThe reaction was heated
  5. temperatureat reflux for 24 h
  6. additiondiluted with ethyl acetate
  7. additionpoured into water
  8. customthe layers were separated
  9. washThe organics were washed again with water
  10. dry with materialbrine, dried over magnesium sulfate
  11. concentrationconcentrated
  12. customColumn chromatography (20% EtOAc/Hex) gave 16.05 g (96%) as faint yellow crystalline solid

Sources & evidence

ORD record
ord-ec07c3a6536c4a1b92f399c5a3389036
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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