4-tert-Butylphenylacetylene → Ethyl-6-(4-tert-butylphenylethynyl)nicotinate

HRID 36358Notes

Reaction equation

HRID 36358 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]#[CH:12])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[CH2:13]([O:15][C:16](=[O:24])[C:17]1[CH:22]=[CH:21][C:20](Cl)=[N:19][CH:18]=1)[CH3:14]>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.C(N(CC)CC)C>[CH2:13]([O:15][C:16](=[O:24])[C:17]1[CH:22]=[CH:21][C:20]([C:12]#[C:11][C:8]2[CH:7]=[CH:6][C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])=[CH:10][CH:9]=2)=[N:19][CH:18]=1)[CH3:14]

Participants

5

Reactant 2

HCID 27573024-tert-Butylphenylacetylene2×HCID 2799611Ethyl 6-chloronicotinate2×

Product 1

HCID 9861388Ethyl-6-(4-tert-butylphenylethynyl)nicotinate

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 477.7 mg (3.02 mmol) of 4-tert-butylphenylethyne (Compound 19), 556.5 mg (3.01 mmol) of ethyl-6-chloronicotinate (Compound 54), 27.8 mg (0.15 mmol) of cuprous iodide, 58.7 mg (0.08 mmol) of bis(triphenylphosphine)palladium (II) chloride and 2 ml of triethylamine was degassed under nitrogen and then stirred under nitrogen at room temperature for 40 hours. The mixture was then heated at 65 degrees C. for 12 hours, cooled to room temperature and the excess triethylamine removed under vacuum. The residue was taken up in water and extracted with ether. The solvent was then removed in-vacuo and the residue purified by flash chromatography (silica 5% ethyl acetate in hexane) to give the title compound as a pale brown solid. PMR (CDCl3): & 1.33 (9H, s), 1.42 (3H, t, J~7.1 Hz); 4.42 (2H, q, J~7.1 Hz), 7.40 (2H, d, J~8.4 Hz), 7.53-7.61 (3H, m), 8.28 (1H, dd, J~8.1 Hz, 2.0 Hz), 9.20 (1H, d, J~2.0 Hz).

Workup

  1. customwas degassed under nitrogen
  2. temperatureThe mixture was then heated at 65 degrees C
  3. waitfor 12 hours
  4. temperaturecooled to room temperature
  5. customthe excess triethylamine removed under vacuum
  6. extractionextracted with ether
  7. customThe solvent was then removed in-vacuo
  8. customthe residue purified by flash chromatography (silica 5% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-c78300b3b1b34114a64816ec3c26243f
Source dataset
uspto-grants-1995_05
Patent number
US05414007

Reaction notes

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