Water → 2-Fluoro-5-phenylethynylpyridine

HRID 1507133Notes

Reaction equation

HRID 1507133 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][N:3]=1.C(N(CC)CC)C.[C:16]1([C:22]#[CH:23])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.O>C1COCC1.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.[Cu]I.C(OCC)C>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:23]#[C:22][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:4][N:3]=1

Participants

9

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 27831792-Fluoro-5-iodopyridine

Product 1

HCID 1178732652-Fluoro-5-phenylethynylpyridineYield 129%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

In an 100 ml 2-necked round bottomed flask under Argon were dissolved 2-fluoro-5-iodopyridine (5.0 g, 22.4 mmol, 1.0 equiv.) in THF (30 ml). After 5 minutes at room temperature were added bis(triphenylphosphine)palladium(II)chloride (944 mg, 1.35 mmol, 0.06 equiv.), triethylamine (6.81 g, 9.32 ml, 67.3 mmol, 3.0 equiv.), phenyl acetylene (2.75 g, 2.95 ml, 26.9 mmol, 1.2 equiv.) and copper(I)iodide (128 mg, 0.67 mmol, 0.03 equiv.). The brown suspension was cooled with water (exothermic) to room temperature and stirred overnight. Then 200 ml of diethylether were added, the mixture was filtered, washed with ether and concentrated in vacuum to yield 5.7 g of a brown solid which was adsorbed on silica and was chromatographed in 2 portions over a 100 g prepacked silica column eluting with a 0-10% ethyl acetate in heptane gradient to yield 3.99 g (91%) of the title compound as a light brown solid, MS: m/e=198.1 (M+H+).

Workup

  1. filtrationthe mixture was filtered
  2. washwashed with ether
  3. concentrationconcentrated in vacuum

Sources & evidence

ORD record
ord-86222ba0544a42638b4e9ac3d27607a1
Source dataset
uspto-grants-2015_12
Patent number
US09221802B2

Reaction notes

Loading…