Triphenylphosphine → HCID 67505124, compound

HRID 1929923Notes

Reaction equation

HRID 1929923 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=1)#[CH:2].[CH3:9][O:10][C:11](=[O:26])[C:12]1[CH:17]=[C:16]([C:18]2[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=2)[C:15](Cl)=[N:14][CH:13]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.C(N(C(C)C)C(C)C)C.[Cu]I>[CH3:9][O:10][C:11](=[O:26])[C:12]1[CH:17]=[C:16]([C:18]2[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=2)[C:15]([C:2]#[C:1][C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=2)=[N:14][CH:13]=1

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 137268EthynylpyridineHCID 73013037HCID 73013037, compound

Product 1

HCID 67505124HCID 67505124, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent2×HCID 81531DiisopropylethylamineSolvent2×

Conditions

Temperature
120 °C

Procedure

A degassed solution of 2-ethynyl-pyridine (2.0 mmol, CAN 1945-84-2) in tetrahydrofuran and N-ethyldiisopropylamine (1:1, 10 ml) was added to a degassed suspension of 6-chloro-5-(4-chloro-phenyl)-nicotinic acid methyl ester (1.0 mmol), [1,1′-bis(diphenylphosphino)-ferrocene]palladium(II) dichloride dichloromethane complex (1:1) (49 mg, 0.06 mmol), polymer supported triphenylphoshine (135 mg, 1.48 mmol/g, 0.2 mmol) and copper(I)iodide (11 mg, 0.06 mmol) in tetrahydrofuran and N-ethyldiisopropylamine (1:1, 5 ml). The reaction mixture was heated at 120° C. for 20 hours under an atmosphere of nitrogen. The reaction mixture was cooled to room temperature and the solids were removed by filtration. The solids were washed with ethyl acetate (100 ml), the organic liquors were combined and washed with saturated aqueous ammonium chloride solution (3×50 ml). The organic layer was then dried over MgSO4 and concentrated in vacuo. Purification by flash column chromatography (20% ethyl acetate/heptane) gave the title compound as brown oil.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customthe solids were removed by filtration
  3. washThe solids were washed with ethyl acetate (100 ml)
  4. washwashed with saturated aqueous ammonium chloride solution (3×50 ml)
  5. dry with materialThe organic layer was then dried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customPurification by flash column chromatography (20% ethyl acetate/heptane)

Sources & evidence

ORD record
ord-a66700e5dc6845d99dd6923d1bd440f5
Source dataset
uspto-grants-2012_05
Patent number
US08188093B2

Reaction notes

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