Potassium Carbonate → HCID 22256611, compound

HRID 1611535Notes

Reaction equation

HRID 1611535 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([O:9][CH3:10])=[CH:4][C:3]=1[NH:11][C:12]1[C:17]([C:18]#[N:19])=[CH:16][N:15]=[C:14]2[CH:20]=[C:21]([C:23]#[C:24][Si](C)(C)C)[S:22][C:13]=12.I[C:30]1[CH:35]=[CH:34][N:33]=[CH:32][CH:31]=1.C(=O)([O-])[O-].[K+].[K+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.CO.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(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([O:9][CH3:10])=[CH:4][C:3]=1[NH:11][C:12]1[C:17]([C:18]#[N:19])=[CH:16][N:15]=[C:14]2[CH:20]=[C:21]([C:23]#[C:24][C:30]3[CH:35]=[CH:34][N:33]=[CH:32][CH:31]=3)[S:22][C:13]=12

Participants

10

Reactant 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 6094924-IodopyridineHCID 22256668HCID 22256668, compound

Product 1

HCID 22256611HCID 22256611, compoundYield 47%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 887MethanolSolventHCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 7-[(2,4-dichloro-5-methoxyphenyl)amino]-2-[(trimethylsilyl)ethynyl]thieno[3,2-b]pyridine-6-carbonitrile (365 mg, 0.82 mmol), 4-iodopyridine (252 mg, 1.23 mmol), potassium carbonate (565 mg, 4.09 mmol), 30 mg of bis(triphenylphosphine)palladium(II) chloride, 43 mg of triphenylphosphine and 8 mg of copper(I) iodide in 10 mL of tetrahydrofuran and 2 mL of methanol is heated at reflux overnight. The mixture is cooled to room temperature and 50 mL of chloroform are added. The mixture is washed with water and saturated aqueous sodium chloride, dried over magnesium sulfate, filtered and concentrated in vacuo. The residue is purified by two flash column chromatographies, first eluting with 5% methanol in dichloromethane and then eluting with 1:1 ethyl acetate:hexane to provide 174 mg of 7-[(2,4-dichloro-5-methoxyphenyl)amino]-2-(pyridin-4-ylethynyl)thieno[3,2-b]pyridine-6-carbonitrile as orange crystals, mp 221-223° C.; 1H NMR (CDCl3) δ 3.86 (s, 3H), 7.43 (s, 1H), 7.59 (d, J=5 Hz, 2H), 7.81 (s, 1H), 7.89 (s, 1H), 8.61-8.71 (m, 3H), 9.89 (s, 1H); MS 451.2 (M−H)+.

Workup

  1. temperatureis heated
  2. temperatureat reflux overnight
  3. washThe mixture is washed with water and saturated aqueous sodium chloride
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue is purified by two flash column chromatographies
  8. washfirst eluting with 5% methanol in dichloromethane
  9. washeluting with 1:1 ethyl acetate

Sources & evidence

ORD record
ord-26aadfe0829b4afba26f9fba5e6897e8
Source dataset
uspto-grants-2006_01
Patent number
US06987116B2

Reaction notes

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