Tributylvinyltin → 4-(Ethenyl)-2-[(4-chlorophenoxy)methyl]-1-trifluoromethanesulfonylbenzimidazole

HRID 1384006Notes

Reaction equation

HRID 1384006 reaction equation
FC(F)(F)S(O[C:7]1[C:15]2[N:14]=[C:13]([CH2:16][O:17][C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=3)[N:12]([S:25]([C:28]([F:31])([F:30])[F:29])(=[O:27])=[O:26])[C:11]=2[CH:10]=[CH:9][CH:8]=1)(=O)=O.[Cl-].[Li+].[CH:36]([Sn](CCCC)(CCCC)CCCC)=[CH2:37]>[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].O1CCCC1>[CH:36]([C:7]1[C:15]2[N:14]=[C:13]([CH2:16][O:17][C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=3)[N:12]([S:25]([C:28]([F:29])([F:31])[F:30])(=[O:27])=[O:26])[C:11]=2[CH:10]=[CH:9][CH:8]=1)=[CH2:37]

Participants

7

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 211887374-Trifluoromethanesulfonyloxy-2-[(4-chlorophenoxy)methyl]-1-trifluoromethanesulfonylbenzimidazole

Product 1

HCID 211886134-(Ethenyl)-2-[(4-chlorophenoxy)methyl]-1-trifluoromethanesulfonylbenzimidazole

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a 250 ml round bottom flask were added 4-trifluoromethanesulfonyloxy-2-[(4-chlorophenoxy)methyl]-1-trifluoromethanesulfonylbenzimidazole (5.00 g, 9.28 mmol), palladium tetrakis(triphenylphosphine) (428 mg, 0.371 mmol), lithium chloride (2.95 g, 69.6 mmol) and vinyltributyltin (2.94 g, 9.28 mmol) to anhydrous tetrahydrofuran. The reaction mixture was heated to reflux and maintained at this temperature overnight. The progress of the reaction was monitored by thin layer chromatography. An additional 428 mg of the palladium catalyst was added and the resulting mixture was refluxed an additional three hours. To the reaction mixture was added cuprous iodide (35.3 mg, 0.02 eq) and the reaction mixture was refluxed overnight. The solvents were removed in vacuo. The residue was redissolved in ethyl acetate (500 ml) and was washed with 1:1 water:28% aqueous ammonium hydroxide (3×). The organic fraction was dried over sodium sulfate. The desired title product was further purified by column chromatography.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux
  3. temperaturemaintained at this temperature overnight
  4. temperaturethe resulting mixture was refluxed an additional three hours
  5. temperaturethe reaction mixture was refluxed overnight
  6. customThe solvents were removed in vacuo
  7. dissolutionThe residue was redissolved in ethyl acetate (500 ml)
  8. washwas washed with 1:1 water
  9. dry with materialThe organic fraction was dried over sodium sulfate
  10. customThe desired title product was further purified by column chromatography

Sources & evidence

ORD record
ord-1cca125557ba4df5a96811379e929188
Source dataset
uspto-grants-2001_07
Patent number
US06255494B1

Reaction notes

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