Lithium Chloride → HCID 22316941, compound

HRID 2086749Notes

Reaction equation

HRID 2086749 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:9]=[CH:10][S:11][CH:12]=2)=[C:4]([CH2:13][CH3:14])[CH:3]=1.C([Sn](CCCC)(CCCC)[C:20]([O:22]CC)=[CH2:21])CCC.[Cl-].[Li+]>O1CCOCC1.C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:13]([C:4]1[CH:3]=[C:2]([C:20](=[O:22])[CH3:21])[CH:7]=[CH:6][C:5]=1[C:8]1[N:9]=[CH:10][S:11][CH:12]=1)[CH3:14]

Participants

7

Reactant 3

HCID 433294Lithium ChlorideHCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 22316938HCID 22316938, compound

Product 1

HCID 22316941HCID 22316941, compoundYield 74.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To a stirred solution of 4-(4-bromo-2-ethylphenyl)-1,3-thiazole (2.35 g, 8.76 mmol) in dioxane (45 ml) was added tributyl(1-ethoxyvinyl)tin (3.48 g, 9.64 mmol), tetrakis(triphenylphosphine)palladium (1010 mg, 0.876 mmol), lithium chloride (928 mg, 21.9 mmol), and the mixture was heated at reflux temperature for 16 hours. The reaction mixture was cooled down to room temperature, and diluted with ethyl acetate. The whole was washed with saturated potassium fluoride aqueous solution, and the precipitate was removed by filteration through celite. The resulting solution was extracted with ethyl acetate. The organic layer was concentrated in vacuo. To the residue was added THF (15 ml), 2N HCl aqueous solution (15 ml), and the mixture was heated at reflux temperature for 8 hours. The reaction mixture was cooled down to room temperature, made neutral by addition of NaHCO3, and extracted with ethyl acetate. The organic layer was washed with brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash chromatography eluting with ethyl acetate-hexane (1:5) to give title compound (1.51 g, 74% yield).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux temperature for 16 hours
  3. washThe whole was washed with saturated potassium fluoride aqueous solution
  4. customthe precipitate was removed by filteration through celite
  5. extractionThe resulting solution was extracted with ethyl acetate
  6. concentrationThe organic layer was concentrated in vacuo
  7. additionTo the residue was added THF (15 ml), 2N HCl aqueous solution (15 ml)
  8. temperaturethe mixture was heated
  9. temperatureat reflux temperature for 8 hours
  10. temperatureThe reaction mixture was cooled down to room temperature
  11. additionmade neutral by addition of NaHCO3
  12. extractionextracted with ethyl acetate
  13. washThe organic layer was washed with brine
  14. dry with materialdried over MgSO4
  15. concentrationconcentrated in vacuo
  16. customThe residue was purified by flash chromatography
  17. washeluting with ethyl acetate-hexane (1:5)

Sources & evidence

ORD record
ord-d8ab1e0d8a13445c9dc8e71eaadc78eb
Source dataset
uspto-grants-2004_04
Patent number
US06727238B2

Reaction notes

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