3,4-Diphenylthiophene → HCID 23432464, compound

HRID 2121315Notes

Reaction equation

HRID 2121315 reaction equation
[C:1]1([C:7]2[C:11]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)=[CH:10][S:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Li])CCC.CCCCCC.Br[C:30]1[CH:35]=[CH:34][CH:33]=[C:32]([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][N:37]=2)[N:31]=1>O1CCCC1>[N:31]1[CH:30]=[CH:35][CH:34]=[CH:33][C:32]=1[C:36]1[N:37]=[C:38]([C:10]2[S:9][CH:8]=[C:7]([C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[C:11]=2[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH:39]=[CH:40][CH:41]=1

Participants

5

Reactant 3

HCID 3105963,4-DiphenylthiopheneHCID 117911522-Bromo-6-(pyridin-2-yl)pyridineHCID 178418244HCID 178418244, compound

Product 1

HCID 23432464HCID 23432464, compoundYield 77.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-30 °C

Procedure

After placing 3.5 g of 3,4-diphenylthiophene and 60 ml of tetrahydrofuran in a flask and cooling to −30° C. in an argon atmosphere, 11 ml of a 1.5 mol/l concentration n-butyllithium/n-hexane solution was added dropwise. The mixture was stirred at −30° C. for 2 hours, and then 4.1 g of a zinc chloride/tetramethylethylenediamine complex was added before raising the temperature to room temperature. After stirring for 30 minutes, 3.8 g of 2-bromo-6-(2-pyridyl)pyridine and 0.52 g of a palladium chloride/bistriphenylphosphine complex were added and the mixture was stirred for 2 hours at reflux temperature. After completion of the reaction, the product was cooled to room temperature, purified water was added, the organic layer was extracted, and the concentrate obtained using an evaporator was purified by recrystallization to obtain 4.5 g of 2-(6-(2-pyridyl)-2-pyridyl)-3,4-diphenylthiophene. After placing 3.3 g of the 2-(6-(2-pyridyl)-2-pyridyl)-3,4-diphenylthiophene and 80 ml of tetrahydrofuran in a flask and cooling to −30° C. in an argon atmosphere, 6.2 ml of a 1.5 mol/l concentration n-butyllithium/n-hexane solution was added dropwise. The mixture was stirred at −30° C. for 2 hours, and then 2.4 g of a zinc chloride/tetramethyl-ethylenediamine complex was added before raising the temperature to room temperature. After stirring for 30 minutes, 2.2 g of 2-bromo-6-(2-pyridyl)pyridine and 0.30 g of a palladium chloride/bistriphenylphosphine complex were added and the mixture was stirred for 2 hours at reflux temperature. After completion of the reaction, the product was cooled to room temperature, purified water was added, and the organic layer was extracted. The organic layer was concentrated with an evaporator and purified by column chromatography and recrystallization to obtain 1.1 g of BPPDPT.

Workup

  1. additionwas added dropwise
  2. addition4.1 g of a zinc chloride/tetramethylethylenediamine complex was added
  3. temperaturebefore raising the temperature to room temperature
  4. stirringAfter stirring for 30 minutes
  5. stirringthe mixture was stirred for 2 hours
  6. temperatureat reflux temperature
  7. customAfter completion of the reaction
  8. temperaturethe product was cooled to room temperature
  9. custompurified water
  10. additionwas added
  11. extractionthe organic layer was extracted
  12. customthe concentrate obtained
  13. customan evaporator
  14. customwas purified by recrystallization

Sources & evidence

ORD record
ord-450741907b0e42aeba97a406b32b8ce3
Source dataset
uspto-grants-2004_02
Patent number
US06696182B2

Reaction notes

Loading…