2-Bromo-6-(pyridin-2-yl)pyridine → 6,6'-(3,4-Diphenylthiene-2,5-diyl)di(2,2'-bipyridine)

HRID 2121316Notes

Reaction equation

HRID 2121316 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[N:12]=[C:11]([C:13]2[S:14][CH:15]=[C:16]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:17]=2[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:10]=[CH:9][CH:8]=1.C([Li])CCC.CCCCCC.Br[C:42]1[CH:47]=[CH:46][CH:45]=[C:44]([C:48]2[CH:53]=[CH:52][CH:51]=[CH:50][N:49]=2)[N:43]=1>O1CCCC1>[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[N:12]=[C:11]([C:13]2[S:14][C:15]([C:50]3[CH:51]=[CH:52][CH:53]=[C:48]([C:44]4[CH:45]=[CH:46][CH:47]=[CH:42][N:43]=4)[N:49]=3)=[C:16]([C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)[C:17]=2[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:10]=[CH:9][CH:8]=1

Participants

5

Reactant 3

HCID 117911522-Bromo-6-(pyridin-2-yl)pyridineHCID 23432464HCID 23432464, compoundHCID 178418244HCID 178418244, compound

Product 1

HCID 234324706,6'-(3,4-Diphenylthiene-2,5-diyl)di(2,2'-bipyridine)

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. addition2.4 g of a zinc chloride/tetramethyl-ethylenediamine 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. concentrationThe organic layer was concentrated with an evaporator
  13. custompurified by column chromatography and recrystallization
  14. customto obtain 1.1 g of BPPDPT

Sources & evidence

ORD record
ord-16ec5745a2c04b0eb737e8fbdf45bcfc
Source dataset
uspto-grants-2004_02
Patent number
US06696182B2

Reaction notes

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