1,1-Dibromo-1,2,2,2-tetrafluoroethane → 6-Bromo-8-(2-ethylhexoxy)-4-(2-ethylhexyl)thieno[2,3-f]benzothiophene

HRID 2363758Notes

Reaction equation

HRID 2363758 reaction equation
[CH2:1]([CH:3]([CH2:26][CH2:27][CH2:28][CH3:29])[CH2:4][O:5][C:6]1[C:11]2[CH:12]=[CH:13][S:14][C:10]=2[C:9]([CH2:15][CH:16]([CH2:21][CH3:22])[CH2:17][CH2:18][CH2:19][CH3:20])=[C:8]2[CH:23]=[CH:24][S:25][C:7]=12)[CH3:2].C([Li])CCC.[Br:35]C(Br)(F)C(F)(F)F>C1COCC1>[Br:35][C:13]1[S:14][C:10]2[C:9]([CH2:15][CH:16]([CH2:21][CH3:22])[CH2:17][CH2:18][CH2:19][CH3:20])=[C:8]3[CH:23]=[CH:24][S:25][C:7]3=[C:6]([O:5][CH2:4][CH:3]([CH2:1][CH3:2])[CH2:26][CH2:27][CH2:28][CH3:29])[C:11]=2[CH:12]=1

Participants

5

Reactant 3

HCID 1686881,1-Dibromo-1,2,2,2-tetrafluoroethaneHCID 582610808-(2-Ethylhexoxy)-4-(2-ethylhexyl)thieno[2,3-f]benzothiopheneHCID 178418339Butyllithium

Product 1

HCID 582610906-Bromo-8-(2-ethylhexoxy)-4-(2-ethylhexyl)thieno[2,3-f]benzothiopheneYield 42%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A dry 500-mL three-neck flask was flushed with N2 and was charged with 8-(2-ethylhexoxy)-4-(2-ethylhexyl)thieno[2,3-f]benzothiophene (8.4 g, 0.020 mol) and THF (200 mL, 0.1 M) via deoxygenated syringe. The reaction flask was cooled to −78° C. and a 2.0 M solution of n-butyllithium in hexanes (10 mL, 0.020 mol) was added dropwise via deoxygenated syringe. After 30 minutes of stirring at −78° C., dibromotetrafluoroethane (7.8 g, 0.030 mol) was added to the reaction flask and stirring continued for 1 hour at −78° C. The cooling bath was removed and the reaction mixture was allowed to warm up to ambient temperature. As the reaction was completed, cool DI water (50 mL) was slowly added to the reaction flask. Then, the reaction mixture was poured into 150 mL of cool water and extracted with hexanes (200 mL) three times. The combined organic layer was dried over anhydrous magnesium sulfate (MgSO4). After the product was filtered, the solvent was removed by rotary evaporation. The product was purified using column chromatography on silica gel with hexanes/chloroform (gradient) to yield colorless oil (4.2 g, 42%).

Workup

  1. customA dry 500-mL three-neck flask was flushed with N2
  2. customvia deoxygenated syringe
  3. customvia deoxygenated syringe
  4. stirringstirring
  5. waitcontinued for 1 hour at −78° C
  6. customThe cooling bath was removed
  7. temperatureto warm up to ambient temperature
  8. temperaturecool DI water (50 mL)
  9. additionwas slowly added to the reaction flask
  10. additionThen, the reaction mixture was poured into 150 mL of cool water
  11. extractionextracted with hexanes (200 mL) three times
  12. dry with materialThe combined organic layer was dried over anhydrous magnesium sulfate (MgSO4)
  13. filtrationAfter the product was filtered
  14. customthe solvent was removed by rotary evaporation
  15. customThe product was purified

Sources & evidence

ORD record
ord-3c34e06166ed4b73a9ec3378bd951129
Source dataset
uspto-grants-2014_04
Patent number
US08691931B2

Reaction notes

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