Potassium Fluoride → 5,5'-Dibromo-4,4'-bis(2-octyldodecyl)-2,2'-bithiophene

HRID 1618064Notes

Reaction equation

HRID 1618064 reaction equation
[Br:1][C:2]1[S:3][CH:4]=[CH:5][C:6]=1[CH2:7][CH:8]([CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[F-].[K+]>C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.[N+]([O-])([O-])=O.[Ag+].CS(C)=O>[Br:1][C:2]1[S:3][C:4]([C:4]2[S:3][C:2]([Br:1])=[C:6]([CH2:7][CH:8]([CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[CH:5]=2)=[CH:5][C:6]=1[CH2:7][CH:8]([CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18]

Participants

6

Reactant 2

HCID 522689Potassium Fluoride2×HCID 670317242-Bromo-3-(2-octyldodecyl)thiophene

Product 1

HCID 670316945,5'-Dibromo-4,4'-bis(2-octyldodecyl)-2,2'-bithiopheneYield 47.8%

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalyst2×HCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
120 °C

Procedure

2-bromo-3-(2-octyldodecyl)thiophene (5.32 g, 12 mmol), PdCl2(PhCN)2 (46.5 mg, 0.12 mmol), potassium fluoride (1.39 mg, 24 mmol), and dimethyl sulfoxide (DMSO) (60 mL). AgNO3 (4.06 g, 24 mmol) was added to a 100 mL of Schlenk tube, in one portion. The resulting mixture was stirred at 120° C. for 3 h. Additional potassium fluoride (1.39 mg, 24 mmol) and AgNO3 (4.06 g, 24 mmol) were then added to the mixture and the mixture was stirred for 8 h at 120° C. The reaction mixture was then cooled and passed through a Celite pad to remove black solids. The resulting cake was washed repeatedly with ethyl acetate. The filtrate was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure, resulting in a crude product. The crude product was purified by silica gel chromatography to produce 2.54 g of the final product, a light yellow oil (48%). 1H NMR (CDCl3, 400 MHz, ppm) δ 6.73 (s, 2H), 2.46-2.44 (d, 4H, J=7.2 Hz), 1.64 (m, 2H), 1.25 (br, 64H), 0.89-0.86 (t, 12H). 13C NMR (CDCl3, 100 MHz, ppm) δ 142.20, 136.03, 124.94, 108.50, 38.51, 34.27, 33.39, 31.93, 31.91, 29.97, 29.67, 29.64, 29.63, 29.59, 29.34, 29.32, 26.53, 22.68, 22.67, 14.08.

Workup

  1. stirringthe mixture was stirred for 8 h at 120° C
  2. temperatureThe reaction mixture was then cooled
  3. customto remove black solids
  4. washThe resulting cake was washed repeatedly with ethyl acetate
  5. washThe filtrate was washed with water
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customresulting in a crude product
  9. customThe crude product was purified by silica gel chromatography

Sources & evidence

ORD record
ord-e5a5e56ba28a435f8f2561a0cfc2ff8a
Source dataset
uspto-grants-2014_07
Patent number
US08765968B2

Reaction notes

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