Water → 4,4-Dihexyl-4h-silolo[3,2-b:4,5-b']dithiophene

HRID 1504238Notes

Reaction equation

HRID 1504238 reaction equation
Br[C:2]1[CH:6]=[C:5]([Si](C)(C)C)[S:4][C:3]=1[C:11]1[S:12][C:13]([Si](C)(C)C)=[CH:14][C:15]=1Br.C([Li])CCC.Cl[Si:27](Cl)([CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39])[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33].O>O1CCCC1.CCCCCC>[CH2:34]([Si:27]1([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])[C:2]2[CH:6]=[CH:5][S:4][C:3]=2[C:11]2[S:12][CH:13]=[CH:14][C:15]1=2)[CH2:35][CH2:36][CH2:37][CH2:38][CH3:39]

Participants

7

Reactant 4

HCID 962WaterHCID 87510Silane, dichlorodihexyl-HCID 158605403,3'-Dibromo-5,5'-bis(trimethylsilyl)-2,2'-bithiophene2×HCID 178418339Butyllithium

Product 1

HCID 578923224,4-Dihexyl-4h-silolo[3,2-b:4,5-b']dithiopheneYield 92.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

3,3′-dibromo-5,5′-bis(trimethylsilyl)-2,2′-bithiophene (Compound E4, synthesized in accordance with WO 2010/136353, 10.0 g) was placed in a 200 mL four-necked flask in a nitrogen atmosphere, and dissolved in tetrahydrofuran (150 mL). This was cooled to −78° C., and a solution of n-butyl lithium in hexane (KANTO CHEMICAL CO., INC., 1.64 M, 27.5 mL) was added dropwise. After about 30 minutes of agitation, dichlorodi-n-hexylsilane (5.7 g) was added dropwise. The temperature was gradually raised to room temperature over the course of about 2 hours, after which water was added, and the product was extracted with hexane. The organic layer was washed with water, dried with anhydrous sodium sulfate, and concentrated by filtration. The resulting yellow-orange oily substance was dissolved in hexane (100 mL) and chloroform (50 mL), trifluoroacetic acid (5 mL) with the internal temperature at 2° C., and after 10 minutes of agitation water was added, and the organic layer was washed, dried with anhydrous sodium sulfate, and then concentrated by filtration. Heptane (70 mL) was added to the reaction solution, which was then concentrated under reduced pressure. The resulting yellow-green oily substance was dissolved in hexane, and subjected to silica gel column chromatography (solvent: hexane) to obtain the target 4,4-di-n-hexyl-dithieno[3,2-b:2′,3′-d]silole (Compound E19, 7.1 g, yield 91%).

Workup

  1. temperatureThe temperature was gradually raised to room temperature over the course of about 2 hours
  2. extractionthe product was extracted with hexane
  3. washThe organic layer was washed with water
  4. dry with materialdried with anhydrous sodium sulfate
  5. concentrationconcentrated by filtration
  6. dissolutionThe resulting yellow-orange oily substance was dissolved in hexane (100 mL)
  7. additionchloroform (50 mL), trifluoroacetic acid (5 mL) with the internal temperature at 2° C., and after 10 minutes of agitation water was added
  8. washthe organic layer was washed
  9. dry with materialdried with anhydrous sodium sulfate
  10. concentrationconcentrated by filtration
  11. additionHeptane (70 mL) was added to the reaction solution, which
  12. concentrationwas then concentrated under reduced pressure
  13. dissolutionThe resulting yellow-green oily substance was dissolved in hexane

Sources & evidence

ORD record
ord-9587d8a5c66d4c0ebfd83f86d3b4f1f9
Source dataset
uspto-grants-2015_12
Patent number
US09212254B2

Reaction notes

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