Water → 4H-Silolo[3,2-b:4,5-b']dithiophene, 4,4-didecyl-

HRID 1504240Notes

Reaction equation

HRID 1504240 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)([CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH3:47])[CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH3:37].O>O1CCCC1.CCCCCC>[CH2:38]([Si:27]1([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH3:37])[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)[CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH2:46][CH3:47]

Participants

7

Reactant 4

HCID 962WaterHCID 158605403,3'-Dibromo-5,5'-bis(trimethylsilyl)-2,2'-bithiophene2×HCID 21889368Dichloro(didecyl)silaneHCID 178418339Butyllithium

Product 1

HCID 1233927074H-Silolo[3,2-b:4,5-b']dithiophene, 4,4-didecyl-Yield 88%

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, 5.0 g) was placed in a 200 mL four-necked flask in a nitrogen atmosphere, and dissolved in tetrahydrofuran (75 mL). This was cooled to −78° C., and a solution of n-butyl lithium in hexane (KANTO CHEMICAL CO., INC., 1.64 M, 13.7 mL) was added dropwise. After about 30 minutes of agitation, the dichlorodi-n-decylsilane (Compound E21) (4.89 g) synthesized in Synthesis Example A19 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 (50 mL) and chloroform (25 mL), trifluoroacetic acid (2.2 mL) was added 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 and concentrated by filtration. Heptane (32 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-decyl-dithieno[3,2-b:2′,3′-d]silole (Compound E22, 4.46 g, yield 88%).

Workup

  1. additionwas added dropwise
  2. temperatureThe temperature was gradually raised to room temperature over the course of about 2 hours
  3. extractionthe product was extracted with hexane
  4. washThe organic layer was washed with water
  5. dry with materialdried with anhydrous sodium sulfate
  6. concentrationconcentrated by filtration
  7. dissolutionThe resulting yellow-orange oily substance was dissolved in hexane (50 mL)
  8. additionchloroform (25 mL), trifluoroacetic acid (2.2 mL) was added with the internal temperature at 2° C.
  9. additionafter 10 minutes of agitation water was added
  10. washthe organic layer was washed
  11. dry with materialdried with anhydrous sodium sulfate
  12. concentrationconcentrated by filtration
  13. additionHeptane (32 mL) was added to the reaction solution, which
  14. concentrationwas then concentrated under reduced pressure
  15. dissolutionThe resulting yellow-green oily substance was dissolved in hexane

Sources & evidence

ORD record
ord-a324fbb3c4a54d87bcb0db8f262e4709
Source dataset
uspto-grants-2015_12
Patent number
US09212254B2

Reaction notes

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