Water → 4-(3,7-Dimethyloctyl)-4-n-hexyldithieno[3,2-b:2',3'-d]silole

HRID 1504249Notes

Reaction equation

HRID 1504249 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.[CH3:26][CH:27]([CH2:39][CH2:40][CH2:41][CH:42]([CH3:44])[CH3:43])[CH2:28][CH2:29][Si:30]([CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH3:38])(Cl)Cl.O>O1CCCC1.CCCCCC>[CH3:26][CH:27]([CH2:39][CH2:40][CH2:41][CH:42]([CH3:43])[CH3:44])[CH2:28][CH2:29][Si:30]1([CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH3:38])[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

Participants

7

Reactant 4

HCID 962WaterHCID 158605403,3'-Dibromo-5,5'-bis(trimethylsilyl)-2,2'-bithiopheneHCID 1232579153,7-Dimethyloctyl-n-hexyl-dichlorosilaneHCID 178418339Butyllithium

Product 1

HCID 1237770084-(3,7-Dimethyloctyl)-4-n-hexyldithieno[3,2-b:2',3'-d]siloleYield 81%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

3,3′-dibromo-5,5′-bis(trimethylsilyl)-2,2′-bithiophene (Compound G4, synthesized in accordance with WO 2010/136353, 11.4 g, 24.3 mmol) was placed in a 500 mL four-necked flask in a nitrogen atmosphere, and dissolved in tetrahydrofuran (200 mL). This was cooled to −78° C., and a solution of n-butyl lithium in hexane (KANTO CHEMICAL CO., INC., 1.59 M, 32.1 mL) was added dropwise. After about 20 minutes of agitation, the 3,7-dimethyloctyl-n-hexyl-dichlorosilane (Compound G18, 9.5 g) synthesized in Synthesis Example B15 was added dropwise. The temperature was raised gradually to room temperature over the course of about 2 hours, water was added, and the product was extracted with hexane. The organic layer was washed with water, dried over sodium sulfate, and concentrated by filtration. The resulting oily substance was dissolved in chloroform (40 mL) and hexane (80 mL), trifluoroacetic acid (3.6 mL) was added, and the mixture was agitated for about 10 minutes at room temperature. Saturated sodium bicarbonate solution was added to the reaction solution, which was extracted with hexane and then concentrated under reduced pressure. The resulting yellow oily substance was dissolved in hexane, and subjected to silica gel column chromatography (solvent: hexane) to obtain the target 4-(3,7-dimethyloctyl)-4-n-hexyldithieno[3,2-b:2′,3′-d]silole (Compound G19, 8.2 g, yield 81%).

Workup

  1. additionwas added dropwise
  2. additionwas added
  3. extractionthe product was extracted with hexane
  4. washThe organic layer was washed with water
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated by filtration
  7. dissolutionThe resulting oily substance was dissolved in chloroform (40 mL)
  8. additionhexane (80 mL), trifluoroacetic acid (3.6 mL) was added
  9. additionSaturated sodium bicarbonate solution was added to the reaction solution, which
  10. extractionwas extracted with hexane
  11. concentrationconcentrated under reduced pressure
  12. dissolutionThe resulting yellow oily substance was dissolved in hexane

Sources & evidence

ORD record
ord-da7cf6093f2240659e14dacb9ea2ef80
Source dataset
uspto-grants-2015_12
Patent number
US09212254B2

Reaction notes

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