Stannous Chloride → 4,8-Bis(10-phenyldecyl)benzo[1,2-b:4,5-b']dithiophene

HRID 405046Notes

Reaction equation

HRID 405046 reaction equation
[Mg].Br[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[S:19]1[CH:23]=[CH:22][C:21]2[C:24](=O)[C:25]3[S:26][CH:27]=[CH:28][C:29]=3[C:30](=O)[C:20]1=2.Cl[Sn]Cl>C1COCC1.[Cl-].[Na+].O>[C:13]1([CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][C:24]2[C:25]3[S:26][CH:27]=[CH:28][C:29]=3[C:30]([CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)=[C:20]3[S:19][CH:23]=[CH:22][C:21]=23)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 24479Stannous ChlorideHCID 288478(Benzo(1,2-b:4,5-b)dithiophene-4,8-dione)HCID 27356021-Bromo-10-phenyldecaneHCID 5462224Magnesium2×

Product 1

HCID 668211144,8-Bis(10-phenyldecyl)benzo[1,2-b:4,5-b']dithiopheneYield 15%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a 100 mL flask under nitrogen was added magnesium (486 mg, 20 mmol) and anhydrous THF (10 mL). The mixture was heated under reflux and 10-bromodecylbenzene (5.95 g, 20 mmol) was added dropwise. The reaction mixture was kept under reflex temperatures until all magnesium was consumed. Subsequently, 4,8-dihydrobenzo[1,2-b:4,5-b′]dithiophene-4,8-dione (1.1 g, 5.0 mmol) suspended in anhydrous THF (10 ml) was added dropwise. After refluxing for 3 hours more, it was cooled down to room temperature. SnCl2 solution (7.5 g in 19 mL 10% HCl) was slowly added dropwise and then the mixture was kept at 60° C. overnight. After cooling down, brine (25 mL) was added. The organic phase was separated and dried over Na2SO4. The residue after vacuum evaporation was purified by column chromatography with hexane/AcOEt 50:1 as eluent and gave a pale yellow oil (466 mg, yield 15%), which turned into a solid upon standing for a few days. 1H NMR (CDCl3, 500 MHz) δ=7.48 (d, J=6.0 Hz, 2H), 7.46 (d, J=5.0 Hz, 2H), 7.27-7.32 (m, 4H), 7.19 (d, J=7.0 Hz, 6H), 3.19 (t, J=8.0 Hz, 4H), 2.61 (t, J=7.5 Hz, 4H), 1.75-1.86 (m, 4H), 1.58-1.67 (m, 4H), 1.42-1.51 (m, 4H), 1.15-1.41 (m, 20H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux
  3. customwas consumed
  4. additionwas added dropwise
  5. temperatureAfter refluxing for 3 hours more
  6. temperatureAfter cooling down
  7. customThe organic phase was separated
  8. dry with materialdried over Na2SO4
  9. customThe residue after vacuum evaporation
  10. customwas purified by column chromatography with hexane/AcOEt 50:1 as eluent

Sources & evidence

ORD record
ord-79e460944c7c4177b0410f284e8df499
Source dataset
uspto-grants-2014_06
Patent number
US08748739B2

Reaction notes

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